INDEX

S. No Topic Page No
Week 1
1 Definition, History, Role of Chemical Engineer 1
2 Basic Features of Chemical Process 40
3 Unit systems and dimensions 80
Week 2
4 Variables and Properties of Material in System 115
5 Pressure and Temperature of Flow Process 157
6 Rate of Process 185
Week 3
7 Principles of material balance and calculation 218
8 Material Balances on Processes with Recycle & Bypass 249
9 Material balances on reactive processes 269
10 Material balances on combustion reactions 290
Week 4
11 State Equation of Ideal Gas and Calculation 317
12 State Equation of non-Ideal Gas and Calculation 338
Week 5
13 Phase equilibrium 364
14 Equilibrium Laws, Humidity and Saturation 393
15 Humidity, Saturation Psychrometric chart 422
16 Process of phase change: Condensation and vaporization 453
Week 6
17 Principles of Energy 486
18 Laws and properties of thermodynamics 518
19 Standard Heat of Formation 566
Week 7
20 The mechanical energy balance 592
21 Enthalpy balances without reaction 619
22 Energy balance with multiplle streams without reaction 650
23 Energy balance on heat of solution 679
Week 8
24 Energy balance with heat of reaction 697
25 Energy balance with heat of reaction (contd..) 713
26 Energy balance with heat of combustion 738
Week 9
27 Material balance of transient process 761
28 Unsteady state energy balance 790
Week 10
29 Least Square Method Linear equation fitting 806
30 Non-linear algebraic equation system 837
31 Numerical Integration 862
Week 11
32 Process Degrees of Freedom 878
33 Process Flowsheeting and codes 904
Week 12
34 Case Study: Cumene Production 945
35 Case Study: Cumene Production (Continuation) 971
 Basic Principles and Calculations in Chemical Engineering
Prof. S.K Majumdar
Department of Chemical Engineering
Indian Institute of Technology – Guwahati

Lecture – 1

Definition, History, Role of Chemical Engineer

Welcome to the massive open online course on basic principles and calculations in chemical
engineering. So in this course, we have 12 modules and around 36 lectures, and we will cover all
the basic principles and calculations in chemical engineering or successively. And today we will
discuss in module 1 as an introduction where some definition history and role of chemical
engineers should be discussed in this lecture.
(Refer Slide Time: 01:03)

So it will include the definition of chemical engineering, history of chemical engineering, and the
role of chemical engineers in society.
(Refer Slide Time: 01:10)

1
Now, as you know that various suspects of chemical engineering which actually leads to for the
welfare of human-being based on industrial focus with some mechanical design of equipment for
the process of production of essential chemicals. Which are very important for our daily life so
for that the knowledge of applied sciences that employs physicochemical and biochemical rate
processes for the design of equipment and plant?

So, if we say about the core of chemical engineering. We have to think about, based on which
that engineering aspect for the welfare of the human being is required. So initially, we have
focused on what should be the basic history of that chemical engineering from where this
chemical engineering profession started? And what are the main aspects of chemical processes?
And also how that chemical engineering processes developed for the production of essential
chemicals in society, which is required for our daily life.
(Refer Slide Time: 02:46)

2
So, in that case, before going to that, we have to say that this engineering, whether it is chemical
engineering or mechanical engineering, civil engineering. All those engineering streams depends
on that some sciences theory of sciences and then that sciences to be applied for the production
of essential chemicals there. So, you have to apply those sciences on how to develop the process
based on that sciences. Like to produce, suppose that some sodium hydroxide solution, calcium
hydroxide, even chlorine gene some organic chemicals LPG even like petrochemical industries
there are several oils those are produced.

That is, of course, coming based on some processes. So, all those processes, whenever being
done that processes, of course, will be based on some fundamentals of the knowledge on
sciences. Those sciences may be Physics may be chemistry may be bioscience, even
mathematics also. So those sciences will be required to develop equipment. And also that plant
accessories to that procure plant to produce that particular a chemical based on a certain process.
So, anywhere if any process is developed that will be depending on the applied sciences.

So, that applied science is converted to chemical engineering based on that knowledge of
physics, chemistry, bio-science, and mathematics, etc. So here one schematic diagram of that
process is shown of that is basically the laboratory scale some process is developed based on
those sciences like physics, chemistry, bioscience, and mathematics. And from those sciences, if
you are applying on a laboratory scale. And what should be the product? Then that process will

3
be scale-up in industrial scale, and chemical engineering represents the scaling of that process
and converting this process. That will be called as the aspect of chemical engineering and related
to that applied sciences.
(Refer Slide Time: 05:32)

Now before going to the discussion on this chemical engineering process and also different
aspects of chemical engineering. And its basic calculations and also principles of that chemical
engineering process. You have to know what is the definition of that chemical engineering.
There was no universally accepted explanation of the field of chemical engineering at its start.
And their some process is developed at early stages basically in the 19th century there.

Whenever process was developed, that processes were actually based on that some engineering
aspect based on some science knowledge and also for that some preamble of consortium to make
this chemical engineering profession and based on that preamble the chemical engineering
actually was defined as that chemical engineering is the area of applied science that puts to use
that physical or chemical biochemical rate processes to produce essential chemicals and articles
for the betterment of human uses.

So, this was the first definition of this Chemical Engineering, which was made based on the
preamble of the chemical engineering aspects of the 19th century.
(Refer Slide Time: 07:24)

4
And as per Dictionary, chemical engineering is defined as; it is a branch of engineering which
involves the design and operation of large scale chemical plants petrochemicals, refineries, and
the like others. So, this is the definition of chemical engineering as per the dictionary of chemical
engineering.
(Refer Slide Time: 07:56)

Even other definitions of the chemical engineering given by different organizations like in that as
per information highway that Global Information and Communication networks. So based on the
aspects of their view the chemical engineering is defined as it is concerned with the process that
causes substances to undergo required changes in their chemical or physical composition,

5
structure, energy content, or physical state there. So this is the definition given by information
Highway.
(Refer Slide Time: 08:31)

And later on, a more appropriate definition of chemical engineering as per the constitution of the
American Institute of chemical engineers. And the organization states this definition of the
chemical engineering as the branch of engineering which deals with the application of principles
of the physical sciences together with the principles of economics, and human relations to field
that pertains directly to process and process equipment in which matter is treated to effect a
change in state energy content and also composition.
(Refer Slide Time: 09:18)

6
And so these are the different definitions of the chemical engineering given by the different
organizations and based on which can say that basically this chemical engineering which is
developed based on the knowledge of applied sciences. So all sciences will be contributing to the
development of chemical engineering. So that is why this chemical engineering now days is the
interdisciplinary profession.

In which all the streams of sciences are contributing a lot for their basic sciences to the
application state to the chemical engineering processes. And what are that chemicals actually?
You also have to understand the meaning of that chemical. This is basically represented by a
substance that involves results from a reaction between two or more substances. You can say that
to relate to the substances that something consists of, so in this way, you have to define that
chemical. What is that chemical means?

The aspect of chemical engineering from where you can say that based on the chemical, how it
can be processed so that that engineering aspects actually represent processing and that
engineering will be based on that the science that is of all streams.
(Refer Slide Time: 10:57)

Now, if we look back to the starting of chemical engineering. So in the 18th century in the last
part of the 18th century especially in 1888. You will see that. The chemical engineering
profession actually began in 1888, and the term, in that case, the chemical engineer, had been

7
floating around technical circles throughout the year 1880s. But there was no formal education
for such chemical engineering profession to given to a particular person recognition at that time.
So this is the beginning of this chemical engineering.
(Refer Slide Time: 11:52)

However, the chemical engineer at this stage that was both a mechanical engineer who had gains
some knowledge of chemical process equipment and also the chemical plant sometimes required
some the observer or foreman. So at that time, a chemical plant foreman with a lifetime of
experience but little education regarded as a chemical engineer. And at that time, it was said that
an applied chemist who can be regarded as a chemical engineer.

If he has some knowledge of large scale industrial chemical reactions. So, chemical engineering
was not defined properly at that time. If anybody works on the chemical plants which some
special knowledge of some chemical reaction or some knowledge of chemical process
equipment. They were regarded as a chemical engineer.
(Refer Slide Time: 13:15)

8
In 1880, George Davis, so at that period, he just made a group of those foremen and some
persons who know that chemical process equipment design as well as the reactions. They are
making together as a Society of chemical engineers, but anyway, these makings of chemical
engineering society were not successful at that period. However, this model state of that appears
to make the society of chemical engineering was changed in 1888.

When this professor Lewis Norton of the MIT USA introduced course X. Thereby, uniting
chemical engineers through a formal degree. And at that time some other organization also was
thinking about how to make that one profession of chemical engineering by giving some post-
work, some peoples also some new peoples are giving the training of that chemical process
equipment design as well as those reactions. So they have started their formal degree in this
chemical engineering.

So, in that case, the University of Pennsylvania and Tulane University quickly followed sweet
adding their 4-years chemical engineering programs in 1892 and 1894, respectively. Just after
that 1888 when this professor Lewis Norton made a course 10 for the chemical engineering
degree by giving those course training there, and after that, there are several persons they got
their chemical engineering degree from different organization and they become renowned
chemical engineer based on their work experience as well as their development of some other
equipment which will be directly or indirectly related to the chemical engineering process.

9
(Refer Slide Time: 16:11)

So, in that case, we have to salute them historical chemical engineer who has developed
chemical engineering based on the science of different streams, and they have regarded it as a
science or chemical engineering. So those historical chemical engineers have contributed a lot
initially to develop these chemical engineering professions. In this case, John Dalton. He is one
of the finer chemical engineers at that time.

And he published atomic weights in their research articles when he was working with this
development of the science of chemical engineering. And he worked on those atomic weights,
how these atomic weights will allow the chemical equations which are to be balanced and also
how it can be established the basis of chemical engineering mass balances. That was done in
1805. And he was at that time the fellow of the royal society and he was English, physicist and
was called as a meteorologist in 1805.

So he was the first person who has developed the chemical equations, how to balance sheet and
also how to do the mass balance for the chemical engineering processes. After that 1824 of
French physicist Sadi Carnot and he also worked on, it is called combustion reactions and what
is the thermodynamic aspects of combustion reactions energy in energy out. And what should be
the different characteristics of the thermodynamic properties on that, combustion reactions?

10
He, in 1824, wrote a book to study the thermodynamics of combustions, reactions. And he
described to the Carnot cycle in his book, how to relate to the theory of heat engines are also
described in his books. And he published that books what was the name was that the reflections
on the motive power of fire. So that was the first book to study the thermodynamics of
combustion reactions.
(Refer Slide Time: 18:59)

After that, in 1850 R. J. E. Clausius, he begins to apply the principles that are developed by
Carnot to chemical systems atomic to the molecular scale. So this was one of the important the
milestone of at that 19th century. Where this chemical engineering processes based on the
development of the chemical systems based on that converting from the atomic to the molecular
scale.
(Refer Slide Time: 19:44)

11
After that, around 10-years, that is 1873-1876 during that period at Yale University. The
American scientist is called Josiah Willard Gibbs. He made significant theoretical contributions
to the study of chemical systems, which are used to calculate the thermodynamics characteristics.
And also, it is called the thermodynamics of Clausius. So this is one of the important periods
where this chemical engineering contribution to that thermodynamic analysis was significant
even remarkable.
(Refer Slide Time: 20:44)

After that 1882, Helmholtz published a founding thermodynamics paper similar to Gibbs. And
he also showed that the measure of chemical affinity that is ‘force’ of chemical reactions, how
that chemical reaction is happened, and based on what is the driving force for that chemical

12
reaction. And he gave that theory to determine and also by measuring the free energy of the
reaction processes. So he gave that theory of force of chemical reactions which is determined by
the measure of the free energy of the reaction process.
(Refer Slide Time: 21:29)

After that 1880, is called George Davis, he proposed to the unsuccessful formation of the society
of chemical engineers in London. That I have already discussed that it was not successful to
make the society of mechanical engineers based on persons, who are working on the chemical
industry and who have some knowledge of that chemical processes. Later on, because of this
unsuccessful formation of this society of chemical engineers in London in 1887, he presented a
series of 12 lectures on the operation of chemical processes.

Now it is called a unit operation that is of the main important subjects in chemical engineering.
And he presented this series of 12 lectures on these operation chemical processes as a unit
operation at the MIT technical school. And in 1901, he also published the first book in chemical
engineering that is called “Handbook of Chemical Engineering.” There he described a lot of
theory, even the development history of chemical engineering and what are the different aspects
of the professions of chemical engineering.

He described in his first book of chemical engineering and how this science can be applied and it
can be processed for the betterment of human life just by developing different essential

13
chemicals. He has given some theory on that. So it was one of the important books in chemical
engineering history.
(Refer Slide Time: 23:29)

And after that in 1883. Osborne Reynolds, he is also one of the renowned peoples in chemical
engineering who has contributed a lot in fluid flow operation based that in which all chemical
processes are assessed. And he defined the dimensionless group for fluid flow. And that
dimensionless group for the fluid flow leading to the practical scale-up. And also understanding
of the flow behavior, heat transfer behavior, and even mass transfer characteristics in the
chemical engineering processes.

Those who are now a day’s still it are hardcore subjects in chemical engineering education as
well as in industry for their design of equipment and other process development.
(Refer Slide Time: 24:24)

14
And in 1885. Henry Edward Armstrong, he offers a course in “chemical engineering” at Central
College, now the name is changed it is called Imperial College London, and he was active in
scientific research and he was working on the subject of the chemistry of naphthalene derivatives
how to naphthalene can be produced. From that crude oil as well as some innovative how we can
be produced from the naphthalene, so she has given that theory on that chemistry of naphthalene
derivations from the crude oils there, he was also fellow of the Royal Society of Edinburg.

He is an English chemist, so from that chemical knowledge of that the conversion of the
chemistry of those naphthalene derivatives from then onwards, there are several syntheses of the
chemicals that were done based on the idea that is opened by ‘Henry E.Armstrong 1885.
(Refer Slide Time: 26:03)

15
And, later in 1888, that is a professor of organic and industrial chemistry at MIT he started a new
curriculum at MIT as a course 10. As a chemical engineering from that basic degree of chemical
engineering started based on this course 10.
(Refer Slide Time: 26:27)

And then, based on this course structure, he made the first chemical engineer. You can say that
the world’s first formal chemical engineer was ‘William Page Bryant’ and his classmates. So in
1891, MIT awards the bachelors of science in chemical engineering to William Page Bryant and
six other classmates of that William Page Bryant, and they were recognized world’s first
chemical engineers group from MIT in that case William Page Bryant was the first of 7 students

16
to graduate from course 10. And thereby become the world's first formal chemical engineer and
he is known as that.
(Refer Slide Time: 27:32)

After that, at the very beginning of 20th century Oliver Patterson Watts, the University of
Wisconsin awarded the first Ph.D. degree to him in chemical engineering, and he was a professor
of chemical engineering and applied electrochemistry at the University of Wisconsin Madison
until 1937. And he is famously known for his development of the hot nickel plating bath and this
is known as that “walls bath.”
(Refer Slide Time: 28:17)

17
After that this Hilda Derrick was also a chemical engineer and she was the first female student
member of the Institute of Chemical Engineers. So these chemical engineers were their
renowned chemical engineers who have got that basic degree and science of chemical
engineering, and they were building pillars of these chemical engineers and they were renowned
historical chemical engineers there.
(Refer Slide Time: 29:03)

From 1945 onwards, that is in the 20th century there are several worlds, there are several
scientists, they were scientist, they were working in chemical engineering, and their several types
of research were done on the chemical engineering development of chemical engineering
professions and based on this now it (the society) is being developed based on this chemical
engineering processes in different ways.

Now, if we looked back on that milestone of that chemical engineering profession in the 20th
century will see that several aspects of chemical engineering development. And from then
onwards will see that this chemical engineering begins as a distinguished profession at the start
of that 20th century. Although elements of water now considered being core chemical
engineering has existed for centuries and more and also you can say that it began as something
amalgam, combining chemistry, having an industrial focus with the mechanical design of
equipment

18
But you can see that this beginning of chemical engineering, you can also say that fermentation
is also developing processor at that century of that beginning. So this fermentation not only that
period but it was also earlier stage in Bibles, it is mentioned that this fermentation process and
also in Homer, it is mentioned that fomentation process so this discipline began as something of
that fermentation process.

Other some chemical processes based on that knowledge of chemistry, which have some
industrial focuses with the mechanical design of equipment and if we say that early triumphs,
which defined profession in the public high to do with the large scale production of that essential
chemicals based on this chemistry of this in amalgam even fermentations processing — even
other forces based on the knowledge of those things and also idea development.

And also the concept of those basic things and later on and also now the knowledge has been
opened up for the development of the further process based on the chemical engineering aspects.
(Refer Slide Time: 32:00)

Now if you talk about that that 1915, in it was regarded as a milestone 1 in that case
fermentation processes have existed throughout human history and the first industrial-scale
formation process other than alcoholic beverages for the production of acetone and butanol
through the anaerobic fermentation of corn by the organism that is called clostridium
acetobutylicum.

19
That is discovered in 1915 by the British chemist that is Chaim Weizmann, and the production of
that is acetone by this route was essential to that British war effort in first world war because that
acetone was required as a solvent of nitrocellulose in the production of smokeless powder. So, in
that case, calcium acetate from which acetone was normally produced based on these
fermentation processes. So this is regarded as milestone one of the chemical in a process.
(Refer Slide Time: 33:22)

Whereas later on this 1930, the early triumphs defined the profession in the public eye had to do
with large scale production of essential chemicals and the invention of the fluid catalytic
cracking in today's date in the chemical engineering aspects can say that process developed by
Warren K.Lewis and Edward R. Gilliland in a late 1930s,

In that case, it was one of chemical engineering advanced process development and that process
is very energetic and also, you can say that it will be economical and also efficient its invention
was crucial to the production of high obtain Aviation gasoline. During the second world war and
also it was the heart of that Centre fees of the modern petroleum refineries still it is the
centerpiece of the modern petroleum refinery, and so this is this invention is regarded as a
milestone two, and that was actually discovered in 1930.
(Refer Slide Time: 34:46)

20
After ten years in 1940, as you say that it was one of the important milestones and in this case
development of the largest scale Arabic fermentation process for the production of penicillin in
early 1940’s it was required because it is one of the outstanding engineering achievement of the
century where that production of the chemical by the biological roots that remains a core part of
the biochemical engineering and which has always been an essential component of the chemical
engineering there.
(Refer Slide Time: 35:28)

After that 1942 to 1945, you can say that this is the war period, of course! That is, unfortunately,
a recurring theme in identifying the great chemical engineering advances in the 20th century. At
that period the Japanese conquest of the rubber plantation of southeast Asia of the start of 2nd

21
world war necessity, today industrial development of the synthetic rubber and in 1942 US
government-sponsored academy consortium and also they are the set out was required to produce
large amounts of synthesis rubber it is called GRS rubber which is mixture of 75% of butadiene
and 25% styrene and by 1945 for the United States was producing around 1 million tones of
synthetic rubber annually.
(Refer Slide Time: 36:52)

Then 1945, onwards you can say that chemical engineers are continued to play a central role in
manufacture and processing of polymer materials and the chemical engineer of the first half of
the 20 century was generally concerned with the largest production of chemicals usually you can
that say through classical Chemical synthesis and also you can say that the beginning of that the
profession of chemical engineering expanded considerably in Outlook during the second half of
the century, so from then onwards this chemical engineering progress continued to date.
(Refer Slide Time: 37:49)

22
From 1951 onward, that is later half of this 20th century several chemical engineers they were
working, when now a day’s also renowned chemical engineers they are working in different that
process development based on the chemical engineering science knowledge in that case by they
were facing a lot of challenges for the development of the process based on this chemical
engineering knowledge’s.

Different challenges like how to make solar energy economical? How to provide energy from
fusion? How to provide access to clean what they are given reverse engineer the brain even you
can say that advance personalized learning developed carbon sequestration method.
Even how to develop its tools for scientific discovery, even restoring and improving the urban
infrastructure? How to do that advanced health Informatics?

How to prevent nuclear reactors or even you can say that how to engineer better medicine? How
to enhance the virtual reality of how to manage the nitrogen cycle? How to secure you know
cyberspace engineering challenges are coming from then onwards for the betterment of our
human life? So for those challenges from different engineers, from different streams, but in that
case, this part of this universe challenges are you know taken by active participation that is active
participation and leadership of chemical engineers.
(Refer Slide Time: 40:26)

23
Now then what should be the role of that chemical engineer today? Based on the walls,
engineering challenges for chemical engineers playing important roles. Today in every industry
and you can service profession in which chemistry or Biology, where those factors including you
can say that semiconductors, nanotechnology, food processing, agriculture, environmental
control, pharmaceuticals energy, even personal care products, finance medicine and of course!
You can say traditional chemical and petrochemicals.
(Refer Slide Time: 41:16)

So, all those challenges are taken by chemical engineers for the better and better way to give
essential chemicals as well as some other services to human development and also the growth of

24
our society in a better way. So chemical engineers have traditionally been involved in both the
design of the process and design of products under those challenges.
(Refer Slide Time: 41:48)

Now, if we talk about how that chemical engineer role on this particular semiconductor
production? Let us look back on those parts as a modern chemical engineer. How are they doing
this year's production of semiconductors? How are those chemical engineers actually important
in this particular production semiconductor production? So, in this case, the production of
semiconductors is given by the chemical engineers who have had derived many of this process
for the manufacture of computer seeds which are dependent on chemical and red processes.

In this case and you grow a chemical engineer who has one of the three founders of the Intel
Corporation and its CEO for many years, so he was chemical engineer, he was working for the
development of the semiconductor, based on their some idea which is development of the basic
sciences and as a chemical engineer, he has contributed a lot for the idea for the development of
semiconductor production.
(Refer Slide Time: 43:25)

25
Now its chemical engineers also are working in controlled drug release in this case. Alan
Michael’s, his one of the pioneer chemical engineers where he contributed lot as a chemical
engineer in this control drug release, where Polymers gels is one of the important material that
releases a drug over time and that issues related to the release like the solubility of the Drug in
the gels and uniformity of the rate of release and also biocompatibility for many materials that
are placed in the body.

Now this aspects of this factors how actually affects on these polymer gels production stage and
in that case this Alan Michael, He has given some Idea even he developed this fundamentals of
these no polymer gels production to control that drug release and in this case, he was one of the
leaders in developing this field but he was a chemical engineer and who was the president of also
alter research in 1970 there.

So, that is why this chemical engineer can work in a different way out of this chemical process,
but he can work on other process development biochemical processes like computer chip
production, semiconductor production, all those things even synthetic biology in that field also
chemical engineers play an important role like synthetic.
(Refer Slide Time: 44:48)

26
Biology that employees the new access to the genetic code and that synthetic DNA to create
novel chemical building blocks by changing the metabolic Pathways in cells within function as
microchemical reactors, so one of the leading figures in this new field is chemical engineer Jay
Keasling, he constructed a practical and inexpensive synthetic Biology root to admission in
which is actually the medication choice for combating

Malaria is resistant to quinine and its derivatives, so this is one of the important that filled where
these chemical engineers can give some idea for the synthesis of Chemicals for this I think that
synthetic biology of it.
(Refer Slide Time: 46:37)

27
And also, chemical engineer plays an important role in environmental control. In this case,
chemical engineers control the environment both through the development of green processes
and improve methods of dealing with air and water quality. In this regard, chemical engineering
John Seinfeld and his colleagues developed the first mathematical models of air pollution in
1972 and they were are also a leader in the development of Urban and regional models of
atmospheric pollution especially the process of that phone Ozone and aerosols.
(Refer Slide Time: 47:25)

Later on David Boger, a chemical engineer managed to the disposing of bauxite residue waste
from the aluminum manufacturing process, which are in the form of a caustic colloidal
suspension, which is called red mart and huge red mart actually were produced at that processing
of that caustic soda in even some other bauxite field there whenever depositing of bauxite
assiduous received us from the aluminum.

Manufacturing processes, so he has actually managed this colloidal suspension that is called red
mart. Just by converting this red mart to valuable products, so he used the suspension to make
valuable materials for the treatment of wastewater for reuse and reducing the volume of waste by
a factor of two.
(Refer Slide Time: 48:29)

28
Chemical engineers also work in nanotechnology, like you can say that the scientific interest was
grown actually to the exploitation of chemical processes with the length of scales of the order of
100 nanometers or less since early 1990’s so from then onwards you will see that there will be
huge change of process development from this macro to the nanoscale range to better process
will get the intensification of the process based on this nanoscale processes.

Thinking of that nanoscale a processes chemical engineers, they have actually did lot of research
on this nanotechnology-based chemical process development (process intensification) just by
based on the different physical and chemical properties from the molar quantities of the same
material in that case catalytic properties of the materials and interfacial phenomena between
unlike materials are now it is determined at this nanoscale for the intensification of the process in
chemical engineering.
(Refer Slide Time: 50:09)

29
Now nanotechnology holds great from this in the development of chemical sensors also if sensor
element is reduced in size to molecular dimensions, it becomes possible to detect even a single
analyze and allied molecule by the sensor development based on this you know that the
molecular properties and in the nanoscale range and how this nanoscale range properties of the
molecules can be utilized to development of this sensor by this analyze molecule by the sensor
.so this sensor development it is actually being developed by this chemical engineers also.
(Refer Slide Time: 51:00)

Chemical engineer Michael Strano used carbon nanotubes to create nanochannel based sensor to
detect very low levels of impurities such as arsenic in drinking water. So, his contribution is one
of the important developments in these nanotechnology-based chemical processes.

30
(Refer Slide Time: 51:25)

Chemical engineer Matteo Pasquali and his colleagues they are also chemical engineers
discovered a process a way you can say to process carbon nanotubes to produce high-strength
fibers that are electrically conductive for the application of reduction of the weight of aeroplane
panels as lightweight electrical conductors for data transmission and for long-distance power
delivery so this chemical engineers they are also working and when they have developed a
nanotube-based high-strength fibers for the design of aeroplane for its reduction of the weight.
(Refer Slide Time: 52:21)

31
Chemical engineer David Soane, he is also one of the renowned chemical engineers who has
invented and commercialized the nanocareTm processes in which cotton fibers are wet with an
aqueous suspension of carbon nanowhiskers that are between 1 and 10 nm in length, it generally
causes liquids to bead up instead of spreading there.
(Refer Slide Time: 52:52)

Chemical engineers also play a significant role in deriving the synthetic polymer industry
development of new materials and their processing to make useful objects for the society, in this
case, Gore-Tex to the power film which was invented by chemical engineer Robert Gore. It is
actually a Porous Film made from polytetrafluoroethylene, or you can say it is a short discord
PTFE and is commonly known by trade name Teflon, and this film is widely used in outdoor
wear. But it also has found medical application as synthetic blood vessels, so in this Robert
Gore’s contribution as a chemical engineer is remarkable.

(Refer Slide Time: 54:00)

32
The Chemical engineers Frank Bates and Glenn Fredrickson, those are also contributed a lot to
the production or development of a new transport plastic poly-cyclohexyl ethylene. These are
generally used in optical storage media, to convert a brittle, glassy material into a tough
thermoplastic suitable for disk manufacture.
(Refer Slide Time: 54:36)

Now in colloidal science which is process of the hardcode chemical engineering in that case we
have to remember this Alice Gast, who was the forefront of the development and exploitation of
wide range of applications she discovered the electrorheology and this the phenomenon viscosity
of the suspension of the colloidal particles containing permanent dipoles increased by orders of
magnitude upon application of an electric field.

33
The possible application to devices such as clutches one of the important you can say that
application, where colloidal science is knowledge, is required in that case the theory for this of
viscosity change of the suspension of colloidal particles which contents that permanent Dipoles
how it can be applied to the application for the development of the device for the clutches, so in
this case Alice Ghat, that one of the important scientist in chemical engineering background.
(Refer Slide Time: 56:16)

Also, a significant role in tissue engineering given by this chemical engineers in this case, Kristi
Anseth, who is a professor of chemical engineering in Howard Hughes Medical Institute .who
has developed, injectable and biodegradable scaffold to support cartilage cells as they grow to
regenerate disease or damaged cartilaginous tissue, where are they have developed a process how
these tissues can be engineers for the replacement of the organ for its respective functions
typically by constructing biocompatible scaffolding on which cells can grow and differentiate.
(Refer Slide Time: 57:20)

34
The treatment of water one of the important chemical engineering process where chemical
engineers play an important role for the water desalination membrane-based separation is one of
the important processes in chemical engineers where you can say this membrane is being used in
a variety of applications for the water treatment characteristics like hemodialysis even oxygen
enrichment development of reverse.

Osmosis process for the water desalination, in this regard, those chemical engineers Sidney Loeb
and the Srinivasa Sourirajan, are famous for the development of Reverse Osmosis process which
was actually developed in 1959, So, this process is still important for the water distillation
process for our drinking water system.
(Refer Slide Time: 58:36)

35
Now chemical engineers works in the development of alternative energy sources away from that
traditional fossil fuel and this case solar energy for electricity production is one area in which the
chemical engineering roll is remarkably you can say, in this regards we have to remember T.W
Fraser Russell, which is a leader to motivate a research and development team for the continuous
production of solar cells and also he designed a reactor that deposits a semiconductor
continuously on a moving substrate. So, In this case, his name of course! is a Chemical engineer,
is remarkable.
(Refer Slide Time: 59:35)

Also, you can say that role in quantitative bioscience; In this case, chemical engineers are
playing an increasingly important role in modern biology and biomedicine. So chemical

36
engineers play an important role in alternative energy sources also, in that case, chemical
engineers work on the development of the alternate energy source away from the traditional
fossil fuel. In this regard, T.W Fraser Russell is a leader in motivated research and development
for the continuous production of solar cells. So in this regard, he is one of the pioneer chemical
engineers for the development of alternative energy sources.

Other than these chemical engineers also play a significant role in quantitative bioscience,
bioscience research, in this case, Rakesh Jain, whose contribution to chemical engineering
developed the network of blood vessels and transvascular transport in tumors and it is of course
!remarkable to say that Dr. A. K Chakraborty is a chemical engineer who uses statistical and
Quantum Mechanics to study molecular conformation.

He gave the first quantitative and testable explanation of the immune systems which is you know
optician process and illuminated the process which gives how much only some humans can
control HIV so other than this chemical process development even role in chemical, biochemical
processes even in other of engineering field.
(Refer Slide Time: 01:02:32)

A chemical engineer can you know plays an important role in public services, also like which is
a recognition process, elimination process which gives some humans can control the HIV virus.
So other than this chemical process development even roll in chemical biochemical process even

37
in other engineering field chemical engineers can play an important role in public services also
like: chemical engineers can act as an administrator of environmental protection agency, he can
be a secretary of energy sector, he can provide expert advice to the government for the research
and development in science and engineering he can act as an evaluator of processor for
destroying stores of Mandvi forms loaded with different essence.

So, other professions can act like: to start the medicine, even to study law, especially patent law,
to enter the financial sector which has been a large employer, in this case, these chemical
engineers can give a beater contribution also in different other professions.
(Refer Slide Time: 01:02:56)

In this case, you have to remember some renowned persons who were chemical engineers but
they have contributed lot in other professions like Adam Osborne, he also developed the first
commercial portable computer in 1981, chemical engineering background the physicist and
Nobel Laureate using now we are called father of the nuclear engineering has contributed a lot
for the uranium separation process.

He was, in fact, chemical engineer by education at all levels and a physicist Edward teller he is
no one of the unknown persons as the father of hydrogen bomb and he also started chemical
engineering for his first university degree. So this chemical engineer works not only in the
chemical engineering professions, but he can act to keep a contribution to the other profession

38
also. So we have discussed several aspects of that chemical engineering development history and
role of chemical engineers in the process development and also the history of chemical
engineering development and also aspects of different other professions how chemical
engineering act.

So, thank you for your attention for giving this lecture, I would suggested to go further reading,
and I have given some textbooks, reference book here and next lecture will be on basic future of
chemical process, so please follow those lectures for the principle and also basic future chemical
process and that will be played in the next lecture.
THANK YOU!
(Refer Slide Time: 01:04:46)

39
 Basic Principles and Calculations in Chemical Engineering
Prof. S.K Majumdar
Department of Chemical Engineering
Indian Institute of Technology – Guwahati

Lecture – 2
Basic Features of Chemical Process

Welcome to the massive open online course on basic principles and calculations in chemical
engineering. So in this lecture, we will discuss something about the basic features of the
chemical process. We have discussed in our earlier lecture that, what is the history and also the
definition of chemical engineering?

And also some contribution of chemical engineers in different disciplines and their role in our
society as a chemical engineer? So, that chemical engineering process, of course, we should
know what are the different types of forces are there in industry, and also in different aspects of
producer essential chemicals. So in that case, we will discuss here.
(Refer Slide Time: 01:31)

.
How can we classify those chemical processes? And also, what are the different modes? And
different features of that are chemical processes? What is the definition of processes?
(Refer Slide Time: 01:42)

40
First, you have to know different definitions of the processes are there. As per Encyclopedia
Britannica, that process is defined as a naturally occurring operation or designed series of
operations that causes physical or chemical changes in substances for a mixture of substances.
Thereby converting raw materials into products and also this process.

What is different from other aspects of from engineering perspective like? That is defined as
Industrial and environmental processes. That is related to the sequences of operations, and
involved events taking up time-space expertise or other resources. Which leads to the production
of some outcome, which is requiring in our social life? So, this is the definition of this process.
(Refer Slide Time: 03:03)

41
Now, if we are talking about that chemical engineering process, this chemical engineering,
resolve into a coordinated series, of like sometimes it can be divided into two parts like unit
operations and unit process. What is that unit operations? It is actually restricted to those
operations in which changes are primarily physical, that caused by the transfer of energy.

As an example, you can say that here crystallization of sugar from sugar solution; in that case,
this operation actually only regarding; the changes of physical phenomena, where caused by the
energy supplied for this operation whereas the unit process involves chemical changes and
implies the commercialization of chemical reactions under certain conditions.

And also, it will be under that economically profitable conditions like, this is basically that
involvement of the chemical changes. As an example, you can say that the production of ethanol
from a sugar solution; which involves a unit operation there. So, this is the division of this
chemical engineering process into two parts like unit operations and unit process.
(Refer Slide Time: 04:54)

Now, if we look into the matter of unit operations, this unit operations can be divided into
different kinds, like this may be mechanical. This may be electrochemical, and this may be
thermo, chemical, and mechanical. That case will not require any appreciable amount of heat and
mass transfer. In that case, like transportation of the materials from one position to another
position or another one location to another location. This is also one kind of process where you

42
can say there will be no chemical reactions, only mechanical parts of the device to be used to
transfer these materials from one location to another location.

Another operation like reactions and there were no other compound forms those operations, like
size reduction bigger particles to be converted to the smaller particles. This is generally of an
important process in mineral Industries, where you will see that to beneficiation of the mineral
particle, sometimes size matters. So, in that case, some small particles are to be converted into
smaller particles.

So, that there will be beneficiation will be easier even sometimes that, in chemical processes
where catalyst particles are being used. In that case, final Catalyst particles give you the more
interfacial area or surface area for its activity, even sometimes saturation of gases particles in
solid particles. There the cursor solid particles to be converted or reduced to the smaller size of
those particles.

So, in that case, this size reduction is one of the important processes for Chemical Engineering
operations. So, these are important mechanical separation. Also, you have to sometimes as an
engineer; it is required to separate those finer particles from the cursor particles. That is called
segregation operation.

So, there it is sometimes to separate that separate of the particles. Even sometimes, from the
slurry system, you have to separate the solid particles from the slurry to clean the water. So, this
is one type of mechanical separation, like membrane separation, when the filter and press
separation. So, these are the basic operations of that chemical engineering process.
(Refer Slide Time: 08:27)

43
So, this is called mechanical operations, whereas another type of operation is called
electrochemical operations. In this case also does not involve appreciable heat and mass transfer
like electrostatic, magnetic separation, even electrodialysis, electrophoresis, Ion exchange, gas
permeation. So these are the operations, are called this electrochemical operation.

And the third one is called Thermochemical operation. In this case, you will see some amount of
heat and mass is required in that case involved, that appreciable heat and mass transfer there. So
like the condensation process evaporation process, here crystallization process, even distillation
process, even drying, humidification, leaching, even absorption, refrigeration etc. All those
operations are regarded as this thermochemical operation.
(Refer Slide Time: 09:33)

44
Now, if we are talking to that type of process. We can have different types of processes like, as
per the mode of that operation. We can divide into different types like this. Sometimes it can be
regarded as based on how the processes are designed to operate, and even sometimes it is
classified as based on how the process varies with time and also special coordinates. And also, it
can be classified based on how the processes are operated with phased contact.

So, as per based on, how the process is designed to operate? It can be called a batch process,
semi-batch process even continuous process. Now, based on how the process varies with time
and special coordinates. It can be classified as steady, unsteady when alarmed even distributed
the processes. Now, if we have another type of process, like where the phases will become in
contact with each other. So, there also you will see that there will be some transfer of mass from
one phase to the phase.

So that type of process is called a multiphase contact process. Like gas-liquid operation, gas-
liquid reaction, even solid-gas operations. In the chemical engineering process of digestion, the
operation is one of the important processes, where you will see that multi-phases come in contact
with each other. So, there will be a mass transfer from each phase to another phase and also heat
transfer operations also take place between the phases, where heat is transferred from to another
phase through the interface.

45
So, we can say that this is one type of process which can be classified based on the contact of the
phases. So, it is called a multiphase contact process.
(Refer Slide Time: 12:03)

Now, what is that the process that based on the mode of operation like batch processes? What is
that batch processes here? In that case, materials leave an enter the processing unit only at the
beginning and at the end of the cycle. Here as shown in the figure in the slide. That at a certain
amount of batch this operation is taking place like ice making, even heating is sealed bottle of
milk in a water bath, even fermentation process, even a small scale chemical production like;
pharmaceuticals.

So, those processes are batch processes, wherein a certain amount of chemicals are to be
processed in a particular unit under certain conditions. In that case, there will be no continuously
supplied amount to processes, those operations in the batch system. So, the batch process is,
generally, we can say that the substances to be entered into the processing unit only at the
beginning and at the end of the cycle of operations.
(Refer Slide Time: 13:36)

46
Whereas continuous process. It involves the continuous flowing of streams, both inlet and outlet
the position and like; you can say that production of nitric acid, pumping liquid at a constant rate
into a distillation column and removing the product distance from the top and bottom of the
column. Even sometimes you will see that the pull filtration process in the distillation process
those are a continuous process.

In that case, continuously, this inlet and outlet will be there and in a certain process unit. The
streams in the inlet and at the outlet will be flowing at a certain rate like here examples is given,
like nitric acid production by Oswald’s process, where Ammonia and oxygen are being sent at a
particular rate through the mixture to the reactors, where a certain temperature like 700 to 800-
degree centigrade and around the tiny bar.

So, continuous here, Ammonia and oxygen are supplied, whereas the outlet, you can say that
nitric acid will be produced at a certain rate. So, this is called continuous operation, where you
can say in both the inlet and outlet streams, these chemicals will be flowing at a certain rate.
(Refer Slide Time: 15:20)

47
Now, what are those semi-batch processes? This is also an important one that some processes are
being taken place, it may be neither is a continuous batch process, where you will see that
process with one batch input but the output bypassing there. Some amount will be continuously
taken out from the output or outlet in a reactor. And this process is regarded as a semi-batch
process in this case; you will see that like one example, feeling the beaker of you will see that are
continuously beaker is filled with water at a certain rate.

Whereas from the outlet in. There is no liquid that is taken out and also slowly draining, while
heating, also suppose, in a greaser, whatever you are using for your bath. You will see that in a
certain batch of liquid, there in the greaser it will be heated. Then for use that hot water will be
used with certain rates from there. So this semi-batch process.
(Refer Slide Time: 16:46)

48
Even you will see blends slowly to liquids in a tank also you will see that two liquids will be
supplied in a tank in a batch-wise, and you will there be blend or mixing of these two liquids and
then the mixture of this liquid should be taken out continuously from the tank. Also, one example
you can see that a balloon, whenever it will be filled with air. It will be a semi-batch process. In
this case, late will be there at a certain rate.

Whereas, there will be no outlet for that. So gas is filled at a certain rate whenever a balloon is
filled with air, where will not come out from the balloon. So, that why it is regarded as the semi-
batch process. Like also washing machine, you will see that there, this is a semi-batch process.
Even the Fermentation process a loaded with batch. Which constantly produces carbon dioxide?
Which has to be removed continuously?

So, these are the examples of the semi-batch process. Now the processes are which classified
batch is on.
(Refer Slide Time: 18:17)

49
The variation of the processing with time and the same your concentration with respect to special
coordinates there. So, process viable, whenever it will be changed with time and with special
coordinates. So, based on which we can classify the processes into the steady-state process, even
transient process also. So, the steady-state process means here process variables like temperature,
pressure, even volume, even fluoride etc.

That does not change with time. So, it is referred to as the steady-state process. Whereas
unsteady steady-state or transient process, those process variables (like temperature, pressure,
and volume or flow etc.) That changes with time. Example batch and semi-batch processes are
by a natural transient process, whereas continuous process can be transient or at steady-state
process there.
(Refer Slide Time: 19:45)

50
Another important classification of this process is called lamed process, where the process
variables change with time but not special coordinates (like x,y,z or special coordinates.) In that
case, process equations are expressed by ordinary differential equations. And most of the process
dynamic equations are made to have simple equations by lumping compact. All the instances
into a single resistance like here.

If we consider that some process variables pi, it changes with respect to time and then, we can
say that this change of this a process
(Refer Slide Time: 20:46)

Variables will be a function of those variables, like this year. So here, if suppose this

51
consignation change with time, that will be a function of some concentration. So in this case, we
can say that these process dynamic equations are made to have simple equations by lumping or
compact, all the resistances into a single resistance there. Examples-
(Refer Slide Time: 21:11)

We can say that the reaction in batch reaction here in a batch reactor. Here like batch reactor
supposes there will be an N mole of the Chemicals are taking part in a reaction. So, that case
molar change of chemical is the reaction rate, which is represented by r, this is called molar
change per unit time Park unit volume and this molar change of chemical.

That is called that reaction rate the time in the volume, and the time will be regarded as this and
dN that will be equal to r into V into dt. So, these molar changes in chemical reaction rate, which
can be regarded as like this.

dN = rVdt

And this can be put into differential equations like this dN/dt that is visible to here rV.
dN/dt = rV
So, we can say that if the volume batch reactor is constant. Then we can represent it as c will be
equal to N/V and then the equation will become like dc /dT that will equal to r.
dc/dt = r

52
So, here in this slide, its shown that in a batch reactor, there is a reaction is going on, and if you
are considering that N the number of moles of a chemical. And the molar change of that
chemical by that reaction will be regarded as dN that will r into V into dt, where r is called molar
change for unit volume per unit time. And this can be put into the differential equations like this.
Here dn/dt equal to RV and if the volume of this batch reactor if you keep constant. Then we can
define this concentration of this reactant as N/v and then the equation can be represented as dc
/dt will be equal to r. So, this is one example of a lump process.
(Refer Slide Time: 23:48)

Another process, it is called distributed processes, where process variables change with both time
and special coordinates. So, here you will that the variables will be changing with respect to time
as well, that is the position there. There, process equations are generally expressed by partial
differential equations. Because here the variables which changing two variables like here time as
well as coordinates there.
So, in this case, all the resistances are distributed throughout the system there, like heat
conduction in solid flow in a pipe, like flowing packed column tubular reactor, even dialyzer
also. So all those processes are regarded as a distributed process, wherein that case will see heat
conduction in solids. That is heat temperature will be changing with respect to time as well as the
solids or that special coordinates s, y, z position of the solid.

Even flow in pipes that you can say that its velocity of the fluid. It may change with respect to y-

53
axis, z-axis even this velocity may change with respect to time. Also, the velocity, whenever
changing with respect to time, it will be called acceleration and deceleration and also if, the
velocity changing with respect to the actual position. Then, it will be called a velocity gradient in
a particular direction.
(Refer Slide Time: 25:45)

An example, you can say that heat conduction in solids. Let us have this derivation of this
equation of that heat conduction in a solid. So that we can have this variation of this temperature
with respect to time as well as special coordinates like x, y or z.
(Refer Slide Time: 26:11)

Now, what are the processes that can be obtained based on the phase contact? Basically, this is a

54
multiphase process, where more than one phase is involved in the process. That is why it is
called the multiphase process and different types of multiphase processes are like the two-phase
processes, three phases process even the four-phase process also there. Now, what is that two-
phase process is the most common class of multiphase processes are two-phase processes and
this includes the following, like gas, gas-liquid operation like.

If you want to absorb the carbon dioxide gas in a Sodium Hydroxide, then it will be called a gas-
liquid process, where carbon dioxide gas from the gaseous mixture to be transported to the liquid
phases or transferred to the liquid phases. So, it is called mass transfer between gas and liquid or
you can say that physical separation of the carbon dioxide gas to the liquid phases.

Even in chemical and physical-chemical also it is there because here you will see that gas will be
absorbed by a chemical reaction in a liquid also. So, that will also be that gas-liquid operation
even gas-solid sometimes absorption of gas into solid. So that it is also a gas-solid operation.
Even you will see that gasification of the coal in that case cash and solid particles should be
there. So this is called to phase process. Even liquid-liquid also like the extraction process.

Suppose a component that is mixed in a certain liquid will be extracted from that liquid to
another unmixable liquid. So this is liquid-liquid operations, even liquid gas. Sometimes for
absorption and desorption purposes, you will see that some liquid will be spread into a
continuous gas in space. So, that you can get the more contact area between gas and liquid and
they are more absorption and desorption or efficiency of the chemical process will be there.

And also, liquid-solid operations also, these are called a two-phase process.
(Refer Slide Time: 28:20)

55
Three-phase processes like various engineering problems actually involve physical and
chemically engineering processes. Where you will see that from the synthesis gas, there are
different types of hydrocarbons produced in a slurry bubble column reactor. Where gas liquid
and solid phases are involved in the reactor there; like carbon monoxide and hydrogen gases will
be coming in contact with the catalyst particle and from that contact that Castile liquid at a
certain temperature and pressure in the presence of catalyst particles.
(Refer Slide Time: 28:44)

You will see that it will be converted into different types of Hydrocarbons there and this is called
gas- liquid-solid. And this gas-liquid-solid operation sometimes it is called that is Fischer-
Tropsch synthesis. So, that is called hydrocarbon production from the synthesis gas and also gas-

56
liquid-liquid operation. Sometimes we will see some chemical engineering operations, where
extraction is being done by gas addition, where more turbulence will be created, even more, the
interfacial area will be produced. And also, there will be that enhancement mass transfer in the
liquid to another liquid.
(Refer Slide Time: 30:13)

Now, also you will see that the solid- liquid- liquid operations also there, like leaching
operations. That some solid particles should be used to extract that contaminated component
from another liquid. So, this is also three-phase operations there and as a four-phase process, you
can say the four-phase flow of oil-water-gas-solid mixture there are complex multiphase flow
.example we can say that in a freeze desalination process.

When butane liquid is added into saline water, that will result in the formation of Ice skates. In
this case, the system is a mixture of butane liquid, water, ice and the butane vapor.
(Refer Slide Time: 32:00)

57
Now, we can divide or we can referred that chemical processes based on multiple contact like;
that liquid-liquid here extraction process, liquid-solid like crystallization, liquid-vapor distillation
process, liquid –gas that absorption, gas-solid like fluidization, solid -vapor it is called
sublimation or adsorption process, even solid-solid is called solid diffusion, even gas-gas system
gas diffusion thermal diffusion, solid-liquid-solid like leaching there,

Even that a solid- liquid-vapor it is called adsorption, gas-liquid-solid it is called flotation,

fluidization. So, these are the various chemical processes based on multiple contacts.
(Refer Slide Time: 32:48)

Now processes which are involving the transportation of the materials. Sometimes the process

58
can be classified based on the transportation of the material, as some materials will be convent
from one point to another point in the industry. In that case, some equipment is being used like
choice equipment for transportation. That depends on the necessary capacity shape also the size
of the material of the distance through which the material has to be transported like pump
compressor human hand blower piping systems are used for transport in the material from one a
point to another in industry.
(Refer Slide Time: 33:38)

The process involving size reduction, like many unit operations in you will see subjected to size
reduction of materials before to be chemical processed. For example, in the core processing
industries, where ores reduce in size before chemical processing and in the cement industry, you
will see that lime, Alumina, and silica reduced in their size before calcination. In food
processing, Mini food products are subjected to size reduction.

In the disintegration of catalytic reduction reaction by reducing the size of the catalyst used.
Chemical processing by fine powder is fluidized in the bed reactor. These are the process
involved in size reduction even in the aluminum production process you will that Bauxite is
reduced in size in a solution of hot caustic soda in our digesters. So, these are the various
examples of the process involved with size reduction.
(Refer Slide Time: 34:55)

59
The crushing process also one important transportation process like based on size reduction
there. Basic principles, in this case, the process of breaking up material into the desired size by
mechanical means a number of phases are called primary, secondary or recycled materials for
direct use further processing. In this case, some equipment for the crushing can be referred as
crusher that called jaw crusher, cone crusher etc.

And also impact-type of crusher, are also available commercially, such as bar blow crusher or
vertical shaft impactors, are important equipment for this crushing process.
(Refer Slide Time: 35:54)

Grinding is also another process for the size reduction there so, it is the surface generation

60
process, where you see that it is being used to shape and finish the components, which are made
of abrasive metals and other materials there. Like Grinding equipment like: belt grinder,
cylindrical grinder, surface grinder, Buhr stone mill, Tower mill, gap mill, even blade mill, even
gear mill also see that the ball Mill, Rod mill, these are some basic equipment by, which you can
do this grinding process.
(Refer Slide Time: 36:44)

And those are very important in the Mining industry basically for beneficiation and also a
separation of the minerals from the ores, even in fluidize operation, whenever catalyst particles
are being used for the chemical reactions in fluidized bed there. The size of that catalyst particles
matters. In that case, the catalyst particles are converted into very fine catalyst particles by the
grinding process. Now another important process, it is called one type of mechanical separation.

In this case, the solid-solid separation process is carried out mainly based on the size or shape of
the solid. And solid-liquid separation, in that case, it is carried out based on the driving force of
the density difference on the pressure gradient. As shown in the slide that, there are two types of
the mechanical separation process based on the phase contact. And that case, like solid-solid
separation the process, based on the size or shape of the solid and solid-liquid separation in that
case driving force of density difference and pressure gradient are consideration for the separation
process.
(Refer Slide Time: 38:15)

61
Another important screening process also one of the mechanical separation processes. In that
case, screening refers to the mechanical separation of solid based on the particle size of shape by
screen plates. For example, in the biological process, you can see that compost is a biological
decomposed organic material that is primarily used as a plant nutrient and soil conditioner to
stimulate crop growth. In this case, stationary screens, vibrating screens, rotating screens are to
be used for this mechanical separation.
(Refer Slide Time: 38:56)

The filtration process is also one of the important mechanical separation processes, where you
will see that solid-liquid involved there even gas-solid is also involved there. In this case, the
removal of solid particles from the fluid by passing the fluid through a certain medium which

62
only the fluid can pass. And in this case, fluid flows from the high-pressure side to the low-
pressure side on the filter. As shown slide that; here you will see that this is one medium per’s
through which that feed particle transferred from one side to the side, based on the presser
difference there.

So, in this case, fluid is flowing from the high-pressure side here this side. This is the low-
pressure side. So whenever this fluid is flowing from the high-pressure side to the low-pressure
side, you will see that leaving some material behind the gravity, vacuum, high pressure,
centrifugal forces. Those are being used or sometime you will see membranes are also being
used to separate these unwanted materials in the feed stream.

Whereas on the other side, it should be regarded as filtrate, which is purified fluid just by
removing unwanted material to the other side. So this is the basic principle of the filtration
process. Now this case you will see different types of filters and also membranes are being used
for the separations of contaminants, even some solid particles in the solution by this filtration
process.
(Refer Slide Time: 41:13)

Another important process is called the decantation process. Here, in this case, the separation of
miscible liquids of different densities by carefully pouring a solution from a container is being
done, which leaves the precipitate at the bottom of the original container. It is also used to

63
separate a liquid from an insoluble solid. Now, decantation is one of the important equipment
which is primarily used for separating materials from the liquid by means of this centrifugal
force. Example like: oil and water that is extracted from olive oil may be decanted to obtain the
olive oil. In this case, decanter, decanter centrifuges are common equipment for this decantation
process.
(Refer Slide Time: 42:20)

Another important process for separating the solid particles in the mixture. It is called settling
and sedimentation, whereas this process involves for the separation of the particulates from the
fluid due to gravity or due to centrifugal motion. Many applications like: settling of crystals from
the mother liquor, mining, wastewater treatment, biological science. These are some examples of
this operation of setting and sedimentation.

Thickening and classification also gravitational settling of solid particles that are suspended in a
liquid, whereas classifications simply the fractions of solid particles based upon their rates of
flow or settling through fluids. In this case, gravity settlers and centrifuge are being used for this
settling and sedimentation, even thickening and classification process.
(Refer Slide Time: 44:34)

64
The flotation process is one of the important chemical processes where you can separate the fine
particles from the ores. Or you can benefice in the ores to separate the valuable materials by this
flotation process. Even this flotation process is being used in the de-inking process there, where
the paper industry there to remove the ink from that waste paper. There using the flotation
process.

Even then, some other chemical processes where you will see that wastewater treatment there
also this flotation process are being used as a merited, where fine particles are being separated by
these variations processes just by using different further. So, this is one of the important
processes in chemical engineering. In this case, you see that gas is actually introduced from the
bottom part of the flotation column.

So that, adhesion of gas bubbles to the solid particles make them buoyant and result in
separation. Like froth flotation, Dissolve-air flotation, some flotation column or flotation
machine where this flotation process is being done. Conventional flotation cell-like (this called
Denver cell), Agitair flotation machine, flotation column cell, Jemson cell are commercially
available flotation equipment, where this flotation process is being done. Another important
chemical engineering process it’s called Agitation and mixing process.
(Refer Slide Time: 45:32)

65
In this case, the reduction of inhomogeneity (of the concentration, phase, temperature) in the
fluid mixture in order to achieve the desired process result like: increase in mass and /or increase
the heat transfer, reaction rate, or produce properties, like this. So in this case, what is that the
agitation and mixing basically are done because of well mixing of the fluid elements, or you can
say that, even phase different phases are particular reacted there.

Just uniformly, how the martial can be mixed inside the reactor. So that is why this agitation
mixing process has been done. It is required for enhancement of mass transfer and enhancement
for heat transfer. Even enhancement of the reaction rate there, in the chemical engineering
process like stirred tank mixture, static inline mixer, rotating homogenizer, these are the basic
equipment for these agitation mixing process.
(Refer Slide Time: 46:49)

66
Now, what are the basic features of the thermochemical processes? Here like condensation is the
process, change in the state of a substance to a denser phase, such as a gas to a liquid. The vapors
condensed by increasing pressure or extracting heat. Generally two-types of mechanism (drop-
wise or film-type). This condensation is being happened so during this condensation basically the
changes in the state of a substance happen.

In that case, in case of condensation, what is moving from vapor to liquid state in freezing? What
is moving from a liquid to solid-state and deposition? What is moving from vapor to a solid-
state? So these are the basic mechanisms of these condensation processes or you can see that
thermo-chemical processes. So equipment and condensation are called a barometric condenser.
The shell-and-tube condenser is a commercial level which is being used for condensation for this
condensation process.
(Refer Slide Time: 48:08)

67
Evaporation processes this all so one type of thermo-chemical process. This case solution is
concentrated by boiling off the solvent by heating by steam at low pressure, such as 0.35 bars to
3 bars. In this case, heat must apply to the solution to finish the energy required for the
vaporization of the solvent and equipment for evaporation is generally long tube and forced
circulation type evaporator.
(Refer Slide Time: 48:52)

The drying process is also another important aspect of the chemical engineering process there.
Before going for any reaction or any other physical separation or mechanical operation, some
drying is important. Even some products which are coming after the reaction that it needs to dry
for its coeternity state further beneficiation operation. So, in this case, it is a process of removing

68
a relatively small amount of water or other liquid from a solid by evaporation. The basic
difference from the evaporator is that the evaporator is used to remove water from the solution
instead of solid.

It performs to remove water at a temperature below the boiling point by circulating air or some
other carrier gas over the material. And equipment of the drying like a rotary dryer, spray dryer,
flash dryer, drum dryer, tray, truck and tunnel dryer, even some other intensive fluid unit like it’s
called freeze dryer, radiofrequency dryer are being used for this drying process.
(Refer Slide Time: 50:25)

And the heat transfer process is also another chemical engineering process. That is heat transfer
operation basically regarded in this. It is processed to transfer heat between two fluids, two solid
or fluid and solid. Heat is transferred from one martial to the other through the surface of the
material due to temperature gradient or temperature difference. It may occur by mechanisms
convection, conduction, and radiation.

What is that conduction? Conduction is basically thermally energy transfer from one position to
another position by direct molecular collisions. And convection transfer heat by fluid motion.
And radiation the energy carried by photons of light in the infrared and visible portion of the
electromagnetic electric spectrum. So, this called radiation. For the heat exchange process
generally double pi, shell and tube, even extended surface, heat exchange serving used, even

69
cooling tower also industrial used for cooling the martial to transfer heat from martial to the
other liquid.
(Refer Slide Time: 52:05)

Humidification and dehumidification processes, in this case, the process is done where the
moisture or water vapor or humidity is added to the air without changing its dry bulb
temperature. It is called the humidification process. The process in which the moisture or water
vapor or the humidity is removed from the air constant temperature. It is called the
dehumidification process.

The cooling and humidification process is one of the most commonly used air conditioning
applications for cooling purposes. In this case, the different types of humidification are: direct
and indirect steam injection, evaporative approaches, evaporative ultrasonic, air wisher sprayed
coils, desert cooler are being used for this air-condition purpose by humidification and
dehumidification process.
(Refer Slide Time: 52:05)

70
Refrigeration is another important process in chemical engineering operations. It is processed in
which work is done to move heat from one location to another. In this case, the refrigerator or
freezer is important. In this case, it is widely used for the current application of refrigeration are
for air conditioning, refrigerating foodstuffs. Even refrigeration is also used to liquefy different
gases like oxygen, nitrogen, propane and methane, gas purification purposes, Even it is being
used for the production of dry ice, for the controlling reaction rate in organic and inorganic
reactions, air conditioning etc. So, these are applications for the refrigeration process.
(Refer Slide Time: 54:03)

Crystallization is also one important unit operations for chemical engineering process. In that
case, the process is being that happens just by the formation of solid crystal precipitating from a

71
homogeneous solution, melts, vapor or a different solid phase, which is called crystallization.
That case tank or batch crystallizers, scraped surface crystallizers, forced Circulating liquid
evaporator – crystallizers are being used.
(Refer Slide Time: 54:43)

The distillation process is the heart of the chemical engineering process there. This also the
thermo-chemical process. You can say that this process generally used to separate two or more
liquid components of a liquid solution into pure fractions that depends upon the difference in the
boiling point of the components or vapor pressure of the components at a given temperature. The
operation involves, in this case, vaporization and subsequent condensation of liquid solution.

The more volatile component vaporizes and passes from the liquid to the vapor phase whereas
less volatile component will be condensing. So, based on this vaporization and condensation and
distillation is being done and you will see the top of the column here? As shown in the slide that
from the top the column, this vapor coming out after vaporization you see that to be condensed to
a product.

And then it will be separated into different component and from the bottom also the heavy
product will be coming. And then, it will be regarded as a bottom product and it will be process
tagging for separate different hydrocarbon there. So, this is actually the distillation process; more
details on the distillation process ofcourse, you will read in chemical engineering unit operations,

72
where all those processes are described in details.

And there are separate courses that you have to do as a chemical engineering there. This actually
lectures just given that very brief of those processes, that introduction that different chemical
engineering process based on that type or classification unit process and unit operation like this.
(Refer Slide Time: 57:13)

Absorption and desorption process the gas absorption is one of the important separation
processes in chemical engineering, where gas absorption essentially involved the transfer of
materials from the gas peace to the liquid phase. And oppositely you can see that, desorption of
course there. It is also sometimes called stripping.

In this case, the transfer in the opposite direction, i.e., From the liquid phase to the gaseous
space, like different types of absorber and stripper in striper as packed columns, spray towers,
tray columns, fluidized bed and bubble columns are being used for the absorption and desorption
purpose.
(Refer Slide Time: 57:54)

73
The extraction process, in this case, the process of separation of solute, is being taken place from
a solution by another insoluble solvent and this is widely known as solvent extraction. Or liquid-
liquid extraction, salutes are separated based on their different solubilities in different liquids.
Mixer-settler, Pulse column, Gravity columns, Mechanically-agitated column, Centrifugal
extractors these are some common equipment that is being used for this extraction process.
(Refer Slide Time: 58:30)

.
Leaching process, like in this case, the martial is treated chemically with a suitable reagent that
preferentially dissolves the active component of the material. The concentrated material formed
is then recovered from the solution by a suitable chemical method. In this case, for example, say

74
that ore concentration by leaching process is the purification of Bauxite using sodium hydroxide
solution as a lea chant.

The Bauxite is digested with a concentrated solution of caustic soda at 150 degrees Celsius in an
autoclave. The Aluminum oxide dissolves in sodium hydroxide leaving behind the insoluble
impurities, which are removed by filtration. This case Zinc recovery from leach residue by use of
sulphuric acid there. So this leaching operation. Here schematic of leaching of Zinc recovery
from leach residue by using sulphuric acid as shown in this slide.
(Refer Slide Time: 59:45).

Similarly, calcination and roasting process is also very important chemical engineering processes
there. In that case, the concentrated material is converted into oxide by calcination i.e. heating it
strongly in the absence of air or roasting there (heating it strongly in the presence of air there).
And this helps in removing volatile impurities like carbon dioxide, sulfur dioxide, organic
matter, and moisture from the ore. Like, calcination is done on the hearth of a reverberatory
furnace there. Roasting is done in a reverberatory furnace or in a blast furnace.
(Refer Slide Time: 01:01:26)

75
Similarly, the reaction process (it) is a process that leads to the formation of new molecules by
rearrangement or redistribution of the constituent atoms. That chemical reaction can be either
spontaneous, requiring no input of energy, or non-spontaneous, typically following the input of
some energy such as heat, light or electricity. So in this case, after reactions, you will see
different types of product output will be coming at a certain condition pressure and temperature.

That you have to maintain and also that depends on that output, depends on other different
variables like flow rate, even martial we shall be used, even catalyst contestation, even uniform
meter, mixing characteristics, fluidized bed inside the reactor. And in this case are CSTR, plug
flow reactor, fixed bed reactor, fluidized bed reactor commonly used for that reaction purpose.

But nowadays the process intensification you will see there are several other different types of
the reactor is now coming for the intensify the chemical process of this reaction you will see that
like micromixer, microreactor. These are reactor which is being used for this reaction process.
(Refer Slide Time: 01:01:55)

76
Electrostatic separation process also regarded as a chemical engineering process where selective
sorting of solid species by means of utilizing forces acting on charged or you can say that
polarized bodies in an electric field. So this case (it) is important in the production of minerals
also the reclamation of other valuable materials, as well as the cleaning of some food products
there.
(Refer Slide Time: 01:02:23).

Magnetic separation is also one mechanical operation there. Magnetic ores like pyrolusite like
manganese oxide and chromite are enriched by this method by this method making use of the
difference in the magnetic properties of the ore and gangue particles.
(Refer Slide Time: 01:02:45)

77
Electrodialysis also an important chemical engineering process, where transportation of salt from
one solution is required. In that case, it is called dilate, To another solution by applying an
electric current and this is done electrodialysis cell that providing all necessary elements of the
process.
(Refer Slide Time: 01:03:10)

In this lecture, I have described different chemical engineering processes in very brief. And also,
the process is classified into different types like: some are mechanical, some are thermochemical,
some are purely thermal, some are purely mechanical, and some are phase contact based. So I
think you have gained some knowledge on that different chemical engineering process.
(Refer Slide Time: 01:03:56)

78
Now next lecture onward, It will be described how these chemical engineering processes are
involved with different calculations? Even how the rate of that input and output even what are
the units are to be used? How is the martial and energy balance to be done for the process
calculation there? So thank you for giving that tenseness for lecture and the next lecture will
discuss something about that unit systems and dimension.

Thank you.

79
 Basic Principles and Calculations in Chemical Engineering
Prof. S.K Majumdar
Department of Chemical Engineering
Indian Institute of Technology – Guwahati

Lecture – 3
Unit Systems and Dimensions

Welcome to message open online course on basic principles and calculations in chemical
engineering to you are discussing this introduction on the basic principles and chemical reaction
engineering under module one. Now in this module, we will discuss. Today about the unit
systems and dimension as we are using a different do your products in our daily life.

Like that, some grocery products in some transported products Pharmaceutical products so all
though products produced based on in principle in process in now that process depends on
different a variable different input and output also whatever it is coming after processing. So, to
quantify all those input and output. It is required to represent the quantity by a certain unit or
dimension.

So that unit system and dimensions it is required to know for the analysis of their process
efficiency based on a certain mathematical expression. Now, to express all those process
efficiencies by that the mathematical expression. You have to assess all those mathematical
expressions by equations with their equations are dimensionally homogeneous or not. How to
analyze those variables are based on the dimensionless quantity to the skill of those processes to
industrial scale.

So that is why you are going to discuss that the different units and dimensions are actually used
for that analysis of process variables and their input and output. And also for the analysis of
model equations are based on the dimensional analysis. So, in this case, we will discuss those
entire variables. Now before going to that, you have to know the definition of that unit or
dimensions.
(Refer Slide Time: 03:03)

80
Now the unit actually indicates the measured quantity actually represents. Now we measure co
counted quantity has a numerical value and unit that measurable units are specific values of
dimensions. That has been defined by convention like for mass you have to quantify based on the
units like gram kg or Pound like this. For the time you have to express it by a unit like seconds
and for the dimensions length that you have to express by a certain unit like Centimeter, meter,
even foot, even inches, all these units. And you will see that dimensions also are one of the
important measurable quantities that the unit represents. For example like length, mass time and
temperature, all are represented as a dimension. Now it also is calculated multiplying or dividing
another dimension there. So whenever you are going to represent any unit by dimension.

That dimension may be multiple of two dimensions or dividing of two dimensions. Combination
of dimensions in such a way that there will be a certain form of that unit there. Like if you are
representing the velocity, then you have to make its unit like what should be the length and what
should be the time. Because velocity is defined by length upon a time. So in that case, what is
the dimension of the velocity? It will be that L by T what is that L is the dimension of length and
dimension of time is T.

So it will be length per time. And similarly, volume what should be the dimension of volume? It
will be actually the length cube volume of that it will be actually L cube. And similarly, density
is basically that defined by mass per unit volume. So in that case, what should be the dimension

81
of that density? It will be like kg per meter cube like that. So In this, we represent any process
quantity or variable quantity by a certain unit or by a certain dimension there.

So any way chemical engineers like any other engineer, they also use units and dimensions for
all the time analysis of process effeminacy based on in the model. For mathematical expression
and what are they to see that there different systems of units are available to represent those
mathematical expressions or quantity or quality of the variables which are being used for
analysis.
(Refer Slide Time: 06:28)

So there are several systems of units, but two primary systems are engineers generally use those
are like International System of units that is SI s system and American engineering system of the
unit. It is actually its short form actually it is called AES. Other systems also available like
centimeter – gram – second which is CGS system. The foot-pound-second system, that is FPS
system short form the and the British System of units like British yard and this case, of course,
all the systems are conventionally used by engineers for analysis of Process.
(Refer Slide Time: 07:15)

82
And next to that you will see that what are units that associated with the systems in this slide in a
table it is shown that the different systems are the units of mass length time and temperature are
given here. So please go through this the units of those the mass length and time, temperature
based on different systems. Here in the SI system generally are internationally uniformly used
the system for any process analysis in that case.

What is the unit for mass? Generally, it is represented by kilogram and length it is represented by
meter and the unit for time always it will be time second and also the temperature it would be in
terms of Kelvin so SI systems are calling like this. Whereas if you are considering that AES
degree systems there you will see that pound (mass) it would be represented as a unit for mass.
Whereas foot would be a unit for length and second the same way as SI it would be taken for
time and the temperature would be Fahrenheit.

Whereas, CGS and FPS system respective units are given here in the table of mass, length, time
and temperature, respectively. For the British system earlier, they have used that slag system foot
second and degree Celsius for mass length time and temperature. So, for this of internationally
for a uniform system that uses their actually using and that system always to be maintained as SI
system so that it will be analyzed through analysis that process uniformly all over the world.

83
And but whenever you are going to express that process variables quantity by other systems, then
you have to convert into one system to another system by a certain factor. That factor, of course,
will be that if you are considering other new systems based on the old system then you have to
multiply by a factor of a new unit by the old unit. So, to convert a quantity expressed in terms of
1 unit to its equivalent in terms of another unit, you will need to multiply the given quantity by
the conversion factor.

So by that conversion factor, you can easily calculate what should be the unit for any variables
quantity, and then to express all those process efficiencies, you sometimes need to express
mathematically that proficiency by an equation. Now, whenever you are going to express those
equations, you have to verify whether those questions are dimensionally consistent or not. So it
is called homogeneousness of the dimensions of the equation.
(Refer Slide Time: 10:33)

So you have to identify and calculate the units or dimensions of both sides of the equations
whether the dimensions are the same or not that will be actually uniform in dimensions on both
sides to express that process efficiency by mathematics.
(Refer Slide Time: 10:48)

84
We can say that some units will not have dimensions. It will be called as exceptions of units like
coefficient in physical laws that do not have units e.g. suppose energy it will be 1/2 into m into u
square so, in that case, we will see that the coefficient half will not have any units yet similarly,
exponents also will be unit less like if you are expressing that u2 or v2 or certain other variables
that to the power some value, then that power or exponent will be unitless.

Similarly, arguments are unit less like X is the angle that may have some unit degree but sinX
that will not have any unit there similarly cosX, tanX or tan theta cos theta will not have any unit
so argument are unit less similarly some quantities some expressions that are very important to
express the process type or you can say that whether that process is highly turbulent or you can
say that laminar like if any liquid is flowing through the pipe.

You will the velocity of the fluid would be in such a way that, that liquid will not be moving
very laminar way or you can say that without disturbing of this molecule. It will be flowing
through the pipe so if the molecule of the liquid is moving without actually displacing on its flat
path. Across its path then you can say that the floor laminar where as when did all the molecules
will be moving in such a way that all the molecule will be randomly moving throughout the pipe.

So it will call as Starwood end now this laminar and turbulent flow how will you access
quantitative. So, in that case, you have to find out some dimensionless numbers. That is called

85
the Reynolds number. Here Osborn Reynolds he did experiment to find out the criteria of making
the flow of laminar of turbulent based on this Reynolds number and this is number cause the
dimension of this quantity will not have any dimensions here of this quantity so it will be a
number.

Because here, you will see that it is defined by this

Rou is the density its unit is kg per meter cube or its dimension is M per L cube and u is the
velocity that is meter per second and d is the unit here. Viscosity is nothing but kg per meter

second. So if you substitute that unit here for these variables . Then you will see that
dimension will be nullified so in that case, it will be converted as a number. That is why this
number will be regarded as Reynolds number.

Now if Reynolds number is less than 2300 you can say that flow will be laminar whereas if it is
greater than 4000. It will be highly turbulent. So by this analysis dimensionless number you can
access the process, it will be there .so this dimensionless group so many other dimension groups
like this there are so many other dimensionless groups like this you will see in chemical process
calculations there and those entire dimension is having no dimensions there.

So this is called dimensionless number so these are called the exception of units there. So all are
different kinds of exceptions of units. That I have found some coefficients in physical laws even
exponents are unit less or dimensionless arguments are unit less dimensionless numbers are
dimensionless. So like this or unit less, you can say. So this you have to remember what type of
laws a dimension this or that will have some dimension.

So in that is based on which have to make the equations, of course, the dimensionless on both
sides. Now have an example like this here make the equation dimensionally consistent.
(Refer Slide Time: 16:02)

86
How to do this. Like if you suppose that composition C which will vary with respect to time a
process that the concentration of solution respect to time express by the equation Y is equal to a
minus b x square Y is concentration whose unit is kg per liter whereas this x denoting for the
time.
y  aebx
so, in that case, the unit will be seconds Now as we know that the exponent will not have any
dimension.

So if you are following that law here so this is the dimensions of having such a way that this
exponent will not be having dimensions. So how to do that so dimensions of ‘b’ will be such a
way that it should be nullified after multiplying of b and t. So what to do the dimension of what
time is second. So the dimensions of 1 by second to so that second one by the second it will be
nullified to convert into 1.

So that way it should be that dimensionless so this part should dimensionless but your left-hand
sides have the dimension of kg per liter. So you have to make the consistency of the equation in
such a way that the dimension of that should be kg per liter. So that way you consider or make
the consistency of the dimensions. So what is unit associated with a and b to make this
educationally dimension homogeneous or consistence you have to make the unit of a as the same
as the unit of y.

87
That is kg per liter, and also exponential function must have dimensionless. So the figure b must
have a unit that is 1 by seconds or second inverse. So in this way, you have to make the equation
dimensionless on its both sides.
(Refer Slide Time: 18:35)

Like another example: consider S is an equation equal to 7t + 8t2 where S is referred to as

distance whose unit is meter and time is represented by t and the unit is seconds. So what are the
dimension of 7 and 8 here .so you can represent that you have just to make it equivalent to
dimensions on both sides of this equation. What is the unit for s? What is the unit for t? What is
the unit for t square?

Accordingly, the other coefficients should have the dimensions to make it a constant for its
dimension. So in that case, the unit of 7 will be meter per second and the unit for number 8
should be meter per Second Square. Similarly, the dimension will be m by l and the also you can
say m by s and also a dimensions of that will be m by square.

The thermal conductivity of k of a liquid metal is the like is predicted by other the empirical
equation. like k equal to A into an exponent of B by T
kx  Ku0.487

88
where k is Jule per second meter Kelvin and A and B are constant so T is absolute Temperature
so what should be the dimensions of units of A or B. so this similarly to make dimension in
dimensionally homogeneous consistent. You have to make the unit of A same as that K .so it will
be Jule per second per meter K. Similar B has unit of T that is K.
(Refer Slide Time: 20:23)

Now you can try yourself this problem yourself to make this dimensionally consistent.
(Refer Slide Time: 20:30)

.
Now another important aspect of dimension for the chemical engineering process like whenever
you are doing any experiment and gating some results of the process of efficiency. Now to make

89
this process be able to industrial scale. You have to express that mathematical expression or
model to make it industrially scale label then what you have to do the dimensional analysis of the
equation from this lower scale to the upper scale there.

So in that case in laboratory-scale sometimes you cannot do that experiment possible to carry out
on its full size of the unit. So, there, experiments are carried out on a small scale so in that case,
to make it that industrial-scale you have to make some model based on the experimental data.
Now, once you make the model equation by universal model equation or empirical model
equation based on your experimental data.

You can predict those processes of output quantity based on this model and was based on the
process variable and you can predict at large scale just by changing the value of process variable
quantity .so whenever you are making that equation. An equation to be used to calculate for the
higher values of a process variable. Then you can get the higher values of or projected values of
what is that process output.

Now based on that industrial-scale process equipment to be developed based on this

experimental data and it's model development so in this way whenever making any model
equation. You have to make it dimensionally consistent and to make that dimensionally
consistent. You have to that made this dimensionless form and that equation to be sometimes to
convert it into a dimensionless group or dimensionless number.

Now to make those dimensionless number you have to do some dimensional analysis. There will
be a certain way to do that so that process will discuss yet.
(Refer Slide Time: 23:22)

90
There are two processes to do dimensional analysis based on the process variables. If there are N
numbers of variables for analysis of that process, then you have to make those entire processes
variable in a dimensionless form in such a way that on the left-hand side and right-hand side of
the equations will be dimensionless. So to make that, there are two processes. One is called
Rayleigh's method and the other is called Buckingham Pi theorem.

Now to analyses by these two methods are the equation dimensionally consistent or
dimensionless number based equation. You have to know some primary fundamental units are
based on which those dimension analysis to be done. Now that primary time fundamental units
are length mass and time based on these fundamental units. You can do that dimension analysis
to make that the dimensionless group. Now we will do that here one by one.
(Refer Slide Time: 24:32)

91
And before going to that you have to know important dimensions also you have to remember
here in this like given some variable like geometrical variable kinematics variable dynamic
variable even fluid property variables and their quantities like geometry like area volume even
moment area. Even you can say those kinematics like velocity acceleration angle angular
velocity quantity of flow mass flow rate. Even dynamic variables like force, moment, torque,
energy, heat, power, pressure, stress all those things.

Even, some fluid properties: density, viscosity, surface tension, kinematic viscosity, thermal
conductivity, specific heat, even bulk modulus of the fluid, like that. So all those quantities
represented by a certain dimension. Here in this slide also these dimensions are given
respectively here all those dimensions should be required to analyze that dimension and to make
it dimensionless group. So for that this- I told that two methods are there that One is Raleigh
method and another is Buckingham pi- method.

So you have to remember these two methods and both the methods of dimension analysis
determine only the relevant independent dimensionless parameters of a problem but not the exact
relation between them. So here will make it.
(Refer Slide Time: 26:06)

92
Let’s discuss about that Rayleigh's method first. The method involves the following steps here.
Step 1 notes all the independent variables that are likely to influence the dependent variable. Like
any process, suppose there is a flow of fluid through the pipe .OK. Now you will see there will a
change in pressure whenever fluid will be flowing through the pipe.

Now the pressure is one dependent variable based on some other independent variables, it will be
changed how like pressure will be changing based on the diameter of the pipe. Pressure will
change if you change in velocity of liquid pressure will change if you change the type of fluid
that is its physical properties.

So based on which you will see that there will be a change of pressure drop so that why here
dependent variables pressure drop where independent variables physical properties of system
diameter of column length of column even velocity of the fluid even there is any roughness of
pipe or not. That also gives a change in pressure drop. So you have to note all the independent
variables that are likely to influence the process and also independent variables on which these
independent variables are affected. Then what you have to do if Y is a variable.

That depends upon independent variables like X1 X2 X3 and Xn then writes the functional
equation. As Y is equal to what is that a function of X1 X2 X3…Xn.
y  f ( x1 , x2 , x3 ,.........xn )

93
There may be n number of variables will there. It may be more number of variables that will be
there. That would be independent whereas the dependent variable will be certain variable there.
OK. So in this way, you have to express the functionality of dependent variables based on those
independent variables.
(Refer Slide Time: 28:31)

After that, what you have to do write the functional equation in the form of like this y is equal to
like C to X1 to the power an X2 to the power b X3 to the power c and …. Xn to the power m .
y  C ( x1a x2b x3c .........xnm )

So, in this case, you are actually making this certain relationship of those independent and
depend on variables like this. Here C is the constant of dimensionless constant and a b c and m is
arbitrary exponents.

Those exponents C a b c all those exponents will be obtained from that experimental data based
on your process. And then after that express each of the quantities in the equation in fundamental
dimension in which is the solution required.
(Refer Slide Time: 29:25)

94
Now after that, by using dimensional homogeneity, obtain a set of simultaneous equations. That
is involving the exponents a b c and m. after that, you have to solve these equations to obtain the
value of exponents a b c and m. Then from then find the dimensionless group by the variables
with like exponents will do that example of these methods like here.
(Refer Slide Time: 29:53)

Let us consider considered a frictional resistance that is represented by F. When a liquid is going
through a pipe. That depends on the viscosity density of the fluid velocity of the flow diameter of
the pipe and the pipe roughness. Now you have to derive a rational equation for the pipe flow. In
terms of the dimensionless group by Rayleigh method. What you have to do the same way that
step1 step 2 step 3 follow like this. As a step 1 you have to first identify what are the dependent

95
variable and independent variables? What are those independent variables? That is frictional
resistance because this frictional resistance depending on the viscosity of the fluid density of the
fluid velocity of the flow diameter of the pipe and also the roughness of the pipe surface. So this
viscosity of the pipe is denoted by miu, density is denoted by row, the velocity of the flow is v,
the pipe diameter is d, and pipe roughness is epsilon.
F  f (  ,  , v, d ,  )

So this dependent variable is f that is resistance and here functional equation as you can then
express as that F equal to that dependent variables should be independent as a function of
independent variables like miu, row, v, d, and epsilon. Now the next step is the function of the
equation in the form there F is equal to Cmiu to the power a row to the power b v to the power c
D to the power d epsilon to the power e.
F  C  a  bvc Dd  e
as per that step.
I have described earlier. Accordingly, you have to express this after that you have to express
each of the quantities in the equation in fundamental dimensions.
(Refer Slide Time: 31:56)

.
Like this F is equal to c miu to the power a row to the power b v to the power c D and epsilon to
the power e.
F  C  a  bvc Dd  e

96
Now in this case dimension of F that earlier I told that you have to remember some dimensions
of quantity so that will be equal to M L T to the power -2 for f and c will not having any
dimensions here. ML inverse and T inverse to the dimension of viscosity and dimension of
density is ML to the power -3 and dimension of v is L to the power -1 and dimension of D is L
and dimension of Epsilon is L.
F C a b vc Dd  e
MLT 2  C ( ML1T 1 ) a .( ML3 )b .( LT 1 )c ( L) d ( L)e
So based on that dimensional homogeneity concept. The simultaneous equations involving a b c
d e can be represented as. If you equalize the dimension on both sides of the equation number 3
here in the slide.

You can write this is the dimensions came first. In the left hand inside dimension of the power of
this dimension M is one where the power of this dimension M on the right-hand side of this
equation number 3 is a and b. so it will be 1is equal to a + b. similarly, dimensions if you
consider for L length then it will be a 1 is equal to –a- 3b + c+ d +e As given in question number
5. Here only for the time that dimensions can be compared and you can make this equation is -2
= a - c that is given in equation number 6.
(Refer Slide Time: 33:40)

After that, you have to solve these three equations that 4 5 and 6. Like this here, you have to
Express that 7. This equation number 4 as b equal to 1–a and then equation 6 is equal to 2–a and

97
equation 5 can be represented as d in terms of 2-a-e. So, in this case, you have to select that b c d
that will be represented by some other exponent as per that equation. Now after that formation of
the dimensionless group like this F you substitute that value of b c and d.

All are in terms of A and B or like this so you substitute that value of BCD there in equation
number earlier that any question number 2. Then you will see that and the segregating those
things, and you can represent this one as the left-hand side and this one will be as a right-hand
side here. So in this, you will see this one is one group and this one is one group this group.
Where these groups are made actually dimensionally you just check it that row b d D b Miu. It is
a dimensionless even epsilon by D is also a dimensionless even F by Row v squire by D squire is
also dimensionless.

So these 3 dimensionless groups are formed and these dimensionless groups are interrelated like
this any suppose if you considering as that dependant variable are there is flow resistance. So the
dimensionless group that is made by that or in terms of that of flow resistance. That is a
dependent variable. This group should be the dependant dimensionless groups. Whereas
independent dimensionless groups are here this one and this one. So, in this case, we can make
this functionality like F by row v squire D squire.

This dimensionless group as a function of the dimensionless group of the right-hand side here.
Now, this is called one equation or functionality which is expressed in terms of some
dimensionless groups. So this is called a rational equation where there will be no dimensions on
both sides of this equation. Whereas all those variables are taking part in this your equations and
the effect of all those variables on those dependent variables will be accessed by this equation
there.

Now, what should be that functionality exact on an equation that you can access by regression
analysis putting that expression with experimental data? In that way, you can ferment equation.
So new jobs to make its dimensional analysis and make it the rational equation by that dimension
analysis. Now this very important here but one important thing you have to remember here that
how many dimensionless groups can be made based on your number of variables.

98
If you have 5 variable then you can make 5 -3 that will equal to two dimensionless groups. If you
have 6 variables total dependent independent all total if you have 6 variables then you can make
6-3 total three dimensionless groups. The basic rule is that if you have n number of variables
then you can make the dimensionless groups or the dimensionless groups will be formed as n- j.
What is j? J is the number of fundamental dimensions.

Generally no. of fundamental dimensions are three.so here the number of dimensions and
fundamental dimensions is three. Whereas the total variables is if it is n. Then it will be equal to
n-j no. of groups will be formed. Here in this example, you see.
(Refer Slide Time: 38:16)

How many variables are there? Here miu is 1 row 2 v 3 D here 4 epsilon 5 and F 6. Total 6
numbers of variables whereas fundamental dimensions number of fundamental dimensions is 3.
So how many groups will be formed? That is 6-3 that is 3 number of the dimensionless group
will be formed. So you will see that after dimensional analysis by this Raleigh method you got
these 3 groups.
(Refer Slide Time: 38:57)

99
Here this one and this one of these three groups you got. Those are dimensionless groups. So this
is the basic theory to get how many numbers will dimensionless groups based on your number of
variables. Now we will discuss about that Buckingham pi method. This method to analyze this
dimension. That is dimensionally making that dimension analysis by this Buckingham method.

This also you can make that rational equation where all the groups not having dimension there
and in this case what you have to do? According to that theory the functional relationship among
variables like: X1X2 ……Xn can be expressed as that the function of X1 X2….Xn that will be
equals to zero and here n equal to no. of variables and if j is the number of fundamental
dimensions such as mettle that is length L and mass M and time as T.

Then MLT these are the fundamental dimensions then a number of dimensionless groups can be
formed n – j that already “I told here during the analysis of dimension by Buckingham method
here also saying the number of dimensionless groups will get.
(Refer Slide Time: 39:55)

100
Now the dimensionless groups that expressed as here according to this Buckingham pi theorem
that pi I is equal to X1 to the power a1 and X2 to the power b I and Xj to the power j I and that
into Xj +1. Here X1 X2 Xj they are called repeating variables and Xj+1 are called non-repeating
variables. So some variables will be repeating again and again it comes for that analysis of
dimensionless groups.

Here like pi I here pi means dimensionless groups here may be n number of dimensionless
groups will be formed. Here three all three dimensionless groups if it is coming then X1a X2a
…..Xja and then Xj+ 1. Accordingly, it will come. Ok, we will see here no. of repeating
variables is equal to the number of fundamental dimensions. You have to consider that repeating
variables will be the number of fundamental dimensions.

That will be three so here X1 X2 and …..Xj these are called repeating variables this should be
only three. Whereas X j + 1ramaining other variables there and general j is equal to 3 here and
functional relationships among the dimensionless group is here this should be then dimensionless
groups as pi I then it will be represented as function of pi 1 pi2and…..pi that will equal to 0.
Here this functionality in terms of what is that? In terms of 5 that is dimensionless groups.

Here also we can analyze this dimension by the Buckingham method by stepwise. Like step 1
you to fast identify the relevant variables and function and then write down the dimensions and

101
then the establishment of the number of independent dimensions and nondimensional groups and
then and then. At step 4, choose that dimensionally Independent and dependent variables
generally that are repeating variables.

Generally, that repeating variable should be first representing repeating variable should be fluid
properties and the second is the flow characteristics and third will be geometric variables.
(Refer Slide Time: 42:34)

So in that way, you have to oscillate these repeating variables. So you have you cannot select
that repeating variable like fluid property three times like that. Now you have to take in such a
way that from the east that characteristic likes fluid property flow characteristics and geometric
characteristics. You have to take one dimension from each of these variables.

Then step 5- you have to create the pi s that is dimensionless groups by non-dimensionalizing the
remaining variables send by solving the coefficient. And then you have to set the
nondimensional relationship and then rearrange for convenience you can say this case you are
free to replace any of the pi s group by a power of that pi or buy a product with the other pi s
provided retaining the same number of independent dimensionless groups’
(Refer Slide Time: 43:49)

102
Like that will do that example again are based on this Buckingham Pi theorem. Let us considered
a frictional resistance again that F when a liquid is flowing through a pipe that depends on the
viscosity density of the fluid velocity of the flow diameter of the pipe and pipe surface
roughness. In this case, is also you just arrived derived the rational equation based on this
Buckingham Pi theorem in terms of dimensionless groups. Now, first of all, you have to consider
as state one that what will be the relevant variables and the function.
(Refer Slide Time: 44:22)

So relevant variables that viscosity density velocity of the flow diameter of the pipe and pipe
surface roughness. So out of which you can say that some will be dependent and some will be

103
independent but altogether all the variables to be noted down and you have to make the
functionality like this here function of f, miu, row, v, D, epsilon that will be equal to 0.
But here the different from that Rayleigh method is that here this f certain dependent variables
will be a function of independent variables.

It is not made here general that may be miu will be a function of some. In this case, directly just
one function to be formed like this and then you have to note down what are the dimensions of
each variable here. What are the dimensions of f? What is the dimension of miu? What is the
dimension of row? What is the dimension of v? And what is the dimension of D? And then
epsilon also. So in this way note down all the dimensions for all variables.

Now in this case what will be the relevant variables number of relevant variables is 6 that n is
equal to 6. No. of independent dimensions are generally 3 that is j that is M, L and T. And the
number of non-dimensional groups will be that made based on the principle of n-j that will be is
equal to3 that 6-3 is equal to 3. Then next is that you have to choose three dimensionally
independent repeating variables.

That repeating variable, you have to take 1 from the fluid property like density one from flow
characteristics like velocity and one from geometry characteristics like the diameter of the pipe.
So these three repeating variables will be chooses here for the analysis. So this is very important
you cannot I told that you cannot repeatedly three variables to be taken as row row row v again
row and you cannot do that.
(Refer Slide Time: 46:35)

104
Separately you have to take these repeating variables, one from fluid property one from flow
characteristics and one from geometry characteristics. OK. And then you have to create those
dimensionless groups. What is the principle that first dimensionless since you are going to from
n – j that is 6-3 3 dimensionless groups. Here that will be pi is equal to what that pi 1 pi2 is and
what is that? pi3. So pi1 what is that will be is equal to row v and D.

These are the repeating variables and non-repeating variables here; one is F other non-repeating
variables miu, epsilon there. So you can make like this with those non-repeating variables with
that repeating variable you can make the functionality of dimensionless groups like this.
Similarly for 2nd dimensionless groups, you can again use that repeating variable of that row v
and D and other non-repeating variables here miu.

And here pi 3 again with those non-repeating variables with those repeating variables. You have
to make the equations like this so in this way you have to that dimensionless groups here. After
that what you have to do that dimensional consistency just by equating that equation. Here in this
case like pi1 is equal to this from that equation here, in this case, pi 1.

If you considered that pi 1 is equal to row to the power a1 v to the power b1 D to the power c1
and F. Then if you consider that dimensions of all these variables in the left hand side and right-
hand side since pi1 be dimensionless group then no dimensions will be there. We can represent it

105
as M to the power 0, L to the power 0, and T to the power 0. What does it mean? There will be
no dimensions here.

Similarly, for the right-hand side. If you note that what is the dimension of the row then it will be
ML to the power-3 and there is a power a1so these dimensions to the power a1 similarly for v,
similarly for D, similarly for F, also you have to write down like this. After that just you equalize
this dimension, power of these dimensions of this left-hand side to the right-hand side. Then you
can make an equation like this. With that exponent here like in this case.

If you are considering fast M, then what the dimension of what is is the power of M 0 and the
right inside what is the power of this M here. Here 1 is M1 and here is 1. So here simply a1+1
that will are equals to zero. Similarly for L if you consider that power on both sides then it will
be as 0 equal to -3a 1 + b1 +c 1 + 1. Similarly for that T if you equalize that the exponent of this
left-hand side and right-hand side then you can have this equation of -b1 -2 that will be equal to
0.

Now solve these three equations, you will see that the solution of this equation should give you
that a1 value will be equal to -1 b1 will be equal to -2 and c1 will be equal to -2. So in this case,
if you substitute that a1 b1 and c1. In this equation and rearrange this you will see that this pi 1
will be as F by row v square D square. You just check it and substitute all dimensions here. You
see this pi 1 will not have any dimensions.

So this is a dimensionless group simply. Now, this pi1 is simply F by row v square D square.
Similarly, consider that pi 2 again that you have to equalize the power of all dimensions from its
left-hand side and right-hand side. After substitution of dimensions of each variable there. You
will see these three equations will be obtained and after solving these three equations, you will
see that the value of a2 will be coming as -1 b2 will be coming as -1again c2 will be coming as -
1. If substitute this a2 b2 and c2 value.

106
Here in this equation, you will see that after rearrangement, this pi2 will be as miu by row v D.
Again you just check it that these groups will not have any dimension. That is why this pi2 will
be as dimensionless groups.
(Refer Slide Time: 51:39)

Similarly, for pi3, you will see that if you again substitute the dimensions of all variables here
and compare the power of these dimensions on the left hand side and right-hand side. You can
have these three equations here and after the solution of these three equations. You will see that
the value of a3 will be 0 b3 will be equal to 0and c3 will equal to -1 and again if you substitute
this value of a3 b3 and c3 in this equation 3.

You will see that it will be epsilon by D because here a3 is equal to 0 means here row to the
power 0 it will be 1 and v3 b 3to the power 0 so it will simply 1 so only remaining D to the
power c3 c3 is -1 and epsilon.
(Refer Slide Time: 52:41)

107
So epsilon there nothing there so epsilon is already so epsilon by D will be there. This is simply
you know that dimensionless groups. So pi 3 another dimensionless group. So we are gating
three dimensionless groups in terms of all the process variables. Now you have to make
functionality based on this formed or developed or you can say that dimensionless groups that is
formed that dimensional analysis.

So that will be equal to function of pi 1 pi2and pi 3 that will equal to 0 and after that, you can
make any relationship like pi 1 is a function of pi 2 and pi 3 or you can say that pi 2 is a function
of pi1 and pi3 or you can say pi3 is a function of pi1 and pi2. So that way you can form but since
in your problem, it is seen that that flow resistance is depending on the other variables.

That is F is depending on the other variables in that case you have to make the functionality like
this. So what are the groups are coming based on that F of then you have to make it those
dependent variables dependent dimensionless groups. And this will be making in terms of other
dimensionless groups so in this way, you have to make the rational equation and then you have
to rearrange it

Like this and then you have to make this as like you can say that if suppose this group 1 or pi 1
so you can pi1 as a suppose some value of Lambda into pi1 function like this pi 1and this is pi 2

108
and this is pi3. So, in this case, this pi1 will be some function like this a into “you can say” pi2
some power b and plus here you can say pi3.
(Refer Slide Time: 57:05)

You can make like this type of functionality also you can make. So either way, that depends on
your experimental data. How this flow resistance will be changing with respect to variables. So if
you have that the different data based on changing of the independent variable and its result of
the dependent variable and after that, you have to feat this equation. Either of this equation if you
feat this with that the experimental data. Then you can form or you can have this.

The value of m and lambda are there. Here a b and some c value there. So this way, you can find
out that Coefficient, and if you know that coefficient, there will be a final form of the rational
equation. And then, you have also to check which equation will be suitable and which will be
given the list error of that fitting of that experimental data with this equation. That is a further
step but up to this, you have to know how you can make that rational equation as a function of
dimensionless groups and this is called dimensional analysis.

There are two methods that “I have discussed here one is the Rayleigh method and another is
Buckingham pi method” which one will be easier, that you have to follow. So any problem you
can solve by this Ok. So here another example here flow-resistance of a sphere. In this again that
Buckingham pi method you can use here. Like the drag D of a sphere is influenced by sphere

109
diameter d flow velocity u fluid density row and fluid viscosity miu.

What is that whenever any a sphere is supposedly fixed in a certain position and some fluid
velocity is flowing over that spherical part or sphere. You see there will some drag or resistance
or you can say that external force acting on that surface of the sphere with that fluid. So that
drag force actually of that sphere is depending on the diameter of that sphere and also how what
is the velocity of the fluid and also the density of the fluid and also the viscosity of the fluid.
(Refer Slide Time: 58:01)

So this drag force actually depending on this diameter of the sphere velocity of the fluid physical
properties like density and the viscosity of the fluid. Now, in this case, how many variables are
there? We can say that drag here spherical diameter flow velocity density total five. Now how
many dimensionless groups can be formed by either of this method very simple 5-3? 5 is the
number of variables and 3 are here the number of fundamental dimensions.

So here 5-3 that is 2 dimensionless groups that you can make by this. So if follow that
Buckingham pi method with these variables row v D as repeating variables. You can make like
this pi1will be equal to this and equalizing that power of the dimensions on both sides of this
equations and making this equation based on which you can solve and you can get that power of
that as -1, -1, -1 and then you can form that pi1 will be equals to this.

110
Similarly, other dimensionless groups again that repeating variables will be there and with non-
repeating variables of other non-repeating variables here miu. Accordingly, you solve these
equations just by equalizing the power of those dimensions on both sides of the equation then
you can get a solution of a power of x, y and z like this and then substitution of those values.
You can get this value of pi2. So here pi2 is one dimensionless group here pi 1 also
dimensionless group.

You just check it that there will be no dimensions on these groups and then you can make that
rational equation just by functionality like that pi1 will be is equal to a function of pi2. Now how
it will be related that is a different issue that depends on the process variables. Now generally
this, suppose, here pi1 that will be is equal to some m into pi2 to the power n like this. In this
way also it will be varied. Now you have to find out what will the value of m? And what will be
the value of n from your experimental data just by fitting this thing with experimental data.

You have to find out what will be the experimental data of pi1 calculation and then pi2. Because
pi1 you can calculate D by row u square d square. All these things known to you because D is
known to you row is density known to you velocity is you are giving that is also known to you,
d is also known to you. Just then, what will the pi 1 similarly if you change in that variable
according to pi1 also change.

Similarly, pi 2 also will be changing accordingly if you change that viscosity, density, diameter,
of pipe, the scalar velocity of the fluid. So accordingly, you will see how this pi1 will be
changing based on that pi2. So then you will get one equation based on this pi1 as a function of
pi2. Then you fit that experimental data of pi1 and pi2and then find out by least square method to
me actually discussing how to find out that all these components letter on.

Ok, to find out this exponent just by fitting with experimental data that we are given in separate
lecture letter on also. So this way so how to make the rational equation based on this dimension
analysis by Buckingham pi theorem or Rayleigh method. You just I think glint here and you can
also practice with some examples given here it. Now for chemical engineering process analysis
like this forms some dimensionless groups.

111
You will see some dimensionless groups will some significant groups that are actually very
important for the analysis of the process performing there. So some dimensionless groups are
given here in this slide. Here like Reynolds number that we got even Froude number Euler
number Weber number Mach number. All those things and relative their significance it is given
here in the slide.
(Refer Slide Time: 01:03:00)

Even in the next slide also it is given some significant groups and their respective significance
and how they are defined it is given their name group and so you have to remember this
dimensionless group you check this group with their dimensionally consistent or not. You can
say that whether this group is having any dimensions or not you will see that no groups have any
dimensions here. So all those dimensions will be used for certain process analyses of the
chemical engineering process.

So in future also if you do some other courses like heat transfer mass transfer; even transport
phenomena fluid mechanics in there. You will see all those processes there you will see their
certain dimensionless groups having for their process analysis like this here for flow generally
Reynolds number Froude number Euler number even Weber number even Mach number all
those groups are actually related to the process where flow off course will be there or fluid
mechanics related any process there these groups will gate.

112
Whereas for heat transfer operation, you will see that Prandtl number is one dimensionless
group Nusselt number is one dimensionless group, even Grashof number. This is one
dimensionless group. These three groups are very important in heat transfer operations where the
chemical engineering processes are related to the heat.

That will discuss the different processes I think we have given the previous lecture that different
processes related to the thermochemical process even mechanical process there all those
processes. Those processes related to the heat energy there also you will see that these
dimensionless groups like Prandtl number Nusselt number Grashof number are very important.
(Refer Slide Time: 01:04:59)

Even for mass transfer operation, suppose if you are actually transferring one phases to another
phase. Like absorption of carbon dioxide gas to the liquid. There, transfer of carbon dioxide gas
to the liquid so this is called mass transfer operation or diffusion you will see that diffusion
process. If you suppose spread of some perfume, you see that perfume will be diffused
throughout the room.

So there transferring of molecules from one position to the position based on that concentration
gradient. So this is called the diffusion process. There also some dimensionless groups are very
important like Schmidt number that is related to that molecular diffusion even Sherwood number

113
that is mass transfer operation like gas vinous molecule transferred from gaseous phase to the
liquid phase. So in this way, these dimensionless groups are very important. I souse you to
remember this dimensionless group throughout your life; I can say that as a chemical
engineering.

If you are doing the course of chemical engineering or studying that chemical engineering course
that you have to remember these groups there. So Thank you for your concentration of this
lecture that I think you understood that how to do the dimensional analysis and how to make
their rational equation and what are the different systems of time and units that you understood.
So, next lecture, we will discuss something more about those physical and chemical properties of
the material which are very important in the chemical engineering process. So thank you for your
attention.
(Refer Slide Time: 01:07:15)

114
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 2: Process Variables and Rate

Lecture – 2.1
Variables and Properties of
Material in System

Welcome to the massive open online course on Basic Principles and Calculations in
Chemical Engineering. In the previous lectures, we have discussed the introduction, about the
principles and calculations in chemical engineering, and the role of chemical engineers in
society and its history of chemical engineering. And also, we have discussed that various
systems and even units and dimensions of how that chemical engineers can use those units
for the dimensional analysis to describe the process efficiency mathematically as well as its
analysis by the different dimensionless groups.

Now, in this lecture, we will start the module 2 as process variables and the process rate.
(Refer Slide Time: 02:21)

Under this module, we will discuss the variables and properties of the material in the system
where chemical engineering processes are dependent on those. Now, if we consider that what
are the different processes variables are important to analyze or to you know that assess the
process efficiency and in a particular systems how those process variables are that affect the
efficiency of the processing system as well as what are different basic principles of that

115
variable like physical or transport properties of those variables that we will discuss in this
lecture obsessively.
(Refer Slide Time: 02:43)

Now, as we know that different process variables like temperature, pressure, flow rates, even
volume of unit, even that diameter of the unit or equipment, even different physical properties
like density, surface tension, even you know viscosity, and other different types of variables
like that is expressed by composition of the materials in a particular mixture in a particular
streamlines. Now, those variables, of course, will be directly or indirectly affecting the
process efficiency, processing yield, process you know that output, the amount based on
those process variables.

Now, if we classify those variables of that process in a certain way that characterize that, you
know, processes streams in the entering and leaving a position of that processing unit and
those process variables will be useful for the design of that process equipment based on their
effect on that process output or process yield. Now, in this case, we are having different types
of variables, one is called state or thermodynamic variables, some are dynamic variables like
geometric variables, physical properties as variables, even others also.

I think we have discussed in our previous lecture that suppose that when fluid is flowing
through the pipe, there will be a certain resistance to the flow of that fluid. In that case, this
flow resistance actually is affected by some variables like you know that viscosity of the
fluid, even diameter of the pie, even surface tension of the fluid, the density of the fluid, and
also you can say that velocity of the fluid. So, these variables are classified in a different way

116
like if we classify the variables in that way, some variables would be state or thermodynamic
variables, that is you know the temperature.

Some processes will be depending on temperature and pressure also, that you have to then
calculate or assess that temperature and pressure based process efficiency based on these
variables. Now, dynamic variables, that are flow rates of the inlet and outlet, you will see that
that flow rates of inlet and outlet, of course, will be influencing the process efficiency. Now,
some variables will be you know geometric variables like the volume of the unit, even
diameter, cross-sectional area, length, etc.

In this case, one other you know geometric variables like if you are doing any process in a
particular multiphase unit like in gas-liquid processing in a particular column, there you will
see that gas will be distributed in the column or equipment as a dispersed phase of bubbles.
So, in that case, to produce that bubbles, the gas will be supplied through a porous media, that
porous media will be regarded as sparger or you can say that gas distributor or gas diffuser.

Now, that gas diffuser will have you know some holes through which that gas will be coming
out through that spudger as a dispersed pressure bubbles in the column. Now that the size of
the bubbles will be depending on that hole size of that distributor. Now, this, you know that if
you have that hole size will be more finer, then you can get that more finer bubbles. Even if
your hole size will be coarser or larger, then you can say that more bigger bubbles you can
get there.

So, accordingly, you will see that there will be a formation of surface area and based on
which that efficiency of the mass transfer will depend on. So, that is why these geometric
variables are very important. Other important geometric variables in a process like any gas-
liquid reactions you know are in the presence of catalyst particles or any fluidization
operation that we have earlier described that for drying for us if particles are fluidizing in a
hot air medium.

So, in that case, you will see that particle sizes matter there, so this particle size, if you have
more finer particle size, their efficiency of the process will be larger. So, that is why this
process variables like geometric variables will you know that affect the process efficiency.

117
Other variables like physical properties as the variables you will see that any process you
have to analyze based on their physical properties.

If systems will have more or higher viscous fluid or liquid or you can say that system inside
that you will see that there will be some resistance to flow or that resistance to give you less
performance of the reactions as well as the physical transfer of the materials from one phase
to another phase. So, in that way, you can say that the process efficiency will be depending
on the viscosity of the fluid. Even other physical properties like density, surface tension, even
you can say that other chemical compositions based on which that effective viscosity will be
changed there.

So, that also will affect the process efficiency. Like, in this case, one example like surface
tension. If you add some surface tension in water, you will see if you pass the gas through the
spudger through this liquid of that surface tension you will see that there will be a number of
bubbles will form and there are you will see that more surface area will be formed in that, in
that case, you will see that there will be a more mass transfer.

In that case, the more interfacial area will give you that more efficiency to transfer of
molecules or more amount of molecules from one phase to another phase. So, this is one
aspect of this efficiency dependence on these physical properties of the system. Like others
here, the total amount of material in the inlet and outlet streams, the composition of the inlet
and outlet streams also are very important for the assessment of process efficiency.
(Refer Slide Time: 10:35)

118
Then, we have what that particular system for a process is. Now, any specified say that
arbitrary portion or whole of a process analyzing the problem will be defined as a system.
Like you will see that if suppose if we produce ammonia gas from the mixture of hydrogen
and nitrogen and it is actually allowed to react that hydrogen and nitrogen under certain
catalyst particles, then you will see at a certain temperature and pressure, you will see that
ammonia will be produced.

Here, on a schematic diagram of this production of ammonia is given here like, in this case,
you will see that nitrogen and hydrogen will be passed through a mixture and you know it
will be passed through a reactor and after reaction, you will see that ammonia will be formed
along with that unreacted ammonia and hydrogen and these outlets streams of reactor that
mixture of ammonia, nitrogen and hydrogen it will be passed through that condenser so that
that ammonia will be condensed at minus 35-degree centigrade and then you can get the
liquid ammonia there.

Now, here you will see that in this process, there are you know several units are required to
complete the process of this. Here, briefly, we are giving that main systems or equipment that
are used for this process are mixture where in this case nitrogen and hydrogen gas will be
mixed there in the mixture and after that, it will be sent to the reactor where this nitrogen and
hydrogen gas will be reacting and then producing that ammonia gas and from the outlet
stream of this reactor, this ammonia gas along with unreacted hydrogen and nitrogen will
come out.

After that, one condenser has been used. There were minus 35 degrees centigrade
temperature. This ammonia gas will be condensed down as liquid ammonia. So, the system
means here you can consider for the analysis of the individual process unit as a system. Here,
the mixture you can consider one system. Similarly, here reactor is one system, and the
condenser is also one system.

Here, you will see that by the dotted blue line that represented is a unit as a system whereas
you can represent the system of combination of all those units also like here red line, dotted
red line is shown here that considered that the whole system considering all these 3 units
there. So, that is why a system may contain more than one process unit also, and in this

119
figure, the entire process is a system, which consists of 3 process units. It depends on what
information is provided and what needs to be determined there.
(Refer Slide Time: 14:11)

Now, we will discuss about the properties of the material in the system that are being used for
a particular process in a processing unit. So, therefore, you know that knowledge of the
system properties is required for engineering design of the equipment that involves different
processes, and there are 2 types of system properties which are physical and transport
properties.
(Refer Slide Time: 14:44)

You will see that some properties will be you know of physical. In that case, that is
measurable and its value describes a physical system state. Now, there are 2 types of these
physical properties, one is intensive properties and another is called extensive properties.

120
(Refer Slide Time: 15:06)

Now, what is that you know intensive properties? Actually, these intensive properties are
defined as a physical property of the system that does not depend on the system size or the
amount of material in the system. Now, this can be, explained with examples like density is
an extensive property of a substance because here it does not depend on the amount of that
substance.

Other intensive properties can be derived from the known values, there some examples are
given here in the slides that like pressure, temperature, chemical potential, density, specific
gravity, viscosity, even you know that velocity, even electrical resistivity, specific energy,
specific mass, even mass concentration, molar concentration like hardness, melting point,
boiling point. So, all those examples are actually called intensive properties.
(Refer Slide Time: 16:19)

121
What is that extensive properties? The extensive property is a physical quantity whose value
is proportional to the size of the system it describes. Now, in this case, these properties are
actually counterparts of intensive properties that are intrinsic to a particular subsystem and
remain constant regardless of their size. Now, if you divide one type of extensive property by
different types of other expensive properties, you will see that property as a whole will
become an intensive property.

For example, like mass is an extensive property, that if you divide it by volume, that is an
extensive property, gives density that is intensive properties. So, that is why mass divided by
volume results in an intensity that is called density where intensity property that is density.
Some other examples of extensive properties like entropy, enthalpy, energy, mass, particle
number, resistance, momentum, number of moles, even volume. So, these are some examples
of extensive properties.
(Refer Slide Time: 17:48)

122
Now, you will see some, you know, intensive properties, you will get analogs to that
extensive properties. Actually, these intensive properties are made by two extensive
properties or even more than two extensive properties. Like here, there are a number of
properties you will see that have corresponding extensive and intensive analogs, many of
which are thermodynamic properties.

In this case, in the table, the slide that is given you will see that some extensive properties are
like volume, and you will see that respective intensive property as an analog you can say that
specific volume, it will be regarded as an intensive property. So, here see interesting that
volume is an extensive property, whereas specific volume is intensive properties because this
specific volume is defined by volume per unit mass, whereas internal energy is an extensive
property, whereas specific internal energy it is an intensive property.

Now, whenever you are talking about that specific of course you have to think about that that
should be divided by mass or by volume. So, some will be you know that mass-based specific
property and some would be volume-based specific property. Now, if you are talking about
that specific internal energy, you can say that this specific internal energy will be defined by
internal energy divided by mass. So, that is why internal energy is an extensive property,
whereas specific internal energy will be called as an intensive property.

Similarly, entropy is an extensive property, then specific entropy will be an intensive

property. Enthalpy is an extensive property, whereas, you know that is specific enthalpy will
be an intensive property. Similarly, other extensive properties are given in the table like

123
Gibbs free energy, heat capacity at constant volume, even heat capacity at constant pressure.
So, respective you know the intensive property will be the specific Gibbs free energy,
specific heat capacity at constant volume, specific heat capacity at constant pressure they are.

In the slides in the table, you will see that there are respective general symbol that is being
used for the process calculation and also their respective units and international systems are
given in the table. So, you have to try to remember most of these properties with their
symbols as well as units.
(Refer Slide Time: 20:48)

Now, we have talked about that there are two properties like one is physical properties and
the other is transport properties. So, here transport properties actually basically it is a
molecule of properties of a substance that indicates the rate at which the specific that is per
unit volume momentum, heat and/or mass are transferred. Here in this case, the specific will
be represented as per unit volume. Like here, some examples are given for transport
properties, viscosity, conductivity, diffusivity, even you know that permeability, chemical
durability, dielectric constant, ion exchange coefficient.

Now, this specific, you know, that momentum, heat, and mass transport case that all those
transport properties will be considered for process calculations there.
(Refer Slide Time: 21:48)

124
Now, we will discuss some definitions of these important properties. Those are very
important for the analysis of the process and their calculations and also these are very
important for the process design and the design of the process equipment. Like one is
important that concentration, in this case, the concentration of a particular species in a multi-
component mixture that can be expressed in different ways, like some are mass
concentration, some are molar concentration or some are other types of concentration like
number concentration, density concentration, this is called density number of concentration.

Generally concentration, mass concentration is referred to as density. Now, for the species i,
the mass concentration, it is denoted by that rho i is defined as the mass of the species i per
unit volume of the mixture.
Wi
i 
V
Here in this slide, it is given that mathematically how that this mass concentration that is
density can be expressed. Here rho i is for density and Wi is for the mass of the species and V
is the volume of the species. If it is in a mixture, then what will be the total volume of the
mixture that is to be represented.
(Refer Slide Time: 23:27)

125
Similarly, you can have a mass fraction. This is also it is required for the process calculation
there. In this case, the mass fraction of the species i that is present in the mixture is the ratio
of the mass of the species i to the total mass of the mixture and is mathematically expressed
by here on this equation given.
Wi i
i  
n

W
i 1
i

In this case, Wi that will be is equal to, sorry omega i that will be equal to Wi by summation
of Wi, what does it mean. Here omega i is the mass fraction is generally denoted by this
symbol for a species and it will be defined by in a mixture that what is the mass of that
species i and what will be the sum of the mass of all species there. Then if you make an issue
of this individual species mass to the mass of whole mixture, then you will get that mass
fraction of that particular species. If you consider there is a binary mixture of component A
and B, you see that here this mass fraction of component A will be equal to mass of A by
summation of mass of A and mass of B.

So, it will be by a mass fraction of component A. Similarly, mass fraction of component B

will be defined as here mass of B upon summation of mass of A and mass of B. So, from this
you can easily calculate what would be the mass fraction of B. You will see interesting that
summation of this mass fraction of A and B components for this binary mixture will be equal

126
to 1. Similarly, if there are n number of components in a mixture, you will see that individual
mass fraction you will calculate as per this and similarly if you make it sum up of all these
mass fractions, it will become 1 there.

So, in this way, you can calculate the mass fraction. Suppose here a mixture of gases like
carbon dioxide, nitrogen, sulfur dioxide, even that other gaseous mixtures. So in that case,
you have first to know what would be the mass of individual gases there. So, that if it is
known by moles, then you have to multiply each molecular weight, then it would become
mass of those gases. So, suppose there are 5 gaseous components in a mixture.

So, individually you have to write what to be the mass fraction of component nitrogen, the
mass fraction of component hydrogen, the mass fraction of component carbon dioxide, the
mass fraction of component like this. So, from there, you can easily calculate what should be
the mass fraction of individual gaseous components there.
(Refer Slide Time: 26:53)

Similarly, molar concentration also you can describe from that mixture, in that case, it is
called molar density. So, there it is actually defined that the molar concentration of species i,
it is generally denoted by c, small c. So, ci mean concentration, molar concentration of
components i is defined as the number of moles of i present per unit volume of mixture. Then
the mass concentration and molar concentration can be related by this equation.
i
ci 
Mi

127
Here in this case like ci that will be equal to rho i by capital Mi, here capital Mi is just
molecular weight of a species and rho i is the mass concentration that is mass per unit
volume. Here interesting that, that mass per unit volume out of that, you just divide it by
molecular weight, then you can say that mass by molecular weight it will become, what is
that, how much molar is there, how much moles will be there. So, then it will be mole per
unit volume, then simply it will be called as that molar concentration.

So, when dealing with gas-phase under conditions in which ideal gas law applies, so in that
case, the molar concentration can be calculated from the ideal gas laws here. So, it will be
defined as ci that will be equal to pi by RT,
pi
ci 
RT
what is pi, pi is the partial pressure of the species i in the mixture and T is the absolute
temperature at which this gas is you know kept and also R is the universal gas constant there.
So, this way you can represent what should be the molar concentration and also mass
concentration if you know that the molecular weight of this component.

Also, how that molar concentration and mass concentrations are related to each other, and
also for the gaseous mixtures if you know the partial pressure of each gaseous there, you can
easily calculate the molar concentration at the particular temperature and partial pressure.
(Refer Slide Time: 29:30)

128
Now, what is the mole fraction? In the similar fashion of that mass fraction, you can also
express the molar fraction or individual component of liquid or gaseous or solid components
there. So, in this case, the mole fraction of the species i in a mixture that will be the ratio of
moles of species i to the total number of moles in the mixture and is given by especially for
liquids and solids, that will be denoted by small x that is here,
ni Wi / M i ci
xi  n
 n

 n  (W / M )
c
i i i
i 1 i 1

whereas this for gaseous mixture, the molar fraction or mole fraction you have to denote it by
yi.
ni Wi / M i ci pi
yi  n
 n
 
 n  (W / M )
c P
i i i
i 1 i 1

So, this is in general how this to be represented. So, xi will be what, that is mole fraction of
the species i that would be is equal to moles of that individual species upon total moles of the
mixture. So, here that is it is defined by this your xi for the liquid and solid should be equal to
a number of moles of i that is denoted by ni and also what will be the total moles of
components in a mixture that will be a summation of all moles of the components.

So, if you divide individual moles number by the total mixture moles number, then you can
easily get that mole fraction of that individual component. Similarly, for the gaseous phase
also, what will be the moles of individual gas and upon the total number of moles of all
gaseous mixture that you can calculate here by this equation, and also you can calculate this
mole fraction for the gases from its partial pressure.

If you know the partial pressure of individual gaseous components and also total pressure of
the gaseous mixture, then you can easily calculate what should be the mole fraction of
individual gases that will be actually the ratio of the partial pressure of individual components
to the total pressure of the system. So, that will be your more fraction of gas. If you are
considering that, the binary mixture of component A and component B.

Similarly, you can easily calculate what should be the molar fraction of that component A
that will be calculated by this equation here, simply what will be the moles of A and what

129
will be the summation of moles of A and B and similarly yi also you can calculate what
should be the moles of A gas and what should be the total most of gaseous mixture that is nA
+ nB in the binary mixture that will be here. Similarly, if you know that in the binary mixture
like mixture of carbon dioxide and hydrogen gas, so there if you know that the moles of
carbon dioxide gas is 70 moles whereas hydrogen gas is only 30 moles.

So, total moles is 100 moles. So, individual mole fractions will be what, that is one for carbon
dioxide it will be what, that will be your 60 by 100, that is 0.6, whereas for hydrogen gas it
will be 30 by 100 that is 0.30. So, in this way even if you know the partial pressure of carbon
dioxide or hydrogen gas in the mixture, then you can easily calculate what should be the mole
fraction of gaseous components just by dividing that partial pressure of each component by
the total pressure there.
(Refer Slide Time: 33:58)

Now, another important variable for the process calculation it is called specific gravity. This
is actually defined as the ratio of the density, that is mass of unit volume, of a substance to
the density, that is mass of the same unit volume, of a reference substance at a specific
condition.
substance at T
SG T 
T
ref
reference T .
ref

Now, the reference substance is nearly always water at 4 degrees centigrade for liquids or as
it is considered for gas specific gravity, the reference gas will be air for gases and
temperature and pressure must be specified for both the samples and references there.

130
  subs tan ce at 25 C
o
SG 4  0.67 
25

reference 4 C .
o

Now, the pressure is nearly always 1 atmosphere to be considered or as temperature for both
samples and references that vary from industry to industry that you can give or you can
mention that in pressure accordingly there. Now, true specific gravity can be expressed
mathematically by this equation that specific gravity at referred like T reference to T that will
be equal to rho substance at temperature T and rho reference at a temperature of the reference
material.

So, in that case, let us suppose specific gravity as 4, 25 is equal to 0.67, what does it mean
that this specific gravity is nothing but that density of the substance at 25-degree centigrade
relative to that reference density at 4 degrees centigrade. If you are considering that, the
density of reference is water, then, in this case, it will be 1. So the only density of that
substance would be 0.67 into 1, it will be simply 0.67 at that particular temperature case as
25-degree centigrade.
(Refer Slide Time: 36:05)

As an example, you can have here suppose a 0.5 molar aqueous solution of sulfuric acid that
flows into a processing unit at a rate of 1.25 meter cube per minute. The specific gravity of
the solution at 20 degrees Celsius is 1.03. Now, in this case, you have to calculate what
should be the mass concentration of sulfuric acid in kg per meter cube and the mass flow rate
of the solution in kg per second and the mass flow rate of sulfuric acid in kg per second and
also what would be mass fraction of sulfuric acid.

131
Now, in this case, you need to calculate first the molecular weight of the sulfuric acid, it is
known to you it is 128 whereas 0.5 molar aqueous solution of sulfuric acid will contain, what
will be the amount of sulfuric acid? This is actually 0.5 into 128 gram because their molar 0.5
molar means 0.5 moles of sulfuric acid in 1 liter of the solution there. So, we can say that 0.5
molar means how much weight of that, so 0.5 into 128 is the molecular weight. So, just you
multiply this, you will get that 64 gram of sulfuric acid.

Now in this case, what should be the mass concentration of sulfuric acid? It will be simply
that since it is 64 gram as per calculation in 1 liter, so it is the mass concentration. Now, you
have to convert it to you know that other unit like kg per metre cube, just simply you have to
divide this gram to kg by 100 and litre to metre cube, again divided by 1000. So, simply
1000, 1000s will be canceled out.

Then it will become 64 kg per meter cube and what from the mass concentration of the
solution, that you can calculate easily just by multiplying the density of water and the specific
gravity of the solution because specific gravity of the solution or specific gravity of the
materials is defined as what is that density of that particular substance upon what is that
reference materials density. So, here we can say since it is a solution we have to take the
reference material as water.

So, you have to multiply this specific gravity of the solution by this density of water, so you
will get that what will be the density of the solution or mass concentration of the solution. It
is simply that since the specific gravity of the solution is given as 20 degree Celsius is 1.03,
just simply you multiply by 1000 of this 1.03 value, then you will get simply one 1030 kg per
meter cube and the mass flow rate of solution it will be coming as mass concentration of
solution into volumetric flow because mass into volume volumetric flow rate will give you
that, what is that.

It is the mass concentration of the solution and volumetric flow rate, it will give you simply
what will be the mass. Now, volumetric flow rate since it is the coming with respect to time,
so simply you can say that mass concentration of solution into volumetric flow rate, then will
be 1030 that is your mass concentration into 1.25 that is what is that volumetric flow rate is
given as per your problem. So, it will come after multiplication as 1287.5 kg per minute.

132
Now, if you can convert it to what should be the unit in kg per second simply you have to
divide it by 60 because 1 minute is about 60 second, then you will get 21.46 kg per second.
Now, the next question is what is the mass flow rate of sulfuric acid in kg per second? You
know that only 0.5 molar concentration of sulfuric acid in the solution. So, you have to know
what will be the exact amount of sulfuric acid in the solution.

Since you know that there will be since mass flow rate mass of that sulfuric acid in the
solution to be 64 gram sulfuric acid and then if you make it mass concentration as 64 kg per
meter cube and if you multiply this mass concentration by this flow rate of the solution, then
you can easily calculate what should be the mass flow rate of that sulfuric acid. So, simply it
is 64, the 64 kg per meter cube, that is mass concentrations of sulfuric acid, and then multiply
by what is that this is your volumetric flow rate of the solutions and then you will get that
here what would be the amount that is kg of or mass of sulfuric acid.

Since it is in terms of minute, then you have to divide it by 60, then it will become kg per
second, so 1.33 kg per second and what should be the mass fraction, very interesting that
mass fraction, you know, that what would be mass of the sulfuric acid in a certain volume,
that is 64 kg per meter cube and also you know that mass concentration of the solution. So,
from that mass concentration of sulfuric acid by mass concentration of the solution, you can
easily get that what is that mass fraction of that sulfuric acid.

So, it will be 64 by 1030. It will be coming as 0.062. So, these examples will give you that
how you can use that specific gravity definition for calculation of that mass concentration as
well as what is that mass concentration of solution and also mass concentration of
components, also mass fraction of that components, and also molar flow rate, how it can be,
related to that density conversion and all thing.

So, in this way, you can calculate, please go through this example, that is one example where
you can understand the basic things how to convert it from mass to molar, molar to mass like
this way, and then you have to go to process calculations in that direction.
(Refer Slide Time: 43:23)

133
Another way of the process, you know calculation by the different process variables like
apparent specific gravity. In this case, the apparent specific gravity is simply the ratio of the
weights of the equal volume of substance and reference substance, water or air for liquid or
gas.
Wsubstance
SGap 
Wreference

Similarly, here you will see that instead of earlier that a true specific gravity there, it is based
on density, whereas in apparent specific gravity it is based on the weight of the substance. So,
the same way that is the ratio of the weight of the substance at a particular temperature upon
the weight of the reference substances and this ratio will be called as apparent specific
gravity.
(Refer Slide Time: 44:18)

134
Another important process variables by which the process can be assessed it is called API
gravity. The American Petroleum Institute they have actually suggested or you can say that
procured one measuring systems of that liquid whether it is lighter or heavier based on certain
quantity. In that case, it is called that API gravity. So, this API gravity is being used as a unit
to assess that liquid whether it is heavier or lighter. So, it is a measure of how that heavy or
light petroleum liquid is compared to water.

If its API gravity, suppose if any petroleum liquid if its API gravity is greater than 10,
remember it, it is actually referred to as a lighter liquid and it will float on the water. Whereas
if its API gravity is less than 10, it is called as heavier liquid and it sinks. So it is used to
compare the relative densities of petroleum liquids and the formula to obtain that API gravity
of petroleum liquids from specific gravity, you can use this equation okay for calculation of
that API gravity as a function of specific gravity.

Once you know that specific gravity of the substance or liquid or fluid, then you can easily
calculate what should be the API gravity there.
(Refer Slide Time: 46:24)

Now, for example, let us see to calculate the specific gravity of that petroleum mixture based
on their degree API. Then in that case, suppose 420 liters of 20 degree API gravity gas oil
blended with 1200 liters of 15 degree API fuel oil. Now, what should be the density of the
mixture in kg per meter cube? Assume that the volumes are additive. The density of the water
at 15 degree centigrade is 0.999 gram per centimeter cube. So we are blending 420 liters of
gas oil with the 1200 liters of fuel oil.

135
The gas oil has API gravity 28, whereas fuel oil has API gravity of 15. Now what should be
the density of the mixture? Now, we know that the relationship between API and specific
gravity, and from that relationship, we can write that specific gravity will be equal to 141.5
by API + 131.5.

So from this equation, we can easily calculate what should be the specific gravity of 28
degree API gas oil. So this will be simply just we are substituting this value of degree API
there in API, then we can get this value of 0.884.

Now, the density of that gas oil, then it will be simply 0.884 into 0.999, that will be equal to
0.883 gram per liter. Similarly, the specific gravity of 15 degree API of fuel oil, it will be as
after substitution of this value, it will be 0.962. So, the density of the fuel oil will be similarly
0.962 gram per liter. Now, the density of mixture will be total mass per total volume, then
what will be the total mass? You know that density of the gas oil and density of the fuel oil,
then what should be the total mass there?

If you multiply that volume of that perspective oil to its density and then add it, then you will
get the total mass of that oil mixture and what should be the volume already given that one is
420 liters and other is 1200 liters. If you add it up, then you will get the total volume. If you
divide this total mass by this total volume, then you can simply get what should be the
density of that mixture. So, in this way, you can calculate the density of the mixture based on
degree API of the substances.
(Refer Slide Time: 49:43)

136
Another one is volume fraction in multiphase systems. The volume fraction of phases is
defined as the volume of each space upon the total volume of phases.
Volume of each phase
αP 
Volume of phase mixture

What does it mean here? Suppose there is a mixture of different phases like gas, liquid, and
solid. Now, individual phases like gas, liquid, or solid will have certain or will occupy a
certain volume in a particular mixture volume. Now, the volume fraction will be defined as
that the volume of individual phases upon the total volume of the phase mixture.

So, that will be called a volume fraction. This volume fraction is sometimes regarded as a
holdup of the phases. Now, here this volume fraction of phase, it is regarded as holdup or
sometimes its called as void fraction of that particular phases, which is represented by here
this equation given in the slide and you will see that if there are 3 phases, then if you sum it
up all void fractions or volume fraction of individual phases, then you will get that will be
close to 1.

Now, if you consider that the only gas-liquid mixture, then what would the volume fraction
of gases that will be denoted by alpha G, then it will be calculated by volume of gas phase by
volume of gas and liquid mixture.
Volume of gas phase
αG 
Volume of gas  liquid mixture

137
Similarly, volume fraction of liquid, it will be volume of liquid phase by volume of gas and
liquid mixture. So, in this case, you will see that the volume fraction of gas and volume
fraction of liquid if you sum it up, then you will get total will be 1.
G   L  1
For similarly, gas-liquid-solid mixture, you can get this alpha G + alpha L + alpha S that will
be equal to 1. That means the summation of all void fraction or volume fraction of individual
phases will be equals to 1.
(Refer Slide Time: 52:01)

Similarly, you can actually calculate the mixture density of the multiphase systems like the
sum of the bulk density for all the phases will be called as mixture density and it will be
denoted by rho m that will be a summation of actual gas density, actual liquid density and
actual solid density.
 m  G   L   S
  G G   L  L   S  S
This actual gas density will be represented by that what will be the volume fraction of that
gas into what is the density of the gash, and similarly for the density of the liquid and volume
fraction of the liquid and also density of the solid and volume fraction of the solids.

If you sum it up all these things, then you will get the mixture density. The bulk density is
related to the true or absolute density that is rho p. Now this gas bulk density generally is
denoted by what is that, rho G bar and it will be close to that, what will be that alpha G into
rho G. So it is called gas bulk density and rho L bar it is similarly alpha into rho L, similarly
rho S bar it is the solid bulk density to be as what is that alpha S into Rho S.

138
G   G G
L   L L
S   S S
This is basically you know that what would the fraction of that density on that particular
phases.
(Refer Slide Time: 53:19)

Another important variable that should be defined is called superficial velocity. Of course,
whenever any fluid streams are actually sent at a particular rate that what will be the flow
rate, what will be the velocity of that fluid that you have to calculate? Now, there are two
types of velocity. It is called superficial velocity and actual velocity or intrinsic velocity.
Now, superficial velocities mean what? Suppose only a single liquid is passing through a pipe
at a particular volumetric flow rate like 5 liters per second, so in that case, this will be liter
per second that is volumetric flow rate.

Now, if you divide this volumetric flow rate by its cross-sectional area of that conduit or pipe,
then you will get that what would be the velocity of that fluid. So, for multiphase flow system
in a pipe, if you are considering only single-phase flows there, then it will be regarded as the
superficial velocity of each phases if you are considering that cross-sectional area of the
empty pipe or vessel and it is the velocity of the phase.

If the phase occupied the whole pipe cross-sectional area which can be defined by here like
this usp, s means here superficial, p for phase, so superficial phase velocity, it may be gas, it

139
may be liquid, it may be solid also. So, superficial gas velocity, the superficial liquid velocity
that will be actually calculated by this equation, it will be defined as Q by A.
Q
usp 
A
What is Q, Q is nothing but volumetric flow rate and A is the cross-sectional area. So,
whenever you are going to calculate the superficial velocity, of course, you have to divide
that volumetric flow rate by its empty cross-sectional area, but that means here only one
phase is flowing through that.
(Refer Slide Time: 55:22)

But you will see that whenever 2 phase will be there, then the quantity will be different
because in that case, you will see that if you supply the gas and liquid mixture simultaneously
in the same pipe, what will happen, gas and liquid will not occupy whole cross-sectional area
by that individual phase. In that case, gas will occupy some portion of the cross-sectional area
and liquid also will occupy some fraction of that cross-sectional area. So, in that case, the
velocity will be changed.

If the velocity will be lower than the original cross-sectional area, of course, that velocity will
increase for the same volumetric flow rate. So, that is why the actual velocity of that phase
whenever multiphase mixture will be passed through the pipe or any vessel, there you have to
consider what will be the actual velocity of that particular phase or it is called the intrinsic
velocity of the particular phases. So, it is defined as what is that, uip, i for intrinsic, p for
phase. So, uip will be equal to Q by A into alpha p.

140
 Q u
uiP   sP
A P  P

In this case, Q is the volumetric flow rate and here you know that alpha p is the volume
fraction of that, for that particular phase. So, it will be defined by Q by Ap. So, it will be
simply Q by A is nothing but usp that is superficial velocity and alpha p is the volume
fraction of that particular phase. So, this actual velocity is related to the volume fraction of
the phases. If your volume fraction is more, then you will see that your actual velocity will be
less, whereas if your volume fraction is less, then you will get the more actual velocity of that
particular phase.

So, it will be considered for each phase like gas, liquid, if there is a mixture of gas and liquid
is flowing through the pipe, then the individual velocity of that phase will be higher than that
superficial gas velocity or superficial liquid velocity there. So, here intrinsic velocity or
actual velocity of gas will be equal to superficial gas velocity divided by its volume fraction.
Q u
uiG   sP
A G  G
Similarly, here intrinsic velocity of the liquid will be is equal to the superficial velocity of
that particular liquid here and then it will be divided by the volume fraction of the liquid. So,
in this case, you can have this actual velocity for the multiphase systems how it can be
calculated.
(Refer Slide Time: 58:25)

Now, another important flow rate by which you can express that process, it will be called as
relative or slip velocity.

141
ur , g l  uig  uil
usg usl
 
g 1g

If gas and liquid both are flowing through the pipe, you will see that maybe gas will be
having higher velocity relative to the liquid velocity. So, there what should be the relative
velocity, of course, it will be the same way in the same direction it is going, then simply you
have to subtract that, that is liquid velocity from the gas velocity, then you will get that
relative velocity.

If you are considering that flow is flowing opposite in direction, then your relative velocity
will be just simply positive, that is summation of those two velocity. Now, what would be the
actual relative velocity or slip velocity that to be calculated based on the, what is that, actual
velocity of that individual phases. So, that actual velocity will be simply for the gas it will be
a superficial gas velocity by volumetric flow rate of gas and superficial liquid velocity of
liquid divided by 1 minus epsilon g, that is simply volume fraction of the liquid. So, in this
way, you can calculate what should be the relative velocity.
(Refer Slide Time: 59:46)

Now, another important variable like viscosity, so viscosity is a measure of the resistance of
the fluid which is being deformed by either shear stress or tensile stress and It describes a
fluid’s internal resistance to flow and may be thought of as a measure of fluid friction. So, it
is generally denoted by this by A, that is shear stress and it is denoted by tau and this is
related to the velocity gradient.

142
F du
 
A dy

Whenever fluid is flowing through the pipe, you will see that velocity of the fluid at the wall
will be zero, whereas away from the wall you will see that velocity relatively will increase
and at the center, the velocity will be maximum. So, in this way, there will be some gradient
of the velocity of the fluid layer in the pipe and based on which this resistance of the flow is
calculated. Now, this resistance of the flow is actually measured by that what is the shear
stress.

This shear stress is proportional to that velocity gradient of the liquid or fluid you can say and
it is represented by mu into du by dy where du by dy is called velocity gradient in the y-
direction and mu is called that proportionality constant, that provisionally constant will be
actually called as viscosity. So, this way, the viscosity this is basically a measure of the
resistance of the fluid which is being deformed by either shear stress or tensile stress. Now,
there are 2 types of viscosity, it is called dynamic viscosity and another is kinematic
viscosity.

Dynamic viscosity also it is called absolute viscosity, the more usual one that we are
considering here that mu and its unit typically are Pascal second, Poise, or Stokes or
sometimes it is represented and similarly, kinetic viscosity is the dynamic viscosity that is
divided by the density and its unit is Stokes or you can say that simply centimeter square per
second or meter square per second.
(Refer Slide Time: 01:02:08)

143
Similarly, the viscosity of gas, how to calculate? You can calculate the viscosity of the gas
from this equation given in the slides and it is related to the temperature. If you increase the
temperature, what will happen, that decrease the viscosity of the fluid. So, in this way, you
can calculate if you know the temperature and also you know some constant as per this
equation.
3/2
T C  T 
  0 0  
T  C  T0 

Here in this case, the C is one parameter, it is called Sutherland’s constant for the gaseous
material.
Based on this correlation, you can calculate what should be the viscosity of the gas and
basically the temperature within 555 K and the pressure at below 3.45 megapascal. You see
that for air, the C, T0, and mu0 are some parameters, then it will be as 120, 291.15 K, and
18.27 micro pascal per second and accordingly, you can calculate what should be the
viscosity of air at 15 degrees centigrade and it will be 1.78 into 10 to the power minus 5 kg
per meter second, you can easily calculate or find out what should be the viscosity of the air
if you know the temperature there.
(Refer Slide Time: 01:03:56)

144
Similarly, viscosity of the dilute gas, it can be calculated by the Chapman-Enskog equation
( MT )0.5
0 10  2.6693 2
6

  (T * )
and the equation requires 3 empirically determined parameters like collision parameter,
collision diameter, the maximum energy of attraction divided by the Boltzmann constant and
the collision integral and based on which you can calculate what should be the viscosity of
the dilute gases. So, from this correlation, you can easily calculate.

Here, in this case, you will see that mu0, mu is the viscosity of the dilute gas, T star is
basically the reduced temperature, it is dimensionless, M is molecular mass that is gram per
mole, and what is that T is the temperature in Kelvin, sigma it is a collision diameter that is in
Armstrong, and also epsilon by K is the maximum energy of attraction divided by Boltzmann
constant, and omega mu the collision integral.

There you will see that Boltzmann constant K is the physical constant that relates energy at
the individual particle level with the temperature that is observed at the collective or bulk
level. So, it is generally this value is given to you 1.380 into 10 to the power minus 23 joule
per Kelvin. So in this way, you can calculate the viscosity of the dilute gas.
(Refer Slide Time: 01:05:26)

145
Similarly, viscosity of the liquid, it is a function of temperature and this functionality given
here.
 (T )  0 exp(bT )
From this equation, you can easily calculate the viscosity of the liquid once you know that
temperature and also other empirical constants as given here mu0 and b, these are coefficients.
So, you can calculate that viscosity. As per this mu0 and b that is actually basically obtained
from the experimental observation.
(Refer Slide Time: 01:06:00)

The viscosity of the blends of liquids also you can calculate, that depends on actually
viscosity blending number. It is generally what is the viscosity of mixture upon is dependent
on the mole fractions of that individual component of that mixture. So, the viscosity of the
blend of two or more liquids can be estimated using this Refutas equation.

146
   VBN Blend  10.975  
  exp  exp     0.8
  14.534 
This Refutas equation basically involves that viscosity blending number which is defined by
this equation here shown in the slides and this for an individual component, this VBN will be
as a function of kinematic viscosity of the liquids there.
VBNBlend   xA  VBNA    xB  VBNB   ..............   xN  VBN N 

VBNi  14.534  ln ln  i  0.8  10.975

So, once you know that kinematic viscosity of that liquid in particular units as shown here in
the slides, you can easily calculate what should be the viscosity of the blend of the two or
more liquids.

(Refer Slide Time: 01:07:11)

Similarly, the viscosity of the slurry also you can calculate. The term slurry because
sometimes some operations will be based on that mixture of liquid and solid. So, that liquid
and solid will be regarded as the slurry. So, in that case, you will see that if you add more
particles there, you will see that viscosity will change, like powder. If any powder like we are
using that maida or atta or suppose some other powder if you mix in water or make a
solution, you will see that if you add more powder in the water, you will see that the solution
will be more thicker and thicker.

In that case, you will see that it will be very difficult to stir that solution if you add more
powder there. So, that means here the solution of that solid particles and water that is slurry

147
will be having more viscosity. So, that viscosity, that will be effective viscosity, how to
calculate that effective viscosity, that depends on how much volume fraction of the solid
powder will be adding into liquid. So, that volume fraction of the solids will be represented
by this Phai.

If you are adding a low concentration of that fine particle or powder particles there, so
according to Einstein’s equation,
  l (1  2.5 )
you can easily calculate what should be effective viscosity of that slurry. So, that depends on
the volume fraction of the powders or solid particles and also what would be the pure water
viscosity there. So according to this, you can easily calculate. If the particle concentration is
very high, then you can use another empirical equation given by Kitano et al in 1981.
2
 
  l 1  
 A
So according to his correlation, you can also calculate what would be the viscosity of the
slurry at its high concentration of particles. In this case, A is one unknown parameter that
depends on what type of solid particles you are using. If you are using the simple sand
particles or other fine particles, then generally, this A value is coming as 0.68 there. So, in
this way, you can calculate what would be the viscosity of the slurry, this is one of the
important process variables where it would be required for any process in your particular
process unit.
(Refer Slide Time: 01:09:52)

148
Similarly, conductivity you know the other variables like there are several different types of
conductivity which will give you that, how that is specified materials conducts electricity
they are in the solution like electrical conductivity, electrolytic conductivity, ionic
conductivity, hydraulic conductivity, thermal conductivity are those different conductivities
are there for the solution.
(Refer Slide Time: 01:10:17)

So, you have to calculate all those conductivity behavior of the solution there. So, electrical
conductivity you can calculate by this equation
A
R
l
given in the slides where all other parameters are given in the slides there. So, accordingly,
you can calculate, this is very important, it is commonly represented by the Greek letter
sigma, but K is electrical conductivity or Y are also occasionally used and also you will see
that this SI unit is siemens per meter and the CGS unit is reciprocal of that second there. So,
in this case, you can calculate this electrical conductivity.

(Refer Slide Time: 01:11:06)

149
Electrolytic conductivity also you can calculate based on the temperature, it is generally
changed with respect to temperature.
 T   Tcal 1   T  Tcal 

This conductivity or specific conductance of an electrolyte solution is a measure of its ability

to conduct electricity and then this conductivity will be actually represented by its behavior or
the ability to conduct the electricity and the SI unit of conductivity is a siemens per meter,
and in many cases, this conductivity is linked directly to the total dissolved solids in the
solution.
High-quality deionized water has a conductivity of about 5.5 micro siemens per meter.
Typically, drinking water in the range of 5 to 50 millisiemens per meter while seawater about
5 siemens per meter there. So, if you know the temperature, what should be the electrolytic
conductivity for a particular solution you can easily calculate. In this case, alpha is one
parameter that is called the temperature compensation slope of the solution that of course,
will be calculated based on your experimental observation for the process.
(Refer Slide Time: 01:12:24)

150
Similarly, thermal conductivity also one of the importance of variables based on which that
process efficiency actually changed that basically for the heat transfer operations, it is very
important. Now, this is a property of the material’s ability to conduct heat. It appears
primarily in Fourier’s law for heat conduction.

When heat is conducting to the solid material, there this conductivity, the behavior of that
material is concerned.

In that case, how to calculate the thermal conductivity of liquid for any solution especially for
n-alkanes based on the Vogel-Tammann-Fulcher-Hesse equation you can easily calculate
what would be the thermal conductivity of that alkane there.
K  K c exp( A / (T  Tc )

For, paraffins hydrocarbon of molecular weight 44 gives its 1.94, 561, 1630 for Kc, Tc, and
A respectively there. So, based on these values, you can easily calculate what should be the
thermal conductivity there.
(Refer Slide Time: 01:13:43)

151
Similarly, other parameters like diffusivity, this is also one of the, in this case how that
material actually diffused through another material, like diffusion of the gas through the
mixture of the gases and also this degree of diffusivity of the gases can be actually assessed
by the diffusion coefficient or simply it is called diffusivity. This is actually a proportionality
constant between the molar flux due to the molar diffusion and the gradient in the
concentration of the species.

So, whenever you are, suppose spray some perfume in the room, what will happen? You will
see that there will be spread of that perfume molecules throughout the whole room, how it
can happen? This is basically there will be some concentration gradient from one position to
another position and based on which you will see that they will try to you know that, based
on that concentration differences, they will try to spread it out.

So, according to that, how that the concentration is spread in a particular length that will be
regarded as concentration gradient and then this diffusion that is spreading of that perfume
molecules or any other gases you can say that, any gaseous molecules or liquid molecule or
any substance, how it will be spread or diffused based on that, that concentration gradient you
can calculate. Now, that molar flux, flux means what, how much amount of molecules per
unit time per unit cross-sectional area, it is being spread that will be called as flux.

Now, that flux is directly proportional to that concentration gradient.

152
 c
J  D
x
Now, that proportionality constant, it will be regarded as a diffusion coefficient or diffusivity.
So, this is one of the important factors based on which you will see that the process will be
analyzed. So, you have to know that what should be the diffusivity. So, similarly, how to
calculate that diffusion coefficient for gases or liquid, you can use directly this equation for
the calculation of the diffusivity, here it is given as in the slide.
1.86 103 (1/ M A  1/ M B )0.5 T 3/2
DAB 
p AB
2


1
 AB   A   B 
2

(Refer Slide Time: 01:16:22)

Similarly, diffusion of or diffusion coefficient for the solvent also you can calculate by this
equation given in the slides accordingly.

1.173 1016 ( M B )0.5 T

DAB 
 B A0.6

(Refer Slide Time: 01:16:33)

153
The diffusion coefficient in the solids also you can calculate this Arrhenius type equation
here. This actually depends on the temperature here.
D  D0e EA / RT
So, once you know this diffusion coefficient, maximum diffusion coefficient as D0 and also
EA is the activation in energy and T is the temperature of the system, then you can easily
calculate what the diffusion coefficient of the solid is.
(Refer Slide Time: 01:17:06)

Similarly, permeability is one of the important parameters based on which you can assess the
process. This is a measure of the ability of a porous material to allow fluids to pass through
the material. Now, the SI unit for the permeability is meter square. The concept of
permeability is of importance in the determination of the flow characteristics of the

154
hydrocarbons in oil and gas reservoirs and of groundwater in aquifers and also the separation
of the solute by a membrane.
(Refer Slide Time: 01:17:42)

So, this permeability you can easily calculate from the pressure difference of that medium
from this side to that side, so in that case, this equation will be useful to calculate that
permeability.
kA ( Pb  Pa )
Q
 L
(Refer Slide Time: 01:17:58)

Similarly, the dielectric constant is also one important parameter. So, this dielectric constant
is actually is a material dielectric constant that of a substance can be defined as that ratio of

155
the permeability of the substance to the permittivity of the free space. It expresses the extent
to which the material can hold electric flux.
(Refer Slide Time: 01:18:21)

So, we have discussed in this lecture different process variables, which are very important for
the analysis of process performance. So, thank you for your attention to this lecture. In the
next lecture, we will try to discuss some thermodynamic variables like pressure and
temperature of the flow processes.

156
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 2: Process Variables and Rate

Lecture – 2.2
Pressure and Temperature
of Flow Process

Welcome to massive open online course on Basic Principles and Calculations in Chemical
Engineering. So, we are discussing about process variables and rate under module 2. So
under this module 2, today we will discuss more about the process variables like pressure and
temperature of flow processes.
(Refer Slide Time: 00:53)

We have discussed in the previous lectures some process variables and their principles about
a system, even physical and transport properties of material in system and mixtures. So, in
this lecture, extension of that part will something more about that process variables like
pressure and temperature, fluid statics and their measurement in flow processes, we will try to
learn something about this.
(Refer Slide Time: 01:24)

157
Now, the pressure at the base of a vertical column of fluid that is not moving and whose
density will have a certain value and if it is denoted by rho and the fluid height is h, then this
pressure exerted by this particular height of this liquid in the container of that particular
density, it will be regarded as hydrostatic pressure and it can be defined as this gh. So, here
see in this figure in the slide to see that in a container some amount of fluid whose density is
rho is kept there.

Here you will see that this amount of fluid will exert pressure at the bottom of this container
even at its wall of this container at a certain value. Now, this pressure you will see that will
be equal to gh, it is called hydrostatic pressure. That means, what will be the length of this
or height of this fluid that shows by this fluid or liquid in the container and also what would
be the density of the fluid if you know that, then you can easily calculate what should be the
hydrostatic pressure, but this total pressure will be what you will see at the surface of this
container.

Some atmospheric pressure will be acting on this container and this atmospheric pressure if
you add on this hydrostatic pressure, it will be total pressure that is acting on this bottom of
this container there. So, it will be regarded as total pressure here. So, this total pressure is
here this atmospheric pressure and the hydrostatic pressure. So, this atmospheric pressure is
represented by P0 as shown here and hydrostatic pressure will be equal to gh, though the
summation of this atmospheric pressure and hydrostatic pressure will be total pressure that is
exerted by the fluid and atmosphere on this bottom of this container.

158
So, we can say that if a vertical container contains a fluid, the mass of the fluid will exert a
force on the base of the container. So, this is the basic of this hydrostatic pressure whenever
fluid will be kept in a certain container and what will be the pressure exerted by the total
mass of this fluid that you can get by this hydrostatic pressure.
(Refer Slide Time: 04:52)

Now, interesting is that sometimes this pressure will be represented by head because it will be
sometimes regarded as what is that length of the fluid there and by which the hydrostatic
pressure will be sometimes will be represented. Now, in this case the height of a hypothetical
column of this fluid if it exert certain pressure at its base and if the pressure at the top will be
0, then from that hydrostatic pressure equation you can say that it will be simply P is equal to
gh. So, here this gh from this equation we can say that here h will be equal to P by rho g.
So, this h will be called as head.

So, pressure is sometimes regarded by this head and its unit will be equal to unit of the length
because this is simply height, but this height you can get it from this equation because P is,
what is that unit for P is Newton per meter square whereas you will get that this gh unit will
be equal to what? So, accordingly after banishing that equation and also unit, so finally you
will get that unit of this head will be h or length or you can say that meter there. So, the
advantage of expressing this pressure as a head is that this quantity is now independent of the
material property.

So, that is why sometimes the pressure is represented by head and now important thing is that
what we told that there will be some hydrostatic pressure on the fluid element. Now, what

159
should be the pressure if you have the certain distance or certain height of that liquid, you can
easily calculate this hydrostatic pressure, but sometimes you see that you need to express this
hydrostatic pressure in more general format.

How to derive this hydrostatic pressure that you can have from consideration of certain fluid
element that is kept in a container or if it is flowing through the conduit, then from that fluid
element, we can easily derive some expression of this pressure within a static fluid element.
(Refer Slide Time: 07:42)

So, in this case if we consider that a fluid element of volume of dimensions like here x, y and
z and its volume will be as you know dx into dy into dz. So, in this case here if you consider
this fluid development here as shown in the figure in this slide, you will see that the pressure
P will be acting at the center of this fluid element and it will have 6 faces and on all these 6
faces, the pressure will be acting from all its directions.

So, you will see that if we consider that x, y and z direction, now if you consider this the
element of this volume of dimensions like dx, dy and dz in x, y and z direction, then we will
get or we can consider that there will be 6 faces, now on each face what should be the
pressure that is exerted from surrounding fluid. So, in that case, we can express this total
force that is acting on the element will be actually as dF, then this dF means here a a small
amount of portion will be acting over this small volume of fluid element that we consider
here.

160
So, total force acting on the element will be dF. Now, this dF actually will be sum of the body
force and what will be the net surface force acting over this small fluid element. So, this
small fluid element will have some body force that will be regarded as gravity force. So, this
body force and what will be the total force acting over the surface of this fluid element that
will be as net surface force because here 2 forces will be subjected to the pressure from the
opposite direction here in this fluid element like in the x direction.

If you consider that, in this direction the force will be acting and from this direction also force
will be acting. Now, since this force will be acting in the opposite direction, then there will be
some net force will be acting on this let us say x direction. So, what should be the net surface
force that you have to calculate. So, what should be the first you have to calculate the body
force. The body force will be equal to what, we know that gravity force that will be called to
m into z. So, what is m here, since we are considering the fluid element volume dx, dy and
dz, this is volume.

So, if you know the density of the fluid, what should be the mass. So, volume into density
that will be your mass. So, you know the density is rho and volume is dx, dy and dz. So, we
can write rho into dx, dy and dz here. So, this will be your mass and if you multiply this mass
with this gravitational acceleration, then you can say it will be your body force. Then you
have to calculate what should be the net surface force acting on six faces. Now, first you
considered in x direction. So, what will be the force acting on this face here as shown in the
figure.

So, that will be your what is that P plus dou P dou x into dx by 2 into dydz. Why it is coming
like this, you know that forces acting at the center as P whereas you will see that since this
face here this what face we can say here, this is simply that here dy and dz, dydz. So, this face
will be at a distance of dx, so what will be the pressure gradient there at this face here. So, it
will be dou P by dou x. Now, since this pressure gradient will be at a length of dx by 2, why
dx by 2 because from this face to this face, total distance is x.

So here since from the center to this face is dx by 2 distance, then we can have this distance
as dx by 2. Now, if you multiply this pressure gradient over this dx by 2 distance, then we can
have pressure difference over this dx by 2. So, this pressure difference will give you that what
would be the pressure at the surface there. So, this at the surface in the positive x direction,

161
we can easily say that at this point what is the pressure and at the surface what would be the
pressure there. So, it will be [P+ (P/y).dy/2]dxdz.

So, in this way, we can calculate what should be the net force here, only that you have to
calculate first in this positive direction what would be the pressure and in the negative
direction in the same way what should be the pressure there. So, if you subtract these positive
two here this side of pressure then you can easily express by this equation here. So, this will
be your in the x direction. Similarly, you know that dxdz front or face, you can express the
pressure like this here.

Similarly, in this dxdy plane or face, you can express what would be the net force over there.
So, if you add all those net force acting on these 6 faces, then you can get here this equation
as -(P/x+ P/y+ P/z)dxdydz

So, in this way, you can calculate what should be the net force acting on 6 faces. Now,
substitution of this net force and the body force in this equation here of total force acting on
the element that can be expressed then by this equation here. So, dF will be equal to -(P/x+
P/y+ P/z)dxdydz + what is that, you know body forces there.

As per Newtonian law, we can see that this small amount of force that will be equal to mass
into acceleration. So, if we consider that small amount of masses, you know that dm and its
acceleration is a, this acceleration will be you know that in x direction, in y direction, and in z
direction also. So, we can write here what will be the dm here, rho dV into a,  is the density
and dV is the small volume that is dxdydz and then rho into dV will be mass, then into a it
will be acceleration.

So, it will be called as force as per Newton, then Newtonian law or you can see that as far
Newton's law of force. They are so it will be mass into acceleration and for static fluid we can
say that there will be no acceleration, so a will be is equal to 0. So, in this case, we can have
this dF will be equal to 0.

(Refer Slide Time: 17:15)

162
Therefore, if we substitute this dF here, this left hand side and that will be close to 0 by this
equation. Then you can say that -(P/x+ P/y+ P/z) + ρg that will be equal to 0. In this
case, g is gravitational acceleration. This acceleration will be acting you know that it is in
general that g can be regarded a general here, but if it is working in vertical direction, then
you have to consider it as gravitational acceleration. Otherwise, in either direction you have
to consider a certain value of acceleration there other than gravitational acceleration.

Now, this g if we consider here, which is equal to 0 in x and y direction, that means in the x
and y direction, there will be no acceleration since the fluid element is in static condition. So,
in the z direction, we can say that that g will be equal to gravitational acceleration and this
gravitational acceleration will be equal to 9.81 meter per second square. So, finally after
substitution of this g in the z direction, we can easily say that minus dp dz that will be equal
to minus g.

So, from these, we can say that here P1 minus P2 that will be equal to minus rho g into Z1
minus Z2. This Z1 minus Z1 is the distance between two points and P1 minus P2 will be is
equal to pressure between two points. So, in this case as far figure shown here in the slides, if
we consider the two points here on this fluid element at the surface, you will see that if we
represent here or denote here as point 1 and at a depth h the point here 2, then you can say
that at the point one you will get the pressure only atmospheric pressure or as at point two
you will get the pressure here at a certain height of h.

163
That h will be equal to hydrostatic head, and based on these, you can express by this equation
as P0 minus P2 because here at this point one pressure is P0 atmospheric pressure and at this
point two pressure is here P2. So we can write here P0 minus P2 that will be equal to minus
rho g into what is that, what is Z minus Z, Z1 minus Z2 here at this point one since we are
considering datum line is at point one, so here distance is 0 and what is that, here h Z2, Z2 is
basically since it is in that negative Z direction, it will be minus h.

So, 0 minus of minus h because Z2 here to be equal to minus h. So, ultimately we can say that
this P2 minus P0 will be equal to gh. So this P2 will be equal to then P0 + gh h. Now this
P0 is the atmospheric pressure. So, in this way, we can derive these hydrostatic pressure
based on the consideration of the small fluid element at its static condition in x, y and z
directions and considering their forced acting on that fluid element from all the directions at a
certain amount.

So, based on which we can derive like this what should be the hydrostatic pressure there and
so we have got this very interesting equation here, this will be equal to P1 minus P2 that will
be equal to minus rho g Z1 minus Z2. This you have to remember because this equation will
be useful to estimate the pressure of the fluid flow whenever it will be flowing through the
pipe or any other conduit or any other system or any other unit where you need to calculate,
you have to estimate, you have to obtain the pressure between two points and this equation
will be helpful to calculate.

So, we will give some example also there, how to calculate, how to use this equation to
calculate the pressure there.
(Refer Slide Time: 22:32)

164
Now, the earth atmosphere can be considered as a column of fluid with 0 pressure at the top
and the fluid pressure at the base of this column like at sea level is the atmospheric pressure
that you have to consider and the absolute pressure of a f.uid is the pressure that is related to a
perfect vacuum there that will be P is equal to 0.
(Refer Slide Time: 23:01)

gauge pressure is basically that is pressure of the fluid, which is the pressure of the fluid
relative to the atmospheric pressure, that is reference pressure. A gauge pressure of 0
indicates that the absolute pressure of the fluid is equal to the atmospheric pressure. So, you
have to use this equation or remember this equation to calculate the absolute pressure.
Basically, whenever fluid will be flowing in a system and the pressure whatever it will be
exerted without consideration of atmospheric pressure, it will be regarded as gauge pressure.

165
So, absolute pressure will be basically the gauge pressure plus atmospheric pressure. So, in
this way you have to remember whereas gauge pressure will be what is your absolute
pressure? If you subtract that what is that atmospheric pressure you will get the gauge
pressure there. So, you have to remember this equation what will be the atmospheric
pressure, atmospheric pressure will be equal to gauge pressure plus, sorry absolute pressure
will be equal to gauge pressure plus atmospheric pressure.

What is the unit for pressure that we told Newton per meter square, in CCS unit it is dyne per
centimeter square whereas in American engineering system, this unit will be psi, that means
pound-force per inch square.
(Refer Slide Time: 24:36)

What are the different types of pressures atmospheric pressure, absolute pressure, gauge
pressure, and vacuum pressure. Vacuum pressure is a gauge pressure that is below
atmospheric pressure. Even other than these pressures, you will have different types of
pressure whenever fluid will be moving through a pipe or any other system, like you will see
that whenever fluid will be flowing, the measurable pressure.

Total pressure will be actually summation of this hydrostatic pressure and frictional pressure
and also if is there any pressure because of change of crosssectional area or any heat energy
supply to the pipe or any other you know that force acting on this conduit or not, like
magnetic force, electrical force, or some other force or if any change of momentum is there
inside the pipe or any system there.

166
So, in that case, the total pressure will be equal to able to pressure due to friction, pressure
due to hydrostatic pressure, and pressure due to the change of momentum or pressure because
of other exerting force on the system. So, these are the various types of pressure that you
have to remember.
(Refer Slide Time: 26:25)

You have to know also what is the standard atmospheric pressure. It is defined as the pressure
that is equivalent to 760 millimeter mercury or 1 atmosphere at sea level and at 0 degrees
centigrade. So, this you have to remember. So, in this case 1 atmosphere will be is equal to
what is the 760 millimeter mercury. That means, in a column if you take mercury and you
will see what will be the pressure if you take that mercury of length of 760 millimeter length.

So, in that case, what will be the two amount of hydrostatic pressure because of that mercury,
it will be actually equivalent to the atmospheric pressure. So, it is actually after calculation
because here you know that it will be again that rho g into h, rho of mercury, density of
mercury will be 13,600 kg per meter cube, g is 9.81 and you know that h is here, it is 766
millimeter, you have to convert it to meter, that means what is that seven pint six zero 7.60.

In that case, you will see that centimeter sometimes it will be represented as 76 centimeter
mercury and you have to convert it to meter like 0.760 meter. Then if you multiply that you
know density like 13,600 into 9.81 into 0.760, then you will get that atmospheric pressure as
like this 1.013 into 10 to the power 5 that will be equal to Newton per meter square. So, it is
regarded as what is that Pascal's also. So, it will be 101.3 kilopascal just divided by 1000,
then you will get.

167
Even this will be regarded as also bar like 1 into 10 to 1.013 into 10 to the power 5 Pascal it
will be called as 1.013 bar. Similarly, this standard pressure can be represented by AE system
it will be equivalent to 14.696 psi or you can say that is 14.7 psi. So, it also will be equivalent
to 29.92 inch of mercury and also you can say that it is 33.91 feet of water column pressure
there. So, in this way, we can represent that standard atmospheric pressure at different or by
different units.
(Refer Slide Time: 29:41)

Now, there are some conversions of pressure from one system to another system. It is given
in this stable in the slide, you can go through this conversion. This conversion table may be
useful for your further calculation.
(Refer Slide Time: 29:55)

168
Now, standard normal temperature and pressure, what is that also you also have to know that
standard temperature and pressure are used widely as a standard reference point for the
expression of the properties and processes of ideal gases. So, in that case, STP set by IUPAC
at 0 degrees centigrade and 100.325 kilopascal or 1 bar. This is STP means standard
temperature and pressure, whereas NTP is another condition it is called normal temperature
and pressure.

It is set at generally 101.325 kilopascal, but the temperature will not be 0 degree centigrade,
whereas it will be 20 degrees centigrade there. So, there is a difference of this STP and NTP
is that pressure will be same but temperature will be different. In case of STP, the
temperature will be 0 degree centigrade whereas in case of NTP, the temperature will be 0 to
20 degree centigrade.
(Refer Slide Time: 31:07)

and Also, you can say that this pressure whatever we are getting that standard pressure or
pressure in a particular system how to measure that pressure. There are various types of
pressure sensing devices are available to estimate the pressure or measure the pressure
whenever fluid will be flowing through the pipe or through the other systems there. Like here
the Bourdon gauge, diaphragm capsule, capacitance sensor, column of fluid, manometer,
barometer, silicon diaphragm and semiconductor strain gauges are used to measure the
pressure.

In laboratory scale even most of the manometer is a U-shaped device that are used to measure
fluid pressure there in the system.

169
(Refer Slide Time: 32:45)

So, this manometer is a U-shaped device that uses a fluid having greater density than other
fluids in the process unit. So, this is very useful and these manometers are actually
inexpensive and simple and also it will give you that accurate measurement. These are
basically used to measure the fluid pressure in the system and also, we can say that there will
be certain principle of the manometer by which you can calculate the pressure. So, there how
it works that manometer there in the fluid system to get the pressure from this manometer that
you have to know.

So, a manometer is a U-shaped device that I told that is being used for measuring that fluid
pressure and in this case whatever fluid is being used generally it will higher density relative
to the fluid that is flowing through the system and it works based on the fact that hydrostatic
pressure at the same level in the same fluid must be same in each leg of this U-tube
manometer. So, the schematic of the U-tube manometer is shown here in the slides.

It will have two legs, the left leg and right leg, you will see the U-tube manometer some fluid
that will be higher in dense relative to other fluid that is flowing through the system and in
this case this higher density fluid whenever pressure will be subjected on this manometer leg,
you will see that the fluid will be moving up little bit and there will be a difference of this
fluid level or you can say that liquid level inside that manometer and based on which you can
calculate what should be the hydrostatic pressure exerted by that fluid in the system.

170
So, whenever we need to determine the hydrostatic pressure that is caused by a mass of fluid,
it is simply given by gauge pressure that will be as P that is F by A that mg by A, that is mg
means Vg by A, rho is the density, V is the volume, and g is the gravitational acceleration,
A is the crosssectional area and then you can say that rho into A into h here as shown in
figure here. Suppose this right leg of this fluid will be above this level of initial left leg level.

So, what should be that force exerted by that liquid that is shown in within this length of h
there. So, here in this case, we can say that it will be rho into A into h into g by A. So, it will
be simply rho into g into h. So, here absolute pressure will be equal to this gauge pressure
plus atmospheric pressure. So, whatever hydrostatic pressure will be based on this small h of
this fluid element, it will be regarded as gauge pressure, whereas on this gauge pressure there
will be extra pressure that is atmospheric pressure will be acting on that on the surface then to
be that atmospheric pressure. Now, sum of this gauge pressure and atmospheric pressure will
be equal to absolute pressure.
(Refer Slide Time: 36:46)

There are various types of manometers are generally used to estimate the pressure. Basically,
3 different arrangements of the manometers are actually used to measure this pressure using a
column of a dense liquid. One is an open-end manometer as shown here. In this case, the one
end of the leg, that is you can see this is manometer, so one end of this manometer will be
open; that is why it is called an open-end manometer and another is differential manometer.
In this case, both the leg will be connected to the process system or like if there is a fluid is
flowing through the pipe.

171
Then at the two point 1 and 2, this manometer leg will be connected. So, it will give you that
pressure difference, that is why it is called the differential manometer. In this case, you have
to remember that the pressure decreases in the direction of the flow. So, that is why if
pressure is given like this at P1 and P2 at this point 1 and 2, you will see that at point 2,
pressure will be lower whereas at point 1, pressure will be higher. So, that is why the pressure
will decrease in the direction of the flow.

So, the pressure difference will be equal to P1 minus P2 or if you are considering that P2
minus P1, it will be as negative delta P or negative pressure difference. A closed-end
manometer also used to actually calculate the absolute pressure. In this case, a manometer
that has one leg sealed and the other leg open measures the atmospheric pressure So, in this
case, very interesting that one leg sealed here like this and another leg that will be connected
to the process system and it is called the barometer or something.

There in this case whenever there will be any seal of that, right leg there, so in between that
denser liquid and that sealed end there will be an open space, not open space, it will be a
space there, but there will be a certain amount of gas may be present or may not be present.
So, if there is no gas is present, the pressure will be 0, whereas if some gas will be there, there
may be some pressure will be exerted by that space there that you have to consider. So, in this
way, this closed-end manometer is also used to calculate the pressure difference.

Sometimes inclined manometers are also used to the generally conventional installment of
pressure measuring instrument as per the condition of that process where have to be installed
there. So, sometimes the inclined manometer are also used to calculate the pressure
difference there. So, in this case also here, the same principles is being followed like
hydrostatic pressure, but here the manometric height that will be actually be shown in here, in
this case, it will be inclined, but for the calculation, you have to calculate what should be the
vertical height of that just because of what is that inclined angle it will come.

Based on which that inclined angle, what will be the vertical height for that you have to
calculate based on that angle, and based on this vertical height from its inclined leg, you have
to calculate what should be the hydrostatic pressure and that pressure will be actually gauge
pressure of your that system.
(Refer Slide Time: 42:15)

172
General manometer equation if we consider that what we have to remember for the balancing
of that pressure on its both sides, you will see that one leg will be connected to the process
system, another leg may not be there. So, in one leg whenever system will give you some
pressure on that particular leg, so, there some force will be acting on that and because of
which what will be the manometer fluid will be used that manometer fluid will be rise on that
right leg of the manometer, and on that right leg if it is kept to open its end, then atmospheric
pressure also will be acting on that open end surface of the manometric fluid.

So, in that case on the leg, there will be a force acting, but at a certain condition, this
manometric fluid will remain static there because of that force balance. Now, from that static
condition of that manometric fluid rise, from there are you can calculate what should be the
pressure just by balancing that force acting over that manometric fluid on both sides. of the
manometer leg. So, that is why you have to calculate what should be the pressure, summation
of pressure on that leg one that is in the left leg and what would be the summation of pressure
on leg two.

So, here shown in figure in the slide that here the leg 1, here this is leg 1, in the leg 1you will
see that this is the fluid whose density is rho 1 that will be coming from the system maybe
since it is connected to the process unit of the system and then this liquid will be as what is
the manometric fluid, maybe higher density, that density is rho 3, that may be mercury and
other part here to be some other fluid may be there. It may be the same of that left leg or
maybe other fluid also, whatever it is, but its density will be certain there.

173
If it is not same from that left leg, then maybe other denser fluid like as density 2. So, at this
leg, we are having what is that some P2 here, pressure due to that this fluid of 2and the
pressure due to this fluid 3, and at this leg, the left leg, leg 1, you will see that pressure will
be exerted from that system and then pressure will be exerted by this fluid of density 1 and
here also you will see that what would be the pressure at this point.

Now, very interesting point here that you have to some datum line at a particular datum line
from which you have to calculate that summation of pressure on the left leg and summation
of the pressure on the right leg of this manometer. So, that datum line or reference line is to
be considered, otherwise it will be very difficult to calculate. You can decide that datum line
anywhere in this manometer leg, maybe you can consider at the bottom of this manometer leg
here itself.

See, I can show you like this, but you can conveniently decide this datum line here at this
fluid interface of this manometric fluid and the other fluid inside the manometer. So, it will
be better to consider the datum line here at this point or manometric fluid and other fluid give
that interface. Otherwise, you can also try it; you will get the same results if you are
considering the datum line at this bottom. So, from this bottom, you have to know what will
be the distance there, that distance you have to calculate from this bottom line.

Now, if I consider that bottom line as shown here in the slide as dotted line like 1, 2 and what
should be then total pressure at this bottom leg of this manometer. It will be here at this point
here; this is P1 and the hydrostatic pressure that is exerted by the fluid of density 1 and its
height is regarded as h1. So, its hydrostatic pressure will be 1gh1. So, it will be your
hydrostatic pressure that is exerted by fluid of density 1. Now, this is your up to this datum
line, what would be the total pressure.

Now, if you consider the right leg of this manometer about this datum line, you will see that
above this datum line, this manometric fluid is raised up to what is that h here. So, from this
to this point, the height is h, and from this to this point that height is h2 and above this h2,
above this point, this pressure is P2. So, in this case, total pressure will be the summation of
this P2 and pressure exerted by this fluid of 2 of height h2 and the pressure exerted by this
manometric fluid of density 3 of height h.

174
So total pressure will be equal to P2 + 2gh2 + 3gh
Now both the total pressure will be same at its static condition of this manometric fluid inside
this manometer. So, from which you will be able to calculate what should be the pressure
difference between P1 and P2. So, from this equation, we can say that P1 minus P2 will be is
equal to here 2gh2 + 3g into h minus 1g into h1. So, in this way, you can calculate what
should be the pressure between two points if this manometer is connected to a certain system.
(Refer Slide Time: 48:33)

Like here one example is given to you, like a nitrogen gas is kept intact in a tank as shown in
figure here. The pressure exerted by the gas is measured by a closed-ended manometer. The
manometer fluid is of specific gravity of 0.87. The manometer shows the elevation difference
of 0.01 meter. So, in this case, what should be the pressure inside the tank? Now, what you
have to do, you have to calculate the gauge pressure inside the tank. Now, this gauge pressure
will be is equal to what?

So, it will be is equal to that rho g into h that is given by this manometric fluid rised from this
interface that is at h whereas inside this that manometric fluid, there will be a vacuum that
will be PA will be equal to atmospheric pressure will be is equal to 0. So, that will be your
tank pressure here. So, what will be that tank pressure here that will be is equal to 0.87 into
1000 into 9.81 okay because here h is given to you, you know that and also what is that
specific gravity is given to you and also this gravitational acceleration is there.

175
So, what is that specific gravity is 0.87 if you multiply this specific gravity with the density
of water, you will get the density of fluid of this manometric fluid and then g is there and
height is given 0.01 meter. So, finally, it will be coming as 85.3 Pascal.

(Refer Slide Time: 50:36)

Then, another example. If suppose gas is flowing through a pipe as shown in the figure here
in the slide. An open-ended manometer is connected to measure the pressure of the flowing
gas inside the pipe. The manometer fluid density is 2.0 gram per centimeter cube and it is
seen that gas bubble is trapped in the left leg of the manometer here, gas bubble is trapped
here. Now, in this case, you have to calculate the pressure of the flowing gas inside the pipe,
how to calculate? So here very interesting that the manometric fluid will be there inside the
manometer, but during that flow, some gas bubbles is trapped inside the manometer.

Now, because of this trapping of this gas bubble, there will be pressure whatever pressure
will be exerted here that will be balanced by this here manometric fluid up to this rise. Now,
if it is there, then how to calculate that pressure here? In this case, if we consider that the
datum line as x dash x here at this interface. So, we can say that at the left leg, what should be
the pressure that will be at x in the right leg that will be x as Px, Px will be is equal to what
here, gh + atmosphere because this rise is given because of this what is that total pressure
and this left leg and this pressure is coming because of this gas inside the pipe.

Now then, what will be the Px here at this that will be is equal to gh + this atmospheric
pressure. So,  is density that is given to you and g is given to 9.81 and h is 0.12 meter it is

176
given to you and then atmospheric pressure you have to add. So, finally, you are getting
0.0232 atmosphere + P atmosphere, that is atmospheric pressure.

(Refer Slide Time: 52:54)

After that, you have to calculate what should be the pressure at that left leg of this
manometer, that is at point x dash that is Px dash, it will be equal to here

this is also hydrostatic pressure because of this gas present here and also fluid like this here,
this fluid, this is 0.10 meter here fluid, so in that case, rho fluid into g fluid into what is that h
fluid you have to calculate.

So, finally, you can get that this P gas plus here at this condition, gas bubble, there is no
pressure. Here also there will be no pressure. So, finally can say that this portion will be is
equal to 0 or as here, since it is here what is that there will be manometry fluid here at a
certain height of the 0.1 meter. So, you can calculate what would be the pressure there. So, it
will be coming as P gas + 0.0194 atmosphere. So, finally, at the equilibrium condition, you
can say that Px will be is equal to P dash.

So, if you substitute that Px and Px dash here, we can say that P gas minus P atmosphere that
will be coming as 0.0038 atmosphere. So, finally, this will be regarded as gas pressure, if you
subtract the atmosphere pressure from this absolute pressure, then you can calculate what
should be that gas pressure, it will be P gas minus P atmosphere. So, it will be 0.0038

177
atmosphere. Now, the contribution to the hydrostatic head from the gas bubble can be ignored
since gas densities can be neglected here relative to the liquid densities. So, that you have to
remember.
(Refer Slide Time: 55:10)

Another example is given here. Air is flowing in a circular pipe during its supply to a
fluidized bed reactor connected with a closed-end manometer to measure its pressure. The
manometer fluid density is given to you. An air bubble was seen trapped in the left leg of the
manometer during the process. The closed end of the manometer is in a vacuum. So, what
should be the pressure of the airflow in the pipe. Similarly, you have to calculate the pressure
at its x point and also pressure at its x dash point here.

So, similarly you can get that Px as 1.777-centimeter mercury, whereas Px dash you can get
that here 0.3-centimeter mercury. So, after balancing these, you can easily calculate what
should be the gas pressure inside the pipe.
(Refer Slide Time: 56:10)

178
Another example where you will see that to measure the pressure drop if you are using
multiple of fluid as well as you are using that manometer in different way, to design the
manometer in different ways, how to calculate that pressure drop measurement. Now, as
shown in here in the figure, you will see that you have to measure the pressure between two
points of pipe A and B and the manometer like this designed here, as shown in figure. It is
connected to this process unit at point A and B and you have to calculate what would be the
pressure difference between A and B.

Now, in this case, the manometer is filled with some portion is with water, some portion is
with mercury, some portion will be filled with oil, and again some portion will be as mercury
and water like this. So, here 3 different fluids are there inside the manometer. So, you have to
calculate that pressure between A and B. Now, you have to use that general equation of that
hydrostatic pressure that we know that P1 minus P2 that will be is equal to minus rho g into
Z1 minus Z2. So, this is your general equation.

If you apply the general equation, you can easily calculate what should be the pressure
difference between A and B. Now how to apply? Before going to apply these things, you
have to mark it out at different interfaces of the fluids inside the manometer, here like this,
her, this is 1 that interface, this is regarded as 1. This is another interface, that is regarded as 2
and another interface 3 and like this another interface 4. So, after giving these marking up 1,
2, 3, 4, we have to calculate the pressure between these points like here if we consider first
the point A and 1.

179
So, what should be the pressure between these two points A and 1? That means here,
according to this hydrostatic equation, it will be PA minus P1, so for that minus rho into g into
Z1 minus Z2, what would be that, here in this rho will be of water because this portion is filled
with water. So, that is why minus rho w into g into ZA minus Z1. What is ZA, here we are
taking the reference line or datum line from bottom of this manometer and the Z direction is
upward direction, here this is positive direction.

So, if we consider that ZA minus Z1 it is simply what is the positive value. So, what is the
length of that, it is given here 10 I think centimeter, so what would be the meter 0.10. So,
finally, after substitution of that water density and the gravitational acceleration and then
finally, we are getting this equation. Similarly, if you consider this point 1 and 2, then you
will see that here density of the fluid will be mercury density like this rho m or else the
distance between these 2 points here Z1 and Z2, in this case here see Z1 is lower point whereas
Z2 is higher point in the positive Z direction.

So, here the difference will be negative. So, that is why it is coming as here in this case, after
substitution of the density of mercury, gravitational acceleration and difference of Z1 minus
Z2, it will be minus 0.03. Similarly, between you know 2 and 3, here again, P2 minus P3, it
will be like this, density will be of fluid oil. So, in that case here again after substitution here
in this case Z2 minus Z3, it will be positive, so it will be +0.04. Similarly, for others P3 minus
P4, it will be between 3 points and 4 points.

So, here it will be is s equal to again here the density of the fluid will be of density of
mercury. So, hereafter substitution of that and what will be the distance between that is given
will be 0.05, but it will be negative because here 4 point is higher than that point 3 in the
positive Z direction. Similarly, here P4 minus PB between this point 4 and B, it will be coming
there. Here again, this fluid element will be only water, so because of that, you have to
consider the density of water there.

So, finally, if you sum it up all those pressure differences at a different point, you will see
that after summing up, here you see cancelling of this P1 P1 here and P2 P2 here, P3 P3, P4 P4.
Finally, you are getting the PA minus PB, that will be exactly after calculating from this right-
hand side of this equation and summing up, you will get this 10131.768 Newton per meter
square.

180
See how you know simple this calculation of the pressure drops from its system by using
different designs of that manometer by using multi-fluid inside the manometer, just by using
simple hydrostatic equation of P1 minus P2 will be is equal to minus of rho g into Z1 minus
Z2, this equation.
(Refer Slide Time: 01:02:29)

Another example here given if it is supposed inclined to you, also you can calculate, please
go through the slides here also. In the same way, we have calculated that here what will be
the pressure difference between A and B if the fluid is flowing through the inclined pipe up
30 degree angle there and the length between these 2 points is given as L and at different
interfaces of the fluid whatever it is being given, the length is given there. So, finally, the
same principle you can use in this problem to calculate the pressure differences as PA minus
PB and you can get this equation and finally, you can get this pressure difference here.
(Refer Slide Time: 01:03:08)

181
Similarly, another like LPG is kept intact in a tank as shown in a figure here. So, what should
be the pressure exerted if you are using that inclined manometer. Here also the same way you
have to calculate, but the only thing is that height will be considered as what is that height
here from the inclined length that you have to calculate. So, accordingly, you can get the
pressure difference.
(Refer Slide Time: 01:03:31)

Now temperature. You know that for the process analysis, temperature is one of the important
variables because this temperature of course will influence that reaction, even other
processes, even physical separation process, reactive separation process, even many chemical
engineering operations, those are actually depending on the temperature. So that you have to
know the temperature, how the temperatures will be distributed, even how the temperature

182
will be measured, and also what are the different units that are considered to calculate that
temperature in a particular system.

Similarly, the same way different systems you can get as pressure also. The temperature you
can measure by different units, even some sophisticated instruments like thermocouple you
can use, even the thermometer you can use, even other different types of a sophisticated
instrument of measuring this temperature are available and devices are available to measure
this temperature.
(Refer Slide Time: 01:04:18)

There are different systems like Fahrenheit, Celsius, Kelvin, even Rankine. These are the
different units that are generally be used to express the temperature like this.
(Refer Slide Time: 01:04:55)

183
There is a certain conversion factor to convert one system to another system for this
temperature. So, please remember this conversion equation of this temperature from
Fahrenheit from this Celsius, even temperature in Kelvin from Celsius, even temperature
from Fahrenheit to Rankin, even temperature from Kelvin to Rankin like this. So, these
equations will give you how to convert this temperature unit from one system to another
system.

Basically, in the SI system, always you have to use that Kelvin unit and if any problem is
given in terms of Celsius, then you have to convert it to Kelvin just by adding to 273.15. So,
we have discussed this process variable of pressure and temperature in this lecture and how to
estimate the pressure or calculate that pressure from the basic fluid static equation and how to
derive it we have discussed.
(Refer Slide Time: 01:06:07)

I think it would be helpful for your further understanding of the calculation of the process and
you have to remember certain things of that hydrostatic equation and also how to use that
hydrostatic equation to calculate the pressure by the manometer. So, next lecture, we will
discuss other things of that basic calculation of this chemical engineering, like what are the
rate of different processes, how to calculate the rate of different processes, which are
involved in the chemical engineering system. Thank you.

184
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 2: Process Variables and Rate

Lecture – 2.3
Rate of Process

Welcome to the massive open online course on Basic Principles and Calculations in
Chemical Engineering. So, we were discussing about the process variables and rate under
module 2. Now under this module 2, in this lecture, we will try to discuss about the rate of
processes.
(Refer Slide Time: 00:51)

So, this lecture will include the flow rate, rate of momentum transfer, rate of heat transfer,
rate of mass transfer, and also a rate of reaction.
(Refer Slide Time: 01:04)

185
Now, the previous lecture we have described the different variables out of which temperature
and pressure was discussed and also we have derived the fluid statics equation based on
which how the pressure drop between 2 points can be calculated by manometer and also we
have discussed that if there are any flow through the pipe, how to measure that flow rates. I
think we have described that different flow measuring instruments like that rotameter and
also other flow meters are there that we have described and by which you can calculate how
to measure that flow rates.

In this lecture, we will try to describe that how to estimate that flow rate and also how to
calculate the flow rate and also whenever that fluid will be flowing through the process unit,
what should be the momentum transfer and also if there are different components present in
the fluid system and if you know that flow is in a certain manner like convictive or other flow
processes and they are how heat is being actually transferred from one phase to another phase
and also from one location to another location within the same system and within the same
liquid or within the same you know that materials.

Also, we will discuss that what is the mass transfer, how that one component in a particular
phase can be transferred to another place that will be regarded as the mass transfer and how
that rate can be calculated. Also, in most of the cases that in chemical engineer processes, of
course, the reaction will be involved. So, in that case, what should be the rate of that reaction
between two components and based on that product components, how the rate of the reaction
can be calculated to be described here.
(Refer Slide Time: 03:55)

186
Now, coming to that point of that flow rates, first that mass and volumetric flow rates which
is to be important aspects are you are going to analyze any process of that chemical
engineering or biochemical engineering in a particular process unit and there you will see
some streams will be coming to the process unit at a particular flow rate and also the systems
will give you that output and that output will be coming out as a particular stream with
certain flow rate.

So, that also to be measured that what should be that flow rate in and also flow rate in outlet
position, and of course, based on this flow rate that process performance will be analyzed and
also you can say that based on this flow rate, there are several aspects of that design of that
processing unit depends on and also these flow rates will give you that particular way of that
different mechanism of transfer like a mass transfer and heat transport there.

Also, this mass flow rate will also govern that how momentum of the phases will be changed
inside the process unit and that momentum change will give you that how much energy is
required, to process that equipment and also to process that particular system and also to
analyze that how this that process can be designed based on this momentum or that energy
transfer. So, what is that mass or volumetric product?

So, if flow rate that is expressed for the fluid flowing through the process unit at which a
material is transported through the process line and in that case the rate of that fluid will be
transferred that will be called as flow rate and the mass flow rate is generally defined as how

187
much amount of that material or that object will be transferred per unit time or flow of that
object or fluid you can say that or gases in that case how it will be flowing at a particular rate.

So, it will be called as flow rate of in terms of mass, then it will be called as mass flow rate
and if it supposes the expression based on that volumetric flow, then it will be regarded as a
volumetric flow rate. The mass flow rate is denoted by m dot generally. So here dot
represents the rate and then it will be defined as mass per unit time and also volumetric flow
rate will be defined as volume per unit time, that is volume of materials flowing per unit time.
So, it will be called us volumetric flow rate.

Now, you can relate this mass flow rate with this volumetric flow rate just by multiplying the
volumetric flow rate by its density of the fluid; then you can get that mass flow rate of that
fluid and volumetric flow rate can also be regarded or can also be defined based on the
velocity of the fluid through the pipe, where mass flow rate also can be converted into
volumetric flow rate and then in terms of velocity you can express.

The volumetric flow rate, it will be actually if you know the velocity of the fluid through the
particular process unit and if you know the cross-sectional area that particular process unit
like when a fluid is flowing through the pipe or in the cross-sectional area of the pipe and if
you know the velocity of the fluid through the pipe, then you can get the volumetric flow rate
in terms of velocity and the cross-sectional area. So, volumetric flow rate will be is equal to
velocity into the cross-sectional area.

Also, you can get the velocity in terms of volumetric area, volumetric flow rate like what is
that, velocity can be then calculated based on that volumetric flow rate and also
crosssectional area. So, velocity will be is equal to volumetric flow rate divided by
crosssectional area. So, in this way you can calculate what should be the volumetric flow rate,
and in this case, you have to remember that whenever you will see that dot above that
particular variables like mass flow, even volumetric flow.

So, in that case dot will be representing here above m and V as shown here in the slides that
will be as a flow rate. Now here see in this figure that mass flow rate of the fluid that is
flowing through the pipe as m dot and volumetric flow rate as V dot and its unit will be kg of
fluid per second that is kg per second and volumetric flow rate will be meter cube per second

188
that is meter per second there. So, in this way, you can calculate the volumetric flow rate of
the fluid whenever it will be coming through the processing unit.

Then another important aspect of that, it is called rate of momentum, that also actually
depending on that mass flow rate of that fluid there and also velocity, so we will be
discussing.
(Refer Slide Time: 10:00)

Before going to that, let us have an example of this mass or volumetric flow rate on how to
calculate. Suppose a gas considering ideal flows from a tank at a rate of 2.72 kg per minute at
a temperature of minus 175 degrees Celsius and it has to be heated at 65.5 degrees Celsius in
a heater and at a pressure of 4.14 into 10 to the power six 6 Newton per meter square around
41.36 bar. So, in this case you have to calculate what should be the volumetric flow rate and
the specific volume of the gas that will leave the heater.

Also, it is given that in this case that gas if it consists of nitrogen and hydrogen gas, then what
would be the molecular weight of nitrogen and also what will be the universal gas constant is
given as for that unit of this consistency here to be considered and in this case as per ideal gas
law, then the volumetric flow rate of the gas can be expressed based on that ideal gas law as

,
and after substitution of this value here, you can get this value of 66.05 liter per minute.

189
So, the volumetric flow rate of the gas leaving the heater, it will be here 66.05 liter per
minute, and in this case, what will be the specific volume. Then the specific volume you can
calculate volumetric flow rate per mass flow rate of that gas. So, it will give you directly after
substitution of this value or from this equation of ideal gas law, you can get it from that like
V dot divided by n dot that will be your specific volume. So, it will be simply RT by P.

So, if you substitute that RT by P value, then you can get it in terms of meter cube per mole
and then if you convert it to mass, you have to then divide it by or you have to multiply it that
moles by its molecular weight, then you can get it in terms of meter cube per kg. So, in this
way you can get this volumetric flow rate. So, this is regarding that gaseous system where
you have to calculate the volumetric flow rate from its ideal gas law.

Whereas if you have that fluid that is not compressible, that is incompressible like water or
other liquid, there we will see that volumetric flow rate to calculate you need to know that
mass flow rate and from that mass flow rate you can get it to just by dividing mass flow rate
that is dividing by its density, then you can get it volumetric flow rate there.
(Refer Slide Time: 13:39)

Another example like in this case, suppose a mixture of component A of molecular weight is
given as 32.04 and component B of molecular weight of this 46.07 is flowing through a
circular pipe at a flow rate of 5 meters per second. Now, the mixer contains 40 weight percent
of A and 60 weight % of B. In this case, the specific gravity of the mixture is given to you as
0.80. Now, if the inside diameter of the pipe is 0.05 meter, then what should be the flow rate
of the mixture in kg per second or kilomole per second.

190
So, in this case here interesting is that the mass flow rate is obtained by multiplying its
density by the volumetric flow rate. So, here it is given to you that volumetric flow rate
whereas from this volumetric flow rate you can get this mass flow rate just by multiplying it
by density. So, you can calculate it as like this here from this
m   vA

 is given here to you that is 0.80 into 1000, this is your rho, v is given here meter per
second, it is given that mixture flow rate is 5 meter per second and crosssectional area is
given to you.

From this, you can get to this mass flow rate as 7.854 kg per second. So, molar flow rate of
the component A, then can be calculated as what should be the first mass flow rate of
component A. Since your component is of 40% for this component A, so you can just
multiply this mass flow rate into its composition, that means here mass fraction or you can if
it is mole fraction, you have to multiply it by this fraction, then it will come as here 0.40 into
7.854. So, this will be your mass, you can say mass fraction into total mass flow rate, then
you will get here total amount of component A per unit time.

So, it will be coming as kg per second of this component A and if you divide it by its
molecular weight, then you can get simply what should be the mole per second to be here
expressed as kilomole per second. Similarly, molar flow rate of component B, you can get it
by the same way after calculation you can get that as 0.102 mole per second. Now, total
molar flow rate then you can get here 0.098 + 0.10 as per these two components here. So, it
will come as 0.2 kilomole per second.
(Refer Slide Time: 16:57)

191
Next, let us consider that momentum rate. The momentum of an object actually is the impetus
or you can say the energy that is gained by a moving object. It is defined by multiplying the
mass of the objects by its velocity. So, momentum will be defined as mass into velocity and
momentum flow would be basically that mass flow into momentum by mass. Now, external
force generally causes this momentum of a system to change.

The rate of change of that momentum of an object is directly proportional to the resultant
forces that is applied to get its momentum and is in the direction of the resultant force at
which it will be applied. So, we can express this force based on which this change of
momentum will be there. So, this F will be denoted by here this equation or defined by this
equation based on that momentum.

So, F will be is equal to delta mv by delta t, what does it mean? How much momentum will
be changed based on this applying force there if per unit time. So, that will be called as
momentum change per unit time, which is actually equal to the external force applied to the
system
(Refer Slide Time: 18:37)

192
Also another term you will see that there will be during the energy balance equation for a
particular process, it is generally expressed by that momentum flux. So, in this case it is
defined as the rate of change of momentum flowing through per unit area. So, it will be a
denoted by J momentum that will be equals to momentum rate per crosssectional area. So, it
can be expressed by this mathematical expression as given here in the slide.
Momentum rate 1 d (mv)
J momentum  
Crosssectional area A dt
Like if a fluid with density  that is flowing at a velocity v, then you can express this
momentum flux by this rho into v square and the unit will be as the unit of force per unit area
or you can express this as part the unit of pressure or stress. This is basically that force, so
force per unit area, so force per unit area is the pressure or you can say stress. So, what will
be the unit for pressure or stress, that unit will be of the momentum flux.
(Refer Slide Time: 19:53)

193
Now, the pressure is the associated momentum flux. For isotropic motion, the momentum
flux which is locally is independent of the orientation of the surface and also it will always be
perpendicular to the surface.
(Refer Slide Time: 20:15)

Next we will discuss how rate of heat transfer can be expressed. There are different
mechanisms of transferring heat. Of course, you will learn in depth in other chemical
engineering subject like heat transfer operation there. So, basically that heat is the flow of
thermal energy that is driven by thermal non-equilibrium and the rate of heat flow is the
amount of heat that is transferred per unit of time in some material usually measured in watts
or you can say joules per second.

194
There are different mechanism of expressing this heat transfer rate like conduction,
convection and radiation. So, whatever mechanism will be there, the heat transport rate will
be expressed as per temperature gradient or you can say that the temperature difference of
these two points of the object and based on which that a heat will be transferred. So, rate of
heat transfer basically will be proportional to the temperature difference. Also, it will depend
on the surface area through which the heat will be perpendicularly flows there.

So, if I consider that there is a mechanism like conduction, so the heat transfer rate by
conduction that will be represented by that is variation of the temperature per unit length and
also it will be depending on the surface area of the object through which heat will be
transferred. So, it is generally expressed as rate of heat flow by conduction is equal to minus
of heat transfer coefficient into area of the body and variation of the temperature per length of
the material.
(Refer Slide Time: 22:41)

So, this mathematical expression given by Fourier. So, that is why it is called Fourier’s law.
So, mathematically the rate of heat flow by conduction can be expressed as

= -KAT/L
where Q dot is heat transfer per unit time, K the thermal conductivity, A is the area of the
emitting body from which this heat will be transferred, L the length of the material, and delta
T is the temperature difference there between the two points.
(Refer Slide Time: 23:27)

195
Let us do you an example based on this. Suppose, the wall of a house that is 10 meter wide
and 5 meter high that is made from 0.5 meter thick brick with thermal conductivity that is K
that will be is equal to 0.6 watt per meter K and the temperature on the inside of the wall is 25
degrees Celsius and that on the outside is 5 degree Celsius. Now in this case, find the heat
flux. Now, the difference of the temperature is delta T, so this T of course always will be in
terms of unit Kelvin.

So, you have to convert it to Kelvin from the Celsius here and since it is the difference you
can say that 25-5, so, it will be 20 degrees Celsius, then it is actually 293 K. Now, the heat
flow is given by the formula here as per Fourier’s law, that is

= -KAT/L
Here K is the thermal conductivity of the material, A is the crosssectional area, L is the length
of the object or you know that here in this case wall that is your width of the wall here in this
case to be considered and delta T is the temperature difference between the sides of the wall.

Now, substituting these values of this heat conductivity coefficient, the area, the length and
the difference of the temperature between the inside and outside, you can get this heat flux,
that is heat transfer rate per unit area that will be is equal to here minus 17580 watt.
(Refer Slide Time: 25:38)

196
Now, let us do another example, like a 25 millimeter diameter PVC pipe of unit length is
used to carry heated water. The external surface of the pipe has a thermal conductivity K that
is 0.19 watt per meter K. It is thick of 2 millimeter. In this case, you have to find out the heat
flux on the pipe when the external surface temperature will be at 75 degrees Celsius and the
surrounding are at 25 degrees Celsius. So in this case, first of all you have to calculate what
will be the temperature difference, that will be you know delta T is equal to Ti minus T0.

Ti is basically what is the temperature at external surface and T0 is the temperature at the
surrounding that will be difference as 50 degrees Celsius that will be is equal to 323 K. Now,
the heat flow rate is given by the formula as per you know Fourier’s law. If you substitute
those values, then you can get Q dot. A will be is equal to what, after substitution and you
calculation you will get that it will be minus 37 watt. So, it is your heat transfer flux or heat
flux you can say based on this temperature difference.
(Refer Slide Time: 27:16)

197
Now, how to calculate that heat transfer rate or unit area based on the convection rate. Before
going to that, what is that actually convection? Basically, convection is the process of heat
transfer by the bulk movement of molecules within fluids such as gases and liquids and the
bulk heat transfer that happens due to the motion of the fluid. The convection is the process
of heat transfer in fluids by the actual motion of matter and it happens in liquids and gases. It
may be natural or forced.

It involves a bulk transfer of portion of the fluid. Here in this slide, 2 pictures are shown here
one is heat is transferring from this plate by forced convection where air will be flowing over
the hot surface or you can say that if there is a hot egg and how that heat will be convecting
by the cold air convection over the surface of this hot egg, then how heat will be transferring
from this hot body of egg to the surrounding of that cold air. So, it will be regarded as forced
convection whereas natural convection there will be no flow by any external force.

In that case, you will see necessarily that it will be transferring to the atmosphere that will be
regarded as natural convection.
(Refer Slide Time: 29:06)

198
Now, the same way you can say that that rate of convective heat transfer depends on the
temperature difference between two locations. Here in this case, one location will be in the
hot surface and other will be in the fluid by which that heat will be transferred by convective
mode and this law is called the Newton's law of heating or cooling and according to that, the
rate of convective heat transfer can be expressed as
Qconv  hA(Ts  T f )

Here Q dot convect is basically heat transfer rate and A is basically heat transfer area through
which the heat will be transferred and h here in this case another coefficient, this is called
coefficient of heat transfer and this coefficient is called convective heat transfer coefficient
and the temporary here Ts it is basically the surface temperature from which heat will be
transferred or on which the heat will be gained by that object from the surrounding and Tf is
the bulk fluid temperature away from the surface by which the convection of the heat will be
there.

So, according to this equation, you can easily calculate what should be the convective heat
transfer rate. So, in this case this heat transfer coefficient depends on different parameters like
that flow rate of the fluid, even sometimes the conduit through which that fluid will be
flowing that diameter of that conduit, even length of the conduit as well as you can say that
material properties of the conduit at which that heat will be flowing and also it depends on
viscosity of the fluid. So, there are several parameters that effect on this heat transfer
coefficient.

199
Now, you will get that heat transfer coefficient in more details in the subject heat transfer
operations and there you will get different correlations to calculate this heat transfer
coefficient. Once you get this heat transfer coefficient and also surface area from which that
heat is transferred or through which it is transferred and also if you know the temperature
difference, you would be able to calculate what should the convective heat transfer rate as per
this Newton's law of cooling or heating.
(Refer Slide Time: 32:09)

Now, let us do an example for this. Suppose a hot gas is flowing through a metal pipe, that
case the metal pipe is not insulated there and its diameter is 8 centimeter and it is kept at 175
degrees Celsius, at which that this hot gas at that particular temperature is flowing through
the pipe. Now, outside the pipe, a cold air is flowing at a temperature of 25 degrees Celsius
due to which the heat from the metal pipe surface is lost by convection. Now, the convective
heat transfer coefficient at the outlet surface or outside surface of the pipe is 2.5 watt per
meter square K, it is given to you.

Now, at this condition you have to calculate what should be the rate of heat transport per unit
length by convective heat transfer and in this case you can neglect the thermal resistance of
the pipe walls. So, as per Newton's law of heating or cooling, the rate of heat transfer by this
convective mode can be defined as this
Qconv  hA(Ts  T f )

Here h is given to you it is a 2.6 here and A means surface area through which actually heat is
transpiring, in this case the surface area of the pipe will be pi d into L.

200
So, it will be a 3.14 into you know d is 0.08 meters and length is 1 meter it is given to you
and Ts is here that inside hot gas temperature is 175 degrees Celsius, we are assuming that
the surface of the pipe will have that same temperature of 175 degrees Celsius and in this
case, then in Kelvin unit it will be 175 + 273. Similarly, what would be the outside
temperature of this pipe, it will be 25 degrees Celsius as per your problem. So, again you
have to convert it to Kelvin unit.

So, finally if you substitute this value and after calculation, you will see that value will be
coming as ninety eight watt. So, this is your convective heat transfer rate based on this
temperature difference of 175 to the outside temperature of 25 degree Celsius and also the
surface area as per this diameter of this pipe, how it is to be calculated.
(Refer Slide Time: 35:10)

Also, we can calculate the rate of heat transfer by radiation. There also it is important
sometimes that if you keep the metals in open atmosphere you will see that heat will be
transferred not only by conduction, not only by convection, there will be a transfer of heat
based on radiation also. Now, in this case the heat transfer through radiation takes place in the
form of actually electromagnetic waves, mainly in the infrared region and radiation emitted
by a body is actually the result of thermal agitation of its composing molecules there.

Radiation heat transfer can be described by reference to the black body. The black body is
basically defined as a body that absorbs all radiation that falls on the surface. If the body is
absorbing all the radiation, then the body will be regarded as black body. So, whenever you

201
are going to calculate the rate of the radiation that you have to refer this black body because
the radiation is basically that reference rate from this black body rate.
(Refer Slide Time: 36:30)

So, in this case the radiation energy per unit time from an ideal black body is proportional to
the fourth power of the absolute temperature and can be expressed as per Stefan-Boltzmann
law as like
q = σ T4 A
Here also, this heat transfer rate depends on the surface area through which this heat will be
transferred and also this radiation depends on the temperature of the surface there. In this
case, you will see that the proportionality constant is coming as sigma here.

This sigma is called the Stefan-Boltzmann constant and its value is 5.6703 into 10 to the
minus 8 watt per meter squared Kelvin to the power 4, T is the absolute temperature, of
course should be absolute temperature you cannot use here only that in degrees Celsius or
Fahrenheit unit, you have to consider it as absolute temperature here in Kelvin, and A is the
area of the emitting body through which that heat is transferred.
(Refer Slide Time: 37:46)

202
Now, let us see an example here, heat radiation from the surface of the Sun. If the surface
temperature of the sun is 5778 Kelvin and if we know that the sun can be regarded as a black
body and then the radiation energy per unit area can be expressed by like here
q/A = σ T4
Now, according to this equation, then what should be the amount of heat that is being
radiated from the sun? So, since we know that surface temperature of the Sun is 5778 K, so
you can directly substitute this temperature here for this temperature T.

So, in this case, you can then write that q by A will be is equal to sigma into T to the power 4,
why q by A we are not actually calculating the surface area, but we can say that here what
will be the radiating heat flux from the sun. So, here the rate of heat transfer by radiation by
unit cross section sorry unit surface area of the sun, it will be is equal to then 5.6703 into 10
to the power minus 8, this is basically Stefan-Boltzmann constant into what is the surface
temperature, it is 5778 Kelvin, then it will be to the power 4 here as per this equation.

Finally, after calculation it is coming as 6.32 into 10 to the power 7 watt per meter square. So,
this is the example based on which you can say that how much heat is being radiated per unit
surface area of the sun.
(Refer Slide Time: 39:57)

203
You know that for objects other than these ideal black bodies, it would be called as gray
bodies. Now, the Stefan-Boltzmann law can be expressed here as per that, that
q = ε σ T4 A
Here, one important parameter is coming as epsilon, this epsilon is basically one coefficient,
it is called as adjustment coefficient or it is called emissivity coefficient of the object where
the object from which that heat is transferred is not the ideal black bodies.

So, other than this ideal of black bodies, we can say that the total heat transfer rate by the
radiation it will be some fraction of that heat radiation rate of that black body. So, that is why
this heat transfer rate per unit crosssectional area to be regarded as it transfers flux by
radiation can be regarded as epsilon into sigma into T to the power 4 based on this Stefan-
Boltzmann law. For the gray body, the incident radiation, it is also called as irradiation, is
partly reflected and in that case absorbed or transmitted.

Now, the emissivity coefficient will be is in the range of you will see that the 0 to 1. There
will be certain fraction of that heat will be radiated compared to that ideal black bodies, that
is why this emissivity coefficient depending on the type of material and the temperature of
the surface.
(Refer Slide Time: 41:42)

204
How to actually calculate the net radiation loss rate. If you know an object which is hot will
be radiating energy to its cooler surroundings, then the net radiation heat loss rate can be
expressed as
q = ε σ (Th4 - Tc4)Ah
In this case, you have to know the temperature of these two bodies, one is hot body, another
is that cold body.
So, in that case based on that temperature difference, what should be the radiation or heat
transfer rate difference there, so you can calculate based on this temperature. In this case, Th
is hot body absolute temperature and Tc is called cold surroundings absolute temperature and
Ah will be is equal to surface area of the hot object.
(Refer Slide Time: 42:38)

205
Let us do an example based on this. Suppose a hot iron ball of diameter 0.01 meter is kept in
an open atmosphere of temperature 25 degrees Celsius. Then what is the heat loss rate by
radiation if the surface temperature of the iron ball is 75 degrees Celsius. The emissivity of
the iron material is given here 0.81, So according to that, you have to first find out what
should be the hot body absolute temperature there. So, it will be 348 Kelvin whereas cold
surroundings absolute temperature it will be 298 Kelvin and area of the hot object it is simply
pi d square.

So, we can say that it will be pi into 0.01 whole square. Since, it is you know that spherical
object, so you have to have this surface area as pi d square here. So, finally, we can calculate
what should be heat transfer rate based on this temperature difference, it will be 0.98 watt.
(Refer Slide Time: 43:44)

Now, let us consider that diffusion. Diffusion is one of the important chemical engineering
processes based on which you can say that that there will be a transfer of molecules from one
phase to another phase through the interface. So, in that case, this diffusion basically depends
on the concentration differences of different location. So, in that case, the diffusion can be
regarded as the net movement of anything from a region of higher concentration to a region
of lower concentration and this law is called as Fick’s law of diffusion.

As per Fick’s law of diffusion, you can say that the diffusion can be mathematically
expressed as

206
where J is called flux that is how much molecules will be transferred per unit time per unit
crosssectional area. Here D is called diffusion coefficient and C is called concentration and x
is called diffusion path. Here negative sign is there because here the concentration is actually
considered here they are higher concentration and lower concentration, but the difference of
what the diffusion process is considering actually final minus initial.

So final is basically the low concentration and initial concentration is higher concentration.
So, final minus initial is to be negative, that is why here you have to consider that the
diffusion will be from higher concentration to the lower concentration in the negative
direction. So, here in this case, this flux will be defined by this Fick’s law. So, rate of
diffusion independent of the time of steady state diffusion, flux proportional to the
concentration gradient.

Then we can say that if there are two concentrations here C1 and C2, then C2 minus C1 will
be regarded as negative one and then x2 minus regarding you can say that x2 minus x1
similarly here it will be coming. So based on which what would be the dC by dx you can
calculate like this.
(Refer Slide Time: 46:03)

Now, let us have an example for this. A 50 millimeter deep liquid container that contains
liquid of concentration here 0.053 moles per meter cube to a level of 20 millimeter and is
exposed to the dry air at 1 atmosphere and 40 degrees Celsius. If the diffusion coefficient of
liquid is 0.25 centimeter square per second, then what is the rate of evaporation of the water

207
and neglecting the resistance to evaporation through interface. Very interesting that here that
liquid the concentration is 0.053.

It is exposed to the dry air and because of this diffusion, you will see that the liquid will be
evaporating to the atmosphere from this liquid and you have to find out then what should be
the rate of evaporation of this water. This evaporation is basically a diffusion process. So,
here in this case x2 minus x1 that will be is equal to your 50 minus 20 and also you can say
that temperature is here 313 and diffusion coefficient is given to you and the concentration of
the liquid in the air liquid interface can be neglected because initially there will be no
concentration here.

So, only the evaporation starts from this liquid concentration to the 0 concentration of the air.
So, the rate of diffusion per unit area can be calculated based on that diffusion equation of
Fick’s law. So, that will be is equal to 1.33 into 10 to the power minus 6 moles per meter
square per second.
(Refer Slide Time: 47:52)

Another important aspect of chemical engineering process is that mass transfer. You see the
mass will be transferred from one phase to another phase like I have given earlier the
example like suppose there is a transfer of carbon dioxide gas molecules in air mixture that
will be transported from this gaseous mixture to the liquid phase. Suppose sodium hydroxide
solution. So, in this case there is an interface of this gas and liquid, gas air mixture of carbon
dioxide and air and then you know that in the liquid there is sodium hydroxide.

208
Now carbon dioxide gas to be absorbed to the liquid sodium hydroxide solution. Now, in this
case, there will be a mass of carbon dioxide transferred from this gaseous space to the liquid
phase of sodium hydroxide solution. So, in this case what will be the mass transfer rate okay?
So, that you have to calculate. Now to obtain the total mass transfer of a species, example
from a liquid into gas or gas into a liquid, you can say that one would need to calculate not
only the contribution of diffusion, but also the convictive contribution there.

The sum of these two terms then leads to the total mass transfer whether expressed in mass or
molar units. For an arbitrary situation in which mass transfer may occur by diffusion as well
as by convection, now the necessary calculation of the composition and velocity at each point
inside the mixture that is often simply too hard. So, that is why that you have to consider
some overall mass transfer phenomena and from that overall mass transfer you have to define
some mass transfer coefficient and based on which you can calculate the mass transfer rate.

So, based on that concentration difference of this gaseous phase and the liquid phase, you
will see there will be concentration difference. Now, based on this concentration difference,
this mass will be transferred from that one phase to another phase. Now, these mass transfer
concentration difference it is called the driving force for the mass transfer.
(Refer Slide Time: 50:12)

Now, if your mass transfer rate is proportional to that concentration differences, then
proportionality constant will be regarded as mass transfer coefficient. Now, in that case so,
the rate of mass transfer across the boundary of some of the system from a liquid into gas or

209
from the liquid into another liquid or from the gas into the liquid, you can represent this
mathematically as by this
NA = kC (cAS - cA)
where this NA is the mole of A transfer per unit time per unit cross section. kC is the mass
transfer coefficient per unit length sorry length per unit time and also CA infinity is the molar
concentration of A that is moles per volume in the bulk of the system that is far away from
the boundary surface as shown in the figure in the slides, and CAS is the molar constitution of
A that is right at the boundary but still on the same side as the bulk of the system, here as
shown in the figure. So, in this way, you can define how that mass is transferred and what
will be the rate of that mass transfer, how it can be expressed. So, by this equation given in
the slide, you can calculate what would be the mass transfer rate.
(Refer Slide Time: 51:38)

Now at a point suppose A where the concentration maybe mole in terms of mole fraction for
the liquid as well as gas, generally for liquid it is expressed as XA and for gas it is YA, so XAL
and XAG. Suppose there is a mole faction in the two phases in the liquid and gas respectively,
then we can write the mass transfer equations for each of the phases in terms of mole fraction
as concentration like this

and

Here in this case, interesting that for a particular phase, we are considering the concentration
difference of the bulk phase from its interface concentration. So, NA here molar flux of the

210
component A that will be mole per unit area per unit time and also ky will be called as mass
transfer coefficient. If you are considering the gas phase, it will be ky, if you are considering
the liquid phase, it will be kx. So, it will be called as individual mass transfer coefficient and
YAG minus YAi that is the concentration difference, here mole fraction difference between
bulk concentration and interface concentration.

So, there is a difference and this is called driving force in the gas phase, that is the mole
fraction whereas in the liquid phase it will be XA minus XAL. So, it will be concentration
driving force in the liquid phase in terms of mole fraction. Now, in this case, this ky and kx
these are mass transfer coefficient of individual phases. So, it is called that individual mass
transfer coefficient or film mass transfer coefficient since only we are considering that
concentration difference from the reference of the interface.

Now, these k values above are also known as film mass transfer coefficient because of that,
and also they are usually determined experimentally or by some correlations.
(Refer Slide Time: 53:45)

Now, mass transfer rate based on overall mass transfer coefficient. In this case, the
concentration difference is to be considered, you know that from the gaseous phase to the
liquid phase. So, in that case the overall mass transfer coefficient will be there and the rate of
mass transfer to be defined as Ky into YAG z minus YA star, here it will be capital K, Y is
for gaseous phase and YAG is the mole fraction in the gaseous phase in the bulk region
whereas YA star it will be represented as what is that in the gaseous phase in that interface or
at the you can say that equilibrium condition.

211
Similarly, for liquid you can express by this equation as shown in here in the slides. Here XA
star and YA star are the concentration in the liquid phase that is in equilibrium with the
gaseous phase and YA star is the concentration in the vapor phase or gaseous phase that is
equilibrium with the liquid phase.
(Refer Slide Time: 54:49)

Then another important that most of the chemical engineering processes actually depends on
is that reaction, so how to express that the reaction rate. Suppose there is a reaction that is or
reaction is represented by this A is giving the product B and the change in the concentration
of the reactant or a product with time here. So, in this case, the average rate of that reaction
will be considered as change in the number of moles B per unit time of change. So, we can
write this equation as

So, it will be regarded as delta B by delta t. In this way also by this symbol you can represent
this reaction rate. Since reactants go away with time, so, we can write here rate of reaction
will be is equal to minus delta A by del t. Here, you can also represent that reaction in terms
of reactant concentration. Not only the product concentration you are expressing this reaction
rate, you can express that reaction rate in terms of reactant concentration also. In this case,
the change will be negative because you know that the A consumed whereas B is generated,
that is why this rate of reaction will be positive there.
(Refer Slide Time: 56:21)

212
Let us consider a decomposition reaction of nitrogen pentoxide to produce nitrogen dioxide
and oxygen based on this reaction given in the slide. So, in this case as for time 0 to 700
seconds. This concentration of the components given here for nitrogen pentoxide that is
consumed at the rate given here, whereas nitrogen dioxide it is produced at a rate here and
also you know that oxygen that is produced based on this reaction as here at this rate, this rate
is mole per liter it is expressed.
(Refer Slide Time: 57:09)

If we express this you know that happening of this reaction reactant and also products flow
rate based on this consumption and also you can say that you know generation. So, we can
express this by this graph here. In this, x axis is temperature and y axis is what would be the
mole fraction, mole that is consumed per unit volume of litre. Then you will see that how this

213
oxygen is actually increasing with respect to temperature, sorry it is not temperature, it is
time, sorry this is time, this is in second.

This is here moles of A or B you can say per unit litre and in this case then how oxygen is
actually increasing with respect to time and also nitrogen dioxide is increasing with respect to
time, whereas this nitrogen pentoxide is decreasing with respect to time because nitrogen
dioxide is consuming to give you that generation of nitrogen dioxide and oxygen.
(Refer Slide Time: 58:30)

So, from the graph, we can say that between the time 300 to 400 second, the rate of oxygen
can be expressed by this equation and rate of nitrogen dioxide can be expressed by this
equation, the rate of nitrogen pentoxide can be expressed by this equation, and to compare the
rates, one must account for the stoichiometry. Here in this case rate of oxygen can be
expressed by this equation, rate of nitrogen dioxide can be expressed by this equation given
in the slide, and rate of nitrogen pentoxide that is consumed can be expressed by this
equation.

Now, in general for the reaction, you can express this aA + bB that will give you the cC and
dD, the general reaction equation and based on these, you can also express the rate or you can
compare the rate based on this stoichiometry. Here in this case, this rate will be here minus 1
by a delta A by delta t that will be is equal to similarly for other components here like this
given in the slides. So, based on this general equation, you can express what should be the
reaction rate based on this stoichiometry coefficient.
(Refer Slide Time: 59:53)

214
Now, what is the rate law and also reaction order? The reaction rate law expression actually
relates the rate of reaction to the concentration of the reactants. Now, each concentration is
expressed with an order like exponent and for that we can say for the general reaction of this
shown in here in the slides, then rate can be expressed by this here for this reaction of aA +
bB which will give you the cC plus dD. Based on this equation, you can express the rate of
the reaction as

Here, in third bracket, we are writing this A and B, it does mean that the concentration of this
component A and B respectively. So, the rate of reaction depends on this concentration of
these reactants A and B and what will be the rate of that reaction. It will be proportional to
the concentration of the A and B and it will follow some power law equation. Here in this
case, it is expressed as k into A to the power x into B to the power y.

Here x and y are the reactant orders that is determined generally from the experiment and k is
called reaction rate constant and overall order of reaction is the sum of the individual orders,
here like here in this case rate in 1 by mole per litre second that will be equal to k into A
suppose B to the power half into C to the power 2. Then we can say that overall order will be
equal to 1 + here half + 2, that will be 3.5, then it will be equal to 7 by 2 or seven-halves
order.

215
So, in this way, we can actually calculate what should be the overall order of a reaction. In
this case, suppose rate is here came to A to the power x into B to the power y, in this case
overall order will be x + y.
(Refer Slide Time: 01:02:08)

Now relation between the rate law, order, and the rate constant like this here. Zero order
reaction will be regarded as or as per rate law as rate will be equal to constant, here unit
should be like this. Here if rate is expressed as k into A, it will be called as first order with
respect to component A or reactant A and first order overall reaction and unit will be 1 by s.
Similarly, if rate is considered as k into A square, in this case it will be second order with
respect to A and second order overall.

Similarly, if rate is expressed as k into AB, here first order with respect to A, first order with
respect to B and will be second order overall. Similarly, rate if it is expressed as k into A into
B into C, then it will be first order with respect to A, first order with respect to B, and first
order with respect to C, and overall it will be third order reaction and then unit will be like
here as given in the slide.
(Refer Slide Time: 01:03:19)

216
So, we have described different laws of the chemical engineering processes, like that mass
flow rate, momentum, heat transfer rate, mass transfer rate, and also reaction rate. So, I think
you have understood the basics of this rate equation. These will be required for further
understanding of the chemical engineering processes or other subjects like you know heat
transfer operations in details, mass transfer operations in details.

Also, fluid flow phenomena where energy balance will be required to express that
phenomena, that momentum equation, then there it will be helpful to further understand. So,
we will describe more about this chemical engineering principles. In the next lecture, so we
will describe that principles of material balance and its calculation based on this rate law. So,
thank you for giving your attention here.

217
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 3: Fundamentals of Material Balance

Lecture – 3.1
Principles of Material Balance and Calculation

Welcome to the massive open online course on Basic Principles and Calculations in
Chemical Engineering. So, we were discussing the fundamentals of material balance in
module 3. In this lecture, we will try to discuss about what are the basic principles of material
balance and how to calculate the balance equation based on these principles.
(Refer Slide Time: 00:54)

So, we will discuss here some flow chart of this chemical engineering processes, general
material balance equation, balances on single and multiple units where chemical engineering
processes are being carried out with recycles and bypass without reaction, and also how to
solve the problems of this chemical engineering process based on the material balance
equations.
(Refer Slide Time: 01:20)

218
Now, see here in this slide, one process unit and systems is given as we have already
described in our previous lecture, that if you are having this process unit like this, one mixer,
reactors and condenser for a particular process like ammonia is to be produced from the
hydrogen and nitrogen gas and for that nitrogen and hydrogen gas will be mixed in a mixer
and after that at a certain pressure, this mixture of this nitrogen and hydrogen gas to be sent to
reactor where this nitrogen and hydrogen gas would be reacting to each other at a certain
temperature and pressure and forming ammonia gas.

Unreacted nitrogen and hydrogen gas, along with this ammonia, will be coming out from this
reactor. After that, this ammonia gas will be condensed at minus 35 degree Celsius to get this
liquid ammonia. Whereas, other composition of this mixture like nitrogen and hydrogen that
is unreacted from this reactor will be sent back to the mixer as a recycle and this will be
running continuously and accordingly, we can get liquid ammonia for a certain amount of
nitrogen and hydrogen gas supplying.

So, this is the process. You will see that to assess this process based on the material balance
equation; you have to first think about each unit of this whole process. Here, you are having
this unit mixer, reactor, and condenser. In each unit, you have to do a material balance like
this, what will the amount of materials is coming in and what is the material that is coming
out, that what amount of material is coming into another reactor that is coming out from the
previous unit, and then after that you have to assess that second unit like reactor.

219
Again based on that material balance equation, what is that input and output, and then output
from this unit will be going to another unit as an input and thereafter processing it will come
out as output and some portion of that, it will be sent back to that initial unit as a recycle.
Now, you have to do that material balance individual to that unit, what would be the input
and output or you can do that material balance just combining two units as a single unit there
and also you can assess based on that.

Now, this is required because you know sometimes you will not be having that unknown, that
means variables like input and output, or you can say that a stream’s composition only by
doing the material balance for the single unit. There you have to sometimes required to do the
material balance just by combining two units or maybe more than two units there. So, we
have already described these things in our previous lecture. So, as a recap, we can consider
here again.
(Refer Slide Time: 05:29)

Now, to do the material balance, you have to do the process flow sheet or process flow chart,
where you have to represent that whole process by a sequence of process units that will be
connected by processes streams and this process flow sheet based on that sequence of process
units connected by processes streams, shows the flow of materials and energy through the
process units, and this is actually the convenient way of organizing that process information
for the subsequent calculations.

To obtain the maximum benefit from this flow sheet in material balance calculations, you
must write the values and units of all known stream variables at the locations of the streams

220
on the sheet. Like here, you will see that one process unit here shown in this slide like mixer
or divider or reactor or condenser or evaporator or separator, like this different type of
process unit. So, you have to express this process unit like this block diagram here, and this is
called flow sheet here, and this block diagram will be connected to this flow streams of input
and output.

From this process in this process unit, what would be the amount of input and output that will
be retaining in that input and output streams there. So, that is why to write the values and
units of all known streams variables at the locations of these streams here, in input and output
streams here in the sheet shown here, and if you do not have that values input and output, you
can also write just by defining a particular symbol or defining terms there for that particular
variables and then keep it there by question marks there what should be the value there.

After that, we will be using what can be used for material balance and unknown values to be
then obtained by solving that material balance equation, and then what you have to do?
Assign algebraic symbols to unknown stream variables and write these variables names and
their associated units on the sheet as well as you have to write should be the unit for that
inputs and outputs there that you have to write on the flowsheet there. So, this is the basic
principle to express that process by a flowsheet.

So, what does it mean? You have to express that unit of that process by a block or it is like a
box like this, or you can simply express other notations also there or other pictures also there
and there you have to, then write down that streams what is coming and streams what is
coming out and then express all the known values and unknown values of about the streams
there. So, this is the basic way to express that.
(Refer Slide Time: 09:07)

221
What are the different process units in chemical engineering processes? Here subleased some
list are given there like a divider. This divider actually basically used to divide the flow
streams into two parts where one part will be sent to one unit, and another part will be sent to
another unit, or it can be sent to utilizing for other purposes like this. The mixer, two streams,
will be coming to that, even more, than two streams also will be coming, and it will be mixed
together, and that mixer stream will be sent to some other unit for the process.

Crusher, it is one unit where you will see that bigger size of particles will be crushed into
finer particles. Dryer, where you will see that the wet materials to be dried up to a certain
equilibrium of moisture. Then the filter is another one important; here what is done that some
fine particulate materials to be separated from the mainstream or main solution.
Dehumidifier, they are sometimes you have to need to increase the moisture there or reduce
the moisture there in the flow streams.

So, dehumidifier and humidifier are used for that controlling that moisture there. Clarifier,
here also to separate that fine particle by just floating in a particular process unit that is called
clarifier. Conveyer, it is basically used to transport the materials from one position to another
position. An absorber is used to absorb some unwanted materials in a certain liquid or solid
material. Partial condenser and flash separator are being used for condensing the vapor. Flash
separator is being used to separate that vapor from the liquid mixer there just by boiling that
liquid mixture.

222
Crystallizer is generally being used for making that liquid to solid material there. Then the
reactor is basically used for reaction purpose, and reactants will be taking part to give you
that another product. There may be different types of reactor will be there, CSTR, fluidized
bed, bubble column reactor, packed bed reactor, trickle bed reactor, microreactor reactor, all
those things you will also know in chemical engineering process like if you do the course like
fluidization engineering.

There you will see different types of reactors like fluidized bed reactor, bubble column
reactor there, and also other operations like absorption, even reaction purpose like CSTR,
packed bed column, trickle bed, even nowadays that as a process intensification
microreactors are coming. So, these are the processing unit where you can do that chemical
engineer process for a particular process yield.

Leaching and extraction units also are being used for extracting oil from the solid materials
that is called the leaching and then extraction is also another important like one material is to
be extracted from another material, maybe liquid-liquid extraction, maybe liquid-solid
extraction there. Distillation column where crude petroleum will be separated into valuable
products just by boiling that crude liquid just based on that boiling point differences.

A Multi-effect evaporator there you have to sometimes evaporate that liquid materials to its
vapor form to get vapor forms and maybe a multi-effect evaporator will be there. There may
be successively more than one evaporator will be there to get that desired fractions of
materials in the vaporized form there. So, these are the several process unit which are being
used in conventional chemical engineering processes. So, for those processes unit, you have
to do the material balance based on that material balance principles.
(Refer Slide Time: 14:15)

223
Now, if we look at the flow chart of mixing in a stirred tank reactor, what we can have here.
So, this is a typical flowchart as given here in the slide. You will see that this is basically a
CSTR and where we can see that mixing of these liquid streams are being done. In this case,
here you will see that methanol and water as feed one that is in this stirred tank and also
methanol and water other propositions from the other streams as from 2 here it is coming and
then after mixing, you will see from this stream 3, this mixer of this methanol and water will
be coming out from this stirred tank unit.

So, here this is one process unit, this is called stirred tank, and this stirred tank is being used
for mixing purposes. Your 2 streams are coming into this stirred tank, and after that, it will be
mixed and it will be giving a product that is mixed a product, with a certain proportion of that
composition. Now in the inlet, you will see the composition of this methanol and water will
be 40%, 60%, whereas other portions of this stream is coming into the stirred tank with the
composition of 70% and 30%.

So, after mixing, you will see that as an output, this mixer will be coming. What will be the
total amount of mixture as coming out from the stirred tank, and what will be the composition
that you do not know? So, if it is not known to you, just you have to write that it is unknown
to you, that is m3 dot here it is shown it is and also x methanol and x water, this is the mole
fraction of methanol and water in these streams, it is unknown to you, that you have to find
out and that can be obtained by doing material balance.

224
So, the flow sheet basically is that representation of this input and output there in this process
unit with the known values and unknown values by its, you know what is that, is symbols of
that feed and also that output amount there.
(Refer Slide Time: 16:48)

Similarly, we can represent this flowchart distillation in a distillation column like this here.
Here in the distillation column, the mixture of that compounds like A, B, C with the certain
feed flow rate will be coming to that distillation column here and from this distillation
column after processing that there will be two output, one will be as distillate, another will be
as bottom product. Now, from this distillate, what will be the amount that is not known to you
and what will be the composition in the distillate that is also known to you.

If it is not known, then you have to express that composition as the mole fraction of A, B, C
here, and in the bottom part if it is known to you that mole fraction of A, B, C that you have
to express even if you do not know that you have to express by this symbol that you have to
find out from the material balance equation. Based on that problem, you have to express all
those known and unknown variables in the inlet and outlet and then you have to assess this
based on these known and unknown values based on this flowchart.
(Refer Slide Time: 18:03)

225
Similarly, process flowchart for benzene production here. This is the multi-unit, more than
one unit may be involved in the particular process. Here, you will see that units are like this
here mixer, reactor, separator, and also divider is there, and then also mixer is there. Now, in
this case, you will see that more than one units and in the flowchart we can represent all those
units which are being used for this particular process like this and for each unit, you have to
express what would be the input and what would be the output there.

Now, you see that if we consider that mixer, here input is feed as F and here one example like
this toluene, 100% toluene it is there. So, mole fraction of the toluene is 1 here. So only pure
toluene is being used, other no components of this feed will be there, but whenever it will be
sent to mixer, of course this mixer will contain other streams like here gas recycle is being
coming to this mixer. Also other stream is coming from the separator as a recycle, as a liquid
for Tolune is recycled to this mixer.

Now, all these streams to be mixed in this mixer and then finally as a gross feed G to be
coming out from the mixer and then it will go to the reactor. Now, this reactor will have this
inlet as a gross feed which is coming out from the mixer, and then after reaction, there will be
some generation of the product and then product along with that unreacted reactant, it will be
coming out from the reactor and it will go to the separator. Now what is the output of this
reactor? It will be input or the separator.

After that, it will be separated and from the separator, you will see that outputs will be here in
this one stream, another stream here, another stream here, another stream here. So, there will

226
be four 4 outputs of this separator, one output will give you that separate that H2 two and
methane and one output will be hundred percent 100% benzene will be there and another
output will be byproduct like diphenyl and another output will be considered for the you
liquid recycle of the Tolune.

So, based on this, you can say that whatever output of this reactor that will be an input of this
separator and output will be more than one here like this you are shown in this slide. Now, up
to separator whenever gas was a mixture, hydrogen and methane will be there, that will be
coming out from that separator, and then it will be sent to the mixer there. Now, you will see
that from this hydrogen methane mixer, some amount of that unwanted materials that is to be
taken out from that mixer.

So, that will be considered as a purge here. So, to take out that purge, you have to use some
divider, so that the divider to be used here as a unit from where you can take out this purge
sooner P, whereas remaining portions to be sent back to that mixer as recycle. Now, before
sending it to the mixer, what you have to do that you have to add some hydrogen gas which is
to be considered as makeup, a 100% hydrogen to be there because some amount of hydrogen
may be lost.

Now, to make up those hydrogen gas in this reactor, you have to supply some fresh hydrogen
gas. Now that fresh hydrogen gas to be mixed to that recycle gas in that mixer here again. So,
there are several units for this benzene production from the Tolune that is represented in this
process flowchart and also what will be the composition, what will be the different input and
output compounds will be there in these different process units that are represented in this
process flowchart.
(Refer Slide Time: 22:28)

227
Now, to label this flowchart, what to do? You have to clearly read and understand the
problem and then write the values and units, same system of all known streams variables at
the locations of the streams on the chart. Like if it is given 500 mole per second or 0.21 mole
of oxygen per mole and also 0.79 mol nitrogen per mole of total feed. Then here, what is the
temperature, what is the pressure to be also given there. So, all these known values to be
written, even unknown values to be written also just by defining some symbols.

Then assign algebraic symbols to unknown stream variables that is here and use all the
known either in mass or more unit wherever necessary that you have to mention, either mole
or mass that you have to consider, but your consideration should be uniform throughout the
process.
(Refer Slide Time: 23:30)

228
Then, labeling a process flowsheet. Let us consider a problem here. An amount of 100 kg per
hour of a mixture of 50% benzene and 50% toluene is separated in a distillation column. The
distillate contains 90% benzene and the bottom stream composition is given as 95% of
toluene and here all the composition is given in weight percent, not in mole percent. So, for
all streams that composition to be considered as weight percent. If you are considering the
mole percent, then all the units, all the streams units should be in mole percent there.

Even you will see that whatever feed as input or whatever output amount to be considered
also that mass if your composition is mass percent or weight percent and it should be mole or
mole percent accordingly also if you are considering all this input and output in terms of
molar weight percent. So, here based on this problem, we can then level a process flowsheet
by these known values of this here as a feed it is told that an amount of 100 kg per hour of a
mixture of 50% benzene and 50% toluene is separated in a distillation column.

That means here this hundred kg per hour of feed mixture come into this distillation column
with the composition of this 50% benzene and 50% toluene weight percent, and after
distillation process, it will be coming out from this overhead as a vapor and then it will be
condensed and then it will be separated into 2 parts, one part will go into the distillation
column, another part will be taken out as distillate where 90% benzene and 10% toluene, it is
mentioned here.

As a bottom product you will see some portions of this bottom product will be re-boiled and
it will be sent to the distillation column as a vapor and remaining portions will be taken out as
bottom products where 95% will be toluene and 5% will be benzene as weight percent there.
Here, what will be the bottom portion, what would be the distillation amount that is as a
vapor amount or distillate amount that is not known to you that you have to give or you have
to define some symbols for this distillation like this D and as the bottom products maybe you
can represent as capital B.

So, out of this distillate, there will be certain fractions of this benzene and toluene and out of
this bottom, there will be certain fractions of this toluene and benzene. So, all this inlet and
outlet streams are now known, whether it is given or not given. If it is given, you have to
directly write this exact amount what is given, and if it is not given, then you have to also

229
define that unknown variables there and form the material balance that you can find out what
will be the unknown variables from this material balance equation.

Now, what will be the general material balance equation based on which you can solve these
to find out that unknown variables like distillate here, bottom products or for other units like
if is there any mixture, what will be the output of that mixed proportions of that compound
that you can find out based on this material balance equation.
(Refer Slide Time: 27:20)

What is that material balance equation? It is given you will see in a particular process unit,
suppose there will be some amount of input is coming to the process unit and some amount
will be coming out from that process unit. If there is steady-state process, that means the
input and output proportions are same, they are in the process that you can say that a steady-
state process, that means it does not change with respect to time. So, in that case, it will be
regarded as that steady state process and there you will see that there will be no accumulation
of the materials inside the processing unit.

So, there will be one important thing that there may be an accumulation, based on that what
will be the output and input rate. If the output is greater than input, then there may be an
accumulation of the materials there. If there is no change of this input and output flow rate,
then you can say there will be no accumulation. So, one important term is accumulation.
Another is input through the system boundary if we consider that processing unit and if we
represent it as like a boundary here around this process unit.

230
Now, within this process unit, what will be the amount of that material is coming into that
processing unit that will be regarded as input. Now, that input, there may be a certain flow
rate that is known to you or may not be known to you. So, anyway, it will be regarded as
input amount and then what will be the amount that will be coming out from that processing
unit from the boundary, it will be called as the output through system boundary, and it will be
regarded as simply output.

Then if suppose the processing unit is like reactor where reaction is being carried out, so
there may be due to that reaction some amount of materials will be produced, may be
generated, so there one term should be coming as generation, so generation within the
system, inside the system, inside the reactor here, as an example there will be some
generation of materials. So, that the generation within the system to be considered. Then also
during that reaction, there may be some reactants that should be taking part for that reaction.

That reactants may be consumed for that giving up product of like some compounds as a
generation product. So, in that case, that reactant will be consumed, that consumption of that
reactant also to be considered here. So, what do we get that for a particular process unit if we
make it or you know that identify with a certain boundary of that process unit and what
would be the input is coming that will be input, what would be the output from that process
boundary it will be coming as output. If there is not a steady state process, there will be some
accumulation.

If there is a reaction is going on, there will be some generation of material. And if suppose
there is a reaction, then, of course, there will be a consumption term will be there. So, all
these 1, 2, 3, 4, 5 terms will be there in the general material balance equation. What are
those? In short, we can write that accumulation, input, output, generation, and consumption.
Now, the principle as per this mass conservation equation, we can write that this
accumulation will be equals to input minus output + generation minus consumption.

So, there will be no materials generated or destroyed there in the universe. So, that is called
the conservation of mass. Now, based on that, you will see for a particular process unit that
this basic equation for the material balance equation can be expressed like this. Now, here in
this case, we are getting some positive terms, some negative terms. In this case, positive

231
contributions to the system, generally input and generation and the negative contributions to
the system is generally output and consumption.

So, based on these principles, you have to solve the material balance equation for a particular
process in a chemical engineering system.
(Refer Slide Time: 31:47)

Now, the simplified equation can be written as if there is no chemical reaction, we can simply
neglect that generation terms and consumption terms. So, the general equation can be written
as simply accumulation will be equal to input minus output. Now, for steady state operation,
there is no accumulation. In that case, then input minus output will be equal to 0, that means
input will be equal to output there. Now for a given system, now a material balance can be
written in terms of the following conserved quantities.

First of all, you have to do the total mass or mole balance and then individual mass or mole
balance of that individual compound there in the system. You can do that material balance
based on atoms of that compound also. So, that is called mass or mole of an atomic species,
and the equation or balance equation to be considered as an atomic balance equation. Now, so
based on this material balance equation, what you have to do? You have to do the total
material balance; first, total material balance means what?

In a particular boundary system, what will be the materials in and what will be the material
out, irrespective of inside what is happening there, we have not to consider all these no
happening inside the system, only just what is the input, what is the output there, that is called

232
total mass or mole balance, and then after that, you have to do the material balance for
individual compounds or atoms.

So, there itself you have to consider that what would be the mass of that compound in, and
then if is there any generation of that mass inside the unit or if there are any consumption of
that materials inside the unit is there or not that you have to consider. So, for that compound
balance, you have to consider all those things.
(Refer Slide Time: 34:11)

Now procedure for material balance equation is given here step by step. First of all, you have
to draw the flowchart and fill in all given variables in the flow streams and then choose an
amount or flowrate of one of the process streams as a basis for the calculations. Then process
time can also be considered as a basis there. Then convert known stream volumes or
volumetric flowrates to mass or molar quantities as per requirement. Label unknown stream
variables on the flow chart.

If you are given mixed mass or mole units of a stream, convert all quantities to one basis,
either mole or mass. It is very important here; you cannot use this mixed unit there. Write
material balance equation. The maximum number of independent equations that can be
derived by writing this material balance, and then solve the equations derived in step six 6 for
the unknown quantities.
(Refer Slide Time: 35:13)

233
Now, in this case you have to remember that for a given system, a material balance can be
written in terms of the following conserved quantities. Total overall mass or mole balance,
mass or moles of each chemical compound balance, then mass or mole of an atomic species
balance. So, for this, either one you can consider.
(Refer Slide Time: 35:36)

Now, source of independent equations relating unknown processes stream variables.

Sometimes you will see that whenever you are doing the material balance for a particular
force, you will see that certain number of equations will be having based on that material
balance equation, but there are you will see that more than unknown variables will be there in
the process, but you are getting less number of equations based on this material balance. So,
what you have to do to equalize this number of equations with the number of process
variables?

234
You have to consider some other relationships is there with the variables or not or some other
relationships is given based on the thermodynamic conditions are not that you have to
consider or is there any other physical law are actually involving without process variables
are not, Is there any physical constraints are there in the systems or not, all those things to be
considered. So, they are, suppose if number of variables are greater than the number of
equations, in that case, you will not get that unique solution or you cannot get the solutions
for all variables.

So, for that you have to consider some of the relationships of the variables, that relationships
maybe some equilibrium conditions, maybe some that pressure, composition relationships,
there may be sometimes some fractions of all compositions will come to that unity that
relation is to be considered. So, here some clues are given. Now, material balance, balance
equations from the number of species or compounds that will be retained, and energy balance
to be written. The process specifications like is there any equations for relating process
variables like m1 is equal to k into m2.

Then physical properties and laws like equation of state, Henry's laws, Raoult’s law that we
will be discussing in the next even in future lecture also. Sum of mole fractions of
components that is 1, that means here some fractions, suppose 3 three components are there,
and fractions are given XA, XB and XC, so, the summation of all those fractions will be equal
to 1.

Similarly, if it is gaseous mixture, then the summation of mole fractions of that gaseous
components will be equal to 1 like this. So, these are the relationships to be considered, they
are for solving that material balance equation to get that unknown variable.
(Refer Slide Time: 38:25)

235
Let us do an example here showing this process unit where how material balance can be
retained here. In this case, suppose this process unit will have that 4 input and 4 outputs are
there. The inputs are P, Q, R, S and outputs are here W, V, U, and T, and in all these process
streams, there will be some compounds like 1 to here I think 7 or 8 here components are
there. In the stream here in this inlet, the amount of P will consist of these components here 1,
2, and 3 with the compositions like mole fractions as Y1, Y2, Y3 three.

Similarly, in these systems here, the amount is Q and compositions are Y1, one y two Y3,
and Y4 for the compounds 1, 3, and 4. Similarly, for this R and S here for this streams like
this and with the composition of 5 and 6 with their respective mole fractions. In the outlet
streams also, you will see that there will be an amount of that outlet streams here like U, T, W
and V here with compositions are given like mole fractions Y1, Y2, Y5; Y5, Y6, Y2; Y3, Y4,
Y6, Y7 and Y1, Y7, Y8 respectively for this streams T, U, V, and W there.

So, in this way, we can express the process by a flowchart or we are mentioning all these
input and output variables with their competitions. Now, you have to do the material balance;
you have to write the material balance. So, I told that first of all you have to write the overall
material balance, that means total amount of material comes into the processing unit and total
amount of material which is coming out from the processing unit. So, here as an overall
balance, you can write here total amount is coming P+Q+R+S here in this input streams.

Whereas, total amount is coming out as T+U+V+W. So, we can write this overall material
balance here like this P+Q+R+S that will be equal to T+U+V+W. Next what you have to do?

236
You have to do the material balance for each compound. Now, like this compound 1 or
component 1, you can say compound 1 balance here like suppose compound 1 here, in the
input, what is the compound 1 here, suppose here Y1, so it will be your P into Y1, this would
be your compound 1 in this input.

Here again in this stream, that total amount is Q and whereas this compound 2 with a fraction
of Y1. So total amount of this Y1 in this stream will be Q into Y1. Similarly, in the output
stream, you will see that we are getting this W into Y1 and another stream here suppose T
into Y1. So, we can write this amount of P into Y1 + Q into Y1 that will be equal to T into Y1
+ W into Y1. Similarly, for compound 2, we can write this balance also in this input what
will be that here, input here coming as P into Y2.

No other you know Y2 is coming into this inlet condition whereas at outlet conditions Y2 we
are having here like this U and in the T streams here. So, here it will be U into Y1 T into Y2
like this. Similarly, we can write here component 3 balance, component 4 balance,
component 5 balance, component 6 balance, component 7 balance, and component 8 balance
here. So, from this material balance equation, we can solve for this Y1 to Y7 and also we can
solve for this P, Q, R, S, T, U, V. W. Now, how many unknowns are there here?

Let it be here what is that unknowns P, Q, R, S, T, U, V, W, here total 8 unknowns are there
and also composition like Y1 to Y8, so 16 unknowns are there. So for this, is it possible to
solve this 16 equations to get this 16 variables, of course they are, but we are getting only
how many equations 1, 2, 3, 4, 5, 6, 7, 8, 9 equations we are getting, whereas we need 16
equations. Another what is that, 7 equations are required to solve these unknown variables.

Now, of course, for a particular processing unit, you see some amount of input will be there,
you cannot have all the unknown variables will be there in the processing unit, some input
will be there, some output of course will be there, that should be experimentally determined
or it will be known to you. So, from those, you can minimize that number of equations and
then with others, you know that is there any relationship.

Suppose Y1 to Y2 or Y3 to Y5 is there any relationships that physical properties relationships

are there are not, then from those relationships also you can reduce those equations and

237
coming into the equality of equations to the number of unit process variables and then you
can solve it.
(Refer Slide Time: 44:28)

Now, next, what is the basis for calculation? The amount of flow rate of one of the process
streams can be used as a basis for the calculation, and it is recommended to keep the
following in mind. Now, if a stream amount or flow rate is given in the problem statement,
use this as the basis for the calculation. If no stream amounts of flow rates are known, assume
one, preferably stream of known composition there.

If mass fractions are known, choose the total mass or mass flow rate of that is stream, like
100 kg or 100 kg per hour like this as a basis. If mole fractions are known, then choose the
total number of moles or the molar flow rate there.
(Refer Slide Time: 45:08)

238
Like here, earlier we have already described this the streams will be you know there will be
known values of like this 100 kg per minute as basis and mole fractions will be like this, here
oxygen and methane gas is 30% and 70%. Here the mass flow rate of the components in the
streams are known and the streams competitions are partially known here, like here stream
amount is given, whereas composition of this here nitrogen composition is not known to you,
but oxygen composition and methane compositions are known to you, but this also unknown
because your XN2 is not given to you.

So, finally, you are getting two unknowns here. And here, stream here again this if it is 100
kg per second the streams, here also you see that the two unknowns are there here. Again if
you know this nitrogen mass here, you can get this methane mass from this amount here,
from this mN2 and then we can say that only one variable is unknown to you.
(Refer Slide Time: 46:17)

239
Now, let us do an example for the single unit without reaction. Like this here one process
unit, some feed is coming in and here another feed is coming in and this amount is coming
out. Now, you can solve this problem either by compound balance or atomic balance. Based
on this material balance equation, here accumulation will be close to o because this is a
steady state process. There is no reaction, so generation and consumption terms will be
omitted. So, only remaining is input and output. So, we can write here input will be equal to
output there.

So, according to the material balance, compound balance can be written. First of all, you have
to write the overall balance. Now our overall balance is here. This is streams m1, m1 + m2 that
will be is equal to m3. So, this is your overall material balance. Now, compound balance, if
we consider here, ethanol C2H5OH, that is ethanol composition. So, in this system, ethanol
will be coming as m1 into 0.750 and then in this here it will be m2 into 0.40 and output is m3,
that will m3 into 0.60, so this one. So, we can write this ethanol balance.

Similarly, for water balance we can write here, here m1 into 0.250 + m2 into 0.60 that will be
equal to m3 into 0.40 like this. Similarly, we can write this atomic balance also. Overall
balance from that, then atomic balance like for carbon only, for hydrogen only what will be
the balance, for oxygen only what will be the balance like this. Now, solving these equations,
you will see that as per compound balance and then overall material balance, you can solve
these equations to get these are unknown variables like here.

240
You will see that after solving these, you can get m1, m2 and m3 and similarly based on this
atomic balance also, you can solve this and you can get this m1, m2 and m3. Now, here very
interesting that you can have the same value of m2 and m3 value, even m1 value, based on
that compound balance and atomic balance. So, either you can do the compound balance or
atomic balance, just based on this material balance equation.
(Refer Slide Time: 48:44)

Let us do another example like separation of a mixture of ethanol and water. Now a mixer
containing 10% ethanol and 90% water by weight is fed into distillation column at the rate of
100 kg per hour. The distillate contains 60% of ethanol and distillate is produced at a rate top
one-tenth of that of feed. Assumptions is given steady-state, no reactions. Consider that the
basis is 100 kg per hour of feed. Now, in this case draw and label a flowchart of the process,
write a proper set of material balance equations, and then calculate all unknown stream flow
rates and compositions.
(Refer Slide Time: 49:22)

241
So, based on this problem, we can draw this flowchart here. This is a separation column. In
this case, feed as an input is 100 kg per hour, composition is ethanol and water as 10% and
90%. In the output distillate is D and ethanol and water is 60% and 40% in the overhead
product and the bottom product is coming as B and composition like this here xE and xW and
the amount is E and W there or ethanol and water respectively. Now, based on this problem,
we can write the overall material balance based on the material balance equation.

Like what would be the feed in, this is you know F we can write and feed out is D + B here. F
is given to you, so 100 will be equals to D + B. Now since D is given as 10% of this feed, so
we can write D will be is equal to 10 kg per hour. So, B will be is equal to from this equation,
F minus D, that will be coming 90 kg per hour. You can do that component material balance
also, like this eternal balance. If we do that, then it will be equal to F into xE1 that will be
equal to D into xE2 + BxE3 that is in the inlet what would be the ethanol.

In the outlet also total amount of ethanol what will be that based on which we can write that,
we can solve this for a fraction of this xE3 exit, that means in the stream 3, what will be the
composition of ethanol there. So, it is coming like this. Similarly, we can do the material
balance for the component water here. So, in the same fashion, we can solve this for xW3, that
is composition of water in the stream 3 and it is coming 0.956.

Now, you can get this xW3 without doing this material balance of compound for water also
because once you know this xE3 in the stream 3, you can get it from the auxiliary equation of
that like xE3 + xW3 that will be equal to 1, from that you can directly calculate what should be

242
the composition for water in the stream 3. So, it will be coming 1 minus xE3, basically it is
0.956, which we have got based on this component material balance per water based on this
material balance equation.
(Refer Slide Time: 52:05)

Similarly, you can do that evaporation process to find out that amount of concentrated liquid
produced per hour also and also based on these what should be the amount of water
evaporated per hour and also what would be the salt precipitated per hour that there. Now, the
problem is given that the evaporator is feed continuously with 40,000 kg per hour of the
solution that contains 15% sodium hydroxide, 15% sodium chloride, and 70% water by
weight.

Now, during the evaporation of water, you know that the water is boiled off and sodium
chloride is precipitated as a crystal and removed from the remaining liquor. The concentrated
liquor leaving the evaporator contains 60% sodium hydroxide, 5% sodium chloride and 30%
water. Now, in this case, you have to assume that process is a steady-state process. So, based
on this problem, you have to do the material balance to find out that amount of salt
precipitated, amount of water evaporated per hour, and also what would be the amount of
concentrated liquor that is produced per hour.
(Refer Slide Time: 53:21)

243
Now, see this you know process flowchart here. In this case, it is an evaporator. What is the
input as per problem, it is mentioned here. What would be the output also as per problem, it is
mentioned here. What is the output in this system also it is mentioned here. Now, since as per
problem it is steady state operation, we can consider that a basis of 1 hour operation, and in
that case, what will the evaporation amount that is not known to you, that let it be E and what
would be the amount of crystals is formed that is you know C it is assumed.

What will be the concentrated liquor is formed that is L is assumed and what would be the
evaporator feed, it is given to you, still we are considering that it is denoted by F. So, based
on that material balance since there is no reaction, we can omit that generation and
consumption terms, also since it is a steady state operations, we can omit that accumulation
term, so simply we can write input will be equals to output.

Now, if you do the component material balance there for the sodium chloride, we can write
this equation and finally substituting the value of this F and C value, then we can have this
here equation number 1 and similarly for sodium hydroxide balance, you can have this
equation number 2. Similarly, for water balance, we can form this equation number 3 and
total material balance is basically that, that is F will be equal to E + C + L, that is given in
equation number 4.

Now, from equation number 2, we can solve for L, from equation number 1, we can solve for
C just by substituting this solution of L, then it will be coming as this 5500. Similarly, from
equation number 3, you can solve for E. From equation number 4, we can solve for E based

244
on this value of C and L, that is solved by equation number 2 and 1. Now, we can then have
these unknown values of E, even C, L like this. So, based on this problem, then what will be
the amount of then water evaporated that we got, amount of salt precipitated that we got, and
then amount of concentrated liquor that we got based on this problem.
(Refer Slide Time: 55:54)

Another example like this here. A mixture of propane in air containing 4.03 mole percent fuel
gas here C3H8 is the feed to the combustion furnace. If there is a problem in the furnace, a
stream of pure air is added to the fuel mixture prior to the furnace inlet to make sure that
ignition is not possible. Now, in this case draw and label a flowchart of the fuel gas dilution
air mixing unit, presuming that the gas leaving the furnace contains propane at the lower
flammability limit of 2.05-mole percent C3H8 and do the degrees of freedom analyzes, that
degrees of analyzes will be done later on.

But in this case, you have to do the material balance just by drawing that label, a flowchart of
the fuel gas dilution air mixing unit. If propane flows at a rate of 150 moles there in the
original fuel-air mixture, then what is the minimum molar flow rate of the dilute air that you
have to find out. Now, according to this problem, this flowchart is given here in this slide.
(Refer Slide Time: 57:17)

245
Now, based on this problem, you have to do first what would be the propane feed based on
these material balance, what would be the propane balance and if you write this and then you
can get this n3 value as part this diagram is given and overall material balance based on
which you can find it out what would be the n2 value there.
(Refer Slide Time: 57:38)

Another example is given like an insoluble gas is bubbled at a rate of this 0.0025 kilomole
per second through a container of liquid propane to vaporize it. The gases stream leaving the
container contains this mole percent of propane vapor. The specific gravity of the liquid
propane is given. What is the outlet flow rate of the gas mixture? Estimate the time required
to vaporize the 10 meter cube of the liquid there?

246
Here also, you will see that some input will be there and you know that initially that some
amount of liquid will be there whereas gas will be you know inlet at a rate of this 0.0025
kilomole per second and gas mixture which is coming out that is not known to you, that can
be denoted by n, and in this case 10 mole propane vapor and 90 mole percent gas will be
there.
(Refer Slide Time: 58:35)

According to that, what will be the component material balance? Now, gas balance will be is
equal to simply input will be equal to output since there is no reaction. So, in that case, since
output is total amount is not known to you, it is assumed that it will be n. So as per that gas
balance, this n will be coming like this. Now propane balance if you do, the accumulation
will be equal to input minus output + generation minus consumption.

Since there is no reaction, we can omit this generation and consumption terms, but here
accumulation will be there because your output rate will not be equal to that input rate there.
So, in case of propane accumulation is negative here, because it vaporizers and hence
decreasing that total content in that container with time interval, no generation, no
consumption, no input. So, we can write this propane balance, so here accumulation will be
equal to minus output.

So, based on which you can write this equation and solve for this time t will be is equal to
this 115.637 hour okay. So, based on which you can solve this problem.
(Refer Slide Time: 59:46)

247
So, we have described this material balance equation, how to write the material balance
equation with example, also how to formulate that process with the flowchart and based on
the flowchart with known composition and unknown composition, writing the material
balance equation. Based on that material balance principle, we can solve those known values
and unknown values. So, in this way, we can do the material balance for the chemical
engineering process.

So, we will discuss more about that material balance based on that chemical engineering
process where you know reaction will not be taking part, but their material balance will be
more than one unit there. So, we will be discussing in the next lecture based on that material
balance equation with nonreactive processes. So, thank you for giving your attention.

248
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 3: Fundamentals of Material Balance

Lecture – 3.2
Principles of Material Balances on Processes
With Recycle and Bypass

Welcome to massive open online course on Basic Principles and Calculations in Chemical
Engineering. So, we were discussing about fundamentals of material balance under module 3
and under that module 3, we have discussed the principles of material balance and their
knowhow for the calculations of the chemical engineering processes based on that
fundamental principle of material balance. Now in this lecture, we will try to discuss about
material balances on the processes with recycle and bypasses.
(Refer Slide Time: 01:09)

So, in previous lecture, we have discussed the flowchart, labeling a process flowsheet,
general material balance equation, basis for calculation, typical single unit material balance
problems, based on those general material balance equations. We have given a lot of
information, even we have done some problems how to do the material balance and on
compound basis total material balance and how to specify that stream by their quantity in
terms of flow rate and also in terms of mass fraction or mole fractions.

So, here also we will continue that material balance problems on nonreactive processes with
recycle and bypasses.

249
(Refer Slide Time: 01:54)

So, we have discussed that before going to that do the material balance equation, we have to
specify the systems on which actually we have to do the material balance of the compounds
or components or atoms and also total material balance there.
(Refer Slide Time: 02:17)

In the process flowsheet how it can be that specified the input and output streams based on
their flow rate and also mass fraction and mole fractions there.
(Refer Slide Time: 02:33)

250
Like here, flowchart is actually discussed for the single unit, how that flow streams are
specified by their quantity, like here in the slides that in the mixer that inlet stream and there
will be 2 outlet streams or there will be two inlet streams and one outlet stream. So, in the
streams that how that component rate of that flow is specified there it is already discussed in
the previous lecture there.
(Refer Slide Time: 03:11)

So, this is also for the multi-unit system that how that material balance can be done after the
specification of the flow rate and mass fraction of the compounds that is flowing through the
streams.
(Refer Slide Time: 03:27)

251
composition of bypass if
splitter, is same as the feed

Now, in this lecture, we will discuss something about the recycle, bypass, even makeup are
what are those process system for that are to be considered for the expression of that
particular process. They are, suppose recycle, here sometimes that in a processing unit that
some unreacted portions will be there in the outlet streams and those unreacted or extra
amount maybe reused for that process. So, it will be recycled to reuse in previous units where
to be actually utilized there.

So, in this case, one example like this that for the recycle unused material beings recycled
back to the feed stream and in this case suppose there are 3 units, one is mixer, another is
reactor, and another is reactor 2. Now, in this case, the feed is going to the mixer or this feed
will be mixed with that unused reactant that is coming out from that reactor. Then these
unused reactants will be mixed in that mixer with the feed.

After that, this mixer will be sent to the reactor 1, and then after reaction in the reactor 1, that
outlet the streams of that reactor 1 will contain that some products as well as unreacted
compounds of that reactor 1. After that, it will be sent to the reactor 2 for further reactions,
even after further reaction, you will see that there will be some unreacted amount and some
products will be there. So, the products will be separated and it will be taken out as a product,
whereas unreacted materials can be reused, and it will be sent to that again mixer.

In the mixer, the feed mixer will be mixed in there and then again it will be sent to the
reactor. So, this streams that these streams will be regarded as recycled stream. Similarly,
some process also will be in such a way that some stream that skips one or more stages of

252
 another process and goes directly to another stage for the downstream. Like here, here feed is
coming to one process unit, it is called divider. Now, in this case, this divider will allow the
streams divided into two parts.

One part of that feed mixer will go to the reactor 1 for its process, and from that reactor, it
will go to separator for the separation of the products, but here you will see that some feed
mixes sometimes to process in this separator or some other units, some portions of the feed
mixer required to directly sent to its process unit here. It is sometimes required for
maintaining that flow rate as well as that component at a certain amount there, and after that,
the product will be coming out.

So, this type of process will actually be regarded as with bypass process. So here in this case,
a stream that escapes one or more stages of another process and goes directly to another stage
for the downstream for its processing.
(Refer Slide Time: 07:05)

if purge is splitter, then composition

of recycle same as purge

Special cases like purge sometimes it is required. In that case, a stream sometimes will be
taken off or bled off from the process to remove and accumulate it unwanted materials or you
can say that some inert materials that might sometimes otherwise buildup in the recycle
streams. So, that unwanted material as inerts materials that can be taken out from the outlet
streams of that processing unit there. Here, in this case, see feed is coming through the mixer
and it will to go to the reactor and after that, products will be separated into a product stream
and unwanted materials.

253
So, in this unwanted mixer of these materials, some will be used and reused, and it will be
recycled back to its mixer here, but some inert materials which will not be actually used for
other processing that can be taken out as a purge there. So, this type of process also will be in
the chemical engineering process. So, how to do that material balance based on this recycle
bypass, even purge that will be considered here.
(Refer Slide Time: 08:19)

Another this makeup also sometimes some number of components will be a shortage in the
flow stream. So, you have to give input as a makeup there in the stream. So, a makeup stream
is required to replace losses to leaks; there sometimes, there will be some leaks and there will
be some losses of that material. So, to fill up those leaks or other carryovers though in that
case, you have to give some makeup in the recycle loop. So, that will be considered as a
makeup here.

Like this in this stream, you will see that process with makeup streams here, the feed will be
going to the mixer along with that recycle of this separator here and in that whenever you are
recycling there from the separator, you will see that some loss amount will be there, so that
that particular flow streams will not be maintained. So, there, of course, you have to give
input as a makeup there to maintain those components here in the mixed stream.

So, after that mixing, then it will go to the reactor again, that product streams of that reactor.
It will be separated in the separator and product will be coming out from the separator and the
unreacted compound to be recycled back to the mixer along with the makeup.

254
(Refer Slide Time: 09:46)

Now, if we recall that general material balance, we know that there will be some
accumulation. That accumulation will be is equal to input minus output + generation minus
consumption. So, this again general material balance equation will be used for calculation, or
you can say do the material balance based on that bypass, even purge or you know that
recycle processes there.
(Refer Slide Time: 10:17)

These things we have already discussed. Even if there is no chemical reaction, even at a
steady-state condition, then you can say that the final equation of material balance will be is
equal to input minus output. So, in this lecture, we will also again that consider that
nonreactive system where consumption and generation terms will be 0, whereas at steady

255
state, we will consider that accumulation will be is equal to 0. So, simply we can do that
material balance as input minus output.
(Refer Slide Time: 10:51)

So, as we know that the principles of that material which whenever you are going to do that
medical balance, you have to do either by mass or mole basis. So, either one you have to
follow or you can do that material balance based on compound balance or you can do the
material balance based on atomic species balance, and whenever you are going to that
compound balances, to solve those equations based on that compound balances, you need to
have sometimes the total material balance.

So, you have to do also the total material balance. So, we have already discussed all those
things. Now, here we will discuss the example with recycle stream. Let us have this example
of separation of benzene and toluene in distillation column with recycle. In this case, suppose
a continuous operation distillation column that operated at 1 atmosphere, which is to be
designed as shown in the figure of the next slide.

To separate 13,620 kg per hour of a solution of benzene and toluene that contains 0.4 mass
fraction benzene that will give you the overhead product that will be containing 0.97 mass
fraction benzene and bottom product will be containing 0.98 mass fraction of toluene. Now,
in this case, you have to write the overall material balance equation, write the overall benzene
balance equation, and estimate the distillate and also bottom products. Now, what will be the
reflux per kg of distillate product to be used if the overhead product is 11,713 kg.
(Refer Slide Time: 12:46)

256
So, in this case very interesting that see this schematic diagram of the process here. In this
case, this distillation column is used and feed coming at a certain rate with benzene
composition as xF, and after distillation, you will see that the benzene and toluene mixer will
be separated out, and from the top portion you will see that heavy product as you can say that
the benzene will be coming out from the overhead of this distillation column is a vapor, and
after that, it will be condensed and after that condensed the liquid benzene will be collected
as a distillate.

Now, from that condensed or as a liquid distillate portion, you have to some portion of that
liquid benzene you have to sent back to the distillation column for the process. Now, that is
called that recycle of that distillate here in the distillation column. So, these some portions
should be taken out as a distillate and some portion of its vapor phase as a liquid form, it will
be sent back to the distillation column, whereas from the bottom, the liquid toluene will be
taken out as an amount of B and there will be some composition of this B there.

Now, in this case, since it is a recycle problem, you have to do the material balance and also
that you have to do the overall benzene balance equation and also from that you have to
calculate what should be the distillate and what should be the bottom product as B. In this
case, what should be the overall material balance? So, we knew that the basic equations of the
material balance they are accumulation would be equal to input minus output + generation
minus consumption.

257
In this case, since there is no reaction is going on, so you can simply omit that consumption
and generation terms and also since this is a steady-state operation. Also you can neglect that
accumulation term. So, finally, it is coming as input will be equal to output as per equation.
So, overall material balance, if we consider that as an input, what would be the flow rate of
that feed that will be F and what would be the output from that it will be D and also B.

Now, very interesting that before going to that material balance, you have to fix it up that
boundary of that process based on which that you can do that material balance. Now, overall
material balance to do that, you can give this boundary you can of that whole process, that is
denoted in blue dotted line here in the slide, and based on which you can calculate. Now, if
you know that F value and if you substitute that F value as per problem, then you can say this
will be is equal to B + D, but this B and D is unknown to you, B is for bottom product and D
is for distillate.

Now, if you do the overall benzene balance, that means what would be the amount of
benzene, and overall it is going to the distillation column and also overall what would be the
output of that benzene product it is coming out from the distillation column. From this
boundary of this blue dotted line, you can say that some input of that benzene will be is equal
to F into xbF. What is F, F is the feed rate and xbF is that mass fraction of the benzene in the
feed stream and B, B is the bottom product flow rate and xbB is nothing but that mass fraction
of benzene.

This b is benzene, small b is benzene, and here capital B is for bottom product. So it will be
mass fraction at the bottom product of that benzene and + Dxb, D is the distillate flow rate
and xb is nothing but that mass fraction of that benzene in the distillate stream. So, we can
have this total amount of benzene is going to that system, that is in the distillation column is
simply Fxb and what will be the mass of that benzene is coming out from that distillate and
from the bottom stream, that is that you have to add it up.

Now, from the bottom part, this mass fraction of the benzene if it is xbB, it is unknown to
you. So, it can be calculated as B into xbB and in the distillate stream, that amount of benzene
that is coming out that will be is equal to xbD. So, from this material balance, you can write
this equation. After substitution these F value it is given to you as in your problem and the
feed benzene fraction is given as 0.4, that is 40% benzene, it is given in the problem.

258
So, we can write this equation here and then you do not know the amount of B, but you know
that in the bottom product, the benzene mass fraction is given as 2%. So, it will be as B into
0.02. Similarly, in the distillate flow rate, you will see that there will be a mass fraction of
benzene is 97%. So, we can write simply that D into 0.97. So, from this equation, you can
have this based on that mass fraction of benzene in the bottom and distillate product and also
in the feed streams, then you can write this equation here.

Now, you got one equation from your overall material balance like this, and another equation
you got overall benzene balance as like this. Now, if you solve these two equations, you just
see there are two equations, but you will see that two unknowns are there B and D and also
two equations are there. So, simply you can solve these two equations, and after solving, we
can get this D will be is equal to 5448 kg, and B will be is equal to 8172 kg okay. So, what
would be the amount of D, what would be the amount of B, simply you can calculate now.

Now, after that, the problem is that what amount of liquid that will be sent back to that
distillation column as a recycle stream that you have to calculate. Now, if you consider the
system unit or you can say process unit as a condenser and there if you do the material
balance, you will see that what should be the inlet and outlet from which you can calculate
what will be the unknown value of liquid there that is coming into the distribution column.

Now, if you do the material balance around that condenser, we can write here, again if you do
the overall material balance around this condenser, we can write this V will be equal to L +
D. What is V, V is actually amount of that vapor mixture, it is coming out from the
distillation column and after that, it will be condensed out and then it will be coming out as a
liquid stream there and some portions will be sent back as a liquid here. So, in that case, we
can write here V that will be is equal to L + D.

So, this is input and these are output there. So simply we can write V is equal to L + D. Now,
if you substitute the value of V, V is given to you and D now you have calculated from here,
so, it is 5448, but here this, what is the value of L here, L is given here that it should be some
fraction of D. So, that fraction maybe you can say that it will be is equal to D, some fraction
it is regarded as R that is called recycle faction and then that recycle fraction if you multiply

259
with that distillate, you will get that what would be the amount of recycle is coming to that
distillation column.

So, in that case, we can represent that L will be is equal to what, D into R, now this R is
called recycle fraction or you can simply it is denoted or you can say it is the reflux there. So,
what should be the R from these two equations, you can simply obtain this R will be is equal
to this. So, it will be around one point one five. So, in this way, you can calculate what would
be the recycle stream and what its amount is and how to do the material balance.

So, here very important that you have to do the overall material balance first of all for whole
system and after that for the recycle portion from where that you know that feed will be
recycled that unit also you can do the material balance or you can say that that recycle
amount where actually it is going to insert as a feed in this process unit, there also you can do
a material balance, so from which you can easily solve the problem for that recycle amount.
(Refer Slide Time: 23:04)

Let us do another example with bypasses stream. Now here, in this case, see one schematic
diagram of the process. There you will see that some slurry as a mixer of solid and water as a
slurry some amount, it would be passed through some mixer. So, some amount of solid and
some amount of water will be put into a mixer and from which some portion of that slurry, it
will be sent to a unit that is called evaporator and there that the slurry will be evaporating and
there that water moisture or water it will be evaporated out.

260
Then you will see that slurry will be thicker and thicker whenever water will be coming out
from that evaporator, and after that, from that evaporator with a certain degree of thickness of
that slurry system. It will be sent to a mixing unit again, and after that, some amount of that
slurry will be taken out, after that, you have to analyze what should be the solid amount along
with that water there, and in this case, you will see that whenever you are sending that slurry
before entering to that or before allowing it to the evaporator, you know that same some
amount of slurry just skipping that evaporator directly to that mixing unit here.

So from this here, you can say one divider you can use, and from the divider, some amount of
slurry will be sent to the mixing unit just by skipping of this evaporator there and some
fractions that will be directly sent to the evaporator and after that removing of moisture or
water by that evaporation, you will see that slurry will be again sent to the mixing point there.
So, in this case very interesting that slurry whenever it will be sent to that evaporator. After
evaporation, some amount of water will be removed by that evaporation process.

Now, before going to that evaporator, that slurry contains maybe you know will be some
amount there, maybe some fraction of solid particles and some fraction of water, so that is
given here. At the inlet as a basis of 100 kg of (suppose) slurry which contains 12% of that
solid and 88% of water per kg of that basis and it will be used to evaporate by this evaporator
and from that some amount will be sent directly to that evaporator and some amount with
some composition here, like this it will be skipping that evaporator and sent to the mixing
point.

Now, this m1 amount to that fraction of that slurry, the same fraction of that slurry component
sent to the evaporator and bypassing to the mixing point. Now, after evaporator, you will see
that composition, that is a fraction of that component like solid and water, will be changing
because of that evaporation of water from the evaporator. So, after that, you will see that that
amount will be as m4 and that fractions it will be changed, that the solid fractions will be
coming as 58% whereas it was earlier only 12% and water will be as 42%, whereas it was
earlier before that evaporator it was 88%.

Then this stream from that evaporator again it will be sent to the mixing point, and it will be
mixed to that bypass amount in that. So, after mixing of that outlet stream of the evaporator
and the bypass amount, you will see that again, that composition will be changed. So, in that

261
case, the composition of that solid will be 42%, whereas water will be 58%, and the amount
will be here only m5. Now, based on this problem, you have to do the material balance and
you have to find out the unknown value of streams of like here that is denoted by m1, m2, m3,
and m4 and also what is that m5. So, in this way, you have to calculate.
(Refer Slide Time: 28:24)

Let us do that calculation here. In this case, you will see that first of all, and you have to do
that overall solid balance. Here S means solid. So, if you do the solid balance, you will see
that in inlet condition, you know that what would be solid in, so there it is you know 0.12 into
100, whereas at the outlet of this whole unit, that is outlet if we denote this here as a
boundary of this system. Now across this boundary, we can do that material balance of solid
like here 0.12 into 100 that is in and out only here from this mixer and also from this here, but
from the evaporator, there will be no solid out as an overall system.

So, in that case, it will be 0. So, only this as m5 streams, that m5, there only 42% of solid is
there, so we can write 0.42 into m5 and also if we do the overall mass balance there, so we
can say that 100 kg of slurry is going to that system and only m5 and m3 kg of that component
will be coming as a whole from that system. So, then we can write simply 100 will be is
equal to m3 + m5. Now, if we do the balance on this mixing unit, on this only mixing unit.

Here we can say that only this inlet is m4, outlet is m5, and also inlet again, another inlet is
m2. So, here two inlets and one outlet are there. So, according to that, what would be the solid
in and what would be water in and what would be the solid out and what would be the water
out that you have to consider. So, in this case, if you do the solid balance over this mixing

262
point, what will happen that we can say that 0.58 into m4 + 0.12 into m2 that is m2 as bypass
amount, that will be is equal to 0.42 into m5.

So, we are getting these 2 equations here again. Now, if we solve this equation number 1 and
equation number 2, then we can easily get that 100 will be is equal to what that amount plus
m2. Again the bypass balance, if we do that bypass balance there, we can say that 100 will be
equal to m1 + m2 two. Now, if we substitute that value of m1 and m2, then we can say that
after solving all these m3, m4 and m5 will be coming out or based on this equation here, all
those equations, equation number 1, 2, 3, 4 and bypass mass balance also here, you can easily
solve these problems for that m1, m2, m3, m4 and m5 there.

This way, you can do either way also, you can do that first material balance of bypass and
then material balance of only what is that evaporator and material balance of mixing points
separately there. So, you can easily calculate what should be the m1 to m5 there. Instead of
solid balance, you can do the water balance also, in that way also you can solve this problem.
So, same amount of this stream of m1 to m5 you can get. Now, what should be the bypass
fraction?

Now bypass fraction is defined here, what would be the input to that bypass and what would
be the amount that is coming out from that divider here as a bypass. So, that is simply m 2
divided by F. Here m2 is actually this is 9.95 kg as per solution of these equations and then
input F is hundred 100 kg. So, simply you can say that bypass fraction will be is equal to m2
by 100, that means here 0.0995. So, you can easily then calculate for the multiple units and
with that bypass, how to do that material balance here.
(Refer Slide Time: 33:09)

263
Now, let us do another example with purge. Now, suppose a fresh feed that contains 55
weight% of component A and 45 weight% of B that flows at 100 kg per hour and enters to a
separator which will remove a portion of pure component A only as a bottom product and the
top product stream of the separator contains only 10 weight% of the component A and the
balance is B. A small part of that separator product stream is recycled and joined in the fresh
feed stream, but some other portion is to be purged.

Now the separator is designed to remove exactly two-thirds of component A that is fed to it,
not the fresh feed there. The recycle loop is used to achieve this goal. Now, you have to
calculate all unknown stream flow rates and compositions there.
(Refer Slide Time: 34:13)

264
According to this problem, you can draw the flowchart like this here. Here, you see that there
will be some mixer and in this mixer, feed stream is coming with the component A and
component B with a certain fraction and then it goes to the separator and from the separator
two products will be coming out, one will be from the top, another will be from the bottom.
Now, from the top portions, you will see that some fraction of that top portion will be taken
out as a purge, and some fraction will be sent back as a recycle to this mixer.

Now, this is the problem. According to the value given in your problem, you have to do the
material balance. First of all, you have to do the total material balance or overall material
balance across the system boundary that is defined by this here red dotted line. Now, if you
consider that boundary and in this boundary what is coming in and what is coming out from
this boundary. Now, in the boundary, the amount is coming here as a whole 100 kg, whereas
the amount is coming out from that boundary as here suppose m4 and here as m6.

Here m4 and m6 rate are not given to you, here it is denoted, or it is assumed that it will be
only m dot 4 or m dot 6, that is rate, dot means here rate, that is the stream 4 what would be
the rate that is coming out as m4 dot. Then in the stream 6, it will be you know m dot 6. So,
overall balance or total material balance, we can say, it can be written as 100, it will be equal
to m dot 6 + m dot 4. Now, you have to do the component balance or component material
balance.

Now, in this case, if we consider component A, you can do that component material balance
of A. Now, in this case, we can write what should be the amount of that is component A is
coming into the that boundary of the system that will be is equal to simply 100 into that is
here A 0.55, so 100 into 0.55 and what is coming out from this boundary only for A, it will be
m dot 6. Here since it is pure A, all the fractions will be as A, that means 100% A. In that
case, the fraction of that A will be 1.

So, here we can directly write here m dot 6 into 1. So, it will be simply m dot 6, and then
from this stream4, what is the amount of that component A is coming out since here the mole
fraction or mass fraction of this component is given as 0.1, then we can simply write the
amount of A is coming out from this stream 4 will be equal to 0.1 into m dot 4. So, based on
this, we can write this component material balance here as 0.55 into 100 that will be is equal
to m dot 6 + 0.1 m dot 4.

265
Interestingly in this problem, there is no reaction is going on and the process is steady-state,
so we can simply consider here input will be is equal to output. Now, from these two
equations, you can solve for m dot 6 from the overall balanced equation, like this here 0.55
into 100 and m dot 6 will be is equal to what, from this equation, you can directly write here
100 minus m dot 4 and then just simply write 0.1 into m dot 4 simply.

So, by these two equations, you can write here this equation and solving here this equation,
we can simply calculate what should be the value of m dot 4 here from this equation. Once
you know that m dot 4 from this equation, you can easily find out what should be the m dot 6
from your total material balance equation. So, it is coming here m dot 6 will be is equal to 50
kg per hour and m dot 4 will be is equal to 50 kg per hour, both are same.

So, in this way, you can easily calculate what should be the amount of purge that is taken off
from the system. So, you had to calculate this bypass amount of m dot 4. So, simply this is
the simple example of doing the material balance for the purge.
(Refer Slide Time: 39:38)

Again, there are some other streams that you have to calculate based on this problem. If you
want to find out that other streams and what are those amount, then you have to do the
material balance for other systems there, and in that case, if we do the material balance for
this unit separator and if we specify here the boundary for this system, then what is the in and
what is the out from this boundary that you have to now consider here. Now, accordingly,
you have to write to the material balance here.

266
Here, if you consider this a separator, this input is m2 and output are m6 and m3. So, we can
simply write here m2 will be equal to here 50 + m3 three because here m6 is 50 that we got
earlier, and then if you do the component balance A again for these streams, then we can
write here mA this is stream 2 into m dot 2 that will be is equal to 50 + m dot 3 into 0.1. Here
in m3 that component A will be is equal to 10% according to the problem and this m dot 6
here since it is a pure component A simply it will be into 1, that is fraction will be is equal to
1.

So, simply that means here 100% will be the pure component A here. So, accordingly you
can write these equations. Now, one condition is that the separator that will remove two-third
of A fed to it in the bottom stream. So, in the bottom stream, they told that this component A
will be two-third of A that is fed to it. So, in that case, we can write here two-third of xA2 into
m2 that will be is equal to m dot 6. So, that will be is equal to 50 kg per hour, which implies
that xA2 into m dot 2 that will be is equal to 75 kg per hour.

Now, if we do the material balance and material balance for the component A that already
done here, now if we use this equation and substitute the value of mA2 into m2 dot here, then
we can simply write this equation from that equation here. Now, from this equation, then we
can easily calculate what should be the m dot 3. So, m dot 3 will be coming as 250 kg per
hour.
(Refer Slide Time: 42:34)

267
Now, if we substitute this m3 as 250 kg per hour into overall mass balance equation around
the separator, then you can write here m2 dot that will be is equal to 50 + m3 dot. That means
here, it will be equal to m2 dot will be is equal to 50 + 250. Then m2 dot will be is equal to
300 kg per hour, and then what would be the xA2, xA2 will be is equal to here again from that
question earlier, so simply we can calculate from this equation. Now, again if we consider
that a split, around the split if we do the overall balance, we can write m dot 3 that will be is
equal to m dot 4 + here that will be is equal to m dot 5.

So, we can simply write that here it will be m dot 5. So, here we know that m dot 3 will be is
equal to 250 and m dot 4 is equal to 50, and then remaining m dot 5 will be there here. So,
that m dot 5 will be is equal to 200 kg per hour. So, in this way, we can do the material
balance for that bypass, recycle, spurge, and makeup also. So, in this way, we can do other
exercise problems also. We will provide some exercise problems later on after finishing this
course.

During that run of that course, we will give some supplementary materials for the practicing
and then you will practice and I think will have more ideas about that input and output and
material balance, how to do that, all these things. So, thank you for your attention.
(Refer Slide Time: 44:41)

Here, I would suggest you to follow that textbook of this given here in the slides for the
calculation and also practicing the problem. In the next lecture, we will discuss something
more about that material balance that will be on reactive processes. Thank you.

268
 Basic Principles and Calculation in Chemical Engineering
Prof. S. K. Majumder
Department of Chemical Engineering
Indian Institute of Technology-Guwahati

Module-03
Lecture-09
Material Balances On Reactive Processes

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So we are discussing about fundamentals of material balance with examples under
module 3. In this lecture we will discuss that material balances on reactive processes.
(Refer Slide Time: 00:45)

Here we have given earlier the examples of material balances with nonreactive processes like
with recycle with bypass and by purge. Here we will discuss something more about that reaction
processes like selectivity yield, extent of reactions and how this you know extent of reaction
concept can be used to do the material balance on this reactive processes.
(Refer Slide Time: 01:09)

269
Now, before going to that calculation have to know some you know terminology of that reactive
system. In this case to consider a chemical reactions, you have to know the stress immature of
that reaction equation. Now, you know that theory of the proportions in which chemical species
that combined with one another in a reaction as represented by an equation and that will be
called as equation of reaction.

And did actually this you know that concept of this you know that reaction equation that is
stoichiometry and it originates from two Greek words. That is, you know stoicheion that is called
the element. And metron that is called measure. So, based on this stoichiometry is coming.
(Refer Slide Time: 00:19)

270
Now, this stoichiometry actually for a particular reaction equation, it will provide a quantitative
means of relating the amount of products that are produced by chemical reactions to the amount
of reactants. Whereas, in this stoichiometry you will see that to stoichiometry, you will get that
the stoichiometry equation, that will give you the statement of the relative number of the
molecules or moles of reactants and products.

But not mass you can say that participate in the reaction and the coefficients accurately
represented by the numbers that will be proceeding a suspicious in the balanced in the reaction
equation and stoichiometry ratio. This will be actually regarded as the ratio of stoichiometry
coefficient of any 2 species. So, these are some you know terminology that you have to you
know remember.
(Refer Slide Time: 02:59)

And you have to understand and also in reaction you will see some reactants will be you know,
limiting reagent or reactant, in that case that reactant that would be first depleted if a reaction,
you know proceed to combustion and proceed to completion. A reactant is limiting if it is present
in less than it is a stoichiometry proportion relative to all other you know, reactants. Now, in this
case you have to identify that limiting reactant.
(Refer Slide Time: 03:34)

271
And now, how to that you know identify that limiting reactant there, first of all you have to select
the reactant with the lowest stoichiometry efficient in a particular reaction. And if there is more
than one reactant with the same lowest coefficient, example like this given here in this slides. So,
in that case you have to select the one with the smallest number of moles fed. After that you have
to set up the stoichiometry ratios with the lowest stoichiometry coefficient that will be identified
as the denominator.

And in doing so all your stoichiometry ratios should be greater than 1, after that you have to set
up the corresponding ratios using actual feed hallows. So, all these things you know earlier also
because you have already completed all those things in you know schools levels also in high
secondary schools, they are still you just go through this you know concept for your you know,
understanding for what the calculation in the material balance.
(Refer Slide Time: 04:43)

272
Now, in that case you will see that with that limiting reactant, how to actually find out that which
one will be the limiting reactant. In that case, if you compare a set of ratios like here in nx by ny
that will be in the feed verses and an x and y that will be in the stoichiometry. So, if nx by ny in
the feed is greater than equals to nx by ny in the stoichiometry coefficient, then you will see that
react and x will not be limiting.

Whereas if nx by ny in the feed if it is less than nx by ny in the stoichiometry coefficient then you
will say that x will be limiting reactant, other terms like fractional access sometimes you will see
that to complete the reaction you have to supply some excess you know reacting to the that based
on this it is limiting reactant and also sometimes the what will be amount of you know reacting
to be supplied in the feed.

You have to you know calculate what should be the actual amount of reactant amount is required
for your complete reaction theoretically and after that you have to you know judge of what
should be the you know excess amount of that reactant is present in your you know feed mixer or
if it is short is then you have to supply excess amount of you know that reacts in the feed mixer.
So, that that you reaction will be completed.

Now, in that case you have to you know assess that you know concept of that you know excess
reactant based on this you know fractional access equation here. So, in that case fractional access

273
will be calculated as here fxs that will be equal to what will be the number of feet of that species i
and also what will be the number of moles of i, but that is required for your complete combustion
that you have to calculate.

And after that, if you divide it this you know that difference of that, you know, species are
present in feed and presses are required for your complete you know reaction theoretically, if you
make a ration then it will be called as that fractional access where i will be the excess reactant
here in this you know reaction in this in this equation.
(Refer Slide Time: 07:17)

Now, if we consider an example of you know reaction like this here, it is given in the slides in
this case see here A is reacting with B and gives you that C and D , in this case here coefficient
stoichiometry efficiencies are 1, 11, 7, 8 respectively. Now, in this case, given 1 mole of C7H16
and 12 you know mole of oxygen. In this case you have to identify what the limiting reactant.

Now you have to find out first what should be the ratio of that oxygen 2 you know, here happen
in the you know reaction then as per stoichiometry you know coefficient this ratio will be
coming as 11 by 1. Whereas the ratio of these molecules in the feed to be 12 by 1. Now, it is
simply that this 11 by 1 is you know less than 12 by 1. So, we can say that oxygen in excess air.
So, oxygen is excess air.

274
So, we can see that oxygen in but excess but the limiting will be that other one that is C7H16 here,
because in this case you will see that this C7 if we compare that it will be you know less than that
feed. So, accordingly we can say that this C7H16 is limiting and what is the you know fraction of
excess of that you know excess of that limiting reactant, here as part that equation earlier given
here like this accordingly you can get what should be the excess of that limiting reactant. So, this
will be your 0.09 in this case.
(Refer Slide Time: 09:16)

Other definitions like suppose there are 2 reactions A + B which will give you C and D and C +
B which will give you E and D. Now, further the reaction of desire products C, and is that
reaction will be there in particular set of reactions. Now, in this case if C is a desire product then
you have to minimize the second reaction from taking place. And also second reaction uses up
react B and desire production C.

It also produces undesired product, let A be the limiting reactant here, so conversion of A = mole
of a reacted by mole of A fed and conversion of B will be represented by mole of B reacted by
mole of B fed.

(Refer Slide Time: 10:01)

275
And you can select that which component to be you know that desirable or undesirable based on
that selectivity. So, that selectivity will be you know defined as mole of C in output by mole of E
in output as far you know that reaction and yield will be defined as here, this total mole of
products by total mole of A fed and yield of C for particular species, then you can say that mole
of C in output by mole of A fed.

And efficiency of the you know that you know productive output of C will be equal to mole of C
in output by mole of A reacted. Now, in this case, the term yield and selectivity are used to
describe the degree to which is a desired reaction predominance over competing side reaction.
(Refer Slide Time: 10:56)

276
And other important you know terminology that you have to you know remember sometimes it
will be required for your, you know material balance calculation based on a reactive system.
Now, in this case, if we consider that certain process you need a reactor where the reaction is
going on and A will be giving to B in that case A is coming at a certain flow rate after mixing
with it is recycle here.

And it enters to the reactor at a certain rate and after that reaction, it will give you the you know
mixture of you know unreacted A and the product B and there will be certain flow rate of that A
and B and after that it will be coming out and to be separated in a certain process unit and then
has a product you will see that some amount of you know product that will be here. It will be you
know taken but remaining you know unreacted you know that reacting to be you know saying
back to each you know, mixer before you know processing the top reactive there.

So, here in this case one interesting term that you have to know that overall conversion of the A,
how you define it. Now, for overall conversion of A you have to consider that whole process
here, whole process means including that mixer, reactor and separator. So, in that case this
overall conversion of the A would be represented by what should the input of A and what should
be the output A output of A there and divided by input of A.

So, here you will see that input is coming as 100 mole per minute, whereas output is you know
that there will be 0 for specifically for component A. So here 100 – 0 by 100 that will be into 100
and that means here to be 100% overall conversion. Whereas, if you are considering that there
will be a single pass conversion that means here what would be the input of A in a particular
process unit like here reactor.

That case only you have to consider here the reactor. So, for the reactor what is the input of A
and for the reactor what will be the output of A. So, in this particular example, you will see that
the input of reactor for this component A is 100 whereas output of component of this A only for
this reactor it will be only 25 as shown here in the figure in the slide. So, you can calculate that
single pass conversion of A will be equal to 100 minus this 25 divided by that 100 that means
input.

277
So input minus output divided by input that will be regarded as single pass conversion of here
particular species. So, here it is coming 75%. So, what is comparison that overall conversion and
single pass conversion will be totally different. Overall conversion as far as here it is coming
100% whereas single conversion rate is coming 75%. So, this sometimes so this concept will be
sometimes required for your you know material balance calculation in the reactive system.
(Refer Slide Time: 14:25)

Now, another important aspect of you know reactive system that actually sometimes at a
particular time what will be the amount of you know reactant is present in the system and what
will be the you know reactant conversion and after conversion what to be the amount of reactant
to be present in the you know system that also you know represented by certain you know
concept is called extent of reaction.

Now, consider the reaction A which will give you a product B. So, in this case, if you assume
that infinitesimal amount of you know dxi here 1 j is considered here some this j amount of you
know that reactant A that changes into B. So, you are considered event some amount of A is
converting to B that some amount of you know reactant will be denoted by this dj. Now, this
change of this amount of A can be represented by the equation here.

278
This dnA = - dj, the change of B similarly, can be expressed as dnB = dj because same amount
of A will give you that you know product B here. So, dnB dj. Now, similar to the extent of
reaction is then defined as di xi will be equal to what will be the change of that component i, now
with respect to you know it is a stoichiometry coefficient that will be divided by you know here
 i.

Here ni denotes the amount of i – th reactant and here i is the stoichiometry coefficient of the i
th reactant So, in this way you can define that extent of reaction.
(Refer Slide Time: 16:13)

And other way it can be defined as like, it is the amount of substance that is being changed in an
equilibrium reaction. Considering that finite changes instead of in finite simple changes on can
write the equation for the extent of reaction as j that will be equal to ni by i, then, it can be
written as ni0 – ni by i.

So, here in i0 that may be you know that equilibrium power concentration that is at the outlet or
at a certain time when it will be coming as equilibrium that equilibrium you know most will be
there in. And initially moles will be in i initial you can say that and divided by stoichiometry
efficient. So, in this way you can define that extent of reaction. The extent of reaction is defined
as 0 at the beginning of the reaction because that is the changes of j is you know extent itself
there.

279
(Refer Slide Time: 17:23)

Now, you know that extent of reaction multiple reaction, how to you know calculate that, that
case that for multiple reactions, this extent of reaction based on which you can you know, derive
this equation as n i that means at a particular time what should be the moles of i present in that
you know process unit that will be equal to ni0 that means what will be the amount of i fed you
know in the feed mixer.

And what will be that you know for summation of vij into j. So, vij here stoichiometry
coefficient of the reaction here j if there is j number of reactions are there, then you have to
consider that vi for particular reaction and similarly the extent of reaction for that reaction j will
be denoted by j. So, accordingly this equation will be used for you know that extent of reaction
calculation for a particular reaction.

Now, in this case interesting that you have to remember the stoichiometry coefficient will be
treated as a negative for the reactant and positive for the product that you have to remember.
(Refer Slide Time: 18:44)

280
Now, let us have an example for this. Now, if water gas shift reactor like carbon monoxide plus
water will give you that carbon dioxide and hydrogen gas, that will proceed to equilibrium at a
temperature T Kelvin. Now, the mole fraction of the you know for reactive species to satisfy the
relation here is given y carbon dioxide into y hydrogen divided by y carbon monoxide into water
that will be is equal to some equilibrium constant.

Now, this you know equilibrium constant it is regarded as the reaction equilibrium constant at
time that is 1105 Kelvin this K will be is equal to 1, now at this condition suppose the feet to a
reactor contains 1 mole of carbon monoxide 2 mole of water and you know no carbon dioxide or
hydrogen and the reaction mixer comes to equilibrium at 1105 K. So, in this you know operating
condition of this reactor you have to calculate the equilibrium composition and fractional
conversion of the limiting reactant.

So, here this yco2 is represented by you know mole fraction of carbon dioxide and yH2 is mole
fraction of hydrogen y co it is you know mole fraction of carbon monoxide and yH2 o is simply
that mole fraction of you know water. So, based on these at equilibrium condition what should
we that equilibrium concentration of these carbon monoxide water you know carbon dioxide and
hydrogen that you have to find out. So, you have to use that concept of extent of reaction here.

XXXXXXXXX

281
(Refer Slide Time: 20:44)

Now, let us solve this problem here as per equation we know that since here only one you know
equation here. So, if we apply this general equation for multiple reaction, here in this case j will
be equal to 1 only. So,

ni  nio   vij j
j

So, in this case, if I consider only for carbon monoxide first then here ni that means here nCO that
will be equal to what that what to be the feed amount of carbon monoxide this 1 mole whereas at
equilibrium condition that extent of reaction will be able to i.

Now, in this case here as per reaction here what is the reaction equation is given carbon
monoxide here, this is CO2 + water that will be giving you what is that carbon monoxide as
carbon dioxide here sorry, this is Co + sorry, Co + water that will be equal to CO2 + hydrogen.
So, this is your reaction. So, in this case you will see that if we consider that carbon monoxide,
so, in the feed this amount of carbon monoxide is here 1.00 mole.

And here we can say that at equilibrium condition this extent of reaction is e. So, here for e we
have to you know that considered this nu here as you know – 1 because this is reactant as we told
that for the reactant this suckerfish and to be considered as negative whereas, product or

282
consideration will be you know positive. So, here in this case this carbon monoxide it will be
then represented by this equation here
nCO = 1.00 mol – ξe .

Similarly for water again you can consider here this coefficient is I think we are H2 here, this
feed amount is here 2 moles is supplied in the feed, then nH2O = 2.00 mol – ξe, again here this
coefficient is 1. So, it will be negative of 1 then it will be - 1 ξe. Similarly, for carbon dioxide if
we represent it to be only here ξe, here in this case coefficient is 1 that will be positive since it is
a product.

But here since there is no amount is supplied in the feed mixer. So in ξi0 = 0 here, whereas,
similarly for hydrogen it will be represented as ξe. Now, after that you have to you know
calculate what will be the fraction in terms of this xi. Now, what would be the total you know
amount of moles that first you have to calculate that you have to sum it up all those things and
then you have to divide individual moles with that total moles then you will get that
concentration.

So, here like this, if you sum it up this whole moles here you will get here simply 3 moles only.
So, this is total mole is 3 moles. Now, then y carbon monoxide will be represented by this and
similarly, y hydrogen will be like this and y carbon dioxide will be like this and y hydrogen will
be like this, because this is simply mole fraction. Now, after substitution of mole fraction of all
these components carbon monoxide, water, carbon dioxide and hydrogen you will see that this
you know that in this equilibrium equation.

Then you can have this you know final form of equation after simplification and then after
solving you will see that ξe = 0.667. So, this is called extent of reaction at its equilibrium
condition. Now after the substitution of xi here again in this you know mole fraction of each
component you will see that this mole fraction of component carbon monoxide it will be coming
as 0.111 and mole fraction of water it will be coming at 0.444.

283
Here just substituting the value of ξi, similarly, for mole fraction of carbon dioxide you will get
up the substitution of xi here and then hydrogen for hydrogen you will get this you know that the
substitution of here So, finally, you can get these small fraction of carbon-di-oxide as 0.22 and
hydrogen will be able to again 0.222. So, these examples will give you how to calculate that
composition of you know that components in the mixer when it will be you know, as part a
certain reaction with each, you know, output or products at a certain equilibrium condition.
(Refer Slide Time: 26:03)

Now, what should be the limiting reactant in this case, you know that if you verify that principle
based on earlier equation that I have discussed. So, it will be you know that the carbon monoxide
will be as you know limiting reactant. Now, at that equilibrium condition what should be the you
know carbon monoxide moles that can be calculated here that is what is the feed mixer and what
to be the you know equilibrium mixer concentration.

So, it will be here simply you can say that that n co moles in the nu moles it is given your what is
that 1 mole whereas, at the equilibrium condition it is coming 0.66 mole. So, based on that you
can see that here it will be at equilibrium condition to be 0.33 mole and then fractional
conversion of carbon monoxide and equilibrium will be as f co that will be equal to 1 - 0.33
mole, carbon monoxide that will be reacted divided by that 1 mole of carbon monoxide fed. So,
it will be coming as 0.667.

284
So, this is your factional conversion of carbon monoxide. So, we can easily calculate based on
that extent of reaction concept, what should be the fractional conversion of carbon monoxide and
what really they are you know equilibrium composition in the mixer.
(Refer Slide Time: 27:32)

Let us do another example of this multiple with multiple reactions. In this case, if we consider
that reactions as follows take place in you know a continuous you know reactor at steady state
condition in a reactor. So, we can say that yeah this is one reaction that we see are ethylene,
ethylene is given that, you know by this you know that by this conversion of you know ethylene.
So, ethyl is actually obtained by you know conversion of you know ethane.

So, it is sorry ethylene is obtained from the conversion of you know that ethane at a certain
temperature and pressure and also it will give you the hydrogen and then also you can see that
this you know that ethane again reacting with that you know products hydrogen will give you
that you know a methane. So, in this way based on this you know multiple reactions, how to
calculate that you know that molar composition of the product cash and the selectivity of the
ethylene into methane production that too can actually obtained by that concept of you know
extent of reaction.

So, let us have these you know reactions that is going on in a reactor and you know that and the
feed contains you know 85% ethane and 15% inerts and a fictional conversion of ethane is given

285
0.501 and the fractional of the yield of the ethylene is given is 0.471. So, as part this you know,
schematic diagram here are closer to you can see that means here if we consider that 100 mole of
mixer is going into the reactor out of is that 8.85 moles you know per mole of a feet, it is that
means here 85% mole.

Then and you know 15% only inerts are going into the reactor and after reaction happens you
will see them some you know methane then some amount of ethylene some moment of
hydrogen, some amount of methane along with inerts to come in you know outlet stream such a
product. Now, in this case very interesting that this is inert you know components will not take
place in the reaction.

So, whatever amount of inerts will be you know going to into the reactor, that amount will be
coming as you know in the outlet streams. So, that should be considered.
(Refer Slide Time: 30:27)

So, if I use that concept of that extent of reaction for the multiple reaction then this is your
governing equation based on this equation you have to calculate all these things. Now, let us
consider that n1 according to this year, you know that flow chart n 1 is for you know C2H6 that
means, ethane n2 power ethylene and what is that n3 for hydrogen n4 for methane and n5 for inert
amount in the outlet streams.

286
So, in that case if I use this, you know this extent of reaction equation here. So, n1 can be
represented by this here, but the feed amount is 85 mole whereas as for this summation of

ni  nio   vij j
j

So, if you substitute that the coefficient is you know 1 since it is you know that in the you know,
reactant stream then coefficient will be negative. Similarly, the first reaction it will be a negative
of 1 to 1 and similarly for the second reaction it will be negative of 2.

Similarly, for n2 you can represent it as n2 = x1 since it is a product, then you have to represent
this coefficient eta as sorry nu as positive terms. So, it will be

This 15 moles since it is not you know taking part in that the reaction and the same amount of
energy inerts will be coming into the outlet to stream as what it is given in your inlet stream.

So, based on this concept of extent of reactions, we are getting this n1 into n3 n4 and n5 ethane
conversion if we consider that, if the factional conversion of the ethane is 0.501 it is given in
your problem, the fraction unconverted and hence, living the reactor must be 1 - 0.501. So,
finally, you can calculate what should be the n 1. So n 1 will be coming as simply up to 42.4
mole C2H2. Now, this n1 actually as for that extent of reaction this simply 85 – 1 – 2.

Similarly ethane yield will be actually represented by the this equation it will be coming as 85
moles as by definition, then n2 will be actually defined as like this, this one 0.471 into 85 then
that will be is equal to as far as extent of reaction, we are no concept and 40 mole of that means,
here ethane that will be equal 1. So, finally, you can get that this 1 will be is equal to here
simply n2.

That is among what is the amount here that will be 40 mole of you know ethane there, so 1 we
have calculated and it will be as what is that n2 and this is this amount is 40.

287
(Refer Slide Time: 33:41)

So, substitute on substituting this 40 mole for 1 in equation number 1 here given h. So, we can
get that what will be the value of xi 2 there. So xi 2 = 2.6 mole. Then, after substitution of 1 and
2 in n3 then you can get that here in n 3 n 3 is basically 1 – 2. So, after you know subtraction
of 2 from 1 you can get this n 3 as 37.4. Similarly, n4 you can calculate like this to 2.

2 you know, so it will becoming 5.2 whereas n 5 is already known to you and then total mole
will be is equal to see that will be summation of all the you know in n1 n2 n3 and n 4 and n 5 in
the outlet steam, it will be coming as you know total amount 140 mole. So, after that you can
easily calculate what from the fraction of all those components there. So, it will be simply
individual amount of that you know component divided by total mole then you will get that by
you know fraction of that you know, individual components.

So, it will be coming as 30.34 you know ethane 28.6 per ethylene and you know that 26.7% for
hydrogen and 3.7% for methane and remaining 10.7% for you know inert in the outlet steam and
based on these you can calculate what will be selectivity, that selectivity is defined as what to be
the mole of you know ethylene produced based on what will be the amount of you know that
methane by product is produced there.

288
So, this is simply 40 by here 5.2 then it is coming 7.7 mole of you know, ethylene in based on
that total mole of you know methane in the outlet stream. So, this is the concept also how to
calculate that selectivity and also what the mole fraction of our different you know, components
are in the outlet streams based on the multiple reaction. So, please go through this you know
examples and practice it. And then you will be able to solve other different problems based on
that multiple reactions.
(Refer Slide Time: 36:14)

So, I would suggest you to follow this you know concept of that extent of reactions in these
books like you know first textbook Felder, and Rousseau, and the elementary principles of
chemical process 4th edition, you will get more information about this extent of reaction there
and please practice some example problems given they are also. So, thank you. So, next lecture
will try to you know describe more material balance based on you know reactive system even
with multiple you know you need to recycle bypassed and you can make up and also some
combustion reactions how to do the material balance on them, thank you.

289
 Basic Principles and Calculation in Chemical Engineering
Prof. S. K. Majumder
Department of Chemical Engineering
Indian Institute of Technology-Guwahati

Module-03
Lecture-10
Material Balances On Combustion Reactions

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about fundamentals of material balance under module 3.
Under this module today will describe the material balances on you know chemical reaction
process especially for combustion reactions.
(Refer Slide Time: 00:55)

And in the previous lecture, we have discussed and also solved the problems of material balances
on reactive processes, especially with selectivity yield efficiency and extent of reaction. Now, we
will discuss some more about that material balance of chemical processes of a reaction will be
involved. But, in this case, will describe something about the processes, which will be involving
chemical reactions as well as you know, bypass, recycle.

290
And you know parts with makeup also, and then next part of this lecture will describe the
combustion processes and also try to you know to solve some problems about that combustion
reaction and how to do that material balance with those combustion reactions.
(Refer Slide Time: 02:00)

So, let us first discuss about that material balances with reactions based on that recycle, bypass,
makeup, and purge. So, before going to that, we of course recall that you know, general material
balance equation, which is basically that
 ACCUMULATION  INPUT   OUTPUT   GENERATION  CONSUMPTION
and since this material balance involving with that chemical reaction, here, we have to consider
that generation and consumption terms. But if this reaction process is at steady-state condition,
then we can see that accumulation will be equal to 0.
(Refer Slide Time: 02:55)

291
So, let us have this problem of that you know chemical engineering processes, which will
involve these chemical reactions here like if we produce a gene from you know toluene then how
this process will be executed with different processing needs.
(Refer Slide Time: 03:15)

Let us have this process unit here, there are several process you need to be utilized here for this.
You know Benzene production from the Toluene, here some mixer, reactors, separator you know
that divider, and then you can see that mixer will be used after makeup there. Now, what is that
actually for that reaction process with this actually going on during that engine production
process.

292
In this case, Toluene will react with hydrogen to form Benzene. But a side reaction will also
occur in who is a byproduct like diphenyl as denoted by D here is formed as far reactions. Here
the reaction is given ah like, you know that in this reaction toluene is reacting with hydrogen and
will give you that you know benzene and you know methane and this production of this you
know that benzene production along with that there will be some byproducts will be produced.

In that case this you know Toluene has been reacting, and then the byproduct will be coming out
as a diphenyl along with that methane. Now, in this case, hydrogen is added to the gas recycle
stream to make the ratio of hydrogen to methane that is 1:1 before the gas enters the mixer. Now,
this ratio of hydrogen to Toluene that enters the reactor at you know, at a certain amount, let it be
G here as per problems given, and that will be equal to 4 times of hydrogen to 1 Toluene.

Now, this reaction conversion of the toluene to be engine will be single pass to the reactor that is
70%, we have described the definition of you know overall conversion of the reactant and also
single pass conversion of the reaction that is you know that for the particular process unit is
given in the previous lecture. So, as for that you can see that the conversion of conversion to
benzene in a single pass to the reactor will be 70%.

And the conversion of toluene to the byproduct that is diphenyl is 6% on the same pass, in this
case, you can assume that 100 moles of toluene in the stream G. So, what should be the
flowchart first you have to draw and also the flowchart you have to write the component material
balance for each component for the unit reactor + separator. Write the component material
balance for each component for the unit mixer.

And then calculate the moles of you know, R G R L M and P per hour. So, here in this slide,
these, you know, flowchart of the process is given here. So, here see that mixer, the mixer you
know the feed is coming that is 100% toluene, that is pure toluene is you know coming to the
mixer and in this mixer, some you know gas will be entering as a gastric cycle along with his
makeup.

293
And also liquid recycle also will be entering here in the mixer and after that from this mixer
gross amount of feed as G will be you know coming into the reactor and after that reaction you
will see that several products will be coming out like you know that is part reactions sort of our
components will be coming out along with the byproducts will be there. After that, those you
know productive streams with the different components with product and byproducts it will be
you know saying to you know separator.

And after that some processing of separation, you will see that it will be divided into several
components, here that the product will be coming as 100% you know pure benzene as a B and
byproducts will be you know taking from that separator as a D here, that will also 100% diphenyl
will be taken at separate a stream and then some amount of you know gas like you know
whatever gas is produced there that is methane gas.

Along with unreacted gas like hydrogen gas you know that that will be you know recycle back to
the mixer, but if there is some you know that unreacted materials are there or inert materials will
be there that will be pas as a P here from this you know outlet and the gaseous cycle as amount R
G it will be you know going to that mixer along with some you know that some amount of
hydrogen gas has a makeup to be given.

Because some you know that hydrogen gas may be lost because of some leakage or some other
you know dispute of that instrument there and after that also whatever liquid product as you
know that will be you know after separation will be taken out as you know byproduct and then
you know that some liquid recycles that is toluene that is unreacted toluene of the liquidity will
be recycled to the mixer again.

And after that, from that mixer the you know that stream as a grass feed are denoted by G it will
be against you and back to the reactor. So, in this way this whole process is going on. So, we can
you know that, you know specify that you know stream amount what will be components are
there and we have you know given here in this slides in the picture here, see this is total you
know flowchart of that process.

294
Now, for this particular process, you have to know the material balance based on that general
material balance equation. Now, let us do that material balance one by one, here one important
things that you have to remember here not only single unit multiple units will be you know
considered for the system at a time even sometimes to you know that units, process units will be
considered as one single system.

Even only one single system or a single process unit will be considered as one single system
there. So, based on who is sometimes for convenience of your calculation, you have to consider
that more than one process in it will be as you know process system there.
(Refer Slide Time: 10:33)

Now, let us you know solve this problem one way here like if we consider that 100 moles of
toluene in stream G after you know mixer here, then if we consider the system as reactor and
separator and considering both the units here as a system and then if we do the you know
material balance for each component here, then what we can you know write. Now, as per
material balance equation we know that if there is a steady-state operation, then we can simply
write there in - out + generation - consumption.

So, here since the reaction is going on, we can consider that generation and consumption there,
but some reactions maybe there will be no generation, but consumption will be there, some
others you know that there may be generation there will be no consumption like this. So, let us

295
have this here, if we consider fast to the toluene then what will happen that what would the input
of that toluene.

This is given that toluene is coming as 100 moles there as a G. So, we can write here this you
know that toluene as 100 here in and then out what do the output of that toluene since here from
this system, this toluene is coming out as a recycle here, then what happened this recycle amount
is considered as R L here. Since it is not known to you, we are considering that that amount will
be R L. So, simply, we are keeping that you know symbol as R L here that amount.

So, 100 – RL, now then + generation Now, what will be the amount of generation of toluene
since here there is no formation or generation of toluene, this is only supplied, but there is no
formation of or generation of toluene based on the reactions. So, we can write simply generation
of toluene = 0 and consumption now since there is a reaction based on that reaction equation
toluene is reacting you know that with what is that hydrogen.

And it will give you that benzene and the methane, so we can write here that consumption of that
toluene will be what, since this toluene is going to that reactor. So, one pass you know
conversion is given 70%. So, here 100 into 0.7, this mass of amount of consumption of toluene
will be there, but along with that there will be other consumption there that here it is said as per
your problem that.

Here you know some conversion of toluene will give you. You know that byproduct diphenyl,
which will be 6% on that same pass. So, you have to consider that 6% of conversion of toluene
there in the consumption term. So, it will be coming as 100 into 0.7 + again 100 into that is 0.06.
So, this total consumption of the toluene will be like this 100 into 0.70 + 0.06. So, this is the
equation we can write for the component toluene.

Similarly, we can write the balance of the component for hydrogen like what should be that you
know, amount of hydrogen is coming into the you know, system that is for that combination of
reactor and separator, we can simply write here that since G amount is 100, but they are you
know that it is said in your problem that you know that hydrogen is added to the gas cycle steam

296
to you know that make the ratio of hydrogen to methane will be 1 : 1 before the gas enters the
mixer.

And also, it is told that that ratio of hydrogen to toluene entering the reactor at G will be four
times of hydrogen to 1 or more of toluene. So, in that case, we can simply write that hydrogen
amount will be you know, four times that toluene amount. So toluene is 100, whereas this
hydrogen then will be equals to what is that this four times of 100 that play 100 4 like this here.

So, it will be your in and what will be the out that outlet amount of hydrogen it is not known to
you. We can simply assume that this amount of mole of hydrogen at this outlet will be equals to
what this is NH2 here and also we can see that here the separation in the separated you will see
that a precipitated this hydrogen will be coming out as this amount and then what is the
generation terms of that hydrogen.

Since you know that there is no hydrogen is you know generic during that reaction, we can
simply say that generation term will be equals to 0 whereas consumption of hydrogen will be
there since there is a reaction with that hydrogen. So, hydrogen consumption will be is equal to
100 into 0.702 into 0.06 into 1 by 2, why that 0.06 into 1 by 2, because 1 mole of toluene is you
know required you know that a half moles of hydrogen in the second reaction production of
byproduct.

So, that is why we can say that here 100 into 0.70, and + 100 into 0.06 into a half mole of
hydrogen is required for, and it will be considered as a consumption there and that will be equals
to total here this as for this equation it will become 0. So, all these equations it is coming 0
because that you know accumulation term is 0. Similarly, you can do that methane balance it will
be in the 100 into four that is in PR and methane that is coming out from that separator here.

It is not known to you let us see that this will be is equals to n methane there, and here what is
that this you know generation terms of the methane because this methane is produced after the
reaction. So, that is why the generation of this methane will be considered there. So, what is the

297
amount of generation of methane will be is equal to per 400 moles what should be that amount
because conversion is 70%.

And also, they are you know 6% of by-product is produced based on that you know reaction with
hydrogen gas. So, 1 mole of hydrogen is required to give you that it is 6% of that diphenyl. So,
accordingly, you can see that total you know, how you know, many moles of that methane is
required for the generation of each methane gas and also consumption in this case methane is not
consumed, because there is no you know participation of the methane for the reaction only. It is
coming out as a product.

Now, solving these you know, 3 equations of this material balance of components, we can have
this R L = 24 moles and hydrogen moles that are coming out from the separator as 327 moles
and within gas which is coming out from the separator that will be is equal to 476 moles. Now,
up to that, there will be other you know variables to be you know estimated based on the material
balance like you do not know what will be the amount of feed in the mixer.

So, based on you know, consideration of the system of you know mixer unit, we can also do the
same component balances, but there will be no chemical reactions. So, accordingly, we can say
that they are only the material balance equation will be is equal to n will be is equal to in – out.
So, based on that, toluene will be equal to what toluene balance will give you that what will be
the amount of toluene is coming into the mixer.

That will be F into you know 1 why 1 because here 100% toluene is there, there is no other
component in this mixer. So, that is why you can write there; this you know fraction will be
simply 1. So, that you know that F into 1 and there you know that other part of that in is what is
that here as a makeup some amount of you know, what toluene whether it is coming or not.

Since makeup is only for 100% hydrogen, there is no makeup amount of what is that toluene
there. So simply we can write that M into 0. Here N is that amount of you know toluene sorry
amount of makeup is considered here and also other quantity, which is coming to the mixer is
you know the amount of gaseous cycle there that is R G. Still, in that R G what will be the

298
amount of toluene since there is no toluene is coming out from the separator, we can say that in
the gaseous cycle stream, there will be no toluene. So, that is why it will be 0 because R G into
then 0 and then other part is coming into the mixer is liquid recycle.

Now, in that case as a liquid recycle amount is R L, but it this recycle stream will not contain
other components except you know, toluene, there 100% toluene is coming to this stream. So,
they are we can say that simply that amount of toluene will be equal to R L into 1.0 because of
100% toluene there so, that why we can write here 1.0. So, we can do this material balance for
the toluene in this mixer like this.

Now, this is your total in, but what from the out, out of course will be that you know, outlet
amount will be G. So, that is why this equation can be written as a material balanced for the
toluene. Similarly, we can do the material balance for the hydrogen, what is the amount of
hydrogen is coming in into the mixer that is as a feed it will be 0 because there is no hydrogen is
coming into the mixer from this feed mixer.

And then what is the makeup amount there of course, there 100% hydrogen will be supplied as a
makeup they are so we can write simply in there and R G they are here, in this case, R G that is
gas recycle, what will be the fraction of that hydrogen will be containing into that R Z, that
simply you can calculate because you know that what the mole of hydrogen and mole of methane
in the mixer that is coming out from the separator here in this gaseous cycle stream.

Now that fraction will be is equal to simply that moles of hydrogen divided by total moles of
hydrogen and methane. So, accordingly, hydrogen mole fraction you can simply calculate based
on this you know the amount at as it is you know pound by solution from this material balance of
component in the system of reactor and separator. So, we can write here R G into 327 by 327 +
476. Why 327 + 476.

This is the total mole of hydrogen and methane, and since this 327 by total mole, this 327 is for
you know hydrogen. So we can write here hydrogen mole fraction. So, R G into hydrogen mole
fraction that will be your total amount of hydrogen that is coming into the mixer and then liquid

299
recycle their R L since there is no hydrogen they are in you know liquid to recycle. So, you can
simply write that to a fraction will be close to 0.

So R L into 0 simply that there will be no hydrogen gas in this liquid recycle. So finally, you can
write that hydrogen balances F 0 + M 1 to RG into what is that this faction + RL that will be is
equal to 400, why 400 here because the amount of hydrogen that is coming out from this you
know that mixer in the G stream as 400 because 1 mole of toluene will carry along with that 4
times of its amount. So that is why that is 400.

Similarly, methane balance, if we do for this mixture, what we can get that what is the feed
amount of you know that methane there. So methane since there is no methane amount in the
feed mixer, we can say that simply to be 0 then you can write here F into 0, and similarly in the
makeup stream, there will be no methane. So, we can write here M into 0, but in the R G that is a
gas recycle stream, we can say that there will be some you know fraction of methane in that you
know gaseous stream that is coming out from the separator.

So, in this case, we can write similar fashion that earlier we have told that the fraction can be
written as here, what will be the amount of methane out of total moles of that meet methane and
hydrogen. So, this is simply 476 divided by 327 + 476 as per that is the amount that we got from
that material balance by considering that system of reactor and separator and what will be the
amount of methane that is coming out from the separator as a liquid recycle there.

Because the liquid recycles, there will be no you know methane, we can write that R L into 0 that
means 0 amount of methane there in the liquid recycle. So, finally, this is your total in and what
will be the out similarly, that it will be 400 because, again as a part problem that you know 1
mole of toluene will produce you know that 4 times of its methane according to the reaction, so,
it would be simply you know 400.

So, we can write here to this you know material balance for this mixer system and after you
know, the substitution of these are R L, it is required of course, there it is required in this
equation and also that you know other moles of hydrogen and you know that methane amount

300
there and solving these equations there again we can get this F = 76 moles, R G = 677.97 and M
= 123.92 moles.

So, in this case, we can then have what to be the makeup amount, what will be feed amount and
also you know that what will be the particularly that total amount of G that we can get there.
Again we have to find out what should be the purge. Now, this purge basically that if we do the
material balance, so what this system here in the divider, this is actually this divider we can
write.

So, this divided if we say that, this total amount of you know purge will be basically that what is
the amount of you know, mixture of methane and hydrogen is coming from the separator into
this divider and then what would the amount of you know, gases recycle to the mixer here. So, if
you subtract out the total amount of gas mixer you know gas recycle from this gas mixer then
you can easily calculate what is the purge.

Basically, you can do the material balance here in this divided. So, it will be simply overall
material balance it will come as here P you know that + R G that will be basically that mixer of
that total amount of hydrogen and methane because here inlet will be is equal to outlet amount.
So, in that way, you can simply write that here P = n mole of hydrogen + n mole of methane -
this R G.

You know this R G already you have calculated based on that material balance and then finally,
you can have this you know, purge amount is you know 125.03 moles. So, this problem is, you
know that is a very good example of material balance, how to do the material balance with
chemical reactions with you know 1 purge reactions and also you know that with multiple units
also you can say that is there any bypass or not is there any you know that you can see that
recycle or not or is there any purge or not or is there any makeup or not.

So, based on all those you know, components you can practice this problem, and you can have
the idea of how to do the material balance here.
(Refer Slide Time: 28:39)

301
Next, we will consider the you know material balance based on combustion reaction, you know
before going to that you know material balance based on the combustion reactions you have to
know that what is that combustion basically. So, combustion basically is burning or oxidation of,
you know fuel to release energy and fuel typically contain carbon, hydrogen and sulpher even
sometimes methane, propane etc. 2 types of actual reactions are in combustion reactions.

One is you know complete combustion or there will be no carbon monoxide and also you can see
that all carbon will be converted to carbon dioxide, all hydrogen will be converted to you know
water and sulpher will be converted to sulpher dioxide. So, as per complete combustion will not
have any carbon monoxide in the outlet streams as a product and also we can say that there will
be no you know there will be a complete you know combustion of carbon to the carbon dioxide
complete combustion of hydrogen to the water and complete conversion of sulpher to the sulpher
dioxide.

Whereas another reaction it is called that incomplete combustion reactions where you will see
that the all-carbon will go to the carbon dioxide as well as carbon monoxide, that is incomplete
reactions okay. So, whenever you get that carbon monoxide, that means, you can assume that
there will be an incomplete reaction. So, complete combustion of propane here, an example is
given that this you know propane after oxidation it will give you that you know carbon dioxide
and water.

302
Similarly, incomplete combustion of propane it will give you that carbon dioxide and water but
again this you know that propane will be you know reacting with oxygen and it will give you that
carbon monoxide and water. So, basically it is an incomplete reaction. Now, for this oxidation
reaction for the combustion, you will see that the source of oxygen will be usually air which will
contain 21 mole percent of oxygen and 79 mole percent of nitrogen.

And product gas that will be you know coming out after reaction it will be called as stack gas or
you can see that flue gas and you can you know, consider that, you know mixer as dry basis for
air the composition excludes water whereas, you know that wet basis it will be there where this
composition of this flue gas or stack gas will become contains, you know water there. So, a gas
with 40% A 40% B and 20% water will be called as wet basis, you know combustion.

Flue gas combusts flue gas and also, you know if is there only 50% A and 50% B there is no
moisture is there you can see that there will be a dry stack gas or dry flue gas. So, this is the basic
concept of that complete combustion and incomplete combustion and these are the reactions you
will see that. So, based on which we will do some, you know calculation as per material balance
equation.

Now, for this, you know that oxygen will be supplied and by that oxygen, you know combustion
will be there. Now, what will be the amount of you know that theoretical oxygen will be required
for complete combustion and accordingly what should be that actually air to be supplied and if
suppose, a certain amount of you know oxygen in excess to be required for the complete
combustion in the feed stream that also you have to calculate.

So, for that, you have to define that you know how to you know estimate or calculate that you
know excess air or do you know that excess oxygen the air on.
(Refer Slide Time: 33:09)

303
So, in that case, excess oxygen will be defined as the amount of oxygen in excess of that required
for complete combustion and theoretical air which is required that is quantity for air that contains
theoretical oxygen there and theoretical oxygen will be moles of oxygen that will be required by
stoichiometry for complete combustion of all fuel. So, these three definitions you have to
remember.

Accordingly, we can say that the excess air will be defined as 100 into excess air by required air.
This is percentage excess air so to be 100 into excess oxygen by 0.21. And by required air, that
means in terms of oxygen it will be oxygen by 0.21. Why that 0.1 because air contains 21 mole
percent of oxygen. This excess air also you can express in terms of you know that what you
know, entering an amount and also required amount of oxygen that you can express in that way.

So, it is defined as 100 into oxygen entering the process minus oxygen required divided by
oxygen required. Similarly, percent of excess air can be calculated based on that excess oxygen
also like 100 into excess oxygen divided by oxygen entering minus excess oxygen like these. So,
these you know definition you can use for you know further calculation for your material
balance.
(Refer Slide Time: 34:42)

304
Let us have an example for coal combustion process and for this coal combustion process, how
to you know do the material balance based on this you know combustion reaction. In this case let
us say that a certain amount of coal that contains 72% carbon, 11% you know, sulpher and
remaining that is 17% hydrogen in mole that will be burnt in a furnace by excess air. Assume all
amount of coal is burned as a part you know following reactions.

The compositions of the outlet streams are you know that are shown in the figure here. And also
in that case, you have to consider that 100 moles per minute of the dry gas flow in stream 3 as
shown in you know figure are in the slide. In this case, we can see that coal contains carbon,
sulfur and hydrogen and if you burn this coal, there will be a combustion reaction.

Now, the combustion reaction can be represented by this equation here that is carbon will be
oxidized to give you a carbon dioxide, sulpher will be oxidized and it will be giving you sulpher
dioxide and hydrogen will convert it to the potential. So, in this way of the internal combustion
reaction, if you consider that 100 mole per minute of dry gas that is flowing in the stream you
know 3 as a dry gas.

They are based on which you have to calculate, what should be the percentage excess air is
required and also what should be the ratio of water vapor and dry gas they are in this particular
process.

305
(Refer Slide Time: 36:48)

So, the solution we can say that first of all you have to find out what should be the molar flow
rate of nitrogen in the dry gas, nitrogen in the dry gas that will be you know that you know that
78% that is in mole percent of nitrogen is in you know that air stream. So, it will be you know
nitrogen amount will be you know 78 mole of nitrogen per minute, but here, if we do not
consider that the airstream.

In this case, very simple that in the dry gas, you will see that they are it is given that only 78%
you know of nitrogen they are in the stack gas. So, here total amount of nitrogen will be here
since the you know flow rate of you know gas in the stream are 3 is 100 mole per minute. So,
there will be nitrogen will be is equal to 78 mole of nitrogen per minute it will be flowing air.
Now, this nitrogen gas is coming from actually air which is supplied in the you know that that
finish.

So, each amount is the same as that in the inlet air. So, accordingly, the inlet air molar flow rate
will be is equal to what, since it is the nitrogen amount and since nitrogen contains in the you
know nitrogen in the air is 70 you know that 9%. So, we can see that air it will be you know that
78 mole of nitrogen per minute divided by 7.79. So, it will be simply as 98.7 mole per minute.
(Refer Slide Time: 38:36)

306
And then, if you do the carbon atomic balance for this, you know system that carbon atoms in the
feed that will be equal to carbon atoms in the product. So, this is you yield equal to out for that
carbon atoms. Now, these carbon atoms in the feet, what is that amount it is you know that of
course, will be equals to what is that 100 moles into 0.09 + 0.03, why because in the outlets
steams that carbon is coming as carbon dioxide and carbon monoxide.

This carbon dioxide and carbon monoxide is basically coming from the source of that coal in you
know that feeds stream. So, what will be that you know carbon dioxide in there by you know
stream and what will be the carbon atoms there that will be basically 100 into 0.09 and similarly,
other the carbon is coming from that you know that coal steam as a carbon monoxide here in that
dry gas.

And its production since it is 0.03 out of that you know, 100 moles of, you know, rate. So, we
can simply say that total amount of carbon will be is equal to 0 that 100 into 0.09 + 0.03. So, it
will be amount of 12 moles of carbon per minute. Now, this carbon, of course, it will from that
you know feed stream. So, what will be that then feed stream you know flow rate that you have
to you know calculate.

See that this feed stream flow rate is n 1. So, we can simply write that this you know carbon
balance for that. So, we can write n 1 into 0.72 that will be actually equals to that you know h

307
carbon in you know dry gas. So, it will be simply 12.0 mole, which implies that n 1 will be equal
to what this here, like this. So, this is per minutes we can write here per minute. So, here it will
be per minute.

So, here we can have here as per material balance that what will be the, you know, feed stream
flow rate in the stream 1 that will be equal to n 1 and it will be equal to 16.7 mole.
(Refer Slide Time: 41:16)

And after that, if you do the atomic sulfur balance, then you can say that, you know the moles of
atomic sulpher in the feed will be equal to 1.8 mole per minute and moles of atomic hydrogen in
the feed will be is equal to 2.8 mole per minute and accordingly the number of moles of oxygen
that will be required for complete combustion of carbon sulpher and hydrogen that basically as
for this equation.

Because here 12 mole of carbon you know that will require how you know many moles of
oxygen simply here to be to 12 mole of oxygen because 1 mole carbon requires you know, 1
mole of oxygen. So, that is why basically 12 mole of carbon will actually require 12 mole of
oxygen. Similarly, since here 1.8 mole of sulfur is in the feed stream we can say that, for this 1.8
mole of sulpher will require similarly, here 1.8 mole of oxygen.

308
Because 1 mole of sulfur will require 1 mole of oxygen, similarly 2.8 mole of hydrogen in the
feed stream. So, this 2.8 mole of hydrogen will require 0.7 mole of oxygen here in this case as
for reactions you will see that you have 2 mole of hydrogen will require 0.5 mole of you know
oxygen as per reaction. So, accordingly, we can see that 2.8 mole of hydrogen will require you
know that 0.7 mole of oxygen.

So, total theoretical oxygen will be required for the complete combustion will be close to this to
2 L + 1.8 1.8 + 0.7. So, it will be total 14.5 mole per minute, this is your theoretical oxygen, but
total inlet oxygen in the feed air, what will be that, you know that total inlet oxygen in the feed
air that will be equal to you know that calculated based on that what would be the nitrogen
amount there in the feed stream and accordingly it will come.

Because in the air you will see that 79% mole of nitrogen will be having along with that what is
that 21% of oxygen and so if there is 78 mole of nitrogen there in the air stream, so, we can say
that how many moles of oxygen will be in the feed stream. So, it will be simply by 20.73 mole of
oxygen in feed by minute. So, this is where you can calculate it for to be the total you know that
inlet of oxygen in the feed air.

So, once you know these that you know supplied oxygen in the feed air is 20.73, whereas
theoretical oxygen required for the complete combustion in the burner or you can find this that
will be equal to 14.5 mole per minute.
(Refer Slide Time: 44:33)

309
And based on that, you know that you can calculate what should be the percent oxygen there and
then what should the percent excess air also there. Now, if you know to calculate that percent air,
then you have to you know consider that what the amount of excess air is required there. Now,
total inlet air is you know that since you know that only nitrogen amount 0.79 mole of nitrogen is
having in 1 mole of air.

So, 78 mole of nitrogen will be having in how many moles of air, it will be simply air as per
calculation 98.7 mole per minute. So, excess air that is equal to excess oxygen okay. So,
according to that total theoretical air will be equal to that is 14.5 is the theoretical oxygen
required. So, you have to convert it to what to be the amount of theoretical air to be required just
by simply dividing this 14.5 by this you know 0.21 of oxygen fraction.

So, it will be simply 69 mole per minute. So, percent excess air will be equal to air excess air
definition that is what to be the supplied amount and what is the theoretical amount of air
supplied is 98.7 and theoretical is 69. So, divided by theoretical air required. So accordingly, it
will be coming as 43% of excess air required for this complete combustion. Now, if you assume
that all water in the product gas is from the combustion process.

Now from you know that 2.8 mole of hydrogen that is reacted 1.4 mole of you know hydrogen
will be produced based on that reaction, then ratio of water vapor to the dry gas will be simply

310
1.4 divided by 100 mole of dry gas. So, it will be simply 0.01 per mole of hydrogen per mole of
dry gas. So, in this way, we can you know that do the material balance for the combustion
reaction.
(Refer Slide Time: 46:45)

Another example we can say that if fuel oil containing 87% wt% carbon, 10% hydrogen and 3%
sulfur that is fed in a furnace and burned with you know 25% access air. Now analyzes of the
furnace exhaust gas results only nitrogen, oxygen, carbon dioxide, sulfur dioxide and water. The
sulfur dioxide emission is actually controlled by some absorption process in and you know
absorber.

So, in that case, the gases like nitrogen, oxygen, carbon dioxide and some of that water and
sulfur dioxide that is entering to the unit that will leave the absorber and pass out to you know
stack and as the absorber is of limited capacity, you see that a fraction of that furnace exhaust gas
would be bypassed directly to the stack there and you will see that the observer removes 90% of
the sulfur dioxide in the gas feed to it.

And combined stack gas contains you know 612.5 ppm it is called parts per million that sulfur
dioxide on a dry basis. Now this means that every million moles of dry stack gas contain you
know 60 sorry 600 12.5 you know most of sulfur dioxide. In this case you have to calculate what
should be the fraction of the exhaust bypassing the observer at this condition.

311
Now, see here the you know flows out of the problem is given here, this is one furnace and in the
furnace you know 100 gram of oil is coming with it is composition here like carbon, hydrogen,
sulpher and oxygen and n mole of oxygen is supplied here in the furnace whereas 3.76 into n 1
mole of nitrogen as 25% excess will be supplied to the furnace for the combustion and after
combustion, you will see that there will be you know it just gases from the furnace will be
containing you know N2 amount of nitrogen.

And N3 amount of oxygen in N4 amount of carbon dioxide, N5 amount of you know that sulfur
dioxide and N6 amount of water. Now, from this you know mixer some amount of this you know
mixer will be you know bypassed here like this as shown here this is bypass they are this is a
bypass that observer unit and some fractions will be you know allowed to pass to the observer to
absorb some you know that gases.

And then outlet gas from that absorber again will be mixing with that you know bypass amount
and it will go to the stack and you know some amount of that you know the gaseous product as a
sulfur dioxide it will be you know taking out from that absorber. You know after the absorption
as you know this amount as shown here in the figure in the flow chart. Now, accordingly, you
have to calculate what should be the fraction of that just bypassing that observer at this
condition.
(Refer Slide Time: 50:17)

312
Let us solve this problem here. So, this is your you know you know flow chart gives in details.
Now, if you are considered that carbon dioxide past to do that material balance, now, you will
see that this carbon dioxide that is in the feed stream it is 87%. So, if it is 100 moles of total feed
then it will be you know that carbon will be you know 0.87 into 100 this gram of carbon.

And since the molecular weight of carbon is 12.01. So, amount of you know carbon in terms of
mole, it will be this divided by 12 and again 1 mole of carbon you know converting to carbon
dioxide that will be 1 mole. So, basically, you can say that this input, whatever it is coming out
from that furnace as a carbon dioxide, this amount will be exactly the same of this you know
87% of carbon in the feed stream.

So, accordingly, you can say that this N 4 = 7.244 after calculation and for this 7.244 mole of
carbon dioxide will require how many moles of oxygen for its you know combustion or this you
know complete reaction. So, it will require 7.244 mole of oxygen. Similarly, for water if you
consider that what will be the amount of water that is you know supplied in that, you know
furnace as a feed stream that will be you know 10% of that as hydrogen.

And that hydrogen, if you convert it gram to mole and then 2 moles of hydrogen will give you
that you know 1 mole of water that means air this amount of water is actually being supplied
there, but N 6 you will get this moisture will come from that furnace as N 6 mole, so, N 6 is

313
equal to like this. Now, for these N 6 of course, you know that how much oxygen will be
consumed there, it will be you know that you know according to that reaction, it will come out
2.475 mole of oxygen.
(Refer Slide Time: 52:19)

Similarly, you can do the same way for sulpher dioxide and in that case, this N 5 as the sulfur
dioxide it to be 0.0 96 mole of sulfur dioxide, which will require 0.0956 mole of oxygen in for its
consumption for the reaction. Now, since there is 25% excesses there of that oxygen, we can say
that this n 1 will be is equal to ask for this, you know, here in this n 1 what is that n 1 here. This
n 1 is here basically that mole of oxygen in that is supplied to the furnace. So, that n 1 can be
calculated this is you know required oxygen and since it is the sorry 25% of excess.
(Refer Slide Time: 53:33)

314
So, it will be you know simply you have to multiply by 1 point you know 25 with this you know
that what is the oxygen consume for that complete combustion. So, it will be coming as 12.27
mole of oxygen. Similarly, if you do you know oxygen balance for n 3 then you can say that
these n 3 will be equal to what basically this n 3 will be is equal to here what will be the mole of
oxygen is coming out, you know from the furnace that will be coming out from the feed stream.

After the reaction consumption and then and then we can write that this amount will be is equal
to your 12.27 that is actually the excess amount of feed of oxygen, whereas the required amount
is 7.244 + 2.475 and 0.0936 as per that oxygen consumption based on that, you know that
reaction. So, accordingly, you can see that this oxygen balance that is n 3, which is coming out as
you know unreacted oxygen this will be equal to 2.46 mole of oxygen.

Similarly you can do that nitrogen balance here and also sulfur dioxide instead sulfur dioxide
balance around that mixing point, in the mixing point if you considered that here in this case at
this location we push stack so, we can have this you know that you know sulfur dioxide in the
stack like this. Similarly, total dry gas in stack assumes there will be no carbon dioxide oxygen
or nitrogen in the absorbed in the scrubber or scrubber you say absorber we can see write here
observer.

315
So, we can see that you know this total dry gas a balance if you do that, in this way, you can
simply calculate what should be the, you know amount of you know a fraction of x, they are for
the sulfur dioxide they are you can easily calculate them. And since 612.5 ppm of sulfur dioxide
drivers in this tear gas. So, we can see that this fraction of bypass will be equal to you know that
0.295 as far that dry basis.

So, this is you know that one example by which you can see that how to do the material balance
for the combustion reaction and also you can you know do the material balance for this
combustion reaction with excess oxygen with the excess you know air and how to calculate that
theoretical oxygen, theoretical air and based on this how to calculate that excess oxygen is
required for that you know combustion reaction or also what will be the you know, excess
amount of air to be required for that complete processes.

So, I think this will be helpful to understand the, you know, how of the material balance for this
combustion processes and also I think you will get the idea to you know do the material balance
further with some other problem. So, I would suggest to follow this textbook given in this slides
for further understanding of the material balance with this combustion process.

316
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 4: Basic Principles of Compressible System

Lecture – 4.1
State Equation of Ideal Gas and Calculation

Welcome to massive open online course on Basic Principles and Calculations in Chemical
Engineering. Here we have discussed many things about that material balances based on
nonreactive systems, even with reactive systems in the previous module. So, in this module,
we will try to discuss more about that the calculations here, but the calculations will be based
on compressible system.
(Refer Slide Time: 00:53)

So, in this lecture, we will try to describe something about the state of equation of ideal gas
and the calculation based on this ideal gas. So, present lecture will include the basic equation
of the state for ideal gas and solving problems with that equation.
(Refer Slide Time: 01:17)

317
Now, as we know that the general material balance equation that earlier these things you have
to remember whenever you are going to calculate any unknown variables by this principle of
general material balance equation there. So that equation is

 ACCUMULATION  INPUT   OUTPUT   GENERATION  CONSUMPTION

So, this will be your basic equation, which will be useful for doing the material balance for a
particular process system.
(Refer Slide Time: 01:45)

Now, if we talk about that in the process system, there are various types of that gas may be
involved to process that process system for a particular operation. So, in that case, you have
to know some extent of that behavior of that gas and how that gas will be changing its

318
characteristics based on that process variables like pressure and temperature. What will be the
basic equations if there is a change of pressure and what should be the volume how it will be
changing with respect to temperature and pressure there, so we will be considering here.

So, in that case if I talk about that ideal gas, though there is no gas in the world that will be
ideal in nature, but still we are considering that there will be hypothetical ideal gas and there
will be certain equation to represent that ideal cash behavior. Now, those gases will and also
follow these certain equation here, as given in the slide

that PV is equal to nRT will be called as ideal gas. So, here in this case P is the absolute
pressure of the gas and V the total volume occupied by the gas and also n here, n is the
number of moles of that gas.

R is the ideal gas constant in an appropriate unit, and also this T is called that absolute
temperature of the gas. So, whenever any gas will be flowing through the process unit you
have to know what should be the pressure that is exerted by the gas or what should be the
volume occupied by the gas and at that volume what should be the system pressure and also
how the temperature will be used to change that volume accordingly. That is why you have to
calculate that pressure or volume based on that temperature change for that particular gases
based on this equation.

So, this equation is called ideal gas equation and based on this ideal gas equation, and you
have to calculate many things for its you know that how the density will be changing based
on that temperature and pressure, even also volume, and also how that specific gravity will be
changing and these parameters or you can say that variables or you can say that the
characteristics of that flow of the gases to be required to calculate before are going to do that
material balance in a particular system.

So, in this case, here you will see that one important constant that is called ideal gas constant
that is required to know here because whenever you are actually going to perform any
process for particular process synthesis, there you will see that you need to calculate that
volume or pressure or you can say temperature at a particular condition, so in that case, by
this equation of ideal gas, you have to calculate those unknown variables.

319
So, in that case here, this ideal gas constant is to be required to know because all the process
unit sometimes will be mixed unit so in that case you have to convert that ideal gas constant
into one unit system to the another unit system there. So, here in this table one conversion
factor for that ideal gas constant is given there. So, if you are considering that calorie gram
mole K there, this R value will be is equal to 1.987, whereas in British system, this will be
also this 1.987, in Btu this maybe it is thermal unit per unit pound mole and degree Rankine.

Similarly, for psi system, they are also it will be in terms of psi means pound-force per inch
square pressure. So, in that case, it will be 10.73. Similarly, for other units in SI system, this
value is generally permitted as 8.314, whereas for SI system but the unit is in centimeter
instead of meter and pressure is atmosphere and also there will be gram mol instead of
kilomole and temperature is Kelvin, then it will be 82.06.

Also, if you are representing that volume in terms of liter and temperature in Kelvin, but mole
in terms of gram mole, but the pressure is in atmosphere instead of Newton per meter square,
then you have to use that gas constant at 0.08206. Similarly, for other unit systems, it is given
like 21.9 if you are using that gas in pressure unit as inch mercury and volume is feet cube
and also mole as pound mole and the temperature is in degree Rankine. So, in this way, you
have to use an ideal gas constant as per consistency of the unit, whatever it will be used for
your particular problem.
(Refer Slide Time: 07:23)

320
After that, you have to consider that ideal gas law with other convenient ways like this here,
the ideal gas law is sometimes written as per molar volume. In that case, you will see that PV
will be equal to nRT, that is you know that equation, but if I divide this V by n, that will be is
equal to volume per unit mole. So, it will be called as a specific volume. So, if we represent
that a specific volume as symbol here small v or you can see sometimes nu, then we can
represent that v, nu is equal to RT, that is a small v, Pv is equal to RT.

So, this v will be is equal to a specific volume, it will be is equal to V by n here. So in the
other way also you can represent this v that will be sometimes it is represented by Vm
sometimes or sometimes it is represented by V you know that hat like this. So, either way,
any symbol that whatever conveniently you are using that you have to follow consistently.
So, here this Vm or V that will be is equal to the specific volume here. So, in terms of the
specific volume, that ideal gas equation will be is equal to Pv RT.

This gas equation to be used for your calculation of the different variables where that
unknown variable will be there in specific problem. Now, at different systems, you will see
that there will be some standard conditions for that ideal gas. In SI system, that standard
condition of the temperature is 273.15 Kelvin, whereas the pressure will be 101.325
kilopascal and this is specific volume that will be is equal to 22.415 meter cube per kilomole.

Universal scientific unit system their standard temperature is considered as 0-degree Celsius,
whereas pressure is 760 millimeter mercury, whereas molar volume will be 22.415 liter per
mole. In the case of natural gas, you will see that that the standard conditions generally
represented by 60 degree Fahrenheit or 15 degrees Celsius, whereas the pressure will be 14.7
psia or you can say that 101.325 kilopascal.

If you are considering that American engineering system, you have to consider that a
standard condition of temperature will be 32 degree Fahrenheit and the pressure will be 1
atmosphere, whereas this specific volume will be is equal to 359.05 feet cube per pound
mole. So, in this way, you have to consider that standard temperature and pressure for a
particular process like okay.
(Refer Slide Time: 10:48)

321
Let us have some example to calculate that unknown quantity based on this ideal gas
equation. It is supposed given to find out the volume that will be occupied by suppose 100 kg
of an ideal gas whose molecular weight is 16 at standard conditions and the standard
temperature and pressure corresponds to a temperature of 273.15 K that is 0 degrees Celsius
and absolute pressure of 100 kPa that will be 1 bar. So, at this standard temperature and
pressure, 1 mole of ideal gas occupies 22.4 liters.

So, at this condition, you have to calculate what should be the volume that will be occupied
by 100 kg of an ideal gas. So, if I considered that here that 100 kg you have to convert it that
what should be that 100 kg of that gas will occupy what will be the volume of that container
at which is it is kept at that particular operating condition. Now, you know that per mole of
that ideal gas will have that is 22.42 meter cube of volume. So, in this case, this 100 kg of
that ideal gas that is A here, it will be converted to its mole.

Since its molecular weight is 16, so it will be 1 by 16, this is mole into 100, then it will be
converted into total mole of that A. Now per mole that volume will be 22.42 meter cube. So,
out of this 100 divided by here 16 will come these moles will occupy how much volume that
will be after calculation, it will be coming as simply that 140.13 meter cube in that particular
standard condition.
(Refer Slide Time: 13:15)

322
Here another example. Let us consider suppose a gas is available under the following
conditions. In this case a pressure of 0.95 bar and a temperature of 288 Kelvin. In this
condition, calculate the volume occupied by 100 kg of the gas. Assume that the molecular
weight of the gas is 44. So, how to calculate? Here in this case, you have to calculate what
should be the volume that will be occupied by 100 kg of the gas. Now, the pressure is given
to you 0.95 bar and temperature is given to you 288 K.

Now, as per that ideal gas equation, that is PV is equal to nRT, so based on which you can
say that at a particular operating condition of temperature, then you can write that PV is equal
to nRT. Similarly, if we consider that other condition of the gas, so it will be regarded as
suppose PsVs is equal to nRTs. So, s it stands for here standard condition. So, for the
standard condition, also, we can write this equation as per ideal gas law and for any
temperature and pressure, then you can write this equation also, this PV is equal to nRT.

Now, if we divide this ideal gas equation here by the ideal gas equation at its standard
condition, then you can write here simply here PV by PsVs that will be is equal to here in this
case nRT at a certain temperature and also by nRTs at a standard condition. So, finally, if we
have the same number of molecules and since the gas constant are same for all the gases here,
so here in this case we can say that all conditions here, so we can say that this R and n will be
canceled out from this portion. So, simply it will be T by Ts here.

So, after rearranging of this equation, we can then express that to V at a particular
temperature and pressure, it will be is equal to Vs into T by Ts into Ps by P. So, here at this

323
temperature and pressure upon that you know comparing on that standard temperature and
pressure, you can calculate what should be the volume at a particular temperature and
pressure. Now, substituting that value at standard condition and the given temperature and
pressure, then you can finally calculate what should be the volume there.

Now let us substitute that value here, what should be the volume at a standard condition, it is
simply that for 100 kg of the gas at a standard condition will occupy this here because 1 mole
will occupy the 22.415 meter cube, so 100 kg you have to convert it to mole first by dividing
its molecular weight here, let the molecular weight is 44. So, here it will be total mole of that
gas that is 100 divided by 44 and then since 1 kilomole you know that will occupy 22.415
meter cube.

So, if you multiply this 100 divided by 44 into 22.415, then you will get what will be the total
volume here. So, it will be your volume at a standard condition. Now, what is the temperature
at your condition given as per problem, it is 288 K as per of your problem, whereas the
standard temperature is your 273.15 Kelvin and also the Ps, Ps is you know that standard
condition pressure is 1 bar, that is 1 atmospheric pressure you can say and the pressure is
given at a particular condition is given as per your problem, it is 0.95 at which is the gas is
intact in a system under that pressure.

So, it will be 0.95 bar here. So, you have to divide this Ps by P here like this. Now, if you are
considering bar, so there you know that this should be 1 bar and this would be 0.9 bar,
otherwise if you are having mixed unit of that pressure, suppose instead of bar it is given here
some value of you know millimeter mercury, so you have to convert millimeter mercury to its
bar, since it is given here what is that bar or whatever it is. So, anyway two pressure’s units
should be you know the same.

So, if it is given mercury, you know that millimeter mercury, then you have to convert it to
bar and accordingly you know that standard pressure is 1 bar or otherwise you can convert it
to standard pressure is 760 millimeter mercury, whereas here it is given certain value of
mercury. So, simply here, it is not required to convert that pressure into other units. So, there
since both are the same, both units will be considered as the same unit, then simply you have
to divide it here based on the same unit; otherwise, you have to convert the unit there.

324
So, finally, after substitution of volume at a standard condition, temperature at standard
condition, pressure at standard condition, and given temperature and pressure here from this
equation, you can finally get that what would be the volume occupied by that gas. So, to be
simply you know that 56.57 meter cube. So, we can say that, that gas at that pressure of 0.95
bar and at a temperature of 288 K, the volume of the gas will be occupied as 56.57 meter
cube.
(Refer Slide Time: 19:36)

Let us do another example like this, you know that here in this problem it is given that to find
out the density of 1 meter cube gas in SI units if the gas is available at a temperature of 300 K
and a pressure of 1 bar. Now the molecular weight of that gas is you know 28. So, here you
have to find out what should be the density of that gas. Now, you know that specific molar
volume how it can be defined based on that standard temperature and condition and from
your gas equation at a certain temperature and pressure.

So, here you can simply write this equation from those equations, one is there like PV that
will be is equal to RT at a given temperature and pressure and here Ps into Vs that will be is
equal to RTs that is a standard condition. If you divide these two equations, you can simply
represent it as v by vs that will be is equal to simply T by Ts into Ps by P here. So, this is
your equation in terms of molar volume, so from which you can calculate what should be the
v that will be equal to vs into T by Ts into Ps by P.

So, if again, these are at a standard condition, what would be the molar volume if you know
and if you substitute here, then you can easily calculate what should be the specific molar

325
volume at this particular temperature and pressure. So, if you substitute here vs will be equal
to simply, we can say that here 22.4 meter cube by 1 one kilomole. This is your actually at a
standard condition the specific mala volume and here T by Ts, T is given temperature it is
given as per your problem, it is 300 Kelvin.

It may be other temperature also according to your problem and standard condition
temperature is 273.15 Kelvin and then here since pressure is kept at that 1 atmospheric
pressure or 1 bar, so here that at a given pressure is 100 kPa and also you can say that the
standard condition of the pressure will be same 100 kPa. So, it will be canceled out. Finally,
after calculation, you can get this specific molar volume at a particular temperature and the
pressure of 1 bar is equal to 24.6 meter cube per kilomole.

Here simply we are getting that without changing the pressure only just by changing the
temperature 273.15 to 300 K, see how that specific molar volume is changing, it is simply
24.6 meter cube, whereas at a standard condition that volume is coming 24.4 meter cube. So,
simply very small amount of volume is changing because of the small amount of temperature
is changing there. Now, based on these specific molar volumes at that particular temperature
of 300 K, you can calculate the density from this specific molar volume, how to do that?

Simply you have to just inverse of this specific molar volume will give you that your density.
So, this density can be calculated from the inverse of specific molar volume. So, specific
molar volume that here given, v here that is kilomole that is 24.6 meter cube per kilomole.
Then density can be calculated 1 by that v, so it will be coming as 1 by 24.6 meter cube per
kilomole and it will be coming as in terms of kilomole per meter cube. Now, if you convert
that kilomole into its mass by multiplying its molecular weight, then you can simply get that
what should be the density of that gas in terms of kg per meter cube.

So, if here simply molecular weight is 28, if you multiply it by its molecular weight, from
which you know inverse of specific molar volume, then you can get that volume that is 1.14
for here at this condition that is kg par meter cube. So, in this way we can solve the problem
what should the density, what should be the specific volume of the gas at a certain
temperature and pressure based on specific volume or a volume or pressure at its standard
condition.
(Refer Slide Time: 25:22)

326
Let us do another example. Here what is the specific gravity of 1 meter cube of nitrogen at
300 K and at 1 bar, that is compared with 1 meter cube of air at 300 K and 1 bar. Here very
interesting that you have to compare that to what should be the specific gravity here density
of that nitrogen and also what should be the density of the air there at a particular temperature
and pressure. Now, these components are different, nitrogen and air here.

So, if you consider that again that ideal gas equation, where we can write that v by vs that
will be is equal to T by Ts into Ps by P based on that division of these 2 equations at a certain
temperature and pressure and to the equation that is based on the standard temperature and
pressure. Now, based on these equations, you can say that the molar volume related to the
standard condition is calculated as like this v will be is equal to vs into T by Ts into Ps by P.

If you substitute that value that Ps will be is equal to what is that 22.4 per kilomole and
temperature is given here 300 K and also the standard temperature is 273.15 and then
pressure is here the same pressure, it is considered the pressure that is atmospheric pressure.
So, the ratio of this standard a pressure to its that you know again at a pressure of that equal
to that atmospheric pressure, then it will be nullify here, to be canceled out here like this. So,
we can say that finally, we can get this specific molar volume of 24.6 meter cube at that
particular 300 K.

What should be the density of that nitrogen at the particular 300 K. So, simply as per earlier
what we have you know calculated that the density of the nitrogen, it will be simply inverse
of that you know specific volume into its molecular weight, then you can calculate here by

327
this equation of this molecular weight by specific molar volume, and then finally you can
have this value equals to 1.14 kg per meter cube. So, this is your density of nitrogen.
(Refer Slide Time: 28:03)

Now, in the same way, you have to calculate what should be the density of air at that
particular 300 Kelvin temperature and the pressure of 1 bar. Similarly, if you substitute that
value, here the molecular weight of air is considered as 29. So, it will be 29 divided by what
is that 24.6. So, it will come 1.18 kg per meter cube. So, specific gravity of nitrogen is equal
to its density divided by the density of air okay. So, we can say that the specific gravity of the
nitrogen it will be simply 1.14 divided by 1.18.

So, it will be coming as 0.97. So, what should be the specific gravity of this nitrogen, we can
simply calculate based on this, but the definition of the specific gravity is the density of any
gas at any temperature and pressure condition divided by the reference gas density. Here
reference gas density is considered air density. So, here that is why we actually calculated the
density of air at that particular temperature and pressure. So, finally, we are getting that
density of air is like this, whereas the density of nitrogen we have calculated earlier based on
that temperature and pressure and from the ideal gas equation.

So, from that if we divide it, we can get this to 0.97 there. So, we have discussed that how to
calculate the specific gravity of a gas just by calculating its density at a certain temperature
and pressure and also what should be the density of that reference gas here like air at the
particular temperature and pressure. So, dividing these densities of gas to its reference gas,
then we can easily get that specific gravity, here as given in this example.

328
(Refer Slide Time: 30:20)

Now, another aspect of that ideal gas is that what should be the partial pressure of the
particular gas mixer by its component gas will be exerted that also to be required for further
calculation of the gas mixture in a particular processor unit. So, in that case, the partial
pressure, that means individual component pressure in a particular mixture of gases, so, that
can be actually exerted by that single component in a gaseous us mixer if it existed by itself
in the same volume as occupied by the mixture and at the same temperature of the mixture.

So, according to that, you can say that if there are suppose n number of components in a
gaseous mixture. So each component will actually exert the pressure individually on that
particular system of the same volume and the same temperature. So, in that case, what should
be that individual component pressure, it will be called as partial pressure. Now, according to
Dalton’s law, this the summation of partial pressure will be equal to the total pressure of the
system and also for individual components for that particular pressure of that component that
is called partial pressure of the component.

If you know the volume of that system, then you can also represent that ideal gas equation
based on that partial pressure. So it can be actually retained as like this here if you know that
partial pressure of component i and volume of the system, total volume of the system is Vt,
then you can write here nRT, here n will be equal to mole of individual component and t will
be here total temperature of the system. So, here we can write the same ideal gas equation for
the partial pressure, but here, in this case, Pi is basically that partial pressure of component i.

329
Now, again if we write that ideal gas equation for the whole system, then we can simply
consider here that it will be P total into V total that will be equal to n total into T total into R,
so in this way so if we divide this equation by this equation, that means here you see this
equation here, then you can get your Pi will be is equal to Pt into ni by nt. From this simply,
this divided by this, it will be simply Pi by Pt and then to here ni by nt and also R R will be
canceled out.

So, it will be T total and T total will be canceled out, so simply it will be Pi will be equal to
Pt into ni by nt, and this ni by nt basically what, this is basically a mole fraction of the gas
okay. So, here it is your moles of component i divided by total moles of the gaseous mixture.
So, it will be regarded as mole fraction of the component i. So, Pi will be equal to here Pt into
Yi, what is that, that means here partial pressure of component will be is equal to mole
fraction into its total system pressure, here Yi is the mole fraction of the component i.

So, in this way, you can calculate what will be the partial pressure of each component in a
gaseous mixture at that particular volume of the mixture and its temperature. So, in an ideal
gas mixture, each component satisfies the ideal gas law that will provide the partial pressure
and also pure component volumes that will be used for your calculation. So, in this way, you
can calculate. Now, according to that Dalton’s law, if we calculate that individual component
pressure that is individual partial pressure and if you sum it up all those partial pressure, then
you will get the total pressure there.
(Refer Slide Time: 35:21)

330
Amagat’s law also important there, here in this case instead of, calculating that partial
pressure, Amagat told that that the partial volume of each component of the gas will give you
the total volume. So, as per Amagat’s law the summation of partial volumes will be equal to
the total volume. Here simply that instead of partial pressure, we are just using what should
be the volume occupied by an individual component of the gas.

So, in that case if we write that ideal gas equation based on that partial volume and also total
pressure and the system, then we can write P total into Vi that will be equal to ni into R into T
total. So based these, we can say that this for the total temperature and pressure, we can also
write here that P total into V total that will be is equal to n total into T total into R. So, if you
divide this equation by this equation, then that means here you can get these and here R R
will be canceled out and T and T will be canceled out, so also you can say that Pt and Pt will
be canceled out.

So, here simply Vi that will be equal to Vt into ni by nt, here Vt is total pressure, Vi is the
individual component volume, Vt is the total volume sorry and ni is the mole of individual
component and nt is the total moles of the total system. So, here we can say that again if we
consider this ni by nt that will be mole fraction of that component i and then simply partial
volume of that component i will be is equal to Vt into Yi. So, in this way, you can say that the
summation of all the components volume, the individual volume, then it will be contributing
to the total volume of the system. Now, let us do some examples for this.
(Refer Slide Time: 37:26)

331
It is given that the gas is intact in a room of volume 1000 meter cube tightly and the room
contains a dry air at 20 degree Celsius and a total pressure of 1 atmosphere. You have to find
out what is the partial volume of oxygen in the room, what is the partial volume of nitrogen
in the room, what is the partial pressure of oxygen in the room, and also what is the partial
pressure of nitrogen in the room? In this case, since gas is here simply dry air and dry air
contains that oxygen and nitrogen only.

So, based on that, some mole fraction or volume fraction or pressure percentage of that
oxygen or nitrogen component will be in the air. So, if we consider that air that is composed
of oxygen and nitrogen where this oxygen and nitrogen composition in the air will be mole
fraction of the oxygen will 21% whereas nitrogen will be 79%. So, according to that, if there
are the volume is 1000 meter cube at 20 degrees Celsius and 1 atmosphere, we can say that
oxygen volume that is Vo2 here it would be simply total volume into its mole fraction.

So, the total volume is 1000 and mole fraction is 0.21 for oxygen. So, it will be coming as
210 meter cube at 20 degrees Celsius and on 1 atmosphere. So, only oxygen will occupy this
210 meter cube volume at that particular condition, whereas similarly for nitrogen, the
volume of nitrogen will be in the system that would be total volume into its mole fraction. So,
it will be 1000 into mole fraction is 0.79. So, it will be coming as 790 meter cube at that
particular temperature and pressure.

So, we are getting here partial volume of that component oxygen and nitrogen. So, total
volume, see what will be that here 210 + 790, it will be 1000 meter cube. So, according to
this, you know that Amagat’s law, we can say that total volume will be contributed by this
individual volume of this component, that is here partial volume, summation of partial
volume will be equal to total volume at that particular operative condition. Similarly, you can
find out the partial pressure.

So, partial pressure also actually is defined as that you know total pressure into its mole
fraction that will be coming as 0.210 atmosphere when V is kept as 1000 meter cube as
constant at 20 degree Celsius. Similarly, you know partial pressure of nitrogen you can
calculate, that is total pressure into its mole fraction, then it will come here as per problem it
will be 0.790 atmosphere, again the volume will be considered as 1000 meter cube at 20
degrees Celsius.

332
So, in this case, we are getting this atmosphere for oxygen and this atmosphere for nitrogen.
Now, what will be the total pressure, simply that summation of this partial pressure that will
be 0.10 + 0.90. So, it will be your 1 atmosphere. So, here also, we can say that this Dalton's
law of gas can be satisfied by this equation, and based on this example, we can simply
calculate what should be the partial pressure, what should be the partial volume of each
component and how that partial volumes or partial pressures will be contributing the total
volume and total pressure respectively here.
(Refer Slide Time: 41:26)

Another example like an analysis of suppose 1 kg fuel gas that will results you 14.0% of
carbon dioxide and 6% of oxygen and 80% of nitrogen at a temperature of 204 degrees
Celsius and pressure at 1 atmosphere or 765 millimeter mercury. Now, in this case, calculate
the partial pressure of each component. Simply the partial pressure of each component will be
is equal to that means here Pi that will be is equal to Pt into its mole fraction, Pt is the total
pressure.

So, if I consider that carbon dioxide, mole fraction here, y is given, Y of CO2 is given as you
know that 0.14 and mole fraction of oxygen it is 0.06 and mole fraction of the nitrogen is
simply 0.8. So, partial pressure of that individual component like PCO2 that it will be is equal
to simply you know that 0.14 into total pressure is what is that 1 atmosphere, is 760
millimeter mercury. So, we can simply write that what should be the partial pressure of that
carbon dioxide.

333
Similarly, partial pressure of oxygen, it will be is equal to what is that mole fraction given,
total pressure is given 765 millimeter mercury into here what is that mole fraction is what
0.06. So, it will be coming as 45.9 millimeter mercury. Similarly, pressure of nitrogen that
will be is equal to 765 into you know mole fraction is 0.8, then it will be coming as 612. So,
if you add it all these partial pressure of all those components, and then you will see the total
pressure will be equal to 765, but here then it is you know that will not be 760.

Here pressure is I think is 765 here, there is a mistake, that you please correct it that 765
millimeter mercury, here it will be not that you know 1 atmospheric pressure, the pressure is
765 millimeter mercury. So accordingly here, we can say that here it will be 765, here 765,
here 765. So, we can say that simply that here, any way you have to calculate that partial
pressure based on this, you know total pressure into mole fraction.
(Refer Slide Time: 44:26)

Now, let us do another example here like this methane gas containing 4% of the oxygen that
flows through a pipe. It is required to calculate that the volumetric flow rate of the gas that is
flowing through the pipe. The condition are for the purpose of the 10 meter cube per minute
of air at 27 degrees Celsius and 760 millimeter mercury are introduced into the pipe and
several meters further down the pipe, a sample is drawn from here at a certain length of this
pipe at the downstream and it is found to contain that 11% of oxygen and nitrogen mixer.

How many meter cube of that initial gas were flowing per minute at 27 degrees Celsius and
740 millimeter mercury through the pipe. So, this is your problem. That means here methane
gas containing 4% of oxygen that will be flowing to the pipe, and in this case, you know that

334
the samples is taken out from this pipe at a certain distance downstream where the oxygen
and nitrogen mixture will contain 11% there. Now, in this case, how many meter cube of
initial gas was flowing per minute at 27 degrees Celsius there.
(Refer Slide Time: 45:49)

Now, in this case, very interesting that let us assume that x meter cube per minute of methane
oxygen mixture that flows through the pipe at 27 degrees Celsius and 760 millimeter
mercury. Now to this 10 meter cube per minute of air is added at the same conditions. Now,
the total volume of the gas mixture that in this downstream will be is equal to 10 + x metre
cube. Then oxygen in methane oxygen mixture will be is equal to 0.04 into x meter cube and
oxygen in air to be is equal to 2.10 meter cube and nitrogen in air it will be you know that
7.90 meter cube accordingly.

So, here oxygen and nitrogen mixture is at the outlet that per the sample, it is coming 11% in
the downstream gas mixture. So, oxygen + nitrogen in the downstream will be is equal to
what is that 0.04x, that means here this is plus here this 2.10 and then plus what is that
nitrogen here this is 7.90. So, in this case, the total amount of oxygen and nitrogen mixture is
coming 10 + 0.04x there.
(Refer Slide Time: 47:10)

335
After that, what will be the mole fraction of that? Here you know the total amount of oxygen
and nitrogen mixture out of total volume is 10 + x there. So, we can say that here it will be
close to you know that element by hundred as per you know given problem here because it is
told that in the sample only containing 11% of nitrogen and oxygen there. So, finally, after
solving, you can get this x value is 127.14 meter cube per minute. So, let that volume of that
initial gas mixture at 27 degrees Celsius and 740 millimeter mercury.

We can say that accordingly of that ideal gas equation if you substitute that value of V and
also pressure at its temperature and also if you substitute that here for that particular
temperature at that condition and pressure is there you know 760. So, after substituting or
equating that ideal gas equation at these two conditions, we can get that volume will be equal
to 130.58 at a rate of meter cube per minute.

Now, this gas flowing through that pipe at 27 degrees Celsius and 740 millimeter mercury,
we can then have this 130.58 meter cube per minute. So, this is your actually flow rate at the
inlet of the pipe of the methane gas here.
(Refer Slide Time: 48:53)

336
So, in this way, we can calculate lot of things based on that ideal gas equation and there are
several others also, you know important equations are there for non-ideal gas. There also we
will consider non-ideal gas equation how to calculate that volumetric flow rate, even pressure
and also mole fractions there in the different stream of the system, and we will discuss that
non-ideal behavior of that gases and properties of that non-ideal gas in the next lecture.

So, there also we will discuss what should be that state equation of that non-ideal gas and
how to calculate based on that state equation there we will discuss. So, thank you for your
attention.

337
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology – Guwahati

Module – 4: Basic Principles of Compressible System

Lecture – 4.2
State Equation of Non-Ideal Gas and Calculation

Welcome to massive open online course on Basic Principles and Calculations in Chemical
Engineering. In module 4, we were discussing something about state question of ideal gas
and based on that some calculations, some material balance we have covered. So, under this
module 4, basic principles of compressible system, in this lecture, we will try to describe
more about that you know state equation, but in this case especially for non-ideal gas state
equation and also based on their equations, we will try to do some problems on further
calculations.
(Refer Slide Time: 01:21)

Now, we will describe about that what are the different basic equations of state or non-ideal
gas and also how that properties of that non-ideal gas will be changing and how we can solve
the problems, we will describe here in this lecture.
(Refer Slide Time: 01:28)

338
Now, as you know that of course, real gas that will be regarded as non-ideal gas and that
many gases are assumed to behave actually ideally at room temperature and pressure that we
know. However, at high pressure, the gas properties that you might obtain using the ideal gas
law that would be at wide variance with experimental data. So, that means at high pressure
and temperature, we can say that we are not actually having that property of ideal gas here.
So, this gas will be behaving at particular conditions differently from that ideal gas.

Here in this case, suppose the behavior will be changing in wide variance as for experimental
data because here in this case, the molecule of this real gases or you can say that non-ideal
gases does not actually in that state or it will interact with each other and all real gases will be
in that case non-ideal. So, in this case in reality, the molecule of gas does interact with each
other and all real gases will be considered as non-ideal, even though the ideal gas equation of
state may be a very good approximation at low pressure and high temperature.

At higher pressure and lower temperatures, the impact of that intermolecular interactions on
gas behavior increases there. What does it mean? Here, we will see that we have actually
used one ideal gas equation to represent this ideal gas behavior, but in that same direction, if
we consider ideal gas equation of state for this calculation of behavior of real gas you will
see, there will be some approximated value you can get at low pressure and high pressure for
the real gases.

But at higher pressures, we will not get the same value that will be used, you know that
differences for these real gases at a higher pressure and also you can say that low pressures,

339
low temperatures. So, in that case, the impact of that intermolecular interaction on the gas
behavior that will be changed because of this higher pressure and lower temperature and
because of what we can say that this ideal gas equation cannot be approximately given the
same value at higher pressure or lower pressure

So, in that case, we need to calculate that pressure, volume and temperature properties on
gases, which are not actually ideal that also to be considered in the same fashion of that ideal
gas equation. So, before going to that, we have to understand that what is the difference of
that ideal and the non-ideal gases.
(Refer Slide Time: 04:54)

You will see that ideal gases that it will not satisfy the laws of that ideal gas at all conditions
of pressure and temperature, whereas that real gas will follow the gas laws at high
temperature and low pressure. There will be certain equations where you can use this that real
gas behavior by which you can interpret that real gas behavior, and in ideal gases, you will
see that no intermolecular attraction force will be there, whereas in real gases that
intermolecular attraction force will be there.

In ideal gases, there is elastic collision of the particles whenever it will be moving in a
particular temperature and pressure, whereas in real gases, you will not get any elastic
collision of the particles during its movement. In ideal gases, you will see that it will not
actually really exist in environment and is a hypothetical gas, whereas this real gas does
really exist in the environment, whereas as this ideal gas we will see that occupy any volume,
whereas real gas will occupy certain or definite volume.

340
Ideal gas it will be independent, whereas real gas interacts with other. This ideal gas obeys
PV is equal to nRT you know ideal gas equation, whereas this real gas will follow some other
equations like Van der Waal equations and other equations of state and in general you can
express that non-ideal equation in the fashion of that ideal equation as PV is equal to znRT,
here z is called compressibility factor, whereas in the ideal gas equation you are not having
that z factor here, only PV is equal to nRT, but in this real gas we are introducing one
compressibility factor to express the general expression of the equation of state.
(Refer Slide Time: 07:01)

Here see in this slide one graphical representation as given by Himmelblau in his text book
that how that real gases are deviated from the ideal gas at high pressure. You he will see that
here this pV by n that means p into you know specific volume, pressure into a specific
volume of real gas and pressure into specific volume for an ideal gas in the y axis whereas in
x axis it will be pressure. So, at different pressure, how that real gases properties of that
product of pressure and specific volume is changing.

So, see that at higher pressure, you will see that these real gases this factor will be higher than
that ideal gases here. So, interesting that in this suppose there is a point here, you will see that
this point will be almost 1.37 like this. So, at this condition, you will see that at higher
pressure more than 500 atmospheric pressure, you will see that this real gas behavior of this
pV will be one point almost three seven times of that ideal gases. At a particular temperature
is around 200 degrees Celsius for hydrogen gases.

341
So, similarly for other gases also you will see that this ideality or you can say that how it will
be deviated at this high pressure and also real gases behavior how it will be magnified at this
high pressure for different gases. So, from this graph, you can easily calculate what should be
that factor here real properties compared to that ideal properties.
(Refer Slide Time: 09:05)

Now, in general, you will see that there are 4 methods of getting or predicting real gas
properties are there. You can predict that you know real gas properties either by equation of
state or by compressibility chart or by estimated properties or by actual experimental data.
So, either of these 4 methods you can follow to predict or guess or you can say that estimate
that non-ideal behavior of the gases or real gases behavior by this.
(Refer Slide Time: 10:03)

342
So, let us consider that generalized equation of state by which you can express that non
ideality behavior or you can say that real gas equation for expressing its pressure and also
volume at a particular temperature. So, one common way is to modify that ideal gas law by
inserting some adjustable coefficient that is called z here. So, this z it is called that
compressibility factor. Now, from that ideal gas equation that is PV is equal to only nRT,
here on the right-hand side you will see that we are just multiplying one factor that is z.

It is called adjustable factor which will be actually giving the same fashion of ideal gas
equation, and in this case, this z it is called compressibility factor and this compressibility
factor you will get from this real gas behavior and based on which you can say what should
be the pressure and volume they are based on this compressibility factor and it will give you
that corresponding value of PV data for this real gas. So, we are actually expressing the same
fashion of that ideal gas equation, here PV is equal to nRT where we are just multiplying a
factor z here.

So, that will be is equal to PV is equal to znRT. Now, this factor actually compensates for the
non-ideality of the gas and it describes of the deviation of a real gas from ideal gas behavior.
And also, you can say that this ideal gas law, whatever you know expressed by this
compressibility factor, will you know give the generalized form of that equation of state.
(Refer Slide Time: 11:43)

Now, based on this generalized form of this equation of state, you will see that there are
several real gas equations that is developed by different investigator, different scientists, and
there they have suggested different equations for predicting non-ideal behavior of the non-

343
ideal gas or real gas. So, in that case, this compressibility factor, whatever it is considered in
this real gas behavior that should be actually expressed by that temperature and pressure at its
critical condition.

Now, in that case, this almost all fluids you can say that will obey the same equation of state
when their properties are written in reduced form. What is that reduced form, that means
here, if we consider that know compressibility factor, this will be actually represented by z by
zc, what is that, z is compressibility factor at a certain temperature and pressure, whereas zc
is nothing bad that that compressibility factor is at critical condition.

We will describe what is that critical condition, that means higher that you will see that the
gas will not be able to be liquefied at higher pressure or that particular temperature. So, that
point of that temperature and pressure will be regarded as critical point of that temperature
and pressure. So, if you express this compressibility factor based on that critical condition, it
will be denoted by zc. So, z by zc it will be regarded as a reduced form of that
compressibility factor.

So, this reduced form of this compressibility factor will be a function of reduced form of
temperature and reduced form of pressure like this. So, we can say that reduced form of
compressibility factor is a function of Tr and Pr, Tr is reduced temperature and Pr is reduced
pressure, and this Tr is defined as T by Tc, that means T at certain that is temperature and Tc
is the behavior at critical temperature. Since here this zc is nearly a constant for many organic
species, it is actually about 0.27, just remember this and the most often used form is then we
can write here z, z will be able to function of Tr and Pr.

So, this is why we can say that this reduced form of this compressibility factor will be a
function of reduced temperature and reduced pressure and as a molar volume of in that case
that the gases, real gases will become converting into or tends to 1 for the compressibility
factor if it is going to 1 there. That means as the molar volume becomes large, we can say
that z will tend to 1. So, the compressibility factor is near about 1, means it will give you that
large molar volume of that gas.
(Refer Slide Time: 15:26)

344
So, here we told that that critical temperature and pressure what is that. So, gases can be
converted to liquids by compressing the gases at a suitable temperature. At high temperature,
liquefaction becomes difficult because higher and higher pressures are required to work on
the increased kinetic energy of the molecules. In fact, there is some temperature above which
the gas can no longer be liquefied regardless of pressure. This temperature is called the
critical temperature. We can say that the highest temperature at which the substance can exist
as a liquid, it will be regarded as that critical temperature.
(Refer Slide Time: 16:07)

Above the critical temperature, the molecules have too much kinetic energy for the
intermolecular attractive forces to hold them together in a separate liquid phase. Instead, the
substance forms a single phase that completely occupies the volume of the container. The
substances with strong intermolecular forces that tend to form a liquid phase over a high large

345
temperature range, in that case, the substance will also have a critical pressure and it will be
the minimum pressure that is required to liquefy it at the critical temperature.

So, we can say that above this critical temperature, molecules have too much kinetic energy
for the intermolecular attractive forces to hold them together in a separate liquid phase and
also substances with strong intermolecular forces will tend to form a liquid phase over a very
large temperature range.
(Refer Slide Time: 17:17)

Now, here in this figure, it is given that critical temperature and pressure of some gases are
given in this stable. For ammonia, this critical temperature will be 132.4, whereas critical
pressure will be equal to 113.5. Similarly, for other gases this critical temperature and critical
pressures are given here and here in this figure you see that if we represent this non-ideal
behavior of this gas, you will see that beyond this critical point at this temperature, this
gaseous mixture will not actually be able to convert into that liquid form.

So, at this critical temperature, even what is the corresponding critical pressure at this
condition you will see, beyond this critical pressure and temperature, you will see that there
will be no formation of liquid gases there and beyond this you will see that there will be
properties of the gases will drastically change. So, these ranges of that operating condition of
temperature and pressure will be regarded as the supercritical condition and the phase
whatever will give you that behavior it will be called as supercritical phase behavior.

346
You will see that this at a certain temperature, even at a low temperature, even low pressure,
you will see that at a certain condition, you will see that some like water, it will give you that
vapor, liquid and solid 3 phases at a particular point. That would be called a triple point and
these are called that equilibrium condition of each different phases. So, in this case, you will
see substances by this profile, it will be representing as some equilibrium between here solid
and vapor, whereas this equilibrium profile will give you that equilibrium between that liquid
and vapor.

In this case, here, this line will give you that equilibrium point of that solid and liquid there.
So, in this way, you can say that at different pressure and temperature, that substances can be
changed into its different form just by changing its temperature and pressure. So, at high
pressure, that means beyond this critical condition, these gases will not be liquefied, whereas,
before this critical point, you can say that some substances you say that gases will be
regarded as vapor.

Even at a particular temperature from this, you will see that and if you change the pressure,
high pressure you will see that the gas maybe you know converting into a liquid phase. Again
for a fixed temperature and if you change that pressure even at this condition, you will see
that this liquid also it will be changing at a particular pressure if you change the temperature
from that initial point here. So, here in this way, you can say that you can change the
temperature and pressure and accordingly, you can get the different points in this region of
the different phases. That means here, that phase will be converted at a particular temperature
and pressure.
(Refer Slide Time: 21:00)

347
Now to represent that non-ideal gas behavior, according to that concept of ideal gas equation,
so we are considering here that non-ideal gas general form of the equation of that it will be
you know Pv is equal to zRT, here small v is nothing but that the molar volume, here this
small v is nothing but capital V by n, capital V is you know that volume of that gas and n is a
number of moles. So, small v that is a specific volume in mole basis that is called molar
volume. So, this V by n is represented here small v.

So, we can write that from the equation of Pv is equal to you know znRT, we can write here z
will be is equal to here Pv by RT. So, this Pv by RT or z that is compressibility factor, you
can represent it as a function of specific molar volume. So, it can be represented by this 1+ B
by v + C by v + D by v, where B, C, D are all coefficients, those coefficients are called Virial
coefficients and Virial coefficients are actually depending on the temperature of that
particular system.

You will see that this is C and D values are relatively going to smaller compared to that this
second Virial coefficient. So, accordingly, we can say that if we neglect these two terms of
right-hand side, so the remaining portion is 1 + B by v. So, from this 1 + B y v, you can
directly calculate what should be the compressibility factor z. Now, in this case, this B can be
estimated from the following correlations given here. So, these coefficients basically depends
on critical temperature and critical pressure.

So, this B value can be expressed as B is equal to here RTc divided by Pc into B0 + omega
into B1, whereas this B0 is a constant that also depending on that reduced temperature. This

348
is the equation to represent is B0 here and B1 also is one constant, that B1 also is expressed
by this correlation given here in the slides, whereas you know that omega is called acentric
factor, this acentric factor will be described later on also. This some another factor, that also
is depending on critical temperature and pressure there.

So, if you know that the acentric factor and also that critical temperature and pressure, you
will be able to find out what will be B value there, and once you know that B value, then
what should be the compressibility factor you can calculate from this equation.
(Refer Slide Time: 24:26)

Now, here one compensability chart is given. This is basically the compressibility factor is as
a function of reduced pressure, it is given here. So, this compressibility factor versus reduced
pressure, it is made, it is also taken from Himmelblau that is from your textbook. So, you can
go through that. Here see that how that compressibility factor, it will be changing with a
reduced molar volume of that particular gases and also how it will be changing with reduced
temperature and also how it will be changing with your reduced pressure there.

So, at a particular reduced temperature, that means T by Tc and also reduced molar volume
there if you know that, then you can easily calculate at a particular reduced pressure, what
should be the compressibility factor. Let us have these some gases here, suppose this reduced
molar volume is here at this point and also that reduced temperature is 1, then at this
particular reduced pressure, what should be the compressibility factor here it will you can get
it from this point. So, this way, you can read what should be the compressibility factor from
this chart.

349
(Refer Slide Time: 26:19)

Now, we told that there are several equations of state that is suggested by different
investigators, different scientists, different academicians. Also, you can say that how that real
gas behavior can be expressed based on their intermolecular force, even their molecular size.
So, in this case, Van der Waals's equation of state is one of the important equation of state for
the real gases by which you can calculate its pressure and also volume for that real gases at its
particular temperature and pressure.

So, in this case, see here, Van der Waal equation is given in the slide. Here it is p P + a into n
square divided by V square into V minus nb that will be is equal to nRT. Here also P into V,
here this part is regarded as P real that is P + a h square by V square. Here a is some
coefficient, it actually depends on the critical temperature and pressure and its value is given
here by this correlation and here V real that is denoted by V minus nb, here b is also
coefficient, this b is calculated by this equation, here also it is depending on the critical
temperature and pressure.

You will see that 2 coefficients are here a and b, this a is correction factor that is accounting
intermolecular force of that real gases, whereas b is another factor that accounts the
molecular size of that particular gases. So, based on which that Van der Waal suggested this
equation of state to represent the non-ideal behavior of the gases. So, here in this case, if you
know the measured pressure and also measured volume, you can easily calculate what should
be the remaining factor of that a and b there just by equating that experimental data with this
equation.

350
So, one way you can express that what should be a value and b value, that a and b value you
can express by this critical temperature and pressure. Also if you know that measured volume
at a certain temperature for that real gases and also if you know that a and b value of that
coefficient at this particular critical reduced temperature or reduced pressure or you can say
that critical temperature and pressure, then you can easily calculate what should be the
pressure of that real gases.

Whereas we have calculated the behavior of ideal gases only by PV is equal to nRT, here in
this case, that will not give you the exact result for that real gases, that is why for real gases,
you have to use this Van der Waal equations because that real gases behavior will be different
from that ideal gases, because of that some intermolecular force and also size of that real
gases will matter. So, that is why based on that intermolecular behavior, the Van der Waals
gave this equation of Van der Waal equations to represent the non-ideal behavior of the
gases.

Similarly, another investigator that is called Redlich-Kwong equation of state by which you
can express that real gases’ behavior for the pressure and volume. So, here also, this equation
even this is also you will see that at this equation here, you will see the molar volume of that
real gases and also some coefficient here b is given here. So, based on these, you can
calculate what should be the pressure if you know that molar volume is there.

So, this again that this Redlich-Kwong equation depending on these 2 parameter this a and b,
those are actually depending on that intermolecular force and intramolecular or molecular
size there, and this coefficients are again depending on that critical temperature and pressure,
and by this correlation, you can directly calculate or estimate the value of a and b. Once you
know that a and b by this correlations and if you know that molar volume at a particular
temperature, then you can easily calculate what will be the pressure of this real gases by this
Redlich-Kwong equation.
(Refer Slide Time: 30:52)

351
Similarly, other equations are also familiar to calculate or predict that real gases’ pressure or
volume. So, those are the Peng-Robinson equation of state here given. Here again, some
factors are here some a and alpha, even you know that b, even you can say that this alpha
value that is an acentric factor, also this alpha value depending on that some acentric factor.
In that case, you will see that some other factors it is denoted that is called K that is also
depending on the acentric factor and also we can see that this coefficient a and b are
depending on that critical temperature and pressure and Vm is here molar volume.

So, based on this equation also, you can calculate what should be the pressure. Similarly, you
can use that SRK equation it is called, Soave-Redlich-Kwong equation. Here also this
equation expressed in terms of some coefficient b and also here alpha and a. Here a is defined
by this correlation, b is defined by this correlation, alpha is again depending on that acentric
factor and reduced temperature and this reduced temperature defined as here T and Tc and
this alpha is equal to here 1 + m into 1 minus root over Tr whole square.

This m is basically that has a function of acentric factor and R is ideal gas constant or
universal gas constant that is you know 0.08205 at this unit of liter atmosphere per mole
Kelvin. So, from these equations, you can easily calculate what should be the pressure and
volume at a particular temperature there.
(Refer Slide Time: 32:52)

352
Now, constants for the Van der Waals and Redlich-Kwong equations are given here in this
table for different gases. That means a value, b value what should be that. So from this table,
you can take this a and b value directly without calculating that a and b constants from the
correlations. So, you can directly use the table for your a and b and after getting a and b, if
you directly put that a and b in your respective Van der Waal equation or Redlich-Kwong
equation, then you can easily calculate what should be the pressure or volume.
(Refer Slide Time: 33:28)

Now, let us do an example based on this Van der Waal equation or you know other equation
of state. Now, as an example, you can say that if suppose a cylinder of 0.15 meter cube in
volume containing 22.75 kg of real gas A stands in the hot sun. Now, a pressure gauge shows
that the pressure is 4790 kilopascal that is in gauge. What is the temperature of the gas in the

353
cylinder that you have to find out? Now, in this case, you can use the Van der Waal equations
because here this gas is real gas.

So, you cannot use that ideal gas equation to find out that here temperature. So, in this case if
we use that Van der Waal equation, for that what we should require to calculate? in this case,
this is your Van der Waal equations. For this, you need to calculate a value. You need to
calculate b value. So, a value can be calculated based on that correlation, so you can get
directly this equation, or either you can take it from the tables, so this a value will be like this
and b value will be is equal to similarly 90.7 or you can calculate it from the correlations that
is given in the earlier slides.

Once you know this a and b value, then again you have to calculate what should be the n
value there because and n is also to be calculated, what will be the number of moles of that
gases? Because in this case, it is given that cylinder contains 22.75 kg of real gas. In this case
if real gas, here molecular weight is 44 let it be here. So, in this case, the number of moles
will be is equal to here 0.517 kilomole. Pressure is given there, I think what is the pressure
given, it is you know that 4790 kilopascal.

So, here it will be absolute pressure will be is equal to, this is gauge pressure, so absolute
pressure will be is equal to 4790 + 101, this is your atmospheric pressure. So you have to add
it up to get the absolute pressure. This is in kilopascal, you know that 101.3 kilopascal is
equivalent to 1 atmosphere, so you can convert it to absolute pressure into atmosphere. This
is 48.3 atmosphere. Then R value is as far that atmosphere it is you know that 82.06
centimeter cube into atmosphere per mole K.

You can say that after the substitution of these n value, a value, b value, and also volume,
volume is given to you, it is given 0.150 meter cube, so, you have to convert it to centimeter
cube and then finally, you can calculate that what should be the temperature from this
equation. So, this is coming this will be equal to 384 Kelvin after substitution of all these
parameters there. So, finally, we can say that the gas in the cylinder will have this
temperature of 384 K.
(Refer Slide Time: 36:51)

354
Another example. In this case, you have to determine the hydrogen pressure in a tank by
using SRK equation, that is the Soave-Redlich-Kwong equation. The tank is at 40 degrees
Celsius it is there. The molar volume of the hydrogen is 0.3 liter per mole. Now, critical
temperature and pressure of the hydrogen are given as 33 K and 12.9 atmosphere
respectively. Now, the hydrogen acentric factor is given as minus 0.216. So, what should be
the hydrogen pressure in the tank?

So, you can use this equation, SRK equation. Based on that, you are having this P is equal to
RT by v minus b minus alpha a by v into v + b. So, in this case, you need to calculate first
what should be the a value there by this correlation, in this case since this correlation or this
value of a is depending on critical temperature and pressure, this critical temperature and
pressure of hydrogen is given to you. So, finally, you can calculate what should be the a
value.

Similarly, what should be the b value, again if you substitute the Tc and Pc, there you will get
this value 0.018 and then you have to calculate what should be the m value there because to
calculate that alpha value it is required that m value. So, m value is a function of acentric
factor, this acentric factor is given to you. So, if you substitute that eccentric factor omega
here in this equation, you can calculate what should be the m value her, so m is coming as
0.143.

Then finally, you can get what should be the alpha value here, before calculating this alpha
value, you have to calculate what is the reduced temperature, because this reduced

355
temperature is defined as T by Tc, T is given to you and then Tc is also given to you. So,
finally, you are getting 9.49 as Tr and then what should be the alpha value. After substituting
of this m value and Tr value, you can get this alpha 0.495.

Now, if you substitute that alpha value, a value, b value, and also molar volume here in this
equation at that particular temperature, what should be the pressure you can easily calculate
there by this SRT equation and it is finally coming as 89.8 atmosphere. So, this is your basic
equation on how to calculate the pressure and volume by this SRK equation. Another
important aspect of non-ideal gas behavior is whenever there are more than one real gas will
be there in a mixture, how then that their reduced temperature and reduced pressure will be
changing.

So, in that case, that also to be calculated and accordingly that compressibility factor of that
mixture of gases will be different. So, once you know that mixture of gases that
compressibility factor, then what should be the pressure and volume from that non-ideal
behavior or non-ideal gas equation, you can calculate those pressure and volume.
(Refer Slide Time: 40:26)

Now, if you have that mixture of gases, then your critical temperature and critical pressure
will be represented by pseudo reduced quantities of those gases to assess the pseudocritical
properties. Now, it is used in generalized compressibility charts. So, according to the rule of
Kay’s, it is called Kay’s mixing rule. So, this pseudocritical temperature will be regarded as
what is the summation of Yi into Tci, i is for an individual component of that gases.

356
Suppose there are 2-3 gases in a mixer, so each gas component will be represented by i and
its molar fraction will be is equal to Yi and Tci is the individual gas components at critical
temperature. So, the summation of all this Yi into Tci will give you that pseudocritical
temperature of that mixer of gases and also what is that pseudocritical pressure of the mixture
of the gases similarly you can have the summation of Yi into Pci.

But in this case you have to remember that sometimes this hydrogen and helium gas does not
follow this particular critical temperature, this pseudocritical temperature and pseudocritical
pressure just by that individual gas component, it is critical temperature and pressure. It is
seen that at this critical condition, this hydrogen and helium gases will give you the
pseudocritical condition if you add it to some factor there with that critical temperature.

Similarly, if you add some factor with that critical pressure, you will see that pseudocritical
temperature and pressure will be there. So, remember that for only hydrogen and helium, this
pseudocritical temperature will be is equal to Tc + 8 K, here only this value of 8 it will be
added to this critical temperature. Similarly, for pressure also you have to add this 8 for the
critical pressure to get pseudocritical constants here Pc dash. So, for hydrogen and helium
that you have to remember this equation to calculate further.
(Refer Slide Time: 43:11)

Now the pseudoreduced pressure and the pseudoreduced temperature are calculated using by
this equation here Tr dash will be equal to T divided by Tc dash, Pr dash will be is equal to P
by Pc dash. The equation of state for a non-ideal mixture is then defined as Pv will be is equal

357
to ZmRT. What is Zm, Zm is the compressibility factor of the non-ideal gas mixture, so m is
for you know mixture.
(Refer Slide Time: 43:45)

Now compressibility factor of the mixture, then you can calculate in this way. This Zm will
be is equal to Z0 + omega into Z1, where Z0 is defined as 1 + B0 into Pr by Tr, where B0 is
defined by this correlation which is a function of reduce temperature and Z1 is another factor
that is a function of ratio of reduced pressure and reduced temperature, whereas this B1 is
coefficient, that coefficient is a function of reduced temperature which can be calculated from
this correlation.

So, once you know this Z0 by this equation and Z1 from this equation and if you know the
acentric factor, then you can easily calculate what should be the mixture compressibility
factor.
(Refer Slide Time: 44:43)

358
Let us do an example here. Suppose a gas mixer is given to you and that will contain 30%
carbon dioxide and 70% ammonia and it exists at 500 Kelvin and 120 atmosphere in the
container. The molecular weight, critical temperature and pressure for that carbon dioxide
and ammonia are given here and also the molecular weight, critical temperature and pressure
for the ammonia also given. Find the molar volume of the gas mixture using the Kay’s
mixing rule?

Here acentric factors of the carbon dioxide and ammonia are given as 0.228 and 0.253,
respectively. So, you have to find out here what should be the molar volume of that gas
mixture. So, to find out here what should be the, first calculate what would be the Tc.m for
that mixture. For that mixture Tc since here molar fraction is 30% and 70%, then you just
simply multiply that molar fraction as here 0.3 into 304 + 0.7 into 405.4.

Here 304 is, it is given that critical temperature of the carbon dioxide and 405 is the critical
temperature of the ammonia gas and their corresponding mole fraction for carbon dioxide is
30% whereas ammonia gas is 70%. So, total mixture critical temperature will be just based
on this equation, it will be coming as 374.98 Kelvin. Similarly, critical pressure of the
mixture, simply you have to multiply with that mole fraction and then add it up for all
components and it will be coming as 101.59 atmosphere.

Here acentric factor also you have to calculate in the same way of what is the mole fraction,
you have to multiply that acentric factor with that respective mole faction and then add it up
for all the gas components, then you get this acentric factor of your as per problem here it is

359
0.2455. Similarly, mixture molecular weight has to be calculated based on that molar
concentration here, so it will be as 25.10. Next, you have to calculate for the reduced
temperature, it is defined as simply T by Tc.m.

T is the temperature at a certain condition it is kept, this is I think 500 K and Tc.m it is
calculated earlier, that is it is coming 374.98. If you divide it this 500 by 374.98, you will get
this 1.333, it is simply reduced temperature. Similarly, you can get reduced pressure as 1.181.
So, in this way, you can calculate what would be the reduced temperature and reduced
pressure.
(Refer Slide Time: 47:48)

After that, you have to calculate that all coefficients given here like B0 and then B1. You
know the Tr that is reduced temperature and reduced pressure if it is required, I think in this
equation only reduced temperature is required. So B0 will be is equal to this. Similarly B1, it
is also a function of only reduced temperature. So, you can calculate this value based on that
reduced temperature. Now z0 is a function of reduced pressure and reduced temperature.

If you substitute this value of B0 and this Pr and Tr here, you can simply get this value of z0
as 0.82 m and similarly, you need to calculate that z1. This, what is that, this is B1 into Pr by
Tr, Pr and Tr here and B1 already you have calculated. So, if you substitute those B1, Pr and
Tr here, you can get this z1 value. Now, since this mixture compressibility factor is a function
of this z0 and z1, then you can have this mixture compressibility factor after substitution of
this value of z0 here whatever you have calculated and z1 whatever you have calculated, but
the acentric factor of that mixture also you have calculated here, it is why.

360
So, after simplification, you can get this value of 0.845. So, this is your compressibility factor
of the mixture. Then what should be the molar volume of the gas mixture? That can be
obtained from this non-ideal gas equation, that is general form of that non-ideal gas equation,
that will be is equal to v that will be is equal to ZmRT by P. So, here Zm already you have
calculated and then R is even there and T is 500 and what is that P is here 120 K. So, finally,
you can get it what will be the value, it is 0.289 liter per mole.

So, in this way, how this case rule of mixing you can apply for that mixture of non-ideal gas
to calculate its mixture molar volume, so you have to follow this equation.
(Refer Slide Time: 50:11)

Another example. Suppose that a container or you can say the tank contains 3.5 kg of liquid
oxygen, which is to be vaporized in that tank of 0.0284 meter cube here and this will be
vaporized at this at about this temperature of minus 25 degrees Celsius. Now, what will be
the pressure in the tank will be and will it exceed the safety limit of the tank what is actually
to be maintained at 100 atmosphere. In this case, given that the critical temperature of that
gases is 154.4 Kelvin and critical pressure of that gas here, oxygen is given 49.7 atmosphere
and reduced pressure is here 1.43.

So, based on this condition, you have to find out what will be the pressure inside the tank.
Now, here this case, we do not know the pressure of the oxygen in the tank. Now, we need to
use the other parameter like here Vri that means for a particular component, what should be
its reduced molar volume? So, to calculate that, first of all you have to calculate molar

361
volume of that gases. So, molar volume is coming that its volume is given is 0.0284 of the
container and mass of that gas is given 3.5 kg.

So meter cube per kg to be 0.0284 by 3.5 and if you convert it to this meter cube into again
into mole, what is that you can get it to the mole just by multiplying it with this molecular
weight. So, in this way, you can calculate that this will be this meter cube per kilomole. So,
this tank will be having this volume of 0.260 meter cube per kilomole of that oxygen. Now,
what will be the Vci, critical molar volume of that component? So, it will be RTc by Pc.

So, accordingly, if you substitute that R value, Tc value and Pc value, you can get it this
0.255 meter cube per kilomole. Again this what will be the reduced molar volume of that
component, to be simply that v by vci,v is already you have calculated and vci also you have
calculated. If you divide this, you will get 1.02, and what would be the reduced temperature,
this is T by Tc. If you substitute that T value and then substitute the Tc, you can get this Tr
value.

Then what should be the Pr, Pr will be is equal to 1.43, it is given to you. Then P will be is
equal to what, P will be is equal to Pr into Pc, Pr is given to you, Pc also to be calculated, and
then Pc is coming here, it is also given 49.7, then it will be coming a 71.1 atmosphere. So, at
this condition, the pressure of tank is 71.1 atmosphere, whereas at its safety level, the
pressure will be maintained as 100 atmosphere, but it is coming as 71.1. So, we can say that it
is in a safe condition.

So, in this way, you can calculate based on that critical temperature and pressure and how to
calculate that molar volume and also add critical condition how to calculate the molar volume
of this component in a particular tank and also what should be the reduced molar volume for
that particular component in the tank and based on which you can easily calculate what
should be that this pressure simply from this reduced pressure and critical pressure there.
(Refer Slide Time: 54:43)

362
So, we have discussed a lot of theories, how to calculate the pressure and volume of non-ideal
gases based on that Van der Waals equation, even RK equation, even you can say that SRK
equation, even other equations also are shown there to calculate that non-ideal behavior at a
different temperature, even at different pressure and volume what should be the other specific
property of the gases and also in a mixture how to calculate that compressibility factor by
case rule that we have discussed here.

So, I think you have understood this matter how to calculate that non-ideal behavior by this
equation of state if you know the compressibility factor. So, I would suggest you to go this
textbook thoroughly and also try to practice some other example problems given in the
textbook, so that you can easily understand, also you can further solve the problem based on
this concept there. So, I thank you a lot for your kind attention here. In the next lecture, we
will try to discuss more about gas system or other systems.

In that case, the separate module will be considered, in the separate module, we will discuss
something more that multiphase systems and how they actually lie in an equilibrium
condition and what are the different laws to express that equilibrium condition will be
discussing in the next lecture. Thank you.

363
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 13
Phase Equilibrium

Welcome to massive open online course on basic principles and calculations in chemical
engineering we discuss basic you know material balance principles and also their applications by
you know discussing with several, you know, examples, and up to module 4 we have discussed
these things. Now, we will start here module 5, where we will discuss the basic principles of
multi-phase systems and also the application of these multiple systems for the engineering
calculations. And in this module has a first lecture we will discuss that phase equilibrium in that
you know that this lecture will you know to cover that.
(Refer Slide Time: 01:24)

you know what is the phase rules and also how to calculate the vapour pressure many chemical
engineering processes are actually being involved with you know, multi-phase systems, what is
actually that multi-phase systems we have already talked about that you know, only single-phase
systems like you know that liquid gash or solid these are you know that when you know that we
will be using has the you know single entity.

364
Then it will be considered as a single-phase even it's you know principles will be for that single
phase principles and also whenever it would be flowing for a particular process that will be you
know single-phase flow. Now, when any chemical engineering operation or biochemical any
other engineering operations, there are if more than one phase will be involving, then the system
will be you know, regarded as the multi-phase systems.

Like, you know that gas and liquid both to be flowing through the system, even gas-liquid-solid
to be you know, simultaneously will be flowing through the system for a particular chemical
engineer operation. Let us have an example for that suppose if there is a flow of gas and liquid in
you know in a particular reactor or in a particular column you will see that there may be used for
chemical engineering operation like absorption process.

If suppose if you want to you know remove carbon dioxide gas from you know atmospheric air
then what do you have to do that mixture of air and carbon dioxide to be passed through that you
know liquid medium like if it is sodium hydroxide or some Ambien solution, you will see that
carbon dioxide gas will be absorbed by that you know by that liquid medium like you know
alcoholic or you know that mean solution this type of operation is called that 2 phase system
even you will see that.

Other chemical engineering operations are not only these 2 phases, they are maybe you know
involving another phase like solid phase will also be involving for a particular Chemical
Engineer operation like in a slurry, you know, bubble column reactor where you will see that
synthesis gas like you know that carbon monoxide and hydrogen gas will be you know supplied
to that you know by liquid medium in the presence of catalyst particles to you know synthesize
that you know different you know, valuable products like gasoline, even elfin and also other
different types of hydrocarbons.

Just by you know that processing of that gas-liquid mixture in a liquid medium in prison sub
catalyst particle. So, this type of operation actually scored that the pitcher drops the synthesis, or
these gas-liquid-solid three phases are important. So, this is called multi-phase systems when you
will see sometimes from you know single phase you can have different you know, form of it is a

365
change of state like liquid may be converting into solid or solid may be converting into liquid or
gas may be converting into liquid or liquid may be converting into gas or gas will be converting
to solid.

So, these are change of state from 1 phase to another phase, you will see, we possible if you
know change the pressure or temporary set there. So, by changing the pressure and temperature
of the system you can change the particular state from either by liquid or either by you know
either from gas for space or either from solid phase to the other phases. Now, you will see at a
particular pressure and temperature there will be you know starting change of these phases.

Now, you have to you know notice down where that particular temperature and pressure by who
is you can get that you know that change of this liquid like here at a particular pressure like 1
atmospheric pressure and 100 degrees Celsius, you will see that water is converting into you
know vapour. So, this type of change of this state like you know that some other sometimes this
liquid will be converting into solid or you will see that a solid may be converting into a liquid
state like this.

So, there will be a certain change or pressure and temperature by which you can get Now, what
will be that equilibrium you know that temperature and pressure at who is that just the phase will
be changing from that its initial to the final state. So, that you know that transition or equilibrium
condition can be represented by you know diagram. So, this diagram will be you know referred
to as a phase diagram.

So, we will be discussing that phase diagram on which you will see that how equilibrium
condition of this you know, pressure and temperatures based on who is that the state will be
changing here before going to that representation of that equilibrium you know condition of
pressure and temperature for compassion of you know, that 1 state to another state, we have to
discuss that other different types of equilibrium maybe you know, they are in the, you know,
different chemical engineering processes, that also you have to know some extent.
(Refer Slide Time: 07:48)

366
So, let us have that different types of chemical, you know, processing equilibrium like here, 1 is
called chemical equilibrium. This is basically a state in which you concentration of the reactants,
and you know that products have you know no net change over time. So, this will be called as
chemical equilibrium. Even sometimes, you will see that there will be a certain change of you
know that concentrations just by diffusion.

So, when the concentrations of the diffusing substance in the 2 components will be equal then
that you know equilibrium condition or equal condition will be represented by diffusion
equilibrium another you will see sometimes in a certain process will see sometimes that ionic
processes there the distribution of ion species between 2 ionic solutions that will be separated by
a semi-permeable membrane or boundary.

So, they are that when this you know ionic you know species will be equilibrium in condition for
its distribution, then it will be called as Donnan equilibrium, another important aspect of
equilibrium It is called dynamic equilibrium. In this case, you will see that the state in Greece,
the two reversible processes will occur at the same time rate, the same rate that is called dynamic
equilibrium.

Now, you will see that, you know, sometimes that chemical equilibrium will be represented by a
certain constant that will be called the chemical equilibrium constant. This is a quantity that will

367
be characterized a chemical equilibrium in a chemical reaction and other important equilibrium it
is called solubility equilibrium. Now, if any chemical equilibrium between solid and dissolve
states of the compound at saturation will happen to be called a solubility equilibrium

And if support any state of thermodynamics system which is you know in thermal or mechanical
or chemical equilibrium exists, then it will be actually referred to as thermodynamic equilibrium.
You will see a for you know when a bar liquid will be you know converting into each vapour,
there will be a certain equilibrium condition at a certain temperature and pressure, so, that when
our liquid will be converting into vapour and the vapor-liquid equilibrium will be there.

So, it you know may you know happened when that you know liquid be converting into vapour
that we said vaporization process before and sometimes you will see that vapour will be again
converting into a liquid since then it will be called as conversation process. So, when the rates of
condensation and vaporization of the material will be you know equal, then there will be an
equilibrium Augusta. We in this vapour and liquid.

So, that equilibrium will be called as vapour-liquid equilibrium. Now, what we actually talked
about that there will be a phase diagram. So, this is basically a graphical representation of
pressure.
(Refer Slide Time: 11:16)

368
And temperature you know, at we saw you can say that you know vapour and liquid will be
coming into equilibrium condition and to be represented in that you know graphical you know
diagram so, it will be called as a phase diagram. So, a phase diagram is a graphical representation
of the physical states of a substance under different conditions of temperature and pressure. Now,
this equilibrium can be actually you know, differentiated in terms of you know state variables by
you know phase boundary or it is called that transition you know boundary or transition
condition or you can say transition points on a phase diagram.

So, this you know, if you have different you know condition point or equilibrium point and if
you add those equilibrium points and represented by a profile or line that will be regarded as
condition blind or it can be considered as a page diagram. So, the equilibrium state is
distinguished in terms of you know state variables by a phase boundary on a phase diagram.
Now, here see 1 phase diagram is shown by in the slides, you will see that.
(Refer Slide Time: 12:49)

This phase diagram if you look into this space diagram you will see that in X-axis, there will be a
temperature in degrees Celsius and Y-axis there will be you know pressure in atmosphere and
you will see that there are some profiles that is here passion like here be here that BO then DA
and also here OC and O like here like this will OB an O dash or OA dash. So, and you will see
that this line will be represented here as a phase boundary or you can see that condition you
know a line or boundary line.

369
Which will you know that distinguish that, you know different phases. Now, if we see that, you
know that different points on this you know, phase boundary what we can see here before going
to that we have to identify for is that other things are there like you will see some vapour you
know it is written here it is written solid here it is retained what that liquid is. Now, see there are
some regions here that will be denoted by this here vapour you know region and there is some
regions to be you know liquid-solid region and where you will see that some other region which
will be you know that regarded as liquid region.

Now, that phase boundary will segregate that region by each you know transition points. Now,
interestingly you will see that these equilibrium points are actually plotted based on that different
you know temperature and pressure change. If you change the system temperature and pressure
and accordingly, you will see that there will be an equilibrium condition equilibrium, you know
temperature and pressure at ease.

Just you know that the phrase will be, you know, changing from its initial state to another state.
Now, if we consider these you know boundary line here that is BO what exactly it means, that
you know that any point here under this you know that this boundary layer or boundary you
know the line you will see that at this point there will be a certain temperature and there will be a
certain pressure.

At this point, the water bar it is that the state will be you are not the vapour stage or vapour
phase. And here, ever this line, there will be you know that solid-phase like other points if you
consider here E point you will see that this is the vapour phase at this temperature of 100 degrees
Celsius and pressure is at 100 you know millimeter marking. Now, you will see here again if we
consider that point D here at this equilibrium condition at a certain temperature and pressure and
this is the boundary of these 2 phases.

Similarly, here at F there will be a you know that point at which certain temperature and pressure
also this point will be represented by a solid state. Now, if we represent the phase diagram of
water, you know that and it is vapour system, what will happen? Now, if you consider that liquid

370
phase is converting into its solid and liquid phase is converting into vapour and vice versa, then
how it can be represented.

Now if we consider that water, you will see that if we consider this point F what will happen at
this point, we are getting here - 40 degrees Celsius whereas, pressure is 10 atmosphere, what
does it mean at this temperature of - 40 degrees Celsius and 10 atmospheric be sharp the water
will become a solid edge and at an equilibrium condition of any via here in the slide you will see
that this is vapour to solid.

So, it will be you know that vapour to solid AB is actually at - 40 degrees centigrade, this vapour
will be what our vapour will be converting into solid now, if we consider here you know that
point A you will see that if we you know that a change the temperature from each you know that
100 degrees Celsius or any suppose that 30 degrees Celsius to you know that - 40 degrees
Celsius, what will happen at the same temperature at the same pressure obtain atmospheric
pressure you will see that liquid, water will be converted into solid.

So, here this how at a particular you know pressure if you change the temperature this liquid will
be converting into solid and at this boundary, you will see that at a particular temperature and
pressure this liquid just changing its you know state 2 it is solid similarly, at this point E what
does it mean that if you know change the temperature from 0 degree Celsius to you know that
100 degrees Celsius, what will happen? You will see that this liquid will be converting into
vapour at a constant you know pressure.

Similarly, you can see that if you fixed your temperature and if you lower its pressure you will
see that liquid also will be converting into vapour. So, at a certain temperature appeal, you know
to decrease the temperature that liquid water maintains to converting into a vapour. Similarly, at
a particular temperature if you decrease, if you know, if you increase that, you know pressure
you will see that vapour will be converting into liquid again at the particular you know that
pressure if you change the liquid from you know 0 degree to you know - 40 degrees Celsius.

371
You will see that or even you know - 1 degree or less than 0 degree Celsius you will see that
liquid will be converting into a solid-state. So, this pace diagram you will see very interesting
that, from this phase diagram, you did be able to save that how or what extent of pressure can be
changed to get you know that the liquid to vapour or you can say that solid to vapour or you can
say that just by changing up it is temperature.

How you can change the solid to liquid or you can say that from liquid to vapour also. Now, at 1
atmospheric pressure if you change the temperature from 0 to 100 degrees Celsius, you will see
that liquid automatically will be a change to you know vapour. So, in this way this space diagram
if you know to read then from this you know pressure and temperature data, you will be able to
say what extent of pressure and what extent of temperature, you can change to get it change of
phases.

Now, one important interesting point here is O point. Now, at this point you will see if you
consider water you will see that this point this is that 0.0075 degrees Celsius and pressure is 4.58
millimeter micrometer at this temperature and pressure this water will be either solid or liquid or
vapour there will be you know that 1 point that you cannot say that will be solid or liquid or
vapour. So, that is a state what is called that triple point state of water.

So, this triple point is basically referred that this water cannot be regarded as either solid or
liquid or gas all the three phases will be you know considered as this point here. So, here, in this
case, this temperature and pressure will be called as triple point of water and this cannot be
changed. You cannot get another value up the triple point of water, this will be you know that
always will be a distance at this particular temperature and pressure.

So, pure water if we consider that here at 130 degrees Celsius and hundred millimeter mercury
that will be a gash that is point E while it is solid at - 40 degrees Celsius and in an atmosphere
but at 100 degrees Celsius and 1 atmosphere it can be a gas liquid or a mixture of both. So that
will be pointed D and at 0.0098 degrees Celsius and 4.58 millimeter mercury. It may be a solid, a
liquid or a gas any combination there.

372
So, it will be regarded as point O and it is called triple point of water. So, at moles, you know the
temperature and pressure a single pure substance at equilibrium, it will exist entirely as a solid,
liquid or gas, but at a certain temperature and pressure two and all three phases may, exist. So,
this way this by the start you know phase diagram, you can assess whether at that particular
temperature and pressure this you know, what will be the state of that substance.

Now, beyond these, you know certain temperature and pressure you will see that the properties
of that substance will drastically change that will be called as you know, critical point. Now,
beyond that critical point of that temperature and pressure, you will see that there will be a
change of properties of the substances, but as you will see that some you know substances were
supposed gases.

You will see that above 374 degrees Celsius and pressure of you know at pressure 218
atmosphere uses some gases will be you know that in condensable that gases cannot be you
know converting into you know solid states so, that temperature will be called as critical
temperature. So, the critical temperature or critical point will be regarded as a condition higher,
the gas cannot be changed into a solid-state or it cannot be condensable.

So, this is the state of you know phase and how that state of phase can be you know that you
know represented in a diagram that would be called phase diagram. Now, as for that phase
diagram, we can say that along vapour-liquid equilibrium.
(Refer Slide Time: 25:15)

373
Pressure known as vapour pressure sometimes to be denoted by P star or sometimes it will be
denoted by P V and T at that equilibrium line temperature will be known as boiling point of the
liquid or new point of the vapour. Along the solid-liquid equilibrium this temperature will be
known as melting point temperature or freezing temperature at particular pressure along this
solid vapor equilibrium t known as sublimation temperature that is regarded as Ts at pressure p
or transition temperatures like Tm, Tb, Ts etcetera are functions of pressure.

Now, to condense it water you have to convert the vapour to liquid by decreasing the
temperature or increasing the pressure to evaporate water what you have to do you have to
convert the liquid to vapor by increasing temperature or decreasing the pressure to freeze the
water you have to convert the liquid to solid by decreasing temperature or increasing the
pressure. So, this is that you know phase diagram will give you.
(Refer Slide Time: 26:43)

374
All this information from each transition point. Now, what I told that to convert this liquid water
into each vapour so, you have to you know specify certain things that what is that temperature
and pressure. So, this temperature and pressures will be integrated as variables. Now, there are
other so many variables will be there. So, for a particular you know representation of the state of
a substance you have to specify certain variables. Now, how many specified variables to be there
or how many variables to be specified that should be you know known to you.

Now, that specification number of that variable can be estimated by a certain rule. So, that rule is
called the Gibbs phase rule. Suppose, you have a close to vessel that contains three components
like ABC that is distributed between gas and liquid phases. And you wish to describe this system
to someone else that is in detail for that person to duplicate it exactly what must you specify
there you have to specify that system either by temperature or by pressure or by moles of that
components or by more fraction of that components or by mass production of that components or
combination of these things.

Now, these variables are not all independent in this case, some of them are specified, others are
fixed by the necessary and in some cases you will see that, it may be required to calculate from
physical properties of the system components there. So, according to these are system variables
to specify the state of that particular you know substance, you need to specify some variables out

375
of these variables. Now that how many variables to be specified to calculate that you have to
follow that Gibbs phase rule what that the Gibbs phase rule actually, you know says.
(Refer Slide Time: 29:23)

Here, in this case, this rule is defined as a degree of freedom, which is basically number of
intensive variables that can be specified independently for a system at its equilibrium condition,
which determines my all remaining intensive properties. So, by that degree of freedom, you will
be able to say that how many numbers of variables will be specified to represent it is intense
properties according to this Gibbs phase rule, the equation here given in the slides as if that will
be equal to 2 + C - P - r.

So, this is your you know mathematical expression for the Gibbs phase rule in this case F is
called degrees of freedom C is called number of components of phases in the system or number
of species are present in the systems and P is called how many phases are they are in the system
and also R is called the number of reactions are going on the system. So, according to these, you
will be able to calculate what should be the degrees of freedom based on this Gibbs phase rule,
and also you will be able to specify that system variable.
(Refer Slide Time: 30:55)

376
To the present its properties let us have an example for this now, in this case, what should be the
degrees of freedom for pure nitrogen gas at equilibrium condition in this case the system here
will consist only component 1 that is nitrogen gas 1 species phase is 1 because only gas was
phase then according to this phase rule, since there is no reaction is going on with this you know
gas phase single gas space then you know degrees of freedom will be they are F = 2.

Then we can say that to represent says you know that intensive properties of this nitrogen then
you have to specify two variables to represent this property that you know that arbitrary to you
know intense properties you can represent in this case, all the intensive properties are here fixed.
Now. So, if we define temperature and pressure for the system and row are fixed for this specific
set of conditions, then you can say that only degrees of freedom will be 2, and accordingly, this
only temperature and pressure will be specified there.

Similarly, determine the degrees of freedom for ease of the falling system at equilibrium to
specify a feasible set of independent variables for the system like pure liquid water here also you
see that degrees of freedom will be you know 2 for this you know that you know nonreactive
system because age is 1 component is 1. So, simply F = 2 similarly a mixture of liquid-solid and
vapour water, in this case, you will see that liquid-solid and vapour 3 phase will be there. P = 3
here and you know component will be only what is that component is if it is coming from the
only water phase and C will be = 1.

377
And then what we can say that F will be = 2 + here C - P - r since it is nonreactive So, r = 0 then
it will be coming as 2 + C = 1 - phase is 3 then - 0 then is simply 0 that means, here a mixture of
liquid-solid and vapour what will give you the degrees of freedom is 0 that means, here you have
to specify a particular you know that specific variable there and it cannot be changed. So here
you know that degrees Freedom will be equal to 0.

So, they will see that it is coming as that only you know that there will be no you know pressure
and temperature or other variables to be you know specified there. So, similarly, here you will
see that other cases like a vapor up liquid mixture of acetone, and we tell it I will be acetone then
you just calculate here.
(Refer Slide Time: 34:23)

Other example like this here is system contains water and carbon dioxide and exists in two
phases vapor and liquid calculate the decrease degrees of freedom there. So, according to this
Gibbs phase rule component is two phase is two reaction r = 0 here since there is no reaction, so,
degrees of freedom will be equal to 2 here. So, 2 of the phase equilibrium variables must be
given to fix all the others for example, pressure and temperature can be fixed or you can say
pressure or A or temperature and yB like more fraction of that component.

378
Variables P, T, yA note yB will be = 1 - yA and xA will be = 1 pure water assuming here carbon
dioxide is insoluble in water does fix any two variables and find the third from the equilibrium
relationship.
(Refer Slide Time: 35:20)

Now, the maximum number of degrees of freedom is equal to what you see that from the phase
rule, 1 component will be 1 phase will be close to only one and there will be no reaction if it is
there, then according to that phase rule, degrees of freedom will be coming 2 So, anywhere you
have to you know minimum 1 phase to be there and component if it is minimum 1 then degrees
of freedom will be minimum of 2.

So, from these, it can be saved that for any nonreactive 1 component system, the maximum
number of degrees of freedom will be 2 and such a system can be presented completely by a 2-
dimensional diagram, and the moles convenient variables are the pressure and temperature there.
(Refer Slide Time: 36:08)

379
Now, in this case, remember that the common form of ice liquid water and water vapor it just
together in an equilibrium at the triple point of water. Since under such conditions C = 1, P = 3, r
= 0, then degrees of freedom will be equal to 0 that means system will be invariant, the triple
point of water will be is equal to 0.098 degrees Celsius and 4.58 millimeters of mercury. And if
P = 1 and F = 2, then you can say that it is by inherent system. If phase 2 and degrees of freedom
is 1 it would be called as a univariant system for as is phase = 3 and F = 0, then it would be
called invariant system. So, this to be remembered.
(Refer Slide Time: 37:03)

bubble point and

dew point same for
pure substances i.e
the boiling point

Next, let us considered that bubble point viewpoint and critical point as far as that phase
diagram. Now, this bubble point is basically it is a temperature at which that saturation occurs in

380
the liquid phase. In the case of liquid solution, you will see that composition of the vapor in the
bubbles that form in the liquid is not same as that of the liquid and you point it will be the
temperature at which saturation occurs in the gas phase for a given pressure.

And Critical point it is basically the degrees of superheat condition that will refer to the
difference in the temperature between the actual temperature and the dew point and you will see
that higher temperature and or higher pressures, the difference between a gas and a liquid
eventually to disappears, and a supercritical fluid is formed and appoint at who is this
supercritical condition of the fluid happened, it will be called as a critical point.
(Refer Slide Time: 38:12)

So, this things to be remembered now, we are talking about that vapor-liquid equilibrium in a
binary system if it is coming then r this you know that vapor-liquid equilibrium will be required
basically in distillation column moles of the you know chemical engineering process they are if 2
phases are involved with the vapor and liquid there you will see that you have to consider this
vapor liquid equilibrium system.

More than 1 component can be transferred from 1 phase to another they are, and is phase may or
may not contain some you know that obviously you know component and occurs in separation
processes. Success distillation absorption stripping and scrubbing processes. So, in this case,
these are important.
(Refer Slide Time: 39:03)

381
And based on that Gibbs phase rule for the binary system of this vapor-liquid equilibrium, since
there is component is 2 and phase is 2 and in that case, degrees of freedom will be too. So, once
temperature and pressure will be specified, the composition of both the phases will be fixed
there. So, according to that, you know based on that, you know you will see that you can you
know represent how pressure will be changing.

According to the mole fraction and temperature will be changing according to you know more
fraction and how that bubble point or viewpoint and at its saturation condition can be represented
that can you know, we, you know, from this you know this page diagram here.
(Refer Slide Time: 39:59)

382
Based on more fraction, now, at this equilibrium condition, you will see that vapor pressure is
important there, because whenever you know liquid will be converting into vapour, evaporate
you know liquid state there will be you know that some pressure will be exerting that you know
vapor phase, then it will be regarded as that you know that vapour pressure now, how that vapor
pressure will be you know, calculated. So, vapor pressure is basically the function of temperature
and there will be sorting a method to estimate in this case, I am not going to derive that equation.

Just simply, I am giving that what is then you know, equation that we are following to calculate
that vapour pressure. It is called the Clausius-Clapeyron equation by which you can calculate
that vapour pressure.
 p v   H v   1 1 
ln  v      
 p1   R   T1 T 
So, as for you know, Clausius-Clapeyron equation the vapour pressure will be you know that
represented by this here dP* by dT. here P* is nothing but you know that vapor pressure and
sometimes these vapor pressure will be represented by Pv also you know vapor pressure and it is
actually a function of temperature.

So, this can be regarded by this equation and what is absolute temperature and here Vg at and
you know that Vl at other specific molar volumes of gas and liquid that is in equilibrium
condition and H at that you know that is the latent heat of vaporization that is energy required
to vaporize 1 mole of liquid unless the pressure is very high this you know that difference in you
know that specific molar volume of you know gas and liquid will be you know equal to you
know that only molar volume of gas.

They are and in that case, assuming gas is ideal, then according to that we can write if this
equation. Now, further assume that you know that enthalpy change will discuss the letter and
also the enthalpy and separate lecture there, and in this case, this enthalpy change is actually
temporary independent in the range of you know certain interest. So, based on two, you know
this Clausius-Clapeyron equation is modified by another equation based on this equation, and it
is called Clausius-Clapeyron equation.

383
And this can be represented by this equation here, where in this case one terms is coming, it is
called you know materials constant. Now, it depends on that temperature and pressure
accordingly. So, at a particular temperature and pressure if you know that, you know vapour
pressure at a particular temperature you know that vapour pressure then if you substitute it and
then if you know, simplify it you can get this equation at 2 different temperatures.

Now, in that case, you need to know that 1 temperature to find it out other temperature and
corresponding its vapour pressure there. So, this equation will be used to calculate to the vapour
pressure as for this Clausius-Clapeyron equation.
(Refer Slide Time: 44:02)

Now, let us do an example based on this Clausius-Clapeyron equation to calculate the vapour
pressure in this case, the, you know, if we say that vapour pressure on 1 propanol is attained 10
torr at 14.7 degrees Celsius. Now, calculate the paper pressure at 40 or 52.8 degrees Celsius in
this case given that heat of vaporization of 1 proportional is given 47.2 kilojoules per mole. So, if
we use this Clausius-Clapeyron equation here.

We can find out what should be the, you know vapour pressure of that 1 propanol at disdain
toward atmospheric pressure at 14.7 degrees Celsius. So, in this case a first of all you calculate
this value, you know these vapour pressure at this you know 14.7 degrees Celsius. So,
accordingly, if you substitute here one you know temperature like P1 you know that P1 you know

384
that or if you know that P or Pv they are then accordingly what should be that will be and you
know that T1 there P1V and T1 there.

So, after substitution of these values you can calculate that you know paper pressure at that
temperature you know, here 52.8 degrees Celsius = 100.2 torr here 1 torr is actually equaled to 1
millimeter mercury pressure.
(Refer Slide Time: 45:55)

So, remember each now similarly, you can try other you know exercise problems like it is given
here, see problems are given here for your you know, practice and accordingly you just you have
to hear use that Clausius-Clapeyron equation to find out that you know vapour pressure there.
(Refer Slide Time: 46:14)

385
Now, another equation is very important to find out that vapour pressure this called Antoine’s
equation.

 
ln p v  A 
B
C T
This is an empirical equation for correlating that vapor pressure with the temperature data over a
restricted temperature range. So, in this case, this equation of this Antoine is represented by this
equation here

 
ln p v  A 
B
C T
here, in this case, the units of vapour pressure and temperature are millimeter mercury and
Kelvin, respectively.

So, when a bar you are going to use this Antoine’s equation to find out the vapour pressure, you
have to convert all the pressure units in terms of you know millimeter mercury and temperature
in Kelvin, then only you will get. So, otherwise, you have to convert other parameters also to get
this paper pressure in other units, in this case, see constants A, B and C are there; these are called
material you know constants or sometimes it is called Antoine is constants or Antoine
coefficients.

And these coefficients actually vary from substance to substance for different substance this you
know coefficients will be different. Here has some of the examples given 4 different components

386
here for like acetone, ammonia, methanol, ethanol, even what are that you know coefficient A,
B, C at different temperature range there. So, you can use these you know coefficients to
calculate the vapor pressure at each different temperatures are based on the Antoine’s equation.
(Refer Slide Time: 48:05)

Now, let us do an example for this. Now, you have given to calculate the vapor pressure of
ethanol at 80 degree Celsius by using the Antoine’s equation. So, in this case the vapor pressure
of ethanol you have to find out whereas, the coefficients are given for that, you know, ethanol are
here A = 21.8045 and here B is given C is given here. So, if you substitute that A, B, C value in
that Antoine’s equation.

And the temperature is you know 80 degrees Celsius you have to convert it to absolute
temperature in Kelvin, so, it would be 80 + 273.15. So, accordingly, after calculation, you will
get this vapour pressure will be you know that will be coming 14,468 you know that millimeter
mercury like this.
(Refer Slide Time: 49:09)

387
Now, you can calculate the vapour pressure by other methods, which is called Cox chart in this
case the vapour pressure you know can be estimated by plotting the logarithm of the vapor
pressure of certain compounds that is related to a reference compound against is an arbitrary
temporary scale based on this Cox chart you are given in this slides on chart is given the higher
vapor pressure off the tunnel is you know how it is changing based on that reference, you know,
materials or reference you know substance of vapour pressure there.

So, this propel for the vapor pressure against a temperature is a straight line mainly for you know
petroleum hydrocarbons and in this case, a reference compound will be mainly water and this
approach is very useful and can be much better than the Clapeyron method and its accuracy is
you know that dependent to a large degree on the readability of the chart. So, this past has given
by Cox in 1923 they are, and it has been published in industrial engineering and chemistry.
(Refer Slide Time: 50:32)

388
So, according to that you can you know represent these are you know vapour pressure by that
Cox chart mathematically and this mathematical form of this equation is

    C
ln p Av1  ln p Av 2
ln  p   ln  p 
v
B1
v
B2

here C important that C constant here in this equation and PvA1 and PvA2. These are you know
that vapour pressure of substance A at temperature T1 and T2, respectively.
Now, if you know the vapour pressure of this either set of this temperature, then you can easily
calculate the other set of this, you know, vapour pressure of the components they are different,
you know the temperature, you know, just by calculating the efficiency here.
(Refer Slide Time: 51:43)

389
These are also are given these vapor pressure at different temperatures based on this Cox chart
how these you know that vapor pressure will be changing, you know, according to the
temperature for the different you know hydrocarbons there.
(Refer Slide Time: 52:00)

Now, let us do an example here. Now, it is told that calculated the vapor pressure of the tunnel at
60 degrees Celsius by Cox chart method, the following data are given in table here. So, in the
table it is given that at a different temperature, the vapor pressure of water and vapour pressure
of water-ethanol. Now, from the equation here you know as per Cox chart mathematical form,
we can say that, if we substitute this value of Pv for the components A1 and A2 you know that at

390
2 at a particular temperature even for vapor pressure of component B at that particular
temperature you will see that you will get that C there.

So, you just substitute here, then you will see that the values of C = 0.966 and therefore, then you
can find it out after a substitution of value of C and then for other temperature what should be
that you know vapor pressure? there you can easily calculate. So, this ratio of vapor pressure of
this component A1, A2 will be equal to 2.164. So, at that other temperature, if you know that
vapour pressure, you know that of component A1.

Then you can easily calculate what the vapor pressure of component A1 based on this you know
that value of this ratio of this vapour pressure of component A1 and A2. So, we have discussed,
you know, that different issues of this vapour-liquid equilibrium condition how to calculate the
vapor pressure at that equilibrium condition and how pressure and temperature can be changed to
get that different equilibrium condition of this you know.

State and also how to calculate the vapour pressure by different methods that have been
discussed in this lecture. And also, some examples are given you just, you know, practice is
based on that examples and also you can collect other examples from other different books and
you can solve that problem based on this, you know, theory of calculating the vapour pressure.
So, I would suggest you to read part that the stakes book here.
(Refer Slide Time: 54:27)

391
And follow some examples problem based on this theory and how you can you know assess this
vapour pressure based on the calculation of this you know, vapour pressure equation and also
how you can assess that equilibrium condition at different temperature and pressure. Next
lecture, we will try to discuss more about that equilibrium. Conditions there I will try to discuss
some laws of equilibrium condition, how to you know, you know calculate that posture pressure.

And vapour pressure at its equilibrium condition and how to be changing with respect to
temperature and how mole faction will be changed of the system and also how to calculate the
humidity and saturation condition based on this equilibrium system condition will be discussing
so, thank you for this.

392
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 14
Equilibrium Laws, Humidity and Saturation

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about basic principles of multiple systems under, you know
module 5. Now in this module we will discuss about that equilibrium law, or humidity and
saturation.
(Refer Slide Time: 00:47)

In the previous lecture, we have described regarding that phase equilibrium, and they are you
know, different laws and also in phase diagram how we can read the different a state of the; you
know substances at you know different temperature and pressure. And how that phase rule is
applied to specified that is variables of the systems to you know identify any properties of the
system and also we have described the vapour pressure of that you know equilibrium condition.

And also, how that vapour pressure can be calculated by Clausius-Clapeyron equation with other
equation like Antoine’s equation and from the Cox Chart how it can be used to calculate that we
have discussed there in this lecture will try to, you know describe mole about that equilibrium

393
condition of the systems. And how all that you know partial pressure and vapour pressure they
are related to that euro liquid phase composition and vapour phase composition at its equilibrium
condition with this partial pressure.

And also will try to describe something about that humidity and saturation, how that humidity
criterion even what is the you know can see that moisture that is present in the atmosphere or in
dry air how it can be calculated from a you know that psychometric salt that will try to learn
something here in this lecture. Now, as we are talking about that multi-phase system of course.
(Refer Slide Time: 02:41)

That in many chemical and biochemical you know that process system you will see that mole
than one phase will be involving for different you know, chemical a new process to you know,
procure or you can sit to get the different products based on that, you know, processing of that
multiple systems. Now, in that case, you will see that those phases maybe sometimes in a
particular condition at a certain temperature and pressure; they will be in equilibrium what we
have described in our previous lecture.
(Refer Slide Time: 03:12)

394
And also we have described that what are the different unit equilibrium condition like
equilibrium constant solubility equilibrium thermodynamic equilibrium vapor liquid equilibrium
and based on that before liquid equilibrium how we appreciate will be changing at that particular
temperature and also how that diagonal partial pressure or moral composition can be calculated
based on that you know that system pressure and also vapour pressure there.
(Refer Slide Time: 03:39)

Now, we have you know that discuss about that Clausius-Clapeyron equation

395
to calculate the vapour pressure and at different temperature, if you know the consume that
vapour pressure of the systems and then you will be able to calculate that you know latent heat of
vaporization or if you know the latent heat of vaporization and this particular temperature of
what should be the vapor pressure of the substance then based on that, you know quantity you
will be able to calculate what should be the vapour pressure of other temperature for that
particular substance based on this you know Clausius-Clapeyron equation.
(Refer Slide Time: 04:15)

Now, we will discuss another law that is called Raoult’s law, which is actually will give you the
you know, characteristics behavior of the you know ideal solution what is that ideal solution will
be generally regarded as the mixture of you know components in a solution whose properties can
be you know, calculated based on the knowledge of the corresponding properties of the pure
components and the composition of the solution.

Now, in this case, the Raoult’s law will be applied when the mole fraction in the liquid phase that
will process unity and, or pore solutions for you know, hit similar in chemical nature. Now, in
this case, this law relates the partial pressure to the mole fraction in the liquid phase. Suppose
there is you know substance like liquid is, you know becoming by its vapor at its particular you
know equilibrium condition or it will see that in a particular solution, you will see that some
components will be there. We need to be leveraging some components will be you know are
going to the vapour phase and some components will be remaining in the liquid phase.

396
Now, what should be the component of that, what should be the unit concentration or mole
fraction or you can say mass fraction in the liquid solution at a certain temperature and also
pressure based on who is you will be able to calculate that, you know what should be the partial
pressure there and also what should be vapour pressure at its equilibrium condition, that partial
pressure also will be related to that.

So, know that this you know, Raoult’s law it generally relates the partial pressure we know that
mole fraction in the liquid phase you can say that this partial pressure will be equal to you know
mole fraction into you know a system’s total pressure and this partial pressure again it will be
related to you know, what will be the mole fraction of that components in the liquid phase that is
denoted by xi and what should be the vapour pressure of that components at that particular
temperature.

So, if you know that mole fraction of that particular component in the liquid phase and the
vapour pressure of that, you know component at the particular temperature then the partial
pressure. That you know that liquid phase will be all purpose particular pressure of that
component, you know that will be related to this you know that mole fraction of that component
in the liquid phase and vapour pressure of the component at that particular temperature.

So, this equation given in these slides is basically the mathematical expression for this Raoult’s
Law. So, this is basically a relation between that partial pressure and the mole fraction of that
you know component in the liquid phase and vapor pressure.
pi  yi P  xi piv (T )

So, here P is the total pressure and pi is the partial pressure of this species i and Piv is the vapour
pressure of the species i at temperature T and we will see that the law applies only to the mixture
in these components are, you know, chemically very similar, and the mole fraction of the
components that will you know, do not interact in any way.

So, based on these you know, criteria this you know, Raoult’s Law will be applied. So, here we
can say that by this Raoult’s Law will be able to know what from the partial pressure at a

397
particular temperature once you know the mole fraction in you know equilibrium condition of
that components and also system pressure, then you will be able to calculate What should be the
partial pressure and also you can calculate that vapor pressure.

If you know the partial pressure and you know the mole fraction of the components in the liquid
phase, then you can also calculate the vapour pressure there. Again, you can calculate the mole
fraction of the liquid phase if you know the partial pressure and the vapor pressure they are. So,
based on these Raoult’s Law and based on this equation, you will be able to calculate the partial
pressure or vapour pressure or you know mole fraction of the component of the liquid phase.
(Refer Slide Time: 08:59)

Now, let us do an example here. Now, what is the change in vapor pressure when 164 gram of
glycerin is added to you know 338 milliliter of water at 39.8 degrees Celsius. In this case, the
vapour pressure of the pure water at 39.8 degrees Celsius is 54.74 torr and the density of the
water at this 39.8 degrees Celsius is even as 0.992 gram per milliliter. So, at this condition, you
have to calculate what should the change in vapor pressure of this amount of you know glycerin
when it is added and added to this 338 milliliter of water at 39.8 degrees Celsius.

Now, in this case, first of all you have to calculate what should be the mole of the glycerin here.
So, this glycerin, mole of glycerin can be calculated just by the amount of that glycerin added
divided by it is you know a molecular weight. So, simply you can get this mole of a glycerin

398
individual to 1.78 mole and also what would be the volume of water it is given that is 338
milliliter of water and this 338 milliliter of the water that means, here how many moles of water
will be there that will be just simply 18.63 mole just by having that you know one mole of you
know components will add particular temperature and pressure that is at normal temperature and
pressure will give you that 22.2 you know pore heater.

So, according to that we can see that how many moles of water will be there simply and after
that, you have to calculate how much with a you know mole fraction of what are in the, you
know solution of that glycerin. So, mole fraction of water if you know that mole of this
individual component of glycerin and also what are then mole fraction will be equal to what that
we saw here mole moles of water divided by total moles of you know mixture that is moles of
water and moles of glycerin.

So, in this way we can say that mole fraction of you know what are will be equal to 0.91
according to this calculation. And then we know as per Raoult’s law that partial pressure of the
components will be able to you know mole fraction in the water into you know, mole fact partial
pressure of water withdrawal mole fraction of water into you know vapour pressure of the water.
So, according to that we can calculate what will the partial pressure of water it will be equal to
you know xwater is 0.91 and vapour pressure is 54.74 is given here.

So, ultimately this coming 49.8 torr, in this case, you will see that the change in pressure will be
as what is the final pressure of that you know what are and also what will be the initial pressure
of that water vapour. So, here in this case, final you know that pressure is coming as what is that
be final here as you know that water partial pressure at that particular condition, then it is coming
49.8 whereas, you know vapour pressure is at that particular temperature is you know 54.74 torr.
So, if you subtract this, you will get that you know changing you know pressure when if you are
adding these, you know ugly certain of this amount. So, it will be coming as - 4.94 torr.
(Refer Slide Time: 13:10)

399
If we consider here a binary mixture for that Raoult’s law, what will happen suppose there is a
mixture of components A and B so, partial pressure of you know component A can be
represented by yAP, yA is the mole fraction of A and that will be equal to xAPAv, x is the mole
fraction of component in the liquid and PAv is the vapour pressure of the component A.

Similarly, for component B that partial pressure of the component B will be equal to yBP and that
will be equal to what xBPBV that means here mole fraction of component B into partial you know
pressure of component B. since we know that binary mixture that is xA + xB that will be equal to
1 that means the summation of you know mole fraction of components or will be equals to 1. So,
here xA + xB, will be close to 1 that implies that xB will be equal to 1 - xA.

So, if you substitute here 1 - xA instead of xB then you can simply right here that (1 - xA)PBv. So,
that is why these PB that means, partial pressure of the component B will be equal to (1 - xA)PBv
now, from Dalton’s law that we have discussed in our earlier you know, lecture that Dalton’s law
basically says that the summation of partial pressures will give you that total system pressure.

So, here, in this case, our total pressure will be local to the summation of this partial pressure of
components A and B, then we can substitute that value of PA and PB here, then we can write like
this xAPAv + (1 - xA)PAv. So, from these who can express here are what should be the mole

400
fraction of you know a small fraction of A can be calculated as PA/P. So, this will be simply that
xAPAv /p.

So, P can be calculated from this equation

P  pA  pB  xA pAv  (1  xA ) pBv
and then a mole fraction of this component can be calculated by this equation.
p A x A p Av
yA  
P P
Once you know the vapour pressure of this component, and also mole fraction of component A
in liquid, and also total pressure, then easily you can calculate for the mole fraction of A
similarly mole fraction of B the vapour phase or that is you know, you can see that equilibrium
condition in the vapour phase then yB that will be equal to 1 - yA. So, in this way you can
calculate what would be a mole fraction of B there.
(Refer Slide Time: 16:16)

Let us do an example based on these you know principles. Now, it is told you to that estimate the
vapour phase composition at 0 degrees Celsius in equilibrium with a liquid mixture that contains
40 mole percent of benzene and 60 mole percent of toluene also have to calculate the
composition of the liquid mixture who is boil set 90 degrees Celsius and 762 torr and vapour
pressure data is given to you at 60 degrees Celsius.

401
This vapour pressure of the benzene is given 385 whereas vapour pressure of toluene is given a
140. They are at that 60 degree Celsius and that 90 degrees Celsius this vapour pressure of
benzene 1013 and vapour pressure of toluene 408 torr.
(Refer Slide Time: 17:11)

Now, if you apply the Raoult’s law to solve this problem, we can write here, watching the partial
pressure of the benzene that is based on that you know Raoult’s law we can write x benzene into
you know that partial pressure of benzene vapor pressure of benzene. So, partial pressure of
benzene that will be equal to mole fraction of benzene to vapor pressure of benzene that will be
equal to what 0.4 into 385, what is that 0.4 it is given that 40% of the benzene will be in the
mixture and vapour pressure of benzene is given as 385?

So, if you substitute this value and then multiply it you will get this 154 you know top of that
benzene. So, similarly afford following that partial pressure will be equal to mole fraction of
toluene into you know, vapour pressure up toluene. So, if you substitute that mole fraction of
being toluene that is 0.6 and vapour pressure up toluene that is 140 after that if you multiply you
will get that 84. Now, from this you can calculate what should be the total pressure. That total
pressure will be equal to the summation of that partial pressure of those components here.

So, it will be coming as 154 + 84 then it will give you that 238 torr now, you have to calculate
what the vapor phase composition at 60 degrees Celsius. So, your vapor phase composition will

402
be at that 60 degree Celsius that can be you know represented as yB of Benzene that will be equal
to PB of Benzene partial pressure opinion out of total you know that the pressure then we can
substitute this partial pressure of Benzene which is equal to 154 and this total pressure is 238.

So, it will be coming as 2.648 whereas, the same way we can calculate that toluene mole fraction
and that can be you know expressed as you know the ratio of that you know partial pressure up
toluene into the total pressure of the system. So, it would be coming as 84 divided by 238 then it
will give you 0.352. So, these are the mole fraction have been benzene and toluene in the vapor
phase. Now, next problem is that you have to find out the liquid phase composition at you know
that 90 degree Celsius.

Now, in this case again you have to you know, calculate what should be the total pressure at that
90 degree Celsius. Now, again that pressure will be, do you know that partial pressure of
benzene and partial pressure up toluene. Now, that partial pressure of benzene as per Raoult’s
Law can be you know expressed as x Benzene into vapour pressure of you know that similarly,
for toluene that is 1 minus Benzene into you know vapour pressure of toluene.

So, after the substitution of that composition, you know that you know Benzene and toluene we
can obtain that you know that total pressure there, but here since that total pressure is not
changing, so, we can write here this you know that 760 as given here, so, this 760 and also
partial you know pressure spot that is what should be the vapour pressure they are also it is
given.

So, that vapour pressure if you substitute here and then the composition of that Benzene. It is not
known to you so, finally, from this equation can calculate what is up the mole pressure of the
Benzene in the liquid at that particular you know temperature here as a 90 degree Celsius. So,
similarly x of toluene that means mole fraction of toluene also you can calculate from this you
know the equation. So, it is coming finally, that mole fraction of Benzene is 58.2% whereas,
mole fraction of toluene is coming here 41.8%.
(Refer Slide Time: 21:28)

403
Now, we have by you know discuss that ideal solution, where you can apply that Raoult’s Law
and if suppose any solution do not obey the Raoult’s Law at every range your concentration and
at all temperatures that will be called as nonideal solutions. Now, nonideal solutions actually
deviate from that ideal solution in 2 way that is that nonideal solutions that will be showing
positive deviation from the Raoult’s Law be regarded as that you know, positive deviated, you
know that nonideal solution.

And this case the vapour pressure of the component will be you know greater than what is
expected in our Raoult’s Law, whereas, some solutions will give you that negative deviation
from that routes law and in that case the pressure that is vapor pressure will be less than what it
actually should be for that system according to the Raoult’s Law.
(Refer Slide Time: 22:28)

404
Now, some examples of that solution that will be showing positive deviation from the Raoult’s
Law like here, Acetone and Carbon disulfide, mixture Acetone and Benzene mixture Carbon
Tetrachloride and Toluene or chloroform mixture, even Methyl Alcohol and Water, Acetone and
Ethanol mixture. Ethanol and Water mixture that will be regarded as you know that not ideal
solution of having positive deviation.
(Refer Slide Time: 22:59)

From Raoult’s Law similarly, some solutions will also show negative deviation from the
Raoult’s Law, like some examples here the mixture of chloroform and benzene mixture of
chloroform and diether mixture of acetone aniline. The mixture of nitric acid and water and
mixture of you know that acidic acid and you know pyridine and also mixture of you know

405
hydrochloric acid and water. So, this combination of this solution you can call that are you know,
non-ideal solution, which will show you the negative deviation from the Raoult’s law.
(Refer Slide Time: 23:45)

And other important properties of this you know, solution it is called that relative volatility. You
will see that this relative volatility will measure the difference in volatility between 2
components and hence their boiling points. And in this case ratio of pure component vapor
pressure will give you that you know that relative volatility and it will be represented by that
alpha AB, this alpha AB then will be defined as that what is that this is your what is that vapor
pressure of that pure component and A and this is a vapor pressure of component B.

So, this is your this is called vapor pressure because we know that from the Raoult’s Law that
partial pressure that will to you know that xi into you know that we get on vapour pressure of
that component. So, in this case we can write then vapour pressure of that component will be
equal to simply you know that by partial pressure by it is mole fraction. So, from this we can say
that for component A that you can write that you know vapor pressure of component will be
PA/xA.

And similarly, for component B it will be able to you know that PB/xB. So, this relative volatility
will be defined as this ratio of this you know vapour pressure of component A to the vapour
pressure of component B and it is denoted by you know alpha AB and this alpha AB also her can

406
be you know defined as these you know mole fraction of component in the vapour phase to it
liquid phase for the component A.

Similarly, what should be that you know that mole ratio of the mole fraction of that component B
in the vapor phase to the; you know liquid phase. So, in this way also you can you know
calculate that relative volatility and if you know that substitute that value of this you know why
in terms of you know xA then you can finally calculate that part should be that or mole equation
of that mole fraction in the vapor phase in terms of you know that liquid phase comes mole
fraction.

So, this equation will give you that you know that some equilibrium equation based on each you
know relative volatility. Now, mole volatile components that is at normal boiling point degree
Celsius and some will be some less boiling component normal boiling point and their relative
volatility here given as yet. Suppose, there is a mixture of Benzene and Toluene here in this case,
more volatile component is Benzene whereas, less boiling point component is Toluene. In that
case, this relative volatility will be equal to 2.34 as part that you know that condition.

Similarly, for following m-Xylene mixture, this latest volatility is 2.31 Benzene and m-Xylene
mixture it will give you a 4.8 to m-Xylene and p-Xylene, which will give you that relative
volatility will be doubled 1.02 Pentane and Hexane it will give you that relative volatility as a
2.59 whereas the mixture of Hexane and Heptane will give you the relative volatility as 2.2 you
know, 45. So, this you can calculate, how to assess that the components whether it will be you
know, volatile and how it will be relatively, you know, mole volatile than other components
there.
(Refer Slide Time: 27:44)

407
Now, vapour liquid equilibrium also can be made, you know, based on that, you know, relative
volatility, and also you know, composition of that, you know, mixture. Now, as we told that this,
here from this relative volatility we can form this you know equation
 ave x
y
1  ( ave  1) x

what is AB just average you know volatility at the range of temperature and also you know, this
x is the mole fraction in the liquid phase and why is the mole fraction in the you know, vapor
phase.

Now, if we consider any components, then we can say that suppose A so, why you will be called
to AB you know that
pA / xA
 AB 
p B / xB

So, similarly for a cam component we can represent these you know that y and x our relationship
in a graphical form like in that case suppose, if we consider that benzene now mole fraction of
benzene in the liquid can be represented as x and mole fraction of benzene in refer as y.

So, as per that equation of

408
  ave x
y
1  ( ave  1) x

then we can you know get this if you consider that that mole fraction will be 0 to 1, and if you
change that mole fraction of x in the liquid phase accordingly, then it will come as you know that
y value had, in this case, av value is you know, given as possible here, suppose, if there is a
binary mixture, then you have to consider that relative volatility will be equal to 2.34.

So, if you write here  as 2 points you know, 3, 4, and if you change the value of x accordingly
you will get that y value. So, if you plot this you will get that 2 different values of you know that
y value based on these different value of x. So, this line will be represented as you know that
equilibrium line, this is equilibrium line. So, this equilibrium line will actually be calculated
when that happens. Actually that you know benzene will be relatively higher volatile or less
volatile relative to that other component and it will be useful for you know basically for you
know distillation operation in chemical engineering process.

So, in that case this you know that vapor liquid equilibrium cap to be generated and also based
on this vapor liquid equilibrium cap, you have you will be able to assess what should be the
different mole fraction of components in different you know temperature as well as at different
stages. And also what should be the mole fraction in that liquid phase of that component at
different temperature and it can different stages of that you know distillation processes. Now,
another important equilibrium law it is called Henry's law.
(Refer Slide Time: 30:51)

409
Here in this case, listen this law will apply for dilute solutions of any compound like it here that
is xA that almost will be close to you know 0 because it is dilute you can see that will release that
partial pressure in the gaseous phase with the mole fraction in the liquid phase that is air
dissolved in water like this so, in that case, this partial pressure of that component will physical
to you know that will be you know professional to that you know that mole fraction in the liquid
phase.
pi  yi P  xA H i (T )

And then professionally constant will be regarded as in this law constant at that particular time
presets and it is generally increased with increasing temperature and you can say that if you have
you know values of you know in this constant you can expect that solubility will be higher at
higher pressures for gases of high solubility. The law actually will not actually valid. So, in that
case, this law loses it is validity and for ammonia in the water at 20 degrees Celsius.

In that case Henry's law constant will be equal to 2.7 atmosphere per mole fraction there so, we
can see that these for dilute solutions of any compound that is partial pressure will be related to
again that mole fraction of components in the liquid phase, but, this air the proportionality
constant will be you know Henry’s law constant and this Henry’s law constant will give you
without this you know components will be soluble or not.
(Refer Slide Time: 32:39)

410
Now, some hint is constant for the solubility of some gases in water is given like here is some
components that have shown here in the slides like hydrogen nitrogen carbon monoxide, oxygen
methane unit in you know, ethane, carbon dioxide, chlorine hydrogen sulphide and their
respective you know that Henry's constants are given the slides at a different temperature, 0
degree Celsius and 25 degrees Celsius at constant pressure.

So, in that case, how this Henry’s law constant will be heading to temperature soon, but you have
to you know, give a special attention to that hot gases nitrogen and hydrogen in that case, both
components you know, Henry’s law is constant decreases by a factor of about 3 as the
temperature is increased from minus 25 degrees Celsius to 25 degrees Celsius, there may be the
unexpected result that the solubility of these gases in you know ammonia is higher at high
temperatures there so, you have to you know, see these changes of this, you know, Henry’s law
constant at this, you know hydrogen and nitrogen gases.
(Refer Slide Time: 34:02)

411
Now, let us do an example based on this Henry’s law. Here, how many grams of carbon dioxide
gas is dissolved in a 1 liter bottle of carbonated water, if the manufacturer uses a pressure of 2.4
atmosphere in the bottling process at 25 degree Celsius in this case Henry's constant of carbon
dioxide in water is given as 1.65 into 10 to 2 or 3 atmosphere by mole fraction at 25 degrees
Celsius.

Now, mole fraction of carbon dioxide dissolved in water to first find out that we Xco2 that can
be you know calculated based on that Henry's law it will be coming as simply you know that
what is the law here this p = x into Ace that means x will be equal to pi, pi is that when p is the
partial pressure of that carbon dioxide and here this is Henry's law constant. So, here partial
pressure is given to you that is 2.4 atmosphere and hinders law constant is given 1.65 into 10 to
the power 3 and then finally coming 0.001452.

This is the mole fraction of carbon dioxide. Similarly, most of carbon dioxide for moles of water
how to be calculated. So, here moles of carbon dioxide divided by then moles of water, so, moles
of our water will be coming becoming as one minus that is moles of carbon dioxide, then, after
calculation, it is coming at 0.00145. Now, 1 liter of water we can see that, that 55.55 moles of
water this is in liter of water then you have to you know calculate in terms of you know moles of
water because 1 bowl of water is equivalent to 22.4 liter of you know water. So, based on that
you can calculate what should be the most of water in this 1 liter of water.

412
Therefore, moles of carbon dioxide dissolved that will be equal to what because one moles of
water will dissolve this mass of 0.00145 moles of carbon dioxide. So, if you have this you know
these 55.55 miles of water then you can easily calculate what should be the most of carbon
dioxide will be dissolved in the water then it will be equal to 0.00145 into 55.55. So, this will
give you that we are 0.081 moles of carbon dioxide, you know that will be dissolved in 1 liter of
water. So, these moles of carbon dioxide simply it will give you 3.553 grams of carbon dioxide if
you multiply it by its molecular wage.
(Refer Slide Time: 37:06)

Now, then vapor liquid equilibrium ratio and other important properties have discussed liquid
mixture at its equilibrium condition, in that case the mole ratio of the component in the vapor to
the liquid at equilibrium is called the vapor liquid equilibrium ratio. And it is also called that
distribution coefficient. How you know most will be you know distributed in the vapor from its
liquid phase and it can be mathematically expressed by this you know that
yi p Av (T )
Ki  
xi P
this Ki will be called as that equilibrium constant or sometimes it is called distribution
coefficient.

413
And it is simply that what is the most of you know that component in the vapor phase and most
of component in the liquid phase and what is the ratio of these 2. And if you substitute that, you
know, if we apply that, you know, Raoult’s law, then we can say that this will be basically as you
know that ratio of vapour pressure to that, you know, to partial pressure of the system. Now, as
per Dalton’s Law we can have that partial pressure will be triggered to y i into p.

As per Raoult’s Law it p i will be equal x i into p iv into T that means, here mole fraction of that
component into vapour pressure of that component. So, according to that, if we substitute here
you can simply say that this k i will be difficult to here p Av that will be a ratio of vapour
pressure of the component to it is you know, total pressure.
(Refer Slide Time: 38:47)

Now, saturation what is saturation you know, you will see that the gas phase sometimes cannot
accommodate at any mole vapor from the liquid phase at particular you temperature and
pressure. Now, any attempt in adding mole vapor from the liquid phase, if you increase the
partial pressure there or you can see if you add mole vapor there, there will be no increase in
partial pressure that may lead to the condensation.

Now, you will see that if you add mole vapor up from the liquid phase and you will see that the
partial pressure will keep on increasing there. So, when you will see it condition, when you will
see that partial pressure will be almost will be close to vapor pressure, you will see that that

414
solution will be you know that necessitated with that you know vapor component. So, we can see
that at a saturation condition, partial pressure will be equal to vapor pressure.

So, we can see that temperature at this point of this saturation. If you know vapor phases, you
know that tries to you know be condense it at that saturated temperature. So, that temperature
will be called a dew point temperature. So, we can say that when a bar you know that any you
know gas or you can see mole vapor from the liquid phase tries to you know condense it higher,
the partial pressure will be equal to vapour pressure the respective temperature will be called as
dew point temperature.

And at that condition, the saturated vapor will have that partial pressure as you know that here
pi  yi P

you know if you know that total system pressure and two components of that component in that
vapor phase, then you can calculate what without partial pressure and the partial pressure will be
equal to their vapour pressure of that particular components. So, when the partial pressure of this
vapor in the gas phase is less than the vapor pressure, that is you know pi less than piv here has
for notation.

Then the vapor phase is report to a partially saturated vapor or you can see that it will be super-
heated vapor and then you can see that pi will be no less than piv. Now, superheated vapor cannot
condense unless that in phase system pressure says that Raoult’s law applies and also decrease
the system temperature to the dew point temperature there so, these are the conditions they are to
you know the superheated vapor who is may not be condensate at this condition.
(Refer Slide Time: 42:00)

415
Now, let us do an example here let us say that a stream of air exiting a condenser at a
temperature of 87 degrees Celsius and a pressure of 1.5 bar contains 25 mole percent of water.
Now, in this case you have to know calculate to what should be the dew point of the air. Now, in
this case you have to first calculate the partial pressure of the water in the air that is entering to
the condenser and it can be calculated as that you know by you know that either by Raoult’s law
or by you know that simply you know the Dalton’s law that will be able to partial pressure will
be able to you know that mole fraction of that components into each start to temperature.

Then it will be coming as here 0.37 pipe bar. Now, if the equilibrium between the 2 phases
against the partial pressure of that water must be equal to the vapor pressure at that dew point.
Now, this can be written as here, partial pressure will be equal to vapor pressure. Now, using that
steam double the dew point temperature at that particular condition of that equality of that partial
pressure to each you know vapor pressure at a particular temperature and pressure that
temperature will be as you know 74.66 degrees Celsius that you can get it from the steam table
and pressure will be as you know 0.375 bar.

So, we can say that simply here that dew point will be that temperature, when this you know
moisture partial pressure in the air will be you know equal to the pressure of that moisture in the
air.
(Refer Slide Time: 44:05)

416
What is that relative saturation and relative humidity that is also important in this case, relative
saturation and relative humidity can be defined as what should be the partial pressure of the
moisture in the air and what will be the vapor pressure of the moisture in the air at that particular
temperature, the ratio will be regarded as relative saturation or it is sometimes called relative
humidity.

And also you can say that, if you apply the ideal gas law, the relative saturation or relative
humidity can be defined as here you can see that what is the ratio of you know partial pressure to
the total pressure it would be regarded as simply you know that mole fraction of that components
in the vapor or you can see they are here in itself for the humidity consideration or in a system of
gas liquid mixture, they are. So, relative saturation to be you know; defined as Pi by P divided by
again the ratio of that you know vapor pressure to that total pressure.

So, here basically the ratio of you know partial pressure to the total pressure to the vapour
pressure to you know total pressure. So, in this way you can write it seems here you can say that
most ratio is equal to pressure issue is equal to volume ratio. So, you can represent it as volume
ratio also here like this and also you can represent it as you know that mass ratio here and from
that mass ratio, if you multiply it by you know molecular weight then you can represent it as
mass ratio at that particular solution condition.

417
Now, from this, you know, principle you can say that suppose relative humidity or relative
saturation, it is a carbon zero percent that means, the air will be totally dry, harassed 100%
relative humidity means that it will be saturated with moisture.
(Refer Slide Time: 46:15)

There is another representation of that saturation called that Molal saturation and also humidity
respective which is called Molal Humidity. Molal Saturation or Molal Humidity is defined as
similarly by that mole ratio here and also it is sometimes you put it as a fraction or a suppose a
percent here sometimes some books they are using as humidity representation like this and also
sometimes, if the system consisted of water species i and air.

Then i-free gas refers to the bone-dry air here for the presentation of this Molal saturation or
Molal Humidity. Now, what is the absolute saturation or absolute humidity that is also defined as
like here given in this equation here so, this is basically the ratio of you know most of that
component i to the moles of its you know, in the, you know, free gas they are in excellent
condition and also that ratio will be in you know saturated condition, how it will be there and
based on that excellent saturation condition if you make it ratio they need to be called as you
know absolute saturation or absolute humidity and it is defined as by this equation.

Now, in this case, you have to remember that, if suppose absolute saturation is less than relative
saturation, then you can say that P i that means partial pressure will not be close to that vapor

418
pressure, but this will come only when then if this partial pressure is you know that changing or
deviated from the vapor pressure so, this absolute pressure will be you know, then defined in
terms of relative saturation and also that ratio of that you know, vapor pressure to the partial
pressure deviated from the total pressure. So, in this case of course, that this you know absolute
pressure will be you know less than saturated pressure.
(Refer Slide Time: 48:21)

Now, another important point is dry bulb temperature in the gas-liquid equilibrium condition. In
this case, the dry bulb temperatures are usually referred to as the air temperature that will
indicate by a thermometer not affected by the moisture of the air and dry bulb temperature is
denoted by Tdb generally, and it can be measured using a normal thermometer freely exposed to
the air but shielded from radiation and moisture.
(Refer Slide Time: 48:53)

419
As wet bulb temperature is the temperature set of adiabatic saturation, this is the temperature that
is indicated by moistened thermometer bulb exposed to the air flow and the rate of evaporation
from that weight you know on about depends on the humidity of the air and that the evaporation
is reduced when the air contains mole water vapor and the wet bulb temperatures are always
lower than the dry bulb temperature. And you have to remember that it will be identical to the
100 percent relative humidity they are if they get to the saturation condition.
(Refer Slide Time: 49:32)

Now, dew point we have already discussed that what is the dew point temperature they are, it is
basically the temperature at which water vapor starts to condense it out of the air that is the
temperature at which that air becomes completely saturated. And above this temperature, the

420
moisture will stay in the air and if the dew point temperature is close to the dry air temperature
then the relative humidity will be high whereas the dew point is well below the dry air
temperature you can see that relative humidity will be low.
(Refer Slide Time: 50:05)

Now here on Psychrometric chart is given to calculate that you know humidity chart and also
what is that different components what is the dry air temperature what is the you know dew point
temperature how that enthalpy access solution condition can be calculated, what should be the
word but or saturated saturation temperature, how to calculate that you know absolute you know
moisture content and also what should be you know humid volume they are how it is defined.
And also there are other properties like you know, what would be the enthalpy deviation, what is
the relative humidity how to calculate. So, I will discuss these things are in the next lecture.

How to you know to use that Psychrometric chart to you know to calculate the relative humidity
and also dew point temperature, dry air temperature are enthalpy even you know that towards the
humid volume and also relative saturation, absolute, you know, moisture content in the air based
on phase. So, we will discuss more about that you know this humidity and condensation and also
what is that you know when saturation problem, condensation problem, evaporation problem we
will discuss more about that in the next lecture. So, thank you for your attention for this lecture.

421
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 15
Humidity, Saturation Psychrometric chart

Welcome to massive open online course on basic principles and calculations in chemical
engineering. We are discussing about the basic principles of multi-phase systems as a module 5
and under that module we have discussed in our previous lecture regarding pressure partial
pressure, how actually those terms are defined and also how to calculate you know that Dalton’s
law, even we have discussed how to calculate the vapor pressure at different temperature based
on that Clausius-Clapeyron equation and Antoine’s equation even how to calculate the vapor
pressure.

From that you know vapor pressure of you know substance you know relative to a you know
different substances and that you know have represented it in a you know how to calculate that
vapour pressure that will be that has already been you know discussed and also we have
discussed that how, you know do you dew point in saturation point can be defined based on that
Vapour pressure and partial pressure under equilibrium condition. So, in this lecture, we will
discuss you know more about that saturation condition.
(Refer Slide Time: 02:11)

422
And before actually considering their saturation condition, you have to know some equilibrium
laws, that is Raoult’s law, and Henry’s law and also relative volatility. So, we have discussed in
our previous lecture also those laws like a Raoult’s law in this law and based on their, you know,
laws, how to calculate that, you know, partial pressure and vapour pressure, relative to the
constitution of the, you know, components in our liquid phases.

So, based on that, we will discuss more about that, you know, equilibrium condition just by
discussing saturation and also how this you know, what vapour will be you know saturated in the
air in a mixture of air and water in atmospheric condition to that is represented by you know
humidity and that humidity how actually absolute humidity, relative humidity and also the
saturation relative saturation or relative humidity how they are actually related and also based on
that you know saturation condition.

What should be the, you know that humid volume of that particular amount of air in the presence
of moisture under equilibrium condition that also to be you know, discussed and those things, of
course, will also be discussed by using a psychometric chart. This is a graphical representation of
you know relation that between you know, absolute humidity, relative humidity, you know
saturation and also dew point temperatures are how you know enthalpy are related to those you
know that variables there so, those are actually represented in a graphical form that is called

423
psychometric chart. And here in this lecture, we will also discuss how to use that you know,
psychometric search to find out those variables there.
(Refer Slide Time: 04:34)

First of all, we have to you know, go through again that what is the saturation, so, we know that
saturation that partial pressure, of course, will be equal to vapour pressure, already we have
discussed that vapour pressure how to calculate at equilibrium condition based on that the
Clausius-Clapeyron equation and Antoine’s equation. So, if you know that, you know Antoine’s
equation or Clausius-Clapeyron equation at a particular temperature, you will be able to find out
what the vapour pressure.

Now once you know that equilibrium vapor pressure with that partial pressure or you can see that
partial pressure will be equal to vapour pressure, then at that condition you will see that if you
know a small amount of addition of that vapour under that equilibrium condition from the liquid
phase in the liquid phase is done, you will see that the you know system will lead to you know
become you know condensed that means, here is called that condensation occur at that particular
condition.

And the temperature at which this you know that saturation occurs that means this partial
pressure will be able to vapour pressure under which that you know that people will be you know
condensing, it is in its first stage, and that point will be regarded as dew point, and the saturated

424
vapour will have that partial pressure. And calculated based on this, you know equation or as this
partial pressure is defined as the pi is equal yip or pi is called partial pressure of component and
yi is called the mole fraction of that component i and here P is called you know total pressure of
the system.

So, yi into p that will be your partial pressure and if this partial you know how pressure if it is
equal to that vapour pressure which is denoted by Piv that already we have discussed in our
previous lecture also so, when this partial pressure of the vapour in the gas phases, you know that
will be equal to vapour pressure then you can see that that saturation starts and the respective
temporary temperature of that solution will be called as saturated temperature or it is regarded as
dew point temperature.

Now, if suppose that a certain condition that vapour pressure is, you know less than the partial
pressure, then what will happen? If suppose, the partial pressure will be you know less than that
you know vapour pressure, then what will happen? Now, in this case, when the partial pressure
of the vapour in the gas phase if it is less than the vapour pressure, then you can see that vapour
is reported to a partially saturated and vapour or you can see that superheated vapour will be
there.

So, for superheated vapor we can see that this partial pressure will be less than equals to vapor
pressure and this superheated vapor at this partial saturated condition cannot be condensed unless
if you know that increase the system pressure says that the Raoult’s law applies there and also if
you are not actually decreasing the system temperature to the dew point temperature, then you
not be able to have that you know that condense it on from the superheated vapour. So, this is
regarding that saturation we know that that partial pressure will be equal to vapour pressure and
after that.
(Refer Slide Time: 08:09)

425
We can see that that the condition of that vapour pressure and you know partial pressure if it is
not equal, then you have to consider it as you know partial or you know saturation condition.
Now, let us have an example of this, you know the saturated condition. In this case, suppose a
stream of the air that will exit from a condenser at a temperature of 87 degrees Celsius and a
pressure of 1.5 bar that contains you know 25 moles of water.

So, at this condition of this temperature of 87 degrees Celsius and pressure of 1.5 bar, you have
to find out what should be you know dew point of the air at this particular condition. Now, in this
case, what you have to do, first of all you have to calculate what should be the partial pressure of
water in the air that is entering the condenser. So, that can be calculated based on that equation
given by Daltons that is partial pressure will be equal to y for that component water into total
pressure that will be equal to what that it will be simply that he had a 0.25 into 1.5 the 0.25 is
basically the more fraction of the water in the air, and system pressure is 1.5.

But, so, this coming 0.375 bar now, if the equilibrium between the 2 phases, that the saturated
condition, the partial pressure of water, Of course, must be equal to the vapour pressure of the
dew point then this condition the mathematical form can be expressed as like this partial pressure
of water will be equal to vapor pressure of water and this will happen only the condition of
saturated condition and the temperature at that saturated condition will be regarded as you know
dew point.

426
So, at this point, you can see that simply partial pressure will be equal to vapour pressure. Now,
you can find out that what should be the dew point temperature from the steam double once you
know this, you know pressure and temperature. So, from the steam table that will be actually
shown later on that bar from the steam table how to you know to find out that dew point
temperature once you know that pressure and the respective temperatures are there, so, the dew
point of the temperature at that 0.75 bar will be equal to you know 74.66 degree Celsius at this
particular this condition of saturation.
(Refer Slide Time: 11:19)

We will discuss the humidity now, what is that humidity basically that sometimes we are saying
in an atmosphere that how I you know it is you know that atmosphere or weather is very humid
or you can say that today's you know that today's high here, you know, humid here. So, what is
that basically that humidity of that air-water vapor mixture in the atmosphere? So, the humidity
of an air-water vapour mixture is basically the water vapor is carried by 1 kg of dry air.

That means per kg dry air is how much water is being carried that will be regarded as humidity.
It depends on the partial pressure of the water vapor and the total pressures what the total
pressure the atmosphere that is one atmosphere you can see. Now, this you will see that the
amount of water vapour per kg of dry air which is actually carrying by the dry air at that

427
particular temperature will be represented by humidity and this humidity this amount will be
changing with respect to temperature.

So, if there is if you know the temperature is you know very high then what will be the humidity
at low temperature what will be the humidity that depends on also usually the partial pressure of
that, you know, components that is water in that you know air water mixture at that particular
temperature. So, humidity basically defined as the ratio of moles of water by what is that moles
of you know that dry air.

So, this humidity basically, you know, are denoted by H, and it is defined by this equation here,
this mole of water by moles of the dry air, now, this since it is you know, mole percentage or
mole ratio you can see, you have to remember this true that in an ideal mixture you will see that
in a system mixture of gaseous always this truth to be you know that remember that mole ratio
will be equal to pressure ratio that will be equal to volume ratio.

Now, if I say that that there is a mole ratio of water vapor to you know mole ratio of the dry air.
So, that is this is the mixture we can say that this is an ideal mixture in that case we can see that
since it is a molar ratio of these 2 components, so, you can express this as you know, pressure
issue now, what pressure issue will be represented here it should be actually partial pressure
issue. Now, what should be the partial pressure of that what are you know in the air it will be
represented by the partial pressure of water.

And it is denoted by PA here you can you know donate you can denote this water as w instead of
here and also what should be the partial pressure of you know dry air if you know the partial
pressure of water as PA and total pressure of P of the system. You can easily say that partial
pressure of the dry air will be equal to total pressure minus partial pressure for that water. So, it
would be P - PA. So, in this case, you can represent this humidity as the PA divided by 1 - PA as
given here in the slide.

So, it will be basically unit as you know molar ratio that means you are moles of water by moles
of air you can represent this humidity in terms of you know mass ratio also so, that will be in

428
case you have water by kg of air. So, in that case, you have to know multiply this moles of water
by each molecular weight and also moles of air by its molecular weight. So, in this case if we
multiply this partial pressure by it is you know, the molecular weight of water, then you will see
that it will be asked is kg of water.

Similarly, here multiply by molecular weight of air that is 28.97 then you can have this you
know, weight of you know that, so, in this way you can represent this humidity in terms of
master ratio. So, it will be coming as this as shown here in the slide. And saturation conditions
the partial pressure of what our vapour will be equal to vapour pressure up your water. So, in that
sense at saturation condition, we can you know called this you know humidity as saturation
humidity.

So, in that case that saturated humidity will be defined by this you know just simply by you
know in terms of that vapour pressure, so, what is the vapor pressure of water that will be PAv
here and remaining is P – PAv. So, they are mixture partial pressure is p so remaining pressure
that will be equal to P – Pav. So, here the saturation humidity would be defined by this PAv
divided by P - PAv and what should be the percent is unity similarly, what will be you know
absolute humidity that means Hs is saturated humidity into 100. So, this will be you know
referred as percentage humidity here.
(Refer Slide Time: 17:27)

429
And you can also represent that humidity in terms of you know that relative saturation or relative
humidity. So, relative saturation that is denoted by RS or you know relative humidity that is
denoted by RH. So, in this case, relative saturation for any liquid and relative humidity,
especially, to water vapour in air will be represented by this ratio of that, you know partial
pressure divided by you know vapour pressure of that you know component attic temperature t.

So, this is called relative saturation. So, very interesting that here relative saturation basically
represented for any liquid, whereas, relative humidity basically represented for the system of
water vapor in air and applying the ideal gas law, you can write this relative saturation or relative
humidity as Pi by P divided by PiV (T)/P. That means, here we are dividing this equation by total
pressure on its both, you know numerator and denominator.

So, we can have this simply the pressure ratio that we represented by you know that volume ratio
as per ideal gas law and also we can then represented by you know molar ratio that means, saw
moles of component i to it's you know moles at its saturated condition. So, we can be represented
by ni by n a saturated and similarly, you can represent it by mass ratio, just you know that in
terms of you know you know mass ratio just by multiplying each molecular weight of that
particular component.

So, in this way, this relative saturation or relative humidity can be you know obtain if suppose,
there is zero percent relative humidity. That means, you can say that that air should be
completely dry whereas 100 percent relative humidity that will mean that here will be saturated
they are with each you know vapour pressure and percentage relativity will be you know defined
as what is you know partial pressure of that component i and double pressure of the component i
and their ratio.

And if you multiply it by 100 then it will be you know called as a percent is relative humidity or
you can simply calculate it as if you have the absolute humidity and the humidity at each
saturation condition and if you multiply it by 100, then you can obtain that percentage relative
humidity.
(Refer Slide Time: 20:43)

430
Now, this humidity also can be represented by molal humidity or saturation can be regarded as
molal saturation. In this case, this molal saturation or molal humidity can be you know defined as
given here in the slides that equation here that image or image will be given by ni free gas in free
gas simply we can see that only you know or dry air here. Here, in this case, i-free gas refers to
the bone-dry gas suppose there is water vapor, and you know dry air mixture.

So, in that case, if i represented as water vapor, so, i-free gas will be simply you know that dry
gas and it will be represented as bone dry gas. So, if the system consisted of a species i and air,
then i-free gas refers to the bone-dry gas and according to that, we can represent that absolute
you know, saturation or absolute humidity that is in terms of bone-dry gas properties. That
means here we can define it as you know, what will be the actual mole fraction of that 2
components of i and bone dry gas in the actual condition.

And what should be the mole ratio of that component i and that bone dry gas at saturation
condition and from you can simply you know, rearrange heat and you can be represented by it is
you know the ratio of moles of that component i that is that extra and saturation condition and
also this you know mole fraction of you know i-free gas that means bone dry gas in saturation
and actual condition. So, based on who is you can say that this absolute you know saturation or
absolute humidity can be you know defined as here RS into P minus PiV by P minus Pi.

431
So, here RS is relative saturation has this you know this ratio of this you know fresh air at each
you know saturation condition, and it is actual condition to be you know multiplied here. So, in
this way, we can define absolute saturation and absolute humidity. And you will see that here
since absolute saturation is equals to relative saturation into this pressure ratio, we can say from
this you know mathematical expression that AS always should be less than you know RS that
means absolute saturation will be always less than you know relative saturation.

But there is an exceptional condition, if you are having this condition at you know, saturation
condition that means, partial pressure will be equal to vapour pressure. Then, in that case, you
can see that you will not get this, you know that absolute saturation will be equal to relative
saturation. They are of course will not be inequality, but there will be simply you know that
absolute saturation and really relative saturation will be equals to you know each other. So, in
that case, at you know saturation condition that absolute saturation and relative saturation both
will be the same.
(Refer Slide Time: 24:18)

Now, another term in this case humid volume now, the humid volume is basically equal to the
volume of one kg of dry air plus volume of the water vapor that it contains at you know what one
atmospheric pressure that is absolute pressure and the given temperature there now, if you use
that ideal gas laws there the humid volume can be represented as here basically what will be the
you know volume of, you know one case you have dry air that can be represented by this you

432
know equation and also what is the volume of that what are we part at that atmospheric condition
and temperature given to that can be expressed by this you know term here.

So, if you add these 2 you know volume at that particular atmospheric pressure and given
temperature, you can have this final form of the equation as given in the slide that will be equal
to 2.83 to 10 to the power minus 3 plus 4.56 into 10 to power minus 3 into H into T. Here H
humidity, so, humidity it is required because, you know humidity means what is the water the
amount of water vapour per kg of your dry air.

So, once you do that amount of vapour per kg of you know, dry air, you have to convert it to
mole and once you know, the mole of that what you will be able to calculate for to the volume of
that whatever vapour they are based on that you know that one mole of molecule exhibit that
22.4 meter cube volume. So, based on that, you will be able to calculate what the volume of that
you know a particular amount of water vapor in the air.

Similarly, the same amount of you know the air will exhibit how much volume that also to be
calculated. So, if you add up these two you know volume, then it will be regarded as the humid
volume. So, it is simply from this concept of humid volume, we can have this equation for that
humid volume in terms of humidity and at a particular given temperature by this equation, but
this will be, of course, will be represented by, you know our volume per kg of dry air.
(Refer Slide Time: 26:57)

433
Another important you know terms off for this, you know, representation of these you know
moisture content in the atmosphere at a particular you know the temperature and how much
energy will be you know, released as an energy of heat that also to be considered. So, in that
case, it is regarded as humid heat. This is basically the amount of heat that is required to raise the
temperature of 1 kg dry air to get its equilibrium, you know, water vapor or that contains by 1
kelvin.

So, it will be regarded as that humid volume, humid heat. So, it is determined by the relationship
like this here this is represented by the symbol here Cs that is humid heat, and it will be based on
that you know temperature change as well as you know that what will be the humidity will be
changing based on that temperature change. According to that, what should be the humid heat
that can be calculated by this equation here, in this case, you will see that 2 terms are there, 2
numerical values are given in this equation, one is 1.005 and other is 1.88.

Now, in this case, 1.005 refers to the specific heat of dry air that is in terms of kilojoule per kg
kelvin as 1.88 refers that you know a specific heat of the water that contains by that one kg of the
dry air in kilojoules per kg kelvin. So, from this equation, you will be able to calculate what
should be the humid heat once you know that humidity of that, you know, air.
(Refer Slide Time: 28:53)

434
And total enthalpy also one important term based on which you can say that what should be the
enthalpy of 1 kg of dry air plus the enthalpy of water vapor that it contains, if you know bubble
point temperature or you can say that you know detum point temperature that is denoted by Tb
for both components here suppose water vapour and here dry gas then it can be determined by
the relationship here given as like
H y  Cs (T  Tb )  H b
 (1.005  1.88H )Cs (T  Tb )  H b

Here in this case b that latent heat in kilojoules per kg of water vapor at that determines
temperature or it is regarded as sometimes bubble point temperature and it can also be
represented by humid heat here in this case, this Cs the heat to be, you know defined as 1.005
plus 1.88 H and that also you know that to be written here, in this case, the Cs will be you know,
Cs  1.005  1.88H
canceled out because Cs we have substituted this value of is here in this slide.

So, please correct it here. So, it will be here

(1.005  1.88H )Cs (T  Tb )  H b

So, once you do that a latent heat of that vapour in kilojoule per kg at that particular reference
temperature and the humidity then at a particular temperature, what should be the total enthalpy
you can calculate by this equation.
(Refer Slide Time: 30:45)

435
Now, let us do an example based on this theory. In this case, you have given that the temperature
of air in a room is 40.2 degrees celsius and under the total pressure is atmospheric pressure that
is 101.3 kilo Pascal the air contains water vapor with a partial pressure Pa is equal to 3.74 kilo
Pascal at this temperature of 42.8 degrees Celsius the vapor pressure of water is given us 7.415
kilo Pascal. Now, you have to calculate what is the humidity and what is the saturation humidity
and percent humidity also you have to calculate for the percentage of humidity.
(Refer Slide Time: 31:37)

Now, as we know that, humidity is defined as this equation given earlier also in the slide that
humidity will be equal to 18.02 by 28.97 into the ratio of this partial pressure of water to the dry
gas. So, in kg of what kg is air now, you know these are partial pressure of what vapour and also

436
you know that total pressure of the system. So, if you substitute this value or partial pressure
there, then you can have this value of 0.0238 in kg of water by kg of air.

So, this is you know that humidity at that particular temperature and what is the saturation
humidity that is also know that this partial pressure basically will be you know vapor pressure of
the water vapor there so, vapor pressure of the water vapor is given to you that is you know that
7.415 and after that if you substitute that vapor pressure here in this equation, you will get to that
saturation humidity will be called 0.04912. That is in kg of water and kg of air.
(Refer Slide Time: 33:03)

So, this is your saturation humidity and what do ratio of humidity that is you know ratio of that
humidity to that at saturation condition into 100. So, it will be basically that divided by this you
know 0.0238 by the 0.0492 into 100 it will come as 48.53 there similarly, relative humidity you
can calculate for the ratio of partial pressure of that component i to the vapor pressure of
component i at the particular temperature into 100 that then you can have this value up to the
substitution of this you know variables there and it will give you the value of 50.43. So, this is
your percentage of relative humidity.
(Refer Slide Time: 33:56)

437
Let us do another example, based on this humidity. Now suppose you know, conditioned air is
supplied to a dryer at a total pressure of 760 millimeter mercury and at a temperature of 50
degree celsius at a humidity of 0.01 kg water per kg of bone dry air. Now, this air leaves the
dryer at 760 millimeter mercury, total pressure and temperature of 50 degrees Celsius, but here
the relative humidity of that, you know, air leaves of 83% of this relative humidity.

If 40 kg of water enters into the air stream per hour, you have to calculate what will be the
weight of bone dry air that is flowing through the dry air given that the vapor pressure of the
water at 50 degrees Celsius is 92.5 millimeter mercury. Here in this case vapor pressure of the
water at 50 degrees Celsius is given to you so, if we draw this, you know, a schematic diagram of
this. Now, let us see that this is your dryer.

Now the airstream at this dryer is coming at a temperature, what is that 50 degree Celsius at a
humidity of 0.01 kg of water per kg of bone dry air for us water along with air with that 40 kg
per hour. So, based on these up to dry of this air will be coming out as you know with 83% of
relative humidity. So, in that case, you have to find out what should be that weight of bone dry
air that is flowing through the dryer. If the water flow rate is 40 kg with this, you know air that is
entering into the dry air.
(Refer Slide Time: 35:56)

438
So if I saw this, you have to you know consider the basis past now, what should be the basis, in
this case, we can consider the basis as one-hour duration of the operation of drying. Now, also
you have to calculate what should be the vapor pressure of water at that particular temperature, it
is given to you is 92.5 millimeter mercury and also you have to calculate for the partial pressure
of the water, but is not given to you have to calculate here anyway is not given to you also you
know that at the relative humidity is 83%.

So, if you know that the relative humidity at this air then you can simply say that, since it is
defined as you know ratio of partial pressure to the vapor pressure of water, then you can say that
Pw by Pw of v that will be equal to 0.83 from which you can calculate easily. The partial
pressure of water.
(Refer Slide Time: 37:04)

439
After that, you will see that this kg mole of water per kg mole of dry air that you have to
calculate that been thought to be the moles of air is entering per kg of you know that dry air there
so, it is basically that you know that partial pressure of water and what to be the partial pressure
of air, what is the ratio and from this ratio, you can say this will be equal to 0.112. What does it
mean that per kg mole of dry air that will contain you know 0.112 kg mole of water.

Now, in terms of weight, you can see per kg mole of water by kg mole of dry air. Simply you
have to multiply it by its molecular weight of that water and air, then you can get to you know
0.07 here. Now, in this case, this 18 and 28.4 basically, they are molecular weights of water and
dry air, respectively.
(Refer Slide Time: 38:11)

440
Now, what is the inlet air condition this kg of water by kg of dry air it will be 0.01 it is given
since the humidity is 0.01 or us outlet air condition that we have calculated based on the
temperature of 50 degrees Celsius and the pressure is 760 millimeter mercury and it is as 0.07.
Now, in this case, since dryer is used to you know moisture air or remove the moisture from that
object or from the air you know that now, how was the amount of actually what air is removed at
that particular temperature and pressure in the dry air.

So, kg of water removed per kg of dry air, this is basically then you know, what is the difference
of that humidity? So, humidity at the outlet is 0.07 and what is the humidity at the inlet that is
0.01 if you subtract it you will get this 0.06 this is basically that amount of water is removed per
kg of dry air then what would be the total water interest to the dry air you know that is given 50
kg. Now, this 50 kg of water you know actually removed by that draft.

Now, can you see then, what will be the amount of water then supplied there to remove all these
50 kg of you know, water by this dryer. Now, you know that to remove that 0.0 kg of water it
actually requires one kg of dryer per this calculation, so, 50 kg of water to be removed, what
would the amount of air to be required. So, simply you just divide this 50 by the 0.06 then you
can get this simply this amount of 833.3 kg.

441
So, that means, here at 833.3 kg of air actually is required to remove this 50 kg of water by this
dry air at that particular temperature and pressure. So, this is one example of you know are doing
the material balance based on this humidity, the air, and of course, you will be doing that you
know unknown parameter here in this case here what would be the amount of air is required.
Similarly, you can calculate if it is unknown parameter is supposed to be the, what would be the
total amount of you know water can be you know remove per you know suppose how kg of air to
be supplied there.

Simply you can calculate up to this, you have to calculate what do that what a remove and for
that for to be the amount of air or amount of water actually remove per 100 kg or 5 kg or
whatever amount will be given for air that you can easily calculate. So, these examples will be
helpful to you know calculate further that requirement of water requirement of you know that air
and also what to be the amount of water to be removed from that you know, device or from that
you know that air-water mixture by the dry air.
(Refer Slide Time: 41:38)

Next, we will discuss the psychometric chart, what is that psychometric chart?. This is basically
that graphical representers graphical representation of moisture content or absolute humidity or
you can say that what will be the relative humidity? What should be the wet-bulb temperature
what our saturation temperatures are how to calculate that enthalpy of the saturation from this
you know graphical representation and also watch the humid volume, what is the dry air

442
temperatures are all are related to each other, and all those relations and based on their relations
profiles are given in this graphical form, and this graphical form of representation of those
variables based on this humidity and saturation condition will be regarded as a psychometric
chart.

So, this psychometric chart to displace the relationship between dry bulb, wet bulb and dew point
temperature and specific and relative humidity here see these psychometrics chart are shown in
you know slides in the x-axis you will see that there is no dry air temperature given you know
that here, this is minus 10 to you know 55 degree Celsius it is given in the y axis it is given you
will see that moisture content per kg dry air even in the y axis is also represented enthalpy at
saturation condition.

And that you know that relative humidity and you know enthalpy deviation with saturation
temperatures are and also you can say that what will be the humid volume at that particular you
know driver compressor all are given here So, from this chart you will get that information of all
those parameters provided 2 parameters will be known to you, and from those 2 parameters you
will be able to you know, you know read that other parameter other you know variables from this
psychometric chart.

And let us have an example of how to you know, read this psychometric chart, or use the
psychometric chart to calculate different, you know, variables or parameters. Now, in this case,
one problem is that humid air is considered at 30 degrees Celsius, which has a dew point of 15
degrees Celsius. Now, using this psychometric chart provided to you, have to determine the
following like what is the relative humidity? What will be the absolute humidity? What do we
the weight bulb temperature? What would the dry bulb temperature what would be the humid
volume?
(Refer Slide Time: 44:44)

443
And what would be the specific enthalpy what would be the amount of you know air that
contains you know, 1.5 kg of water and also you have to calculate the volume occupied by air
that contains 1.5 kg of the water there so, all those you know things to be you know calculated
based on these psychometrics reading.
(Refer Slide Time: 45:07)

Let us have this past, you know relative humidity. Now, how to calculate that or how to read that
relative humidity from the psychometric chart, first of all, you know that dry bulb temperature, it
is given in your problem that it is 30 degrees Celsius. Also, it is given to you that they are you
know that dew point temperature is 15 degrees Celsius. So, we know that humid air is at 30
degrees Celsius and dew point of 50 degree 15 degrees Celsius.

444
So, here 30 degrees Celsius to be considered as, you know, dry-bulb temperature. Now, this dry
bulb temperature and if you know that dew point temperature, this is actually that saturation
temperature, so, this is 15 degrees Celsius and this is 30 degree Celsius. Now, if you know go
forward from this 15 degrees Celsius point here up to these and then also you consider this 30
degree Celsius that is dry bulb temperature.

And what would be the intersection points, you just decided this intersection point you will see
you will get another profile of that, you know here it is given like you know that this type of
profile like you know the percent is 40% is 50% is 60% is these are actually relative humidity.
Now, at this intersection of this dew point and dry air temperature, what is the percentage you
know that is humidity or relative humidity in percentage, you can you know identify so this line
will give you that 40% relative humidity.

So, very interesting that what will be the relative humidity here, it will be simply 40% here. So,
based on these 15 degrees Celsius dew point and 30 degrees Celsius dry bulb, where is the cross
intersection point and at that intersection point, what would be the profile of that relative
humidity? You have to go through that and you have to read what should what is that relative
humidity. So, this will be your 40%. So, you got this what would be the relative humidity at that
particular temperature of dry bulb and dew point. Next part of the absolute humidity.

Now, you will see that if you know that go along with that line of dew point from that point here,
intersection point and if you go to here the moisture content, you know to access and you will
see that this will intersect at this point of 0.011. So, this will give you that value of you know,
absolute humidity. So, what is your absolute humidity? This is basically 0.011. So, what we did
is simply that from that intersection point along with that, you know that dew point line you go
up to moisture content per kg dry air access and what is the intersection point there, that value
will give you the absolute humidity.

Next, you have to calculate what should be that you have to be what should be the wet-bulb
temperature. Now, to get this wet bulb temperature, but the comparison that what is the

445
intersection point of dew point temperature and wet-bulb temperature that is here at this 40%
relative humidity. Now, from this, you will see that another line like this here, this slide this type
of lines here at shown this line. So, here if you go just you know following this line up to you
know hundred percent you know saturation line.

So, this is you know 100% saturation line. So, from this 100% saturation line or from this
intersection point, if you go 100% saturation line and what will be the intersection point that will
give you wet bulb temperature, so, it is coming 20 degrees Celsius. So, this intersection point is
20 degrees Celsius. So, here you can see that this wet bulb temperature will be equal to 20
degrees Celsius. So, what we did here, this is your intersection point and along with this you
know wet bulb temperature where it intersects at 100% saturation 100% you know relative
humidity or saturation line.

So, that point will be regarded as a wet-bulb temperature. So, here, in this case, it is 20 degrees
Celsius and then what is the dry bulb temperature is simply that 30 degrees Celsius as given in
into a problem.
(Refer Slide Time: 50:31)

And after that, you have to calculate what will be the humid volume. Now, again if you follow
that you know the wet-bulb temperature line and if you go along that you know wet bulb
temperature line up to you know there is an enthalpy line there here it will intersect at this point

446
and you will see that value will be coming as you know at you know the certain value and it will
be regarded as what is that specific enthalpy there now, this is specific enthalpy will give you
that what will be you know humid volume also and if you go beyond these here at this
intersection point.

And this line will intersect this you know that enthalpy deviation line there, from that you can
calculate the enthalpy deviation of what also you can calculate that humid volume just from this
you know line here, this line will give you that humid volume there is some humid volume
profiles are given in this chart here like this and this is also humid volume. Now in between this
humid volume, you are getting the intersection point here.

Now, based on this intersection point, where exactly that humid volume will be there and if you
know, interpolate or extrapolate of this line or interpolate this line here and you can get this what
should be that you know, that humid volume here. So, humid volume to calculate that at that
intersection point you have to see that, what should be the, you know humid volume line, it is
intersected and that corresponding value will give you that humid volume and specific enthalpy.

From the intersection of dew point and dry bulb compressor, if you go along with that you know,
that is you know that wet bulb temperature, and where it is intersected, it will be 20 degrees
Celsius at the saturation line. And if you go for that to that enthalpy curve, then you will get that
intersection point as a specific enthalpy and also these intersection points. Why are these this
slide here you will see that these are some you know line or profile that will that is represented
for you know enthalpy deviation?

Now, at this intersection point where this enthalpy deviation curve will come, that also to be you
know known by interpolating or extrapolating of this, you know the volume of two profiles near
about this, then you can get the corresponding value of enthalpy deviation there. So, based on
this, you know, the psychometric chart we can easily calculate we can easily obtain what will be
the you know, that humid volume specific enthalpy, enthalpy deviation, even dew point
dependent dry bulb temperature even, you know, wet bulb temperature are also.

447
You can get the relative humidity and also humid volume there. So, in this way you have to read
this psychometric chart.
(Refer Slide Time: 54:02)

Next is that you have to find out what should be the amount of dry air that contains you know 1.5
kg of water. So, as per this case 1 kg of water that means here will be actually, you know,
contained by that air that can be calculated just by you know dividing that humidity of you know,
dry air that is here, we know that absolute humidity is 0.011. So, if you divide this, you know
that 1.5 kg of water by the humidity you can easily calculate what should be you know a dry air
to you know contain that 1.5 kg of water.

Similarly, what should be the volume occupied by that air that contains 2 kg of water, you can
easily calculate it from you know humid volume. That humid volume from the psychometric
chart is 0.855 and we know that absolute humidity if you divide this humid volume by these you
know that absolute humidity and then multiply by this you know the amount of water, then you
can get the total volume of you to know, here that is they are to contain that 2 kg of water there
so, it will be amount 160.59 meter cube.
(Refer Slide Time: 55:26)

448
Let us do another example, you know regarding this you know humidity and also what is that
partial pressure based on who is let us see that other you know material balance problem. Now,
air flowing at a volumetric flow rate of 8.8 meter cube per hour under the temperature of 25
degrees Celsius and a pressure of the bar that is paid to a process here now, the air has a relative
humidity of 80% given the molar composition of dry air is 21% oxygen and 79% nitrogen.

Now, in this case, you have to find out what should be the molar flow rate of water dry air and
oxygen that interrupts the process. Now, in this case, you have to you know first calculate the
partial pressure of water by using the definition of relative humidity. So, relative humidity is
given to you that is 80% that means 0.8 that is defined basically partial pressure of water by
vapor pressure of water. So, it is represented by this equation here.
(Refer Slide Time: 53:37)

449
And after that you can calculate the vapour pressure at the 25 degrees Celsius and the pressure of
0.03 as by this equation here 0.8 to, you know, the partial pressure of water by 0.03. Vapour
pressure is given a 0.03 bar therefore, the partial pressure of water will be coming as here from
this equation 0.8 into 0.03. And this partial pressure can be represented by this equation here
partial pressure of water with regard to y water into pressure now substitute this value here in
this equation, you can simply you know get this you know partial pressure of you know that
water here.

And then you can represent it as what to be the mole fraction they are based on the two equations
and then you can get what will be the mole fraction of water there that will be 0.008. Now,
hence, in this case, the mole fraction of water will be equal to 0.008 mole of water per mole of
humid air and the more fraction of dry air will be able to here zero point you know 0.992 just by
you know subtracting that mole fraction of water from the total moles of the mixture. It is there
one minus 0.008. So, that will give you this 0.992 moles of you know mole fraction of you know
dry air in the mixture.
(Refer Slide Time: 58:09)

450
Now, in that case, you have to now follow that molar flow rate of air that can obtain using ideal
gas equation of state using you know volumetric flow rate given in the problem statement,
whatever it is after substitute that known information into this equation, we can get that n will be
equal to PV by RT. Now, in this case, P is given to you, and also V is known to you and R value
is 8.314 into 10 to the power minus 5.

Of course, you have to remember this unit because this value of will be different for different
units. So, you have to you know, be, careful to use these different values of R value based on the
unit and temperature is given to you, and in that case number of moles of dry air, it will be
simply that, you know, mole fraction of air into total mold rate is given year 96.87 as per this
calculation, and then if you multiply it by that mole fraction, that already we have calculated in
the previous slides, that will be the mole fraction of air is coming. So, based on that we can see
that total mole of dry air will be equal to 96.1 mole per hour.
(Refer Slide Time: 59:32)

451
So, we have land here in this lecture, that what is the saturation what is the humidity what is the
different definition or different form of humidity and how that humidity can be you know,
explained or can be read by that psychometric chart and how to you know obtain that different
value of that humidity and also a different uniform of that you from the psychometric chart and
also we how we can actually you know, do the material balance based on the value in a particular
process.

You need basically for dry air, we have learned I suggest going further through text books to,
you know, practice several problems that is given in their examples. And I think it would be
helpful for you for your further understanding of doing the material balance based on the
humidity and also it will be helpful how to read that psychometric chart and from that
psychometric chart, how to use those values for the material balance equation thank you. Next
class, our next lecture will be discussing that you know, processes of phase change like you
know, condensation process, and vaporization process.

452
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 16
Process of Phase change Condensation and vaporization

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about the basic principles of multi-phase systems under the
module 5. Now, in this module, today is lecture will be on process of a change, basically, for the
process of condensation. And vaporization and their calculations in the previous lecture we have
described about the equilibrium laws like Raoult’s law even principles of humidity.

And saturation there and based on which we have you know obtain how to you know find out
that dew point in pressure even saturation temperatures even humid volume how to calculate the
you know that moisture content in the open atmosphere and also how from the psychometrics
chart. How to you know how to actually estimate or you can see find out they are humid volume
even you know dew point and also relative saturation all those things we have discussed in the
previous lecture in this lecture, you know the further extension on that equilibrium condition
basically for dark you know condensation.
(Refer Slide Time: 01:51)

453
And vaporization process and in this case, since, you will see that page will be changing from 1
phase to the another phase So, phase condensation of method is you know, that is related to this
you know topics like you know that the different you know states of the you know materials that
will be called as phase also. So, in that case solid liquid gas and plasma all those are you know,
different you know state and from this state or from this phase that will be you know converted
into another phase of state like here.

You know that solid you know, can be converted to you know, a liquid after melting and solid
maybe you know convert it into gash by sublimation process, even liquid you will see that it will
be you know converting into solid state after freezing, even liquid can be converted into vapor
after vaporization process and gas maybe you know, converted into you know solid after the
position and it may be converted into the state of liquid after condensation also this gas of
course, sometimes to be you know convert it into plasma state by ionization process.

But from the ionization you know how condition or plasma state condition it may be you know
converted to gas by you know recombination process. So, these are the different you know that
phase transition process here. So, that is you know that called you know that freezing the
physician condensation sublimation, vaporization recombination ionization. So, these are the
different you know processes. In this lecture are mainly will focus on then you know that
condensation and also you know vaporization process.
(Refer Slide Time: 03:55)

454
So, what is condensation we have already described this condensation basically is the conversion
of the physical state of matter from the gas phase into the liquid phase and it is also called that
inverse vaporization that may be you know that vapor to converting into you know liquid phase.
So, that is why it is also called that inverse vaporization. It is also be defined as the change in the
state of water vapor to you know liquid water when it contact with the liquid or you know that
solid surface there. So, this is basically you know condensation process.
(Refer Slide Time: 04:32)

And you know that we have described that psychometry principles and also start their
psychometry that measures the rate of condensation through evaporation into the air moisture at

455
various atmospheric patients and temperatures. And in this case, you will see that water has the
product of its vapor condensation. Condensation is the process of such phase conversion it is an
important component of you know that the distillation process or you know that sometimes vapor
component that is coming out from the distribution column.

It will be condensed to a liquid phase and again it will be sent to the distillation column at the
liquid phase and some portion of that liquid phase will be unified there you know processed for
you know useful product, it is also important in power generation water desalination process
thermal management vaporization process and air conditioning process. So, all those processes
are basically involved with this condensation process.

Now, before going to that calculation you have to know that what would be the partial
condensation basically.
(Refer Slide Time: 05:53)

This is you know that the you know mechanism by who is that you know why that metal will be
partly condenser into a vapor stream and in that case partial condensers generally being used and
it will have the you know, characteristics like you know pre distribute contains only condensable
vapor components and also it will you know have some existing streams that will contain the
liquid and vapor have we who said in equilibrium.

456
So, condensation is caused by cooling or you know that increasing pressure and liquid and vapor
that emerging from the partial condenser are separated using a flash separator. So, here you will
see that you know that the liquid and vapor emerging from the partial you know condenser are
separated using a flash separator here and in that case you will see that they are vapor and liquid
will be coming up that you know our flash separation of flash vaporization process.
(Refer Slide Time: 06:58)

Now, how to do that material balance on the condensation in this case you have to you know,
noted down that if you know the dew point of water we have already described that how to find
out that you find from the psychometric chart higher that you know partial pressure will be equal
to a vapor pressure of the you know a gas was component or any method or any you know that
components.

So, in that case if you know that dew point of that water in a gas you know, you can estimate that
partial pressure of the water vapor in a gas and also when you partially saturated gas is cooled at
constant pressure as in the cooling of air containing some water vapor at atmospheric pressure,
you will see that the volume of the mixture may change slightly. But the mole fractions of the
gas and water vapor remains Constant until that you point is reached there.

457
So, at this point water begins to condense that is that that the dew point and the gas remains
saturated as the temperature is lower to the air. So, this is to be remembered before going to you
know do the material balance on condensation. Let us have.
(Refer Slide Time: 08:22)

An example for this condensation process. Here in this case you will see that if suppose in winter
season in a day it is seen that that atmosphere at evening is at 30 degrees Celsius and 80%
relative humidity at a pressure of you know 0.96 atmospheric pressure. But condition it changed
at night necessarily it is happening during the period of winter and it did not seem that the
temperature at that, you know, night is 20 degrees Celsius at that 0.98 atmospheric pressure now.

You will see that here important that relative humidity at 80% at 30 degrees Celsius or pressure
is 96, but at the night you will see that the temperature is start you know lowering to 20 degrees
Celsius for after with Chris it also will be interested there are 0.98 atmosphere. Now, because of
this temperature and pressure change, there is a depletion of water as you do at night. Now, at
this condition you have to find out what should be the percentage of the water in the afternoon
air per mole of air.

You have to calculate which is deposited as day add that night basically you have to find out
what would be the amount of that is water in percentage that is constant condensed as dew at
night. Here in this case simply that you temperature is lowering Pressure is increasing relative

458
humidity that at the day you know, but for the relative humidity at night that also you do not
know, but this let us see how to calculate these things that how much water is actually
condensing as a do at night and that particular condition.

Now, in this case, we have to consider that this is a closed system that resists equilibrium. Now,
they are in this case, if we draw the schematic diagram, supposing day this amount is dryer and
here water vapor will be there. So, dry air contents water vapor at the temperature 30 degrees
Celsius and pressure is 0.96 atmosphere. Whereas at night you will see that this you know that
amount of you know vapor will be you know that lower that night after condensing out as a
liquid, that amount is W.

And at night that condition is pressure is 0.98 atmosphere and temperature is you know 20
degrees Celsius. So, this is your problem in this case what a part of the amount of water that is
you know condensed as it do you have at night.
(Refer Slide Time: 11:15)

That you have to find out now, as a solution what we can say that first of all you have to find out
what should be the vapor pressure of the water at 30 degrees Celsius. So, this vapor pressure of
water at 30 degrees Celsius it is you know that given here 31.8 millimeter mercury that is in
atmosphere 0.042 harass this vapor pressure of water at night that is at 20 degrees Celsius. This
will be equal to 17.5 millimeter mercury that was 0.023 atmosphere.

459
Now, the partial pressure of the water in that day air that will be equal to what 31.8 millimeter
mercury into 0.8 because 0.8 is the relative humidity, this relative humidity basically that you
know, it ratio of you know ratio of what is that means, here pressure to the vapor pressure. So,
from pressure you can say that what should be the washer pressure of the water that will be
simply you know that 31.8 this is vapor pressure into humidity.

So, it will be coming as 25.44 millimeter mercury it is around 0.033 atmospheric pressure. Now,
in this case is implies that dew point temperature will be 27 degrees Celsius. So, at this you know
partial pressure at you know in the day that here in this case at this particular partial pressure, it
is seen that this the dew point temperature will be 27 degree Celsius from this because you can
get also some you know from that you know 20 degrees Celsius or 30 degrees Celsius at that day
condition from the psychometric site.

If you go to that, you know 80% relative humidity and from that, what should be that dew point
that you go to that you know up to that hundred percent saturation, it is seen that dew point to be
= 27 degrees Celsius at 80% relative humidity at 30 degrees Celsius. So, from this psychometrics
art you can calculate here what should be the, you know dew point there. Now, consequently,
you can say that what does condense from the air as it cools. Now, we need to get the
composition of the dry and night so, the composition of the day and night here so, we can carry
out the material balance there.
(Refer Slide Time: 13:51)

460
You then calculate the partial pressures in the day and night is streams and result off which is in
effect, we will give it up composition of the 2 streams. So, here we know that total pressure will
be equal to what partial pressure of air and partial pressure of whatever. Now at today, so, you
can see that partial pressure of will be equal to here total temperature is given 0.96 for a partial
pressure of water at day 0.032. We have already.

You know, calculated and then it will be finally after subtraction from the total pressure, then
partial pressure of air will be equal to 0.927 and then at night also what through the partial
pressure of water that also can be calculated from this total pressure by subtracting the water you
know, partial pressure, so, it will be coming as 0.98 - 0.023 then it will be coming at 0.957
atmosphere. Now, from this we can say that moles of water at night by moles of dry air.

That will be equal to push pressure of water at night by partial pressure of you know or dryer.
So, that will be equal to 0.023 0. Divided by 0.957 that will be 0.024. Similarly, moles of water
at night that will be equal to 0.024 into 1 moles of dry air then it will be at 0.024 moles there and
the moles of water a day by moles of dry air you know that will be sure to you know partial
pressure of water at day divided by you know partial pressure of dryer there then it will be
coming as air 2.036 and therefore, moles of water a day it will be as what is that 2.036 into 1
mole of dry air than it will be coming at 0.036 moles.

461
So, moles of water that will deposited at night it would be what is that simply this is you know
that daytime and this water moles at nighttime is here. So, if you subtract these you know 0.024
moles at night from you know what are moles of the day that is 0.036 then you can get this you
know that he had 0.012 moles of water are deposited at night. So, this will actually will be you
know, that coming out as a deal at night. Now percent is of water in that day air then deposited as
a deal that will be equal to 0.01 to this amount divided by 4.

You know that amount of, you know that moles of water in the day, so, it will be coming as you
are like this suit will be around 33.3% so, in this way you can calculate that how to be the
amount of water that is you know, deposited into you at night there.
(Refer Slide Time: 17:09)

(Refer Slide Time: 17:10)

462
Let us do another example here are now drying process by condensing out of water in this case a
gas stream containing 40% oxygen 40% you know hydrogen and you know 20% water in mole is
to be dried by cooling the stream and condensing out the water if hundred more per hour of a
gaseous dream is to be processed, what is the rate at which the water will be condensed out and
what is the composition of the dry gas.

So, very simple that you have to you know draw fast that schematic diagram here it is shown on
the slide that gases stream of hundred moles per hour is flowing through that, you know You
know, dryer, you know in this case here a composition of the gas stream is 40% oxygen 40%
hydrogen 20% water vapor. Now, you have to you know, that is to be dried by then is cooling the
stream and condensing out the water.

Now, you will see that at this stream 2 this condense it will come out as among C, higher water
will be 100% no other competition will be there like oxygen hydrogen will not be there, but the
dry gas it will be you know containing oxygen some, you know more fraction that is xO2 and also
hydrogen that will be 1 - xO2. So, right gas amount is D it is not known to you. So, based on this
problem, you have to find out what is the rate at which that water will be condensed out and what
is the composition of the dry gas there.
(Refer Slide Time: 19:14)

463
Now, let us do this example here to solve. Now, let us consider these basic hundred mole per
hour that wet gas here the composition of 40% oxygen particles and hydrogen and 20% water
and consider the overall total material balance and you know that component balances and also
component balances here like your 2 component balances here first of all you have to do that
total material balance like 100 will be equal to D + C, this is input these are output.

So, 100 = D + C and component balance for water all water in the heat is here condensed. So,
you can see that 0.2 in 200 that will be coming as you know see, and so, we can say that hundred
into 0.2 it will be you know that simply you know that 20 moles of water as a condensed. So, C
will be equal to 0.2 into 100 that will go to 20 similarly, if we do the component balance for
oxygen then you can see that 40% of oxygen in the feet there in 0.4 into 100 that will be exactly
close to the outlet you know oxygen contents that will be here in this stream 3.

That will be you know that then D xO2 here this 3 will not be here, this is in suffix. So, it will be
basically you know that by xO2 in the stream 3 then it will be coming as you know D xO2. So, by
solving we can see that D = 80 mole per hour and xO2 then to becoming point 5. So, once you
know that xO2 at stream 3, then here xO2 at a stream 3 that is = 0.5 so, similar so, we can say that,
at this time hydrogen will be equal to you know x hydrogen at a stream 3, it will be coming as 1 -
0.5 that will go to 0.5.

464
So, this is your mole fraction of hydrogen in stream 3 dry gas suppose of course, that amount D
what is amount 80 mole per hour will contains that 50% you know oxygen and 50% hydrogen
there. So, in this way you can you know, do that material balance and in this case total material
balance and also component material balance to be done and how much water will be condensed,
you can get it from this material balance.
(Refer Slide Time: 22:23)

Next we will go for you know that vaporization process what is that vaporization this
vaporization basically caused by that reducing the pressure or by heating vapor and liquid
streams are in equilibrium there. Now, to calculate that amount of the respective vapor and liquid
phases that evolve at equilibrium condition, when a liquid of known composition flashes in a
flash operator of flash vaporizer it is called flash vaporization at a known temperature and
pressure.

You must use that you know use the following equation of an equilibrium constant of K you
know together with a material balance.
yi piv
Ki  
xi pt
So, in this case at equilibrium condition of that you know vaporization condition, you will see
that vapor and liquid will be in you know that equilibrium condition at this vaporization
condition and at this plus vaporization you will see that at equilibrium condition, some amount of

465
you know vapor will be there from the top of that vaporizer and from the bottom there will be
equilibrium.

Now, at that condition vapor and liquid will be in equilibrium and the composition there will be
that in the vapor. Let it be considered as yi for that component and you know that in liquid phase
composition will be xi. So, at equilibrium condition, you will see that this competition in why i
that is in vapor that will be you know equal to that you know mole fraction of you know liquid
just by you know that just adjusting with some equilibrium constant.

So, here we can say that that if suppose, yi the mole fraction of component i in the vapor phase
and add that equilibrium condition with the mole fraction of i if it is equilibrium in condition
then we can write yi will be equal to some Ki into xi. So, in this case this yi = Kixi from these we
can right here Ki it will be equal to yi by xi this Ki called that equilibrium constant for the
component i and this seems it is mole fraction at that equilibrium condition. So, in the vapor
phase that you know, pressure will be of that component it will be vapor pressure at that
equilibrium condition.

And you know that what will be that you know total pressure of the system from which you can
calculate what from the equilibrium condition or equilibrium constant. Now, in this case, this Ki
are you can calculate also from you know that, if you know that reduced temperature and also
you know that critical pressure there and from that you can calculate this equilibrium constant
from this correlation suggested by Sandler.

You know, this empirical equation in this case, this empirical equation will be valid only if you
are you know that ratio of critical temporary set to you know total pressure. So, the critical
temperature to the temperature of the system is greater than 1.2. So, you can directly use this
correlation to find out this equilibrium constant. Otherwise, the equilibrium constant you can you
know find out from you know, table that is given in your textbook in the appendix you can find it
out what the equilibrium constant there.

466
Now, you have to remember that at xi = 1 they are that means that your partial pressure will be
equal to vapor pressure there. So, you have to that remember for 100% top 5 new molecules of
that component i in the liquid phase then there will be partial pressure of that vapor pressure will
be equal there.
(Refer Slide Time: 26:51)

Now, calculating that related equilibrium vapor liquid composition, what you have to do first of
all you have to calculate the bubble point temperature of the liquid mixture that is given at the
total pressure and liquid composition. So, you have to know first that you know bubble point
temperature at which temperature this you know that mixture is exist and also it is supplied for
the processing that can be considered as the bubble point temperature.

And also add that bubble point temperature what is the pressure and the liquid composition there.
Now, calculate that dew point temperature of a vapor mixture given that total pressure and vapor
composition also you have to calculate the relative equilibrium vapor liquid composition. So,
what the range of mole fractions of you know 0 to 1 as a function of temperature that is given at
that particular total pressure.

Then you have to calculate the composition of the vapor and liquid streams and the respective
quantities when a liquid of you know given composition is partly vaporized that is called past

467
vaporization at a given temperature and pressure in this case the temperature must a between the
bubble and dew point temperature of the feed.
(Refer Slide Time: 28:16)

Now, method to calculate the bubble point temperature and pressure, how to calculate that
bubble point temperature here will describe that here to calculate the bubble point temperature at
a given total pressure and liquid composition, you have to solve this equation like this, all you
have to do that at that equilibrium condition in the vapor composition and you know that liquid
composition you will see that summation of that you know composition will be equal to 1.

That means here summation of yi will be equal to 1. So, at least condition at what temperature
you will see that this summation of this, you know, mole fraction of the components in the vapor
page will be equal to 1. So, at that condition, it will be given it will be their respective
temperature of that you know bubble point temperature. So, here if I substitute here yi as Ki, so,
we can say that summation of Ki will be equal to 1 here also in this way you can calculate that at
for whose condition you can get the summation of Ki into xi will be equal to 1.

So, respective temperature will be called as you know that bubble point in person. Now, this Ki
air function of solely that temperature and you know, because each of the Ki increases with a
temporary said there for an ideal solution, it can be written as that this total pressure will be
equal to what summation of this you know that Pivxi that means, partial pressure of that you

468
know component you know in mixture. So, summation of that partial pressure can be you know
calculated from the vapor pressure at that equilibrium condition.

That is why the submission of this stop before pressure into more fraction at that particular
equilibrium condition will be equals to you know total pressure. So, that if you are getting that
total pressure will be equal to the submission of vapor pressure into more traction, then you can
say that at that particular condition, the you know that temperature will be you know that is
called bubble point temperature.

Now, once that bubble point temperature is determined the vapor composition can be calculated
from the you know relationship here, yi will equal to you know that this is you know this is
called partial pressure at that equilibrium condition that is Pivxi as per hour slots and what will be
the temperature there. So, from this equation, you can easily calculate what would be the vapor
composition at that particular bubble point temperature.
(Refer Slide Time: 31:04)

Now, let us do an example based on this concept. So, in this case, suppose a liquid mixture
containing 5% normal hexane and 95% are normal octane is to be vaporized in a flash vaporizer.
Now, you have to find out what should be the composition of the vapor formed, if the total
pressure will be 1 atmosphere and what is the bubble point temperature said to before is that

469
liquid at its equilibrium condition with the vapor. Now, in this case, you need to calculate the
vapor pressure of the component i.

Now for that, you have to use that Antoine’s equation but at his temper we said this, you know
that vapor pressure to be calculated that is not known to you. So, you have to you know, keep
that temperature a certain temperature like you know that if it is denoted by T then keep it as T
and that at that temperature you have to find out what should be the vapor pressure by this
Antoine’s equation. Now, to calculate that vapor pressure by Antoine’s equation you need to
some equation constant.

So, it is given here for the component for normal hexane this sentence constant is given here and
for normal octane also this sentence constants are given in this table as shown here in the slide.
Now, we need to solve this following equation to get that bubble point temperature based on this
problem. Now, we know that, to get this bubble point temperature, if you equilibrium condition
will give you these saw you know equality of that total pressure will be equal to summation of
that is Pivxi.

So, for all components in the mixture you have to sum up this you know product of this posture
pressure of that component into each you know more fraction.
(Refer Slide Time: 33:13)

470
So, after that what will happen? Now, let us see here since total pressure is given to 1 atmosphere
that is 760 millimeter mercury and here in this case this vapor pressure of you know that
components will be there considered. So, we first of all these i component i = 0 here it is 2
components because only you know hexane and octane out there. So, for hexane we use these
rotation A, so here are 760 equal to then PHv for hexane into xi, you know, A is for hexane.

And similarly for you know that octane also we can write here Pov and you know that hexane
here will follow 10 is for hexane. So, here if you substitute this value for vapor pressure for
hexane and octane, what is the vapor pressure of you know, hexane here as per Antoine’s
equation exponent of you know A–B/(C+T), this is your know Antonio's equation for that
component, you know that for hexane.

And similarly component topics and easy access and again if you substitute that you know
equation for the vapor pressure for octane and then if you multiply 8 composition x as x0, you
can simply express by this equation based on that, you know total pressure and vapor pressure.
Now, substitution of this A, B and C and then solving the equation the value 4042 will come,
you can get that you will equal to 239 2.2 Kalvin which is a bubble point temperature.

So, from this equation you can easily calculate the mobile point in person. So, here you need to
know that only that in Antoine’s equation and also be vapor pressure at that particular
temperature that solving this you know equality of this total pressure with this you know that
submission of this vapor pusher into its components then you can get easily what will be the
bubble point temperature.

Now, at this bubble point temperature as for Antoine’s equation, you have to find out past what
will be the vapor pressure of hexane and what was the vapor pressure of octane and it is coming
as 150.0 millimeter mercury for hexane and 607.65 millimeter mercury for octane at that bubble
point temperature up 392.2 Kelvin after that you have to find out what the you know vapor phase
competition of you know here hexane.

471
so hexane why hexane can be calculated from this you know, equation here PHv access by PT,
then you can easily calculate what should be the composition here it is coming 0.2 there is 20%
of action and remaining will be your you know opt in that will be 80% there. So, in this way you
can solve for you know bubble point temperature and also vapor composition when a liquid
mixture will be you know partially vaporized.
(Refer Slide Time: 36:31)

Similarly, you can you know calculate that what is with the bubble point pressure also. Now, in
this case, you will see that a liquid mixture that contains 50% pentane and 30% hexane and
remaining that is 20% you know cyclohexane all in mole percent that is x1 = 0.5; x2 = 0.3 and x3
= 0.2 now at this temperature of 400 K you know the pressure is gradually decreased, what is the
bubble pressure and composition of the past vapor that is formed there.

Now, assume that idea liquid mixture and ideal gas there and it will follow that Raoult’s Law.
So, here in this case instead of bubble point temperature you have to find out what is the bubble
point pressure. Now, in this case first of all you have to calculate vapor pressure of each
component at 400 K by Antoine’s equation. So, this will be your you know that here it is given
the component 1 this vapor pressure is here and for component 2 it is given and for component 3
is given.

472
Now, at the bubble point the liquid phase competition is given so, that partial pressure of each
component is as like this. So, partial pressure will be calculated based on this you know equation
you know that you know vapor pressure of his components by the Antoine’s equation then you
can get that partial pressure of peace component p1, p2, p3 respectively. So, from which you can
easily calculate what should be the mole fraction of in the vapor based on this unit of partial
pressure.

Then you can get this mole fraction of each component as y2, y3 he are shown in the slide. So,
the bubble pressure will be able to hear what is the total pressure will be there that will be able to
you know summation of all partial pressure of that components 1 2 and 3, so, to becoming a
7.189. So, it will be called as bubble pressure. So, in this example, you practice it and you can
you know that have idea how to calculate that bubble point pressure.
(Refer Slide Time: 38:44)

Similarly, how to calculate that dew point temperature here, this is also reverse that you know
vaporization to you know condensation. So, in this case to calculate that dew point temperature
at a given total pressure and vapor composition equilibrium condition you know you have to
solve the equation here the summation of xi = 1 and also you can see that from that relationship
of equilibrium y is equal to yi = Kixi from that you can write after simplification as summation of
yi/Ki it will be equal to 1.

473
Now, for an ideal solution, we can say that this summation of this will be equal to 1. So, from
this here we can say that respective temporaries are at which this you know equality satisfied will
be called as dew point temperature. So, in selecting a particular form of the equation to be used
for phase equilibrium calculations, you must select a method of solving that equation that has
desirable convergence characteristics to there.
(Refer Slide Time: 39:51)

Now, how to calculate that dew point temperature accordingly like, you know, asked the same
question problem given in previous example, like a vapor mixture contains 50% painted 30%
hexane and 20% cyclohexane or y1, y2, y3. x is given to you and add pressure high bar the
temperature is gradually increased and what is the dew point temperature and the composition of
the liquid that is formed and assume ideal you know liquid mixture and ideal gas law.

So, in this case also here pressure and composition of that component i are given and also
provides the equation that follows an implicit equation for you know that temperature which
needs to be solved numerically here. So, in this case summation of xi that means summation of
PT into y by Piv that should be equal to 1. Now in this case when this you know that at which
temperature you can get this equality is equal to 1 after substitution of Antonio's equation.

You see that we have to solve for temporary certainty and then it is coming through 93.3 K. So,
this is you know that you know that you find comparison. Now, in this case the xi then can be

474
obtained as you know from this relationship and which will give you that respective you know
our competition for that our components 1, 2 and 3.
(Refer Slide Time: 41:29)

This way you can calculate this point in process similarly, we can also calculate the dew point
pressure in this case the same you know mixture of 50% pentane, 30% hexane and 20%
cyclohexane. With this composition at 400 you know Kelvin temperature the pressure is
gradually increased and what is the dew point pressure and the composition of the form liquid
that is formed that you have to find out. So, in this case again this equality to be you know
followed that is put into summation of y by Piv that will be equal to 1.

So, in this case vapor pressure at 400 k by Antoine’s equation are here calculated as like this for
component 1, 2 and 3 respectively. So, from those you can easily calculate rush with a, you
know more fraction of those components once you know that, you know vapor pressure. So,
from this vapor pressure of components 1 2 and 3, you can you know calculate watch with this
value of 1 by PT that will be as part this equation here.

And then this after substitution of this yi and Piv they are then you can easily calculate what
should be you know that total pressure there. So, it is coming here like this 0.1729 and since will
imply you that total pressure will be implies 5.78 bar.
(Refer Slide Time: 43:00)

475
Flash vaporization with vapor and liquid in equilibrium that we have already discussed that at
that flash you know vaporization condition that
yi piv
Ki  
xi pt
from which you can calculate that what is the you know partial pressure what would be the total
pressure what would be the temperature at which that you know vapor will be condensing or
liquid will be you know vaporize to the air.

So, to calculate that amount of respect to vapor and liquid phase that evolved at equilibrium.
When a liquid of known composition flashes in Flash vaporization at unknown temperature and
pressure, you must use that equation that will follows together with a material balance.
(Refer Slide Time: 43:42)

476
Now, material balance in the flash vaporization to be done based on this suppose there is a
vaporizer and in this vaporizer the liquid feed coming with some composition and at that
vaporization power you know process you will see that some amount will be coming out from
the top of this unit vaporizer and some amount will be coming you know out from the bottom as
a liquid composition at unknown you know total pressure and temperature.

Now in this case what would that feed amount and what was the vapor amount and also you
know liquid amount after vaporization then it is if it is not known to you then you have to do the
material balance once that is provided at least 1 variables there. So, based on that if we do the
total material balance for this vaporization who can write simply equal to L + V. And also if you
do the component material balance we can write for component i in this way that
FxF ,i  Lxi  Vyi

yi  Ki xi
Since we add equilibrium condition we know that . So, we can you know write this
equation of this component material balance of the substitution of this yi are you know equal to
Kixi here then finally, you can write here
 y 
FxF ,i  L  i   Vyi
 Ki 
at this equation. Now, you will see that from this equation, we can simply you know, to express
that.

477
You can get it or you can express this in terms of here like this
FxF ,i xF ,i
yi  
L / K i  ( F  L) 1  ( L / F )(1  1/ Ki ) .

So, in this case, if you are new this xi and also at equilibrium condition under vapor phase all the
components are you know, composition will sum up to 1 then you can see the summation of y is
equal to 1. So, if you substitute that from this material balance equation and you can then express
like here as shown here in this slide that equation.
FxF ,i xF ,i
yi  
L / K i  ( F  L) 1  ( L / F )(1  1/ Ki )
And here in this case, we can write
n xF , i
 1  ( L / F )(1 1/ K )  1
i 1 i

So, here l by F is unknown to you, what would be the amount of liquid and got to be the amount
of faith it is not known to you, but if you know that vapor composition, amount of vapor
composition, then you can calculate what you know if an L or what without L, V, F also you can
calculate from the material balance or if is given to you what from the B and l that also you can
calculate.

So, in this case, very interesting that this equation as shown here, L, V, F if you keep on
changing that L and F value, and also respective, you calculate that summation of this, you
know, Antoine is here you see that particular liquid and you know that that is al and if you know
value, you will see that the submission. Will you know tends to you know becoming 1. So, at
that particular condition you are you know value of liquid and you know feed amount will be
known and that condition also you can say that what to be the composition there. So, according
to that you can have.
(Refer Slide Time: 47:31)

478
That you know what will be you know composition in the vapor phase and liquid phase. So, this
is basically depending on that material balance overall. So, let us do an example based on this
material balance of this flash vaporizer. Now, you know that during that ammonia synthesis from
nitrogen and hydrogen the products are cooled and separated in a partial condenser that is
operated - 33.33 degree Celsius and 138 bar absolute as shown in figure below here in the slide.

Now calculate the composition of the vapor and liquid streams in this case considered that
hundred mil of feed is processed for the synthesis. Now, here x is given to you and the
compositions are nitrogen hydrogen ammonia air methane as for you know figure and in the
vapor composition as you know that if we denote that composition as 1, 2, 3 for that respective
nitrogen hydrogen ammonia and methane then in the vapor phase what will be the composition.

It is not known to you also want to be the total amount of vapor It is also not known to you that
you have to find out similarly in the liquid phase, the amount L is not known to you and also
composition That respective components are not known known to you, but equilibrium constants
are given to you for nitrogen as like this for hydrogen for ammonia for our you know that our
gun and also for methane these are given to you.

So, with these you know that parameters or you know that data you can find out what should be
you know composition of the vapor and liquid streams.

479
(Refer Slide Time: 49:26)

First of all what you have to do you have to do the total material balance. Now, in equation
number 1 to assume that this material balance will be as 100 will be equal to V + L because it
will be = V + L that means, your input will be equal to total output that is material balance
concept. So, to be coming as hundred that we are going to V + L. Now, after that you have to do
the component material balances for each component like this pore nitrogen.

What would be the component material balance you can do it under this composition is given in
the you know inlet phase there. So, and in the you know outlet phase it is not given it is are you
know assume that to be y1 and x1 similarly for other components also for hydrogen this is your
material balance for ammonia this is your material balance for argon this is your material balance
and methane also this is your material balance support nitrogen to meet in this material balance
equations are given from equation number 2 to 6 here in the slide.
(Refer Slide Time: 50:32)

480
Now, next you have to do the summation of these are mole factions in the vapor phase and liquid
phase in the vapor summation of the you know vapor phase competition will be equal to 1 and
also summation of the liquid phase composition will be equal to 1. Now, at equilibrium
conditions you know that yi will be equal to Kixi we know that yi was equal to Kixi that is that
equilibrium condition. Now, based on this equilibrium equation, you have to express for each
component.

What will be the equilibrium equation for nitrogen here it is given why you want that will be to
go to 66.67 into x1, here has 66.67 is the equilibrium constants for this nitrogen. Similarly, for
other components you can find out that hydrogen for hydrogen it will be yi too, similarly for
ammonia similarly for argon similarly, for methane what will be the equilibrium relations or
equations there. So, it can be expressed by this equation number 9 to 13 for respective
components of nitrogen into the methane as shown in the slides.
(Refer Slide Time: 51:16)

481
Next, you have to express this equation 2 to 6 by rearranging it what will be the, you know more
fraction of x1, what would the more fraction of y1 what should they do? What should the y2
similarly x2, y2 similarly, x4, y4 and also x5, y5. So, by this equation number 14 to 18 you can
express what will be the more fraction of the components based on that material balance by
unknown values of liquid composition and vaporization also unknown amount of liquid and
vapor there. So, by this perspective you know that equation from 14 to 18.
(Refer Slide Time: 52:28)

we can you know that, rearrange these things h here like this, with that equation number 9 that
equilibrium relations, we can get that to you know equation here for component 1, in the liquid

482
phase and component 1 in the vapor phase similarly for component 2 is it can be retained and
similarly for componentry these are can be retained for x component for and component 5 like
this, now, we will see that all this you know, liquid phase composition for all components, if you
sum it up it will be coming as 1.

And also similarly, if you consider that here before phase composition, then summation of yi will
be equal to 1. So, either 1 you can consider at a particular vapor amount and liquid amount then
when that ratio of liquid and vapor will give you that summation of this xi equal to 1 or similarly
yi = 1 so, based on this.
(Refer Slide Time: 53:40)

You can say that at a particular you will see that you know vapor and liquid amount, this
summation of this yi summation of xi will be equal to 1 now by trial and error method just by
changing up your liquid amount and vapor amount and once you will see that this you know
submission will come to you know approximately 1 you cannot say that 100% to 1, but there will
be you know very least error to get this you know 1 value that means maybe 1.001 or 0.999 like
this.

So, when to come that means a near about to 1 you can say that at that particular vapor and
liquid, you know amount, we give you this you know equality of the summation of excite or
summation of why you will which you can do 1. Now, once it is finalized for this you know that

483
liquid and vapor amount here, you can see that this at this amount, we can see what should be
that, you know, vapor composition and you know that liquid composition for all components
here for nitrogen and for hydrogen and for ammonia argon and also methane there.

So, you can find out they are respectively just by putting that value up you know that liquid and
vapor amount in the respective equation here in this equation number 14 to you know 18 there.
So, in this way you can calculate what should be that you know our liquid and vapor amount by
this unit + vaporization you know condition in a vaporizer with this material balance. So, I think
you understood that you know how to solve that you know vapor composition and liquid
composition to find out at a particular you know that temperature and pressure by this material
balance also at an equilibrium condition.

how to calculate the vapor composition liquid composition from each vapor, you know pressure
or you know that from the you know the dew point temperature or above Temperature also, you
have I think, you know understood that how to find out the dew point temperature how to find
out that bubble point temperatures are just by calculating the vapor pressure by Antoine’s
equation and substitute needs to the you know.

If you know equality at that equilibrium condition of you know pressure will be due to you know
submission of partial pressure of the components and then partial pressure will be related to that
you know, vapor pressure there. So, accordingly you can calculate what the new plant or to the
vapor you know bubble point temperature based on that vapor pressure. So, I think I should, you
know suggest you to you know go partner that some example that is given in your textbook and
also more about this you know, flash vaporization you can get it more information from this, you
know, takes textbook can also reference books here.
(Refer Slide Time: 56:57)

484
In the next class I will, you know, describe, you know, regarding the principles of energy and
also we will start that new module there and under that, you know, principles energy, how to do
that material balance for energy and also some, you know, that different forms of energy and
how it can be, you know, used to calculate that, you know, material balance and or that, you
know, this energy balance will be required. We will be discussing the next lecture. So, thank you
for your attention.

485
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 17
Principles of Energy

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, in this module you have energy and its forms will discuss about the principles of
energy in the previous.
(Refer Slide Time: 00:44)

Module in lecture 16 we have discuss about the process with phase change and also based on that
principles of the you know p change, we have discussed about you know different laws of you
know that equilibriums when there is a change of phase, especially for condensation and
vaporization process they are also have described how to do that material balance with those, you
know that principles, laws of that condensation and polarization.

And those are actually based on the, you know, vapor pressure concept at equilibrium conditions
and also the partial pressure which is depending on that, you know vapor pressure as well as you
know that mole fractions of the components in the liquid phase which are in equilibrium with the
vapor pace and also we have described that different phenomena of you know that process

486
variables for this you know, equilibrium condition or during the phase change like humidity, dew
point, even bubbled point temperature.

Relative humidity saturation, unit volume enthalpy, absolute humidity, how to calculate all those
things who have described to there. In this lecture, we will discuss the concept and units of you
know, that energy system and how to do that, you know, energy balance and what are the basic
equations for that, you know, energy balance in this module. We will start this energy balance in
this lecture especially for the you know that how that energy has been defined and also what are
the units.

And how that energy balance can be done in open system and close to the system and based on
this, you know energy conservation law will be doing, you know that energy balance for the
process systems in successive lectures of this module and so, we can first.
(Refer Slide Time: 03:38)

talk about that concept of that energy what is that energy that we have to know fast, how it can
be defined basically, this energy is represented by the phenomenon of you know that ability of
work. All you can say that for the strength of you or particular system or any you know process
equipment or you can see that there will be a you know execution of any plant, what should be
the overall strength or power you can see that ability of that you know, overall plan to give you
certain you know it. So, in that case, we can say that that energy can be you know, defined as the
term is strength or ability to work.

487
Which is basically derived from the utilization of physical and chemical resources and this
especially, to provide, you know, light and heat or to work machines there. And in overall based
on this, you know that heat or work of the machines will be you know, regarded to you know
assets that whole process plant and adjust systems and also we can say that this energy is
basically a quantitative property that must be transferred to an object in order to perform work
on.

So, in physics generally, this energy is the actually considered as a quantity to property and this
quantity poverty must be transferred to an object in order to perform some work on the system.
In this case, you will see that whenever you are going to you know assess some you know
process stem based on the quantity of energy you have to express this energy by a certain
symbol. Generally, the symbol for energy is represented by E.

And of course, you have to express this quantity by a certain unit that is basically in SI system is
you know Joule. So, the common symbol for the energy is you know used by the later you know
that he and standard unit is generally considered as you know, joule there.
(Refer Slide Time: 06:28)

And you will see that whenever we are talking about that energy, you cannot actually destroy or
create that energy who said you know universally available their only thing is that this energy
whatever available that you can you know that convert this from one form to another form And

488
this energy can also be transferred from one point to another or from one body to another body,
like any heat object is in tossed with record object what will happen you will see that heat energy
will be transferred from these hot body to the cold body.

So, this heat energy is transferring from one body to another body and it can be also transport
from point to point like in a same object already or in the same material. If there is a temperature
you know difference between 2 points you will see that the temperature will be you know
moving from higher temperature to the lower temperatures. So, in that way you can say that the
heat energy will be you know transport from one point to another point.

And also this energy transport, you can say, it will occur by flow of heat or by transport of mass
or by performance of work like suppose, if any heat is supplied to any object you will see that
that object or material will be heated with respect to time and it will be you know changing its
temperature from you know higher temperature to the lower temperature or cold body may be
transporting from lower temperature to the higher temperature.

So, in that case the flow of heat is the main unit carrier for the transporting of energy In that case,
sometimes you will see in the convective mode if suppose fluid element if it is heated and if it is
you know flowing with a certain velocity or at a certain flow rate, you will see that the mass of
this fluid will be you know carrying that heat energy from one location to another location. And
this you know transport of this you know heat by this mass flow rate will be you know that
enhanced by just you know changing each saw you know flow rate.

You can you know transport that heat energy at a certain rate based on the fluid properties and
also you can transfer this energy by part 4 minutes of work also if suppose any uniform is you
know that transferring any liquid from one position to another position you will see that there
will be a you know certain heat energy will be generated because of that friction of that fleet to
the you know surface of the that is conduit to his that flow to be moving.

So, because of that to discuss effect or fiction of that fluid element over this you know solid
surface you will see there will be some frictional energy that friction analogy will be converted

489
into heat energy. So, in this case, you can see that how much work is done by that farm to
transferring this fluid from one position to another position. They are according to that, the heat
energy will be produced another system like you know that.

If suppose any closed system if you know that increase the movement of the molecules just by
you know doing some work on the system, you will see that the closed system will be heated up
because of that internal friction of that fluid element or you know the carious element in the
close to B cell just by changing the temperature, and also you can say that, this change of this
energy by raising this temperature because of that work done on the system, you will see there
will be increasing energy and that increasing an energy will be called as internal energy
increased.

So, in that case, you can say that you can increase the heat energy or internal energy or you can
say that if you are working on a particular system like flash on at a certain pressure and if you
decrease the volume or increase the volume just by you know, increasing the pressure and
lowering the pressure respectively, you will see that the systems will be you know generating
some you know energy that energy change will be considered as that internal energy.

So, in this way the heat may be you know that produced or you know generated or by transport
by you know performance of the work.
(Refer Slide Time: 12:43)

490
Before going to that, you know performance and analysis of the system. You have to know that
why we should know that about energy. We should be you know, required for that particular
system. Now, we have to know you know certain energy systems, how much energy is being
consumed, how much energy is supplied there in a particular system. So, before going to you
know analyze that you have to design that system and after designing that system, you will see
that this mass of energy will be released or consumed.

But, that design of course, will be related to that you know, energy consumption and that you
know that energy you know, utilization there, so, how much energy will be required for the
operation of particular systems based on who is that you know design system will be designed or
unit will be designed so far that the knowledge of that you know energy to be required for the
design of the process unit. Like it will be you know helpful to design pump motor, you know that
if you suppose supply some electrical energy.

and this motor will be you know rotating and based on which you will see that some energy will
be produced and based on his that energy will be transferring to another pump to you know, do
some work that will be you know, some, you know useful you know to produce some you know
that valuable products. So, in that case, you know, the designing of that pump motor or some
other process unit that will be requiring.

how much energy to be required or power to be required, that is basically especially for that
pump to pump certain amount of liquid from a storage vessel to a process unit also how much
energy is required to convert certain amount of liquid at a particular temperature to you know
that Steam at another temperature. So, it is also required and also you know that hydrocarbon
mixture is you know distilled to produce a liquid and vapor useful products in that case some
energy is required to distill that you know hydrocarbon mixture.

Because any way you have to you know heat up that hydrocarbon mixture and based on the
boiling point of that hydrocarbon mixture components, you know that lower boiling point
liquidity will be you know, vaporized easily and it will be you know, coming off to that column
and it will be separated from that liquid phase and then it will be you know collected as a you

491
know liquid after you know condensed session and for boiling off you need some you know
boiler.

And they are also you know that heat is required so, for this boiler you need heat energy and also
condensation you need also that some external work to be done they are. So, for this operation of
distillation to you know get this useful productive liquid and vapor they are energy will be
required and this energy input to that you know distillation column based on who is it will be
assessed how much it is required for a certain amount of steam that is to be supplied to the
process a certain amount of you know hydrocarbon mixture.
(Refer Slide Time: 16:48)

Also you will see that some other aspects also the heat energy or some energies required they are
supposedly highly exothermic chemical reaction that is takes place in a continuous reactive now,
if there is a certain percentage of conversion is to be saved by that reaction. Now you have to you
know supplying some energy. Now, you have to know what rate of energy to be supplied from
the reactor. So, that you can keep that you know reactor at a constant temperature.

Because whatever energy will be you know released by that reaction you have to remove that
energy now, to removing that energy you have to do you have to use some you know that
process unit like heat at here or you can see that some other cooling you know or device by who
is you can you know that he moved that heat energy which is produced by the reaction now, in

492
that case, you have to know what will be the amount of heat to be you know that required to be
you know removed to keep the contents in the reactor at a constant temperature.

Another important aspects where the energy is required to know that how much coal must be
burned each day to produce enough energy to generate the steam, we know that particular energy
we are getting maximum energy is coming from burning of coal by producing different valuable
you know, gases mixture and from which we are separating and then we are getting different
type of useful products and daily life.

Now, also you will see that whatever electricity we are using, that is actually being produced
based on burning of coal. Now, in this case, how much coal will be banned to produce this type
of this mass of energy support that you need to know that how much energy to be required for
each of kind enough to generate the steam to around the turbines to produce you know enough
electricity to meet the daily power requirements of a particular city or some other you know, that
other required mercury.

So, in that case, you will see that whenever coal burn that coal will give you a certain amount of
you know, gases mixture and that is that gases mixture you will see that will give you know or
will be used to you know, that are rotating that turbine or that gases mixture can be used to
synthesize some hydrocarbon mixture that will be useful for our daily life and also coal is also
used to you know, that generate the steam from the water.

So, that heat energy is produced by simply you know burning of coal. So, burning of coal will
give you the heat energy and that heat energy will convert that liquid water to steam and then the
steam to be you know supplied to the turbine. And whenever turbine will be rotating that rotates
the rotating turbine will generate that electricity. So, this a how much you know electrical energy
will be produced by you know burning the coal and when you burn coal will be burned.

How much energy will be produced and also what will be the amount of coal will be supplied
based on who is what will be their energy will be produced that should be you know, known for
that operation.

493
(Refer Slide Time: 20:46)

Another important you know, aspects of that chemical processes which are being executed and
also, you know, those are required for their operation several units and like a number of reactors
in number of compressors, distillation column mixing tanks evaporators filter precious and other
you know materials that handling and separation process unit ease of the unit either recourse or
releases some energy. So, that amount of energy to be calculated and also that should be
controlled based on that you know among which are being coming as per calculation as per
requirement.

Also how can the process operations can be designed to minimize the total energy requirement.
So, that also can be assessed based on that energy balance and also how much energy to be
required for that and also overall process plant analyzes whether it will be economic or not, that
is actually SS based on that you know, energy requirement for the whole plant for you know,
producing certain, you know useful products there. So, that is why we need to.
(Refer Slide Time: 22:11)

494
You know, that energy and it is also importance of that balance they are now, before going to
that energy balance equation again you have to know what are the different types of energies also
they are and what are the sources of that energy, you know that there are 2 types of energy one is
called renewable energy another is called non-renewable energy. Now, renewable energy is
called what is that? The solar wind water hydro geothermal biomass who title this type of energy
is called renewable energy.

And this case, many of the arts energy resources are available on a perpetual basis. So, these
include these solar, wind, water, geothermal biomass and these are these energy are called you
know renewable energy and some energy sources can be replaced over relatively short periods of
time and this includes wood and other biomass all are considered as a renewable energy.
(Refer Slide Time: 23:25)

495
Whereas, you will see that in our modern you know industrial society, which are dependent upon
for the energy and those energy comes from you know that, just by you know come from that,
you know, natural resources like fossil fuels coal, petroleum, oil and gas like this, that case,
fossil fuels are the major sources of energy in developed and industrialized, you can see that
nations solar energy from the ancient past is stored in fossil fuels such as coal and petroleum and
fossil fuels are released in the elements of carbon and hydrogen.

And these sources of energy take very, you know, long period of time to form and once depleted
are essentially non-renewable. So, these are non-renewable, you know that necessarily occurring
you know, sources from which you can get this energy.
(Refer Slide Time: 24:36)

496
Now, we have to know that the different forms of energy and also what are the energy
conservation law. So, energy conservation law is sometimes called this past law of
thermodynamics. In this case this law says that you cannot create or you know, destroy the
energy only, you can change this energy from one form to the another energy into another form
like you can say that a car engine that bonds gasoline, that will convert the, you know, chemical
energy in gasoline into mechanical energy.

And solar cells, the change radial as a radiant energy into you know that electrical energy and
also heat and light energy can be, you know, converted into mechanical energy, chemical energy
and electrical energy and back again. So, energy, you know, changes, it is form but the total
amount of energy in the universe remains the same. So, this is called that energy conservation
law and this law is sometimes referred to as First Law of thermodynamics.
(Refer Slide Time: 26:01)

497
Now, what are the different forms of energy there may be you know, there is some kinetic
energy that will be potential energy, thermal energy, electrical energy, magnetic energy work and
also energy, chemical energy. Even you can see that some other different types of energy you
can have like you know nuclear energy, fusion energy, all those different types of energy.

Now, kinetic energy is basically the energy of motion whenever to the element with change, it is
you know, kinetic from one you know, quantity to another quantity, you will see that the motion
of this fluid at each different, you know, flow rate will have some your own energy. So, this is
called kinetic energy and potential energy is basically due to the position of the system in a
potential field to anybody any object it is change its position, you know particularly or you can
see at an inclined to another position you will see there will be a change of potential energy.

And you will see that this potential energy maybe of different types like gravitational energy or
gravitational due to the gravitation and also due to some you know that chemical bonding of the,
you know, atoms and also some other you know, forms like, if suppose the spring needs, change
its location, there will be you know that, you know, that potential energy will be you know,
really there. So, that is why how can say that her potential energies basically due to the
opposition of the system in a potential field.

498
And thermal energy it refers to several distinct thermodynamic quantities, whereas the internal
energy of the system, heat or sensible heat, you can see, who said defined as the types of you
know that energy transfer other forms like electrical energy magnetic energy work, which are
done by machine work done on system like this chemical energy or this is basically a potential
and achieve up chemical bonds. The energy that is stored in chemical moles is does considered a
form of you know potential energy.
(Refer Slide Time: 28:50)

Electrical energy is the movement of electrical charges moving to a wire that is called electricity
and lightning is another example of electrical energy you can say. Sound is also regarded as an
energy basically, the movement of energy is through substance in longitudinal are based on
compression or rare fraction waves. And, this sound energy is produced when a force causes an
object or substance to vibrate.

The energy is transferred from the substance in a wave and radiant energy. It is basically a you
can see that electromagnetic energy that traverse in transports waves and this radiant energy
includes, you know some visible light X-ray gamma rays and you can see radio waves and light
is one of one of the you know, the top radiant energy and solar energy is an example of radiant
energy you can say.
(Refer Slide Time: 30:06)

499
Sometimes you will see that some energy will be you know that stored as a mechanical energy
that is called elastic energy. And this is stored in objects by your application of stored
compressed speeds there and stressing use and also stressing a proper bands are some examples
of stored mechanical energy. Nuclear energy this is also one type of energy which is being stored
in the nucleus of an atom. In this case the energy that holds the nucleus together and the energy
can be you know released.

When the nuclear combined or split apart and nuclear power in a process that will be called as
efficient process you will see that the sun that combines the nuclei of hydrogen atoms in a
process which is called you know fusion. So, fusion is the process where 2 light you know nuclei
that combines together releasing past the amount of energy and fission, this is a splitting of
heavy you know unstable nucleus into 2 lighter nuclei by reusing each energy.

So, that is fusion is one process by which you can have some energy just by splitting of a heavy
unstable nucleus into, you know, 2 light a nuclear whereas as fusion is the process for the
releasing of energy by you know, that combining, you know 2 light a nuclei together into, you
know, a combination to release this past amount of energy.
(Refer Slide Time: 32:00)

500
and heat energy is the result of that movement of the in particles that is called atoms, molecules
or ions in the solids, liquids and gases and heat energy can be transferred from one object to
another the transfer or flow due to the difference in transfer between the two objects and you will
see that due to the you know, molecular or atomic or some subatomic, you know motions and
also that interactions among the molecules you will see that there will be you know energy
released and this energy release will be called as internal energy.
(Refer Slide Time: 32:44)

And this internal energy you can you know produced by you know supplying some, you know,
extra work on this. So, that will be called as work energy and that work is actually regarded as
energy that flows in response to any driving force they are like applied force torque other than

501
temperature you can say and it is defined as the positive for if it flows from the system that is
work done by the system in chemical processes work may for instance come from pumps,
compressors moving pistons and other moving you know turbines.

So, in that way you can you know, get this work for you know chemical processes just by you
know pumps compressors moving pistons and moving turbines and also you can you know get
this type of work based on that you know, applied force as a torque or some pistons or you can
see less thick, you know, forces there. And these, you know work, energy will be utilized for
transporting of fluid from one position to another position or you can use this work energy to
change the internal energy or enthalpy of the systems to you know that particular process prior.

You can get that useful products by its processing and so, we can see that what about heat or
work that will be refer to the energy that is being transferred to or from the system and based on
who is that you know, that process would be you know, assist and you can see that performance
of the process will be analyzed. And if there is no motion along the system boundary for a
particular process that you can say that, that work done will be you know non or negligible there.

So, basically two things are here heat and work that will be supplied or it will be you know that
released from the system and based on based on which you can say that what will be the you
know process out and order the efficiency the process that can you can assist based on this and
because this you know supplying up work to the system or by the system, you know or you can
see that supplying of heat to the system or releasing from the system.

you will see that there will be change of internal energy, kinetic energy and also potential energy
and based on who is you know, case to case that different chemical engineering processes to be
assessed based on that you know, based on each process you need, how it is being used based on
this energy supply.
(Refer Slide Time: 36:05)

502
Now, we know that how that energy can be transferred to you know utilize it for you know
getting that useful products that energy whatever heat or work can be transferred by flow of heat
by transport of mass or by performance of work.
(Refer Slide Time: 36:29)

In this case, you have to remember what are the units generally being used for these energy and
also the rate of energy which is called power what will do what should be the units that also to be
you know are required to know, because, different systems are you know they are to be used or
to be you know that access based on this you know, system of units and based on which you will
see that quantity of the heat indifferent systems will be different. So, in this case, generally the
unit for energy is actually denoted by joule and it is basically that Newton meter.

503
So, 1 joule is equal to 1 Newton meter, where you can see that 1 kg of you know mass of any
object anywhere it will be accelerated at a certain you know value like kg per meter is a meter
per second described then you can say that there will be 1 joule of energy is produced or work
done will be produced to there. So, we can regarded this joule as a unit of you will see that
energy and in British thermal unit it is you know that.

BTU and this you know that what will be the you know conversion factor for this dual to you
know that British thermal unit and also to the calorie also another important unit by which you
can you know access these are quantified this that is energy. So, that will be joule calorie when
British thermal unit here in the slides, this unit conversion of this energy from one system to
another system is given also the units for power also given in this slides.

It is regard it is generally regarded as you know that horsepower or kilo watt. So, one
horsepower is basically 0.74570 kilowatt and also 1 kilowatt joule 1000 joule per second that
means, the how much energy is released or work done per unit time that will be called as power.
So, here the slides the unit for power at different, you know systems is given.
(Refer Slide Time: 39:18)

Let us talk about the different forms of energy and how it can be calculated. Now, we have truly
described regarding that, different forms of energy like kinetic energy potential energy, internal
energy, heat energy, electrical energy all those. So, what is that kinetic energy, this is basically

504
associate with an object saw motion and it is the energy that is carried by your moving system
because of its velocity and the kinetic energy of a moving object of mass m traveling with this
speed suppose KE can be you know defined as (1/2)mv2.

If it is regarded as a rate then you can say that it will be you know that rate of kinetic energy they
need to be you know defined as the rate of kinetic energy to go to hop into m dot into p square
your m dot is you know mass flow rate and p is the velocity. So, half into m dot into v square it
will be you know called as kinetic energy and this unit you need to be you know that joule per
second. So, simply to come as you know that watt is watt is the power unit are as joule per
second it will be the energy per unit time. So, what is regarded as watt now, let us do an example
for this.
(Refer Slide Time: 40:59)

Suppose water flows from a large tank into a process unit to a 0.02 meter inside diameter pipe at
a rate of 2 meter cube or work calculate the change in kinetic energy for this stream in joules per
second. So, in this case, you will see that it is given that what will the volumetric flow rate here,
this volumetric flow rate at this flow rate you will see that water is flowing through the pipe for
us inner diameter of the pipe is given to you that is 0.02.

So, what we the velocity of the fluid that is flowing through this pipe first of all you have to
calculate since volumetric flow rate is given to you can get these you know velocity just by
dividing the volumetric chloride by its cross sectional area you have to calculate first cross

505
sectional area since its diameter is given. So, what should be the cross sectional area simply
volumetric flow divided by you know volumetric cross section area to be simply you know that
by the square by four is the diameter.

And if you know that cross sectional area, then you can easily calculate watts velocity simply
volumetric floated by cross sectional area, so, here you can get this velocity. Now, these velocity
will be you know that through the, you know, pipe from each, you know initial condition initially
that fluid was, you know, at rest. So, initial velocity of that fluid will be, as you know that 0. So,
you can say initial velocity, u1 = 0.

And the final velocity as you know that u2 that will equal to just simply Q by cross sectional
area. So, you can get it and you can say, after that you can calculate what should be the you
know the kinetic energy. So, kinetic energy that will be half into m dot into v2 square – v1
squared. So, v2 is known to you as part this problem u20 here u10 here but again you have to
calculate what to the mass flow rate.

Since you are you have given only you know that volumetric fluoride of the fluid. So, you can
get the mass flow rate just you know that multiplying this volumetric flow rate with rage say
density then you can get the ah mass flow rate since era the fluid is water. So, density of the
water is 1000s. So, we can say that the master it will be equal to this 2 into 1000. So, it will be
coming as you know that 2000 you know, Kg per work here. So, if you substitute here this mass
flow rate.
(Refer Slide Time: 44:26)

506
You can get this kinetic energy finally, after substitution.
(Refer Slide Time: 44:33)

Then you can get this kinetic energy as here 0.88 joule per second. So, from our 2 second you
have to then multiply you know that this you know kinetic energy you know they are second to
hour are hour 2 second that you have to you know conversion factor of 603 we have to use there
So, finally here in the slides, it is given the details calculation of these V2 and also mass flow rate
also which is given here as it is 0.56 and then finally, this kinetic energy is like this.
(Refer Slide Time: 45:15)

507
Let us do another example here. Suppose a liquid is pumped from his storage tank to a tube of
2.5 centimeter in diameter at the rate of 0.005 meters joule per second, what is the specific
kinetic energy of the water here, density of the you know liquid as water you can say it is given
1000 Kg per meter cube. In this case you have to find out what should be the specific kinetic
energy. Now, this specific kinetic energy basically the kinetic energy per unit of mass you can
calculate here.

First of all you have to calculate it is kinetic energy based on then you know, velocity change.
So, to calculate that, first of all you have to calculate or to the mass flow rate of that water, this is
basically volumetric flow rate into density then it will be coming as your 5 kg per second and
then calculate the cross sectional area of the phi it will be you know quiet discouraged by for
here d is given to you, then after calculation, you will get this cross sectional area of 0.00491
meter squared.

And then velocity of the leakage you can get it volumetric flow rate divided by cross sectional
area then after substitution of those values, you can get this velocity as 4.07 So, kinetic energy
rate will be equal to half mv squared. So, after substitution of this, you know, value of this.
(Refer Slide Time: 46:53)

508
You know mass flow rate even you know that velocity, they are and finally you can get this you
know kinetic energy rate as 41.41 joule per second. Now kinetic energy per unit mass that will
be regarded as that specific kinetic energy. So, that can be calculated just by dividing this kinetic
energy by you just you know mass flow rate, then it will be coming as 8.28 joule per kg, here,
now what is potential energy, the potential energy is energy by the system, that is possesses.

Because of the body force that exerted on its mass by a gravitational or some other you know
that field force field you can see with respect to a reference surface, now this potential energy for
a gravitational field can be calculated by this equation per field called potential energy. M is the
mass of that you know object or material you can say and g the gravitational isolation and z is
the height of that you know object from the star reference surface and the specific potential
energy can be regarded as we had that is basically this us potential energy per unit mass, then it
will becoming as simply gz.

So, potential energy change you can calculate what should be the, you know, height change
based on which you can calculate its change. It is basically in m dot g into z2 – z1 here z is the
distance from the reference surface and at 2 locations if it is there then you can see that z2 are
from the different subjects surface z1 also from the references and then you know subtracting it
will give you that change of you know potential energy based on this equation given in the slide.
(Refer Slide Time: 49:11)

509
Now, let us do an example here this case again that water is pumped at a rate of 5 kg per second
from a point 100 meters below the earth surface to a point of 100 meter above the ground level.
So, in this case, you have to calculate the rate of change in the potential energy. So, simply here
m dot is given to you g is the gravitational acceleration that is 9.81 here, this saw you know that
level change like this z2 to z1 here in the load, z1 into z2.

This is basically this difference is coming as you know that here, z1 is - 100 meter and z2 is +
hundred so, we can say that this difference will be 100 - of - 100. So, it will be coming as 200
here. So, if you multiply this with this mass flow rate and this gravitational isolation, we can
have this rate of change of potential energy as you have 9.81 kilowatt.
(Refer Slide Time: 50:18)

510
Now, if we you know compared this potential and kinetic energy and how it is actually changing,
just converting this potential energy to the kinetic energy. Now, let us see this discuss of a roller
coaster have you know greatest potential energy at the top of the first hill here. Now, as they start
their descent, the curse, loss potential energy and they gained their kinetic energy, the energy of
motion there, here seen this video in the slides here throughout the ride is time for you can see
that discuss or train loss height it gains the speed as a potential energy.

and then it is transferred into kinetic energy here and then is transferred into again ah kinetic
energy just by changing it is different you know height of this you know hill like this time it
gains height it losses to speed as kind of energy is transformed into potential energy there so
based on whose we saw in the bar it is the same g you know a location you will see that this
potential energy will change and whenever it is changed, you know this velocity its kinetic
energy will change.

So from that you know that changing its position by its changing its velocity how these potential
energy and kinetic energy will be changed and this converting this energy from potential to
kinetic to potential that you can easily you know, has is based on this you know preview or you
can understand this.
(Refer Slide Time: 52:07)

511
Now potential energy is energy that is not in us that is physically installed and is available to do
work and if an object can fall it has gravitational potential energy, the chemical energy in ah you
will see that in fossil fuels is considered potential energy until released. Fossil fuels have
chemical potential energy, you know from chemical bonds with stored energy taken long ago
from the sun. And also you can see that biomass or batteries have also chemical potential and
achieve here also.
(Refer Slide Time: 52:43)

The spring energy is shown the slides that how this potential energy is changed whenever, you
know that expand this spring at a certain link takes there. So, therefore, that potential will
become potential energy will be calculated based on this expansion of this unstretched spring

512
here So, it will be simply half of k into x squared here case called here some constant that is you
know less g constant here. So, based on PC you can calculate what the potential energy.
(Refer Slide Time: 53:12)

Like here example is given here a compressed spring is, you know displaced at 0.5 kilometer by
each potential energy change, the spring constant is given 200 newton per meter in this case what
should be the potential energy that you have to calculate based on this displacement of this
spring here K is given here 200 newton per meter x is given .5 meter then potential energy will
be equal to half of k into x squared that simply you know half into 200 into 0.5 squared that will
come 25 of Joule.
(Refer Slide Time: 53:51)

513
So, we have discussed here regarding that you know concepts of energy and how different forms
of energy is converting from one form to another form. Now, in this case before going to that
balance of energy in a particular system, you have to know that what is that particular system in
this case the system generally is an object or a collection of object that and you know analyze is
carried out on each the system has a definite boundary called the system boundary.

Which is so then and is specified at the beginning of the analysis. Once the system is defined to
the size of a system boundary everything external to eat to be called as the surroundings and all
energy and materials that are transferred out of the system entered the surroundings and vice
versa and based on this.
(Refer Slide Time: 54:50)

You have to analyze that you know, our system energy which is coming out which is coming in
and also what are the change of internal energy you know enthalpy potential energy kinetic
energy inside the system, there are different type of system you will see that some systems will
be isolated, some systems will be closed some systems will be open some systems will be eidetic
some systems will be isothermal.

Isolated system there are that does not exchange heat work or material with the surroundings and
closed system they are in which heat and work are exchanged across its boundary, but material
will not be open system will be defined as the system by our you know that heat work and

514
materials would be you know, extends to the surroundings and adiabatic systems in that case
most significant heat exchange with the surroundings will be happened.

And such a systems is said to be sometimes eidetic and whenever the systems will be operated at
an you know constant temperature and also you know that there will be a certain time and for a
particular you know a special coordinates, then you will see that heat crosses the boundary will
not happen. So, in that case it will be regarded as you know isothermal system.
(Refer Slide Time: 56:18)

So, here one system here is given this is the closed system and here red dotted line is regarded as
boundary and outside the boundary it will be called a surroundings. Now, to these closed systems
will be heat will be in and out there simulate what can be done on the system and work will be
done by the system also. So, energy can cross this boundary of a closed system in the form of
heat and work and the energy balance of the system will be used to determine the amount of
energy that flows into or out of his process unit.

So, these systems can be regarded as one processing unit also and the balance, which would be
you know, that used to calculate the net energy requirement for the process and they need to be
assets as ways of reducing energy requirements in the systems.
(Refer Slide Time: 57:16)

515
Then, after doing that system or defining that system boundary, you have to do that balance
energy balance now, to do that energy balance, you have to you know that basic energy balance
equation. Now, ask for this you know that conservation of this energy we can you know
formulate this energy balance equation as like it is anesthetic that heat is there gaining and it is
losing and also you can see that there will be accumulation of some heat energy.

So, if there is unsteady state operation, so, based on which you can see that there will be some
accumulation there will be some energy there will be some output of energy. So, based on this
you know concept of this energy equation, we can say that there will be some accumulation of
energy based on you know, what will be the energy in the final system and what will be the
energy that in the initial system and also what would be the net energy that is transferred to the
system to change the spinal system energy from its initial system energy.

So, we can then represent it as the accumulation as final system energy - initial system energy
and it will be then equals to that input - output like this and that what will be the net energy here
input - output that is transferred to the system like maybe you know that some heat energy or you
know that work done by the system or work, heat energy to be supplied to the systems there. So,
based on which there will be changed on that system energy.

516
It may be gaining its final system energy from its initial system energy they are now, initial
system energy can be regarded as you know that a summation of internal energy, kinetic energy
and potential energy final system and it will be regarded as that you again that internal energy of
that final state or final condition, kinetic energy and funded into potential energy and net energy
transport that will be Q - W.

So, if you substitute this, you know, quantities here in this you know energy balance equation,
we can write this energy balance equation here, we can see that that net change of energy in the
system as an output or you can see that that will be changed by that you know supplying of
energy or losing its energy from the system here. So, based on this net input to the system that
may change these you know that system energy from its initial to each final stage.

So, based on this, we can then formulate this you know energy balance equation. So, here Uf -
Ui, the analogy is you know that internal energy change from its initial to final and kinetic
energy as KE this kinetic energy, this is a favorer final and kinetic energy that is i for initial to
this kinetic energy will be changing from initial to the final similarly, potential energy also may
be changed from initial to the final.

So, to be the total change of the saw submission of internal energy change, kinetic energy
change, stage potential energy change, all those will be coming based on that net energy supplied
to this you know system. So, we have we are, you know described this energy balance based on
the system boundary and also how that unnatural within more details of this energy balance will
be, you know, described in the, you know, next 2 lectures there.

So, the next lecture will describe this, you know more details of this energy balance and also
other, you know, conditions of this energy balance equation and based on base will, you know,
do some, you know calculations based on this energy balance. So, thank you for giving attention
for this lecture.

517
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 18
Laws and properties of thermodynamics

Welcome to massive open online course on basic principles and calculations in chemical
engineering. We are discussing about energy and it forms under module 6 or in this module, we
will discuss today about the laws and properties of thermodynamics.
(Refer Slide Time: 00:47)

In the previous lecture we have described regarding concepts and units of that energy and also
what are the different forms of energy and also how it can be calculated that given some you
know idea and also described that different forms of energy and also we have given the general
energy balance equation and how that energy balance equation can be you know used to you
know assess that process for an energy analyze.

This will also give more examples on that, you know calculation based on that general energy
balance equation, you know successive you know, lecture series. Now in this lecture will try to
even know something more about that energy and its forms in this case that, thermodynamics,

518
and it is law and also different properties of law that thermodynamics like enthalpy, entropy and
how those entropy and enthalpy can be calculated will be discussed here.
(Refer Slide Time: 02:10)

As we know that that energy balance equation for any closed systems you know to represent
each.
(Refer Slide Time: 02:19)

We are having this you know energy balance equation like accumulation that is input minus
output and because of that you know heat input or work output or work input by or heat output
based on these there will be a you know change of you know internal energy and also you know

519
other you know system energy change and based on which you can see that how much energy
would be accumulated based on this input or output of the energy of heat.

And you know work by energy transferred so, in that case the system and it will be changed from
initial to final stage and because of this you know energy transferred this a change of this, you
know final system energy from its initial system energy can be represented by this general
energy balance equation here as shown in the slides.
(Refer Slide Time: 03:33)

And we can you know that, express this equation in this difference form here like this delta U
that is a difference in internal energy and difference in kinetic energy and difference in potential
energy. And these changes will be equals to that, you know, heating input or output or lot of
done by the system there and here you can see that this heat energy or that work that is done by
the system or on the system that will change this different system energy like you know that
internal energy, kinetic energy and potential energy they are so, based on who is who can you
represent is a general form of equation.
(Refer Slide Time: 04:30)

520
So, in this case you have to remember that, if there is no temperature change, even phase change
also it is not there are no chemical reactions occur in a closed system and if pressure change our
less than if you atmosphere in that case we can see that that internal energy will be negligible or
almost zero. Now, if your system is not accelerating, in that case kinetic energy you know, that
will be close to zero. And if your system is not rising or falling, we can say that there will be no
potential energy change.

And also if your system and its surroundings are at the same temperature or the system is
perfectly insulated, then we can say that there is no heat you know supply to the air or to be
coming out from the system and work done on or by the system is generally accomplished by
you know movement of the system boundary and in that case, there are no moving parts or
electrical currents or radiation of energy of this type at the system boundary, then you can see
that this work will be equal to 0.
(Refer Slide Time: 05:49)

521
So, if we express that general energy balance for an open system can have this you know, energy
input and energy you know what can output for us here in the initial state that the kinetic energy
potential energy and what will be the internal energy also how this pressure they are in the inlet
change and also you know volume of that in the condition. Similarly, at that outlet condition
what are those you know system variables are there as an energy.
(Refer Slide Time: 06:27)

So, based on which we can write this you know.

(Refer Slide Time: 06:29)

522
(Refer Slide Time: 06:30)

Final form of general energy balance here so, this will be your change your potential energy
change of kinetic energy, change your potential energy here this, you know that this no work
done by the fluid system here that will be represented by this PoutVout - PinVin then it will be close
to here as general balance equation given. So, this is you know that final forms of general energy
balance equation for an open continuous system.

So, in this case here to final system energy minus rate of initial system energy that will be close
to rate of energy transfer to the system. Now, this rate of initial system energy can be represented
by these terms and the final system energy can be represented by these terms and energy transfer

523
that will be q dot minus w dot, this Ws dot is basically that shaft work and this P1 you know Pin
Vin and also the outlet PoutVout the difference of this you know that we are done by this changing
of volume or pressure by this you know quick flow it will be regarded as that work done by the
fluid and in this case this you know that were done by the shaft and work done by the fluid you
know flow then it can be regarded as total work energy as w.

So, that is why we can you know that here that W will be equal to Ws + Wfl here in this case Ws
dot is shaft to work that done by the fluid on a moving part within the system example like piston
turbine and rotor. Similarly Wfl here this is a flow work that is rate of work done by the fleet at
the system outlet minus the rate of work done on the fluid the system in inlet. So, this summation
of this you know shaft work and the flow work will be you know, regarded as the total work
done by the system.

This you know that the difference in that you know heat energy supplied all this work done by
the system what is the difference that difference will give you that change of internal energy
kinetic energy and potential energy and also we can say that that will be added to that you know
that changing flow was so, input rate to the system will change the rate of change of energy in
the system as an output there.
(Refer Slide Time: 09:40)

524
Now, the energy balance for an open process system can also be actually expressed by this
equation
U  KE  PE  ( PV )  Q  W
here in terms of you know different forms there so,
U  KE  PE  ( PV )  Q  W
(Refer Slide Time: 10:01)

So in this case, we can say that this delta U dot is the internal energy change, delta KE dot is,
kinetic energy change and delta PE dot is potential energy change and delta PV dot the work
performed on the system in order to push the fluid in or out of the system. And here Q dot is the
rate of heat energy in and Ws dot is the rate of work done by the system as output and you have
to remember that this summation of this internal energy change and this an pro work performed
on the system will be close to or will be regarded as enthalpy of the system.

So, this enthalpy change will be you know defined as delta U dot plus or you know delta PV dot.
So, this this delta H dot is called enthalpy change. So, the enthalpy that will be to call to then
internal energy plus that pressure into volume, we can see that the steam turbine is an open
system where you can apply this you know energy balance equation to solve this problem even
other problems also, you can apply this general balance equation.

525
We will do some problems in our next lectures there with this you know, energy balance
equation. So, before going to you know, use this energy balance equation for a particular
chemical engineering process you need. We have to know some, you know thermodynamic
properties and it is a law because here this internal energy enthalpy change all those are basically
thermodynamic properties. So, these are how these thermodynamic properties are defined and
how to calculate we have to learn first.

Then we can use these you know these thermodynamic properties of like this internal energy,
how enthalpy change and also how potential energy kinetic energy, all those things are change
based on that will be able to you know do the energy balance for a particular process. So, let us
know something about that laws of thermodynamics, here the laws of thermodynamics define
actually which physical quantities like equilibrium temperature and achieve and entropy that
characterize thermodynamics system set you know thermal equilibrium.

So, there are you know different laws of thermodynamics that well you know, give that you
know, idea of that physical quantities in terms of equilibrium temperature energy entropy, which
will characterize this thermodynamic system. In this case, we can see the law of
thermodynamics, first law of thermodynamics second law of thermodynamics like this. Now,
what is that zeroth law of thermodynamics here according to this, you know law, it is said that
the 2 systems is in equilibrium thermally with the third system then you can say they are in
thermal equilibrium with each other.

So, this law helps to define the concept of temperature actually so, this temperature will you
know higher temperature will try to you know distribute in saturated with that it will equal it will
make all you know that equilibrium of this 2 temperature of higher to lower. So, based on which
you can say that if suppose 2 systems are in contact with each other in a thermal equilibrium
condition with third one, then of course, this third system will scout will come try to come in a
thermal equilibrium.

So, that they are in equilibrium with each other. So, this is called zeroth law of thermodynamics,
but first law of thermodynamics gives you know that concept of you know conservation of

526
energy in that case when energy transfers as work as heat or with matter into or out of the
system, then systems internal energy as per the law of conservation of energy will be you know
they are accordingly. So, when energy transfers as work as heat or with matter into or out of the
system, the system internal energy will change accordingly to give you that, you know total
energy of the system without you know destroying.

So, that is why this first law thermodynamics will give you that how much energy will be formed
internal energy will be forms based on the you know that work done on the system or work done
by the system or heat energy will be supplied or that energy may be you know transferred by the
metals. So, based on which you can see that how that system will be changing its energy.
(Refer Slide Time: 15:48)

And also the second law of thermodynamics says that processes that involve the transport or
conversion of the heat energy that will be you know, irreversible and it is about the quality of the
energy and it states that that energy which is transferred or transformed and more and more of it
is generally being wasted. And according to the second law, it is also you know, say that there is
a mutual tendency of any isolated system to actually degenerate into a more disordered state.

So, we can say that, according to these second law of thermodynamics, that whatever transfer or
conversion of that heat energy will be there, you cannot make it to you know, reversible or to its
original state. So, it is called the irreversible process. And in the case of you know that third law

527
of thermodynamics, you know that there will be a change of entropy because of that, you know,
our conversion would, you know, heat energy into each other forms like internal energy change
or potential energy kinetic energy change there.

You will see that this phenomena of changing this state of this system that will you know a
process a constant value as the temperature approaches absolute zero. So, all these you know that
whatever internal energy will be changed by, you know, supplying that heat energy from the
surroundings to the system. And in that case, this internal energy portability change that actually,
depending on the temperature change.

So, anybody we are talking about the, you know, some characteristics which are being changed
in terms of that internal energy or you can see that some you know environment will be changing
who should be called as the entropy that depends on the temperature. Now, you will see that if
there is you know in equilibrium condition of the temperature distribution in inside the system
you will see there will be a certain characteristics of the system that will be represented by the
entropy.

Now, that entropy will you know be to absolute zero or in temporary setup process that up to
absolute zero that you will see that the entropy of the system will recess to a constant value. So,
there is you know that this is a something is qualitative, you know, thinks that some you know
the characteristics of that, you know systems will change and it will reach to a constant value
when this temperature will reset to its absolute zero.

Now, this entropy of the system at absolute zero is typically close to zero. And in that case the
entropy of the perfect crystal is regarded as zero and the temperature of the crystal is equal to the
absolute zero for the pure substances like few crystals in that case this entropy will be zero at its
you know absolute zero whereas, in other cases you will see that at its absolute zero temperature,
this entropy will resist to a certain value that is a constant value, you cannot actually get that
absolute zero entropy.

528
They are because of that any systems of real system you can say that that may not you know,
have extemporary converted into absolute zero because they are anyway they are restarted you
know that you know frictional energy movement of that are molecules will give you certain heat
energy there. So, at that cases, you will see that this temperature is going to or approximately
close to zero that you can see that this entropy will be you noticing it is constant value and how
does entropy actually quantitatively can be estimated.
(Refer Slide Time: 21:26)

So, in this case, here one, you know that mathematical you know, representation here shown
here, that, how do you entropy change can be calculated, if you are changing your, you know,
heat energy for a small amount you will see at a particular temperature, you will see that at that
temperature that entropy change will be, you know, defined by that change your heat upon at its
temperature. So, we can see that entropy is basically a physical measure of the lack of physical
information that is called characteristics, how that system will change about the microscopic
details of the motion and configuration of the system.

When only the macroscopic you know states are known to you. So, we can observe that there is a
change of that entropy only by change of that macroscopic you know states whereas, this entropy
basically happens when there will be a microscopic change of this physical activities, they are or
you can see that some characteristics they are and like you know that if suppose, there is a
motion of that particles even if you are you know changing the configuration of the system.

529
So, they are then microscopically you can say that because of this microscopic change of this
motion or system configuration you will see that there will be a change of entropy and that
entropy you cannot actually measure by that microscopic change, but only you can realize it by
the macroscopic state change of that you know system. So, according to that second law of
thermodynamics or you know that laws or you can say thermodynamic PVR in a theoretical and
you know, fictive reversible heat transport.

We can say that an element of heat transferred that is

 Q  TdS
delta Q is the product of the temperature are both the system and the sources of our destination of
the heat with increment delta is of the systems that conjugate variables and this is called that
entropy. So, as part the saw you know concept the mathematical representation of this you know
entropy can be you know expressed as you know delta Q because to T into ds also this entropy
can be a you know measure of systems thermal energy per unit temperature that is, you know
unable for doing useful work there.

Because in this case this work is obtained from the order of that you know order or you can see
regular fashion of that molecular motion and also this can be a measure of that you know,
molecular disorder or you know, randomness of the system there. So, this basically a you know
that, how that systems you know environment will be changing based on that you know heat
energy supplied at a particular temperature and this may change of you know, molecular order or
disorder or fashion or you can see some configuration of the systems. So, based on who is this
entropy can be you know measured.
(Refer Slide Time: 24:02)

530
Another important thermodynamic properties you can see for that energy consideration is the
enthalpy it is generally that you know, how much you know internal energy will be changed
there and also if you know supply or if you apply some pressure and because of it there any you
know that the volume of that you know systems will change, you will see there will be you know
change of you know system energy because of that applying or that heat energy there. So, that
you know change of that, you know systems, you know energy in terms of internal energy and
also system energy.

They are, we can define this term and an improved quality as an enthalpy now, this enthalpy can
be actually known as qualitatively and also quantitatively also qualitatively, we can say that it is
a thermodynamic property of a system that will be capable to do non-mechanical work and
capable to release some heat or you can say that the enthalpy is a measurement of energy in the
thermodynamic system, which is equivalent to the total heat content of your system. So, it is a
function of state and its value depends only on the starting and final states of the system.
(Refer Slide Time: 25:42)

531
And quantitatively, we can define this enthalpy as the sum of the internal energy and the product
of the pressure and volume of then you know thermodynamic system. This is basically the
summation of internal energy and the flow energy there. So, this enthalpy you know can be
denoted by H and it can be done it can be defined by this equation given in the slides
H  U  PV
here H is in enthalpy and U is the specific internal energy and PV is the pressure and specific
volume has a specific enthalpy can be defined as here as or it can be denoted by H hat.
So, H hat will be H by m that means, per unit mass what will be the enthalpy there it could, it can
be you know regarded as specific enthalpy so, this is specific enthalpy can be defined H by m as
per the equation H by m will be equal to U by m for this equation here. So, H by m will be equal
to U by m plus PV by m. So, H by m is basically that specific enthalpy and this U by m can be
you know denoted by you had it is called specific internal energy and PV by m that you can
regard it as being to be PV hat and this for you know specific volume of the system. So, we can
then represent this, this specific enthalpy by this equation here.
H / m  U / m  PV / m
 Hˆ  Uˆ  PVˆ
(Refer Slide Time: 27:29)

532
Now, let us do an example, for this calculation of a specific enthalpy based on that internal
energy change there. Now, if we say that a system under a you know certain condition at least
you know that the rate of enthalpy is transported by stream with a molar flow rate of 200
kilomole per hour, in this case, the specific internal energy of that system of a gas at 25 degrees
celsius and one atmosphere is you know 3.79 kilojoule per mole and also specific molar volume
is given that is under same condition is 24.5 liter per mole.

So, under this condition of this system at the rate of flow of 200 kilometres per hour stream,
which will you know transport this enthalpy change because of this you know internal energy
and this pressure or flow energy and what we that you know rate of enthalpy will be there that
you have to calculate. Now, in this case we know that the specific enthalpy is defined as you
know that the summation of specific internal energy plus that P into V hat.
Hˆ  Uˆ  PVˆ
So, according to this equation, if you substitute this internal energy that is given in this problem
specific internal energy is given and then substitute this air pressure is in one atmosphere. So,
you have to convert it to Newton per meter in square.
(Refer Slide Time: 29:11)

533
And also what would be the volume this specific volume is what will be that, this is given here,
the specific volume is 24.5 liter, then you have to convert it to meter cube, we know that one
meter cubical 1000 liter. So, you can see that, conversion of this volume will be equal to 24.5 by
1000 liter to be mole than and one atmosphere to be converted to Newton per meter square just
by multiplying 1.01325 into 10 to the power of 5.

And then finally the unit for this specific enthalpy becoming a joule per mole and final value
after calculation it is coming 6 to 72.46 per mole. So, that total enthalpy transport rate can be
then you know that calculated by this equation here to tell you know enthalpy transport rate, it
will be difficult to you know specific enthalpy into molar rate. So, here molar rate you have to
convert it to you know that like this you have molarities given 200 kilomole per hour.

Then you have to multiply again into 1000s it will come to that you know more per hour few you
know substitute the value of that is a number of moles there with this you know, this in specific
enthalpy of 6 to 72.46 then, finally, you can have this you know 1.25 into 10 to the power of 9
joule per hour, that will be equal to 348.47 kilojoules per second. And this calculation of
enthalpy change, you know who are getting here, based on that internal change that change in
enthalpy can occur because of change in temperature change in phase mixing of solutions and
reactions.
(Refer Slide Time: 31:08)

534
And this enthalpy also can be regarded as a sensible heat, this is basically a heat transport to raise
your lower the temperature of a material in the absence of a change and this sensible heat change
is basically determined by using a you know property of matter called the specific heat capacity
at constant pressure or constant volume and it is represented by you know that joule per mole per
K or calorie per gram per degree Celsius.

So, in this case, this sensible heat basically that one type of enthalpy change because of the
temperature change. Now, that enthalpy change or sensible heat can be calculated based on that,
you know temperature change and that temperature change will give you that sensible heat based
on that, how much you know materials sexually being heated is being heated and also what will
be the heat capacity or specific heat capacity of that material.
(Refer Slide Time: 32:18)

535
So, based on which we can calculate that sensible heat as you know that delta H or you can see
delta Q in that case that will be equal to CP into dT or
 Hˆ 
CP (T )   
 T  p
this CP is the specific heat capacity there at constant pressure and also you can get that you know
internal energy change based on that temperature change
 Uˆ 
CV (T )   
 T V
also and for that also how that you know specific heat capacity at constant volume is changing
that also to be required to know for that particular materials.

So, in that case specific heat capacities for most substances very temperature where the values of
CP vary the range of the change in temperature and within a certain range of temperature that
specific heat capacity will change with respect to temperature. So, according to that, there will be
a you know, there is a you know a correlation to calculate that specific heat capacity for constant
pressure and specific heat capacity at constant volume.

Since, it is you know temperature dependent, but for the specific heat capacity at constant
pressure it will be you know nonlinear it generally follows that polynomial equation of
temperature and it is you know expressed as by this CP which is equal to

536
CP  a  bT  cT 2  dT 3

Here, T is the absolute temperature, or you can see that in Kelvin and a, b, c and d are the, you
know constants and this constants depends on the material or you can say that gas or liquid like
that.

And for you know that specific heat capacity for material at constant volume will be a linear
function of temperature, it will
CV  a  bT
where a and b are also constants which are depending on the nature of the substance or method
or material you can say and these coefficients you can get it from your textbook is given in the
appendix for different you know, materials how what will be the value of a, b, c and a and b for
that specific heat capacity for constant pressure and volume respectively.

As an example for nitrogen gas at one atmospheric pressure efficient this specific heat capacity
of the nitrogen gas kilojoules per mole per degree Celsius is given here in the slides here see how
this a, b, c are they are this a, b, c and d value for this specific heat capacity at constant pressure.
So, accordingly you can say that this a, b, c and d coefficients would be varying with other gas
even other materials also. So, those you can find it out from the textbook at it is given in the
appendix.
(Refer Slide Time: 35:33)

537
Now, for ideal gases, you will see there will be a certain relationship between these you know
specific heat capacity at constant pressure and a specific capacity at constant volume. So, this
relationship here as expressed as you know, CP will be equal to CV + R, where R is called you
know universal gas constant. For liquids and solids the CP will almost will be equal to CV
according to Kopp’s rule, this CP can be estimated for a particular materials based on their
atomic composition.
(Refer Slide Time: 36:12)

Now, how you can get you know that specific heat capacity for a mixture will see for any
chemical engineering operation you will see there are several components will be you know
mixed or it is actually processing to have certain you know product. In that case, you have to find
out what should be the specific capacity of that mixture. So, the overall heat capacity in that case
you have to define since the overall this capacity will be changing from its individual
components.

And since there is a mixture of different components and it will have different units specific heat
capacity, but you cannot directly add those you know that specific capacity of all components to
air it depends on also mole fraction of all those components in the mixture. So, overall specific
heat capacity can be you know defined as that summation of the specific heat capacity of that
pure material into each you know mole fraction in that mixture.

538
So, it can be retained mathematically by this equation as given in the slide here then CP is at
particular temperature that will be called
CP ,mix (T )  
all mixure
xi CP ,i (T )
components

Here xi is called mole fraction of component i and Cpi is the specific heat capacity at constant
pressure of that particular component. Similarly, you can express that you know a specific heat
capacity at constant volume for the mixture and this overall heat capacity can be you know
expressed again by this you know equation as you know value of this equation that will be close
to
CV ,mix (T )  
all mixure
xi CV ,i (T )
components

In this case xi is that mole fraction of that components in the mixture and CV is the specific heat
capacity of that particular components at constant volume, your index i ranges over all, you
know, over all of that components of the mixture and excited is the mass production or it may be
mole fractions also according to your calculation.
(Refer Slide Time: 38:47)

Now, in enthalpy change as a result of temperature, how it can be actually calculated. Whenever
temperature will be changes, then how enthalpy will also be changed and how it can be
calculated basically, there are several methods, you can you know, calculate this enthalpy based
on who is you can say that if you know that a specific heat capacity of a particular material, then

539
this enthalpy change can be calculated based on that temperature difference from the reference
temperature by this equation here given in this slide.

Here delta H will be equal to m into CP into T minus Treference here,

H  mC p (T  Tref )
Suppose the temperature is increasing from Treference to that you know, a final temperature of T
and if you know the material property of its specific heat capacity at constant pressure and also
want to be the mole or mass of that materials then you can easily calculate enthalpy change
based on this temperature change from its reference temperature and this you can express these
in you know, in integral form also based on this integral form we can write here delta H dot that
will be equal to m dot integration of CP dT.
T
H  m  C p dT
Tref

Here in this case, since CP is a function of temperature, so, within a certain range of temperature,
what would be the enthalpy change you can directly get after him you know integration of that
you know function of specific heat capacity at constant temperature with temperature and also
have to multiply it with the amount of that material there. So, by this equation you can easily
then calculate for with enthalpy change, if that CP will be changing with temperature.

Now, you know that that CP capacity is the most substances period that temperature where the
values of CP vary for the range of change in that temperature. So, this functionality of that CP can
be expressed by this you know polynomial equation of function T.
CP  a  bT  cT 2  dT 3

(Refer Slide Time: 41:23)

540
Let us do an example for this you need to calculate what is the change in enthalpy of 100 gram
per second brine solution heated in a counter flow heat exchanger form 20 degrees Celsius to 80
degree Celsius? If the average heat capacity at constant pressure is 3.12 kilojoule per kg. So, in
this case you have to fast calculate the temperature change there in absolute you know
temperature and also you have to first calculate cash flow rate there.

And then what is the you know that specific heat capacity there, if this is specific heat capacity is
constant over a range of that temperature that you can directly you know, use that you know
specific heat capacity of that constant value. Otherwise, you have to use that to you know a
functionality of specific capacity which is you know, given earlier as like this
CP  a  bT  cT 2  dT 3

and after substitution of that CP value within a range of that temperature up here it is given 20
degrees Celsius to 80 degrees Celsius.

Then, you can get this you know that enthalpy change at the rate of you know 18.72 kilojoules
per second. So, in this way, you can actually calculate how this enthalpy change will be there, if
the specific heat capacity will be changing within a certain range of temperature.
(Refer Slide Time: 43:15)

541
Also, according to that second law of thermodynamics, you can see that there will be a change of
internal energy, if you supply some heat energy into the system. In that case, the change in
internal energy again it will be a function of you know heat capacity at constant volume and that
heat capacity again will be a function of temperature there. So, according to that, you should
multiply the mass by the heat capacity as follows by this equation to get that internal energy
change.
(Refer Slide Time: 43:50)

Now, let us do an example for this internal energy change also, in this case, if a closed rigid
vessel that contains 200 kg of fluid is what is heated from 20 degrees Celsius to 150 degree
Celsius. In this case you have to calculate the heat required for this purpose, the constant volume

542
heat capacity of the fluid is given by the following relation here for that particular material as for
general energy balanced for closed system in this case, there is no change in kinetic energy, there
is no change in potential energy also, there is no moving part there.

So, in that case you can say that there will be no shaft work done on the system. And as the
system is received vessel we can say that mass is constant there. So, according to that, we can
write this you know, an energy balance equation as Q will be equal to delta U and this delta,
delta U will be calculated based on this equation here,
T
U  m  CV dT
Tref

according to that, you know, a specific heat capacity change with respect to temperature.
So, after substitution of the heat capacity at constant volume and integrating within the range of
temperature of 20 degree 250 degrees Celsius, you can get this internal energy change as 24312
kilojoule.
(Refer Slide Time: 45:29)

Now, how to calculate the enthalpy of ideal mixture, you have to remember that, for an ideal
mixture, the enthalpy of mixing will be zero. In this case, if the mixing itself does not contribute
to a change in enthalpy. The specific enthalpy of the mixture is simply equal to the sum of the
enthalpy of the mixture components. But the condition is that if the mixing itself does not
contribute to a change in enthalpy, so, we can represent this mixture enthalpy as

543
Hˆ mix (T )  
all mixure
xi Hˆ i
components

where xi is the mole or mass fractions of that components in the mixture and xi is the enthalpy
that is specific enthalpy of the particular component side.

In this case the assumption that a mixture behaves ideally nearly always works well for mixtures
of gases and it also works well for liquid mixtures when the species are being mixed or chemical
is similar sauces to aromatic species or to lead your hydrocarbons.
(Refer Slide Time: 46:42)

Now enthalpy of non-ideal mixture also to be you know, because mixtures are not ideal
anywhere in real application. This is because of the mixing of two or more species alters the
molecularity interactions which is experienced by the molecules being mixed to their does the
internal energy and hence you can say that there will be a change of enthalpy and for non-ideal
mixture up that enthalpy change for that mixture can be repeated at specific enthalpy change of
that mixture.

As you know that he specific internal energy of the mixture that changed plus you know, how
that flow work or flow energy can be changed for that mixture they are so, we can expressed by
this equation that is given in the slides.
Hˆ mix  Uˆ mix  ( pVˆ )mix  Uˆ mix  p(Vˆ )mix

544
And in this case, very interesting that the change of volume of this mixture will be you know
different from that, you know summation of that volume change of individual components based
on each more factions.
So, in this case
Vˆmix  Vˆmix  
All mix
xV ˆ
i i

components

So, it is important to do that, that how that volume of that mixture will be changed that especially
the volume of that mixture will be changed if there is a change of individual you know specific
volume of that components will be changed and in that case, what would the total mixture
volume that is specific mixture volume that you have to subtract those you know summation of,
you know, specific you know, volume of that components there.

In this regard you have to remember also that there may also be a change in volume when 2
species are mixed. In this case, the final volume of mixture B does not equal to the sum of the
volume of the components that are mixed together. So, this is very important to note here.
(Refer Slide Time: 49:09)

Let us do an example here, let us see that 1000 kilo moles per hour of liquid mixture of 70 moles
percent acetone and 30 moles percent benzene is heated from 10 degrees Celsius to 50 degree
Celsius in a shell and tube heat exchanger using a steam as the heating medium in this case you

545
have to calculate the changes in a specific enthalpy of acetone and benzene mixture in this case
is the mixture contains 70% acetone and 30% benzene.

You have to first find out what will be the most of that acetone and benzene since total amount is
you know, given to you as you know, 1000 moles kilomoles. So, in that case, the moles of
acetone will be equal to 700 kilomole whereas, moles of benzene will be equal to 300 kilomole
the change of mixture specific enthalpy can be written as here in the slides. So, in this case if we
substitute that more factions of individual components.

And enthalpy a specific enthalpy change of individual components we can get that you know,
total you know change of mixture specific enthalpy their so can be written as here enthalpy
specific enthalpy change of mixture will be equal to 0.7Cp,acetone hat and 0.3 into Cp,benzene hat that
can be represented by this you know, equation here integration of you know Cpmix dT within a
range of 10 degrees Celsius to the 50 degree Celsius temperature.
(Refer Slide Time: 51:00)

Now, you have to then calculate the Cp,mix, has specific heat capacity of the mixture then given
by this equation here, and then Cp,acetone can be calculated based on this equation and Cp,benzene can
be calculated based on this equation. And then after substitution of the heat capacity of acetone
and benzene, and after rearranging we can get the Cp,mix will be equal to this and then
substitution of this Cp,mix in that integral form.

546
And after integration and substitution of this, you know, limit of these 10 to 50 degrees Celsius
and finally, you can get this 5200 per mole. So, this way we can calculate what should be the
specific enthalpy change of the mixture.
(Refer Slide Time: 51:59)

Similarly, we can calculate the change of internal energy of the mixture in this case the changes
in a specific internal energy associated that mixing processes, which is the internal energy power,
you know, amount of mixture that will remind us the internal energy of the species that are
mixed there so, this way you can calculate here given as equation the slides
Uˆ mix  Uˆ mix  
all mixure
xUˆ
i i

components

In this case, Ui hat is the specific internal energy popular species whose fractions are given as
you know xi. So, from this equation you can easily calculate the internal energy change of the
mixture.
(Refer Slide Time: 52:46)

547
Similarly, you can express that you know how heat will be changing a solution based on that you
know enthalpy calculation that is called as a heat of solution or enthalpy of the solution. So,
enthalpies of mixing are often expressed in terms of that heat of solution, it is the change in
enthalpy that results from dissolving one mole of solute inserted moles of liquid solvent at
constant temperature. Now, in this case when one mole of solute is dissolving and infinitely,
large amount of solvent in the heat of solution will be approaching to a limiting value, which is
known as heat of solution at infinite dilution.
(Refer Slide Time: 53:32)

implication of 2 dof in
2 P 2 C system

You also have to sometimes calculate the enthalpy change when you but there will be a change
of state like you know that suppose liquid water is you know are becoming into paper. So, in that

548
case what will be the you know change of you know enthalpy when exchanges it is you know
phase from liquid to paper or sometimes solid is becoming you know, liquid, then how the
change of enthalpy will be there from you know it is a phase change from solid to liquid.

Similarly, from gases to liquid whenever it will be changing how that enthalpy will be changed
that you have to calculate. So, in this case you have to remember that the state of your system
can be changed, for example, by increasing its temperature or changing its composition
properties of the system will change depends on the on the initial and final states of the system
but not on the manner used to realize the change from the initial to the final state as referred to as
a state properties.
(Refer Slide Time: 54:54)

In this case when a bar you know, phase will be changing from one phase to that another phase
the respective enthalpy you know, can be you know, regarded as like latent heat here like fit
changes like you know evaporation and melting are accompanied by relatively large changes in
internal energy and enthalpy and in that case you have to you know referred what will be the
change of that heat or change of that internal energy and that heat you know change and which
will give you that result of that enthalpy change at a constant temperature for changing it is you
know phase from one to another.

549
So, that you know heat of change of that phase is called Latent heat there are different types of
Latent heat of vaporization. Which is actually required to vaporize the liquid letting it to a fusion
which is required to melt a solid letting heat of sublimation which is required to you know
directly vaporize a solid. So, this latent heat of vaporization, latent heat of fusion, latent heat of
sublimation, this is basically an enthalpy change temperature change at a constant temperature
when there is a change of you know phase from its original to another.
(Refer Slide Time: 56:35)

Now, latent heats are in general a function of pressure and temperature, however, then depend
much more strongly on temperature, then on pressure. Therefore, we can say that, when
calculating heat associated with the change of phase it is important to ensure that the latent heat
value used for that calculation with that it is that for that actual temperature or not at which this
phase transformation occurs.

So, in this case, remember that latent heat of vaporization cannot be the same as what it is in 30
degrees centigrade or some 30 degrees Celsius which is in which is at 100 degrees Celsius. So,
you can see that the latent heat of vaporization at 30 degrees Celsius is not same as that 100
degree Celsius.
(Refer Slide Time: 57:37)

550
Now, sometimes you will see that in the particular chemical engineering process, there will be a
process unit and that process unit will have several input and several output streams. Now, in that
case in a particular streams there will be mixture of components and also you can that that you
know components may be the inlet and that components may be in the outlet streams also,
sometimes if there is no reaction on the physical operations will be there in the inlet stream you
know that components will be there after a physical operation, there may be you know that some
unwanted or you know that unused you know components are also will be in the outlet streams.

So, there will be a mixture in the inlet outlet streams of that several components. So, in that case
that this you know how that enthalpy change will be there, based on that you know different
mixing in different streams their let us see 1 process unit given here they are 3 you know that
streams 1, 2, 3 here for has mentioned in the slides in stream 1 here in a mass flowrate is given
mass is coming and then in the outlet streams that the mass 3 and mass 3 are coming out there.

So, in this case, you will see that there will be several you know components will be coming in
and coming out from this inlet and outlet streams. So, according to that, you have to you know
calculate that enthalpy change because of this you know, final stream and this you know inlet
streams enthalpy So, how to be the enthalpy change in the live streams first you have to calculate
and what will be the change of enthalpies in the outlet streams, it may be in that mixture of
components in heat streams also.

551
So, the enthalpy change because of this you know, change of enthalpy in different you know
inlet and outlet streams, we can say that this enthalpy overall enthalpy change it because to zero,
so, we can have this equation as like this summation of you know enthalpy in outlet the streams
minus summation of enthalpy in the inlet streams, there will be more than one inlet. So,
accordingly you have to sum it up that total enthalpy change in the inlet streams. So, the general
energy balance for an open system after applying that assumptions is reduced to like this delta H
will be equal to 0. So, according you can see that delta H is equal to here.
H  H 3  H 1  H 2  0

(Refer Slide Time: 1:00:41)

H3 minus H1 minus H2 is H3 is basically that what is that outlet streams H1 and H2 are the inlet
streams there so, according to that enthalpy of those streams we can simply write this here
H  H 3  H 1  H 2  0

and also you can represent it as you know, this equation here H3 hat H1 hat and these H2 hat are
the specific enthalpy at each you know that inlet and outlet streams there.

So, we have learned here some thermodynamic properties like internal energy enthalpy, latent
heat of vaporization and also how this you know enthalpy can be calculated, how enthalpy
change can be calculated for the mixture components, how enthalpy can be calculated while in a

552
you know, specific process you need having more than 1 inlet and outlet streams, also internal
energy how it can be calculated.

And also that enthalpy an internal energy, how it can be calculated from the specific heat
capacity, you know, which is a function of temperature all those things. So, I think you
understood a little bit about this you know this enthalpy change an internal energy change and
how it can be calculated from the energy balance equation, I would suggest you to go to this
textbook and reference books for more information about those you know, thermodynamic
properties.

And in the next lecture we will try to you know, discuss more about that, you know enthalpy.
They are some heat of solution heat of formation in the reactive mode, how that in enthalpy will
be changing and also in internal energy, how it will it will be changed that would be, you know,
discussed in the next lecture. So, thank you for your kind attention.

553
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 19
Standard Heat of Formation

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, you are discussing about the energy and its arms hundred module 6. Now under
this module, today we will discuss more about that energy and its forms and we will discuss how
about the standard heat of formation.
(Refer Slide Time: 00:50)

In the previous lecture we have law described laws of thermodynamics, in thermodynamic

property is like enthalpy entropy and how to calculate that enthalpy change based on you know
phase change as well as without phase change based on the material characteristics like specific
heat of fluids particular you know temperatures and also specific heat capacity at a particular you
know, pressure and you know constant volume.

So, we have discussed and also we have done some, you know, examples and based on who is
how to calculate that, enthalpy changes and how this enthalpy changes can be assessed. So, in
this case, we will discuss about that, heat of formation when there will be you know, certain you

554
know, chemical reactions and during that reactions how heat will be you know, released or
adsorbed and based on that release and absorption of that heat.

how you can calculate that enthalpy for the formation of particular compounds, they are in the
reaction and also in necessarily occurring substance what should be that heat of formation that
we will discuss here and also how that heat of formation can be calculated, if there is a change
your phase of that particular components there in the mixture.
(Refer Slide Time: 02:27)

So, before going to that, we have to go through again how that what is enthalpy we have already
described about that enthalpy and what is the definition and we have actually narrated about that
enthalpy that it can be you know, a you know property of the system, we should be capable to do
non mechanical work and capable to release heat and it is generally a function of state and its
value depends on you know, the starting end point I will state of the system.
(Refer Slide Time: 03:06)

555
And quantitatively that enthalpy can be calculated based on the you know, what will be the
internal you know energy change if any heat or work done by the system or on the system there
and also what will be the, you know, through energies you know their change, because of that, if
any work by shaft is done on the system or that system is doing some work on a particular fluid
element and based on who is how that a flow energy will be changed and based on that internal
energy change and flow energy change

How that enthalpy can be, you know, calculated or estimated that we have already given
discussed in our previous lectures. They are and based on that enthalpy calculation also how to
calculate that the specific enthalpy just you have to you know, divide that in therapy by each you
know, moles or mass then you can get that specific enthalpy there.
(Refer Slide Time: 04:13)

556
And also we told that the change in enthalpy can occur because of that change in temperature,
because, specific heat capacity depending on the temperature and also this entropy change can be
resulted because of the change in phase and also how that solutions and their components are
mixing with other components also, they are it depends on how what the amount of enthalpy is
supplied or at least to the system also, the stage of enthalpy can be happened because of that
have reactions to that.

So, we will discuss all those things, 1 by 1 already we have discussed that how enthalpy can be
you know calculated if there is the temperature change and also how that enthalpy can be
calculated, if there is a you know, phase changes. So, still we will discuss here about that.
(Refer Slide Time: 05:10)

557
Now, we have calculated that sensible heat because of that temperature difference and this is
basically enthalpy change, because of that temperature. And when heat is transferred range or
allow the temperature of a material in the absence of you know phase change then it will be
regarded as sensible heat and, but it depends on that specific you know heat capacity of that
material at a constant volume or a constant pressure and it is usually generally Joule per mole
power k.
(Refer Slide Time: 05:41)

And heat capacity of the material this is you know, are defined by that CP is equal to what is the
change of entropy per unit change of temperature that will be called as you know, heat capacity

558
and if it is done power unit molar mass, then it will be called a specific heat capacity as similarly,
this specific heat capacity you know be assessed for constant temperature and constant pressure
and also constant volume. Now, if there is no change of temperature of course, there will be no
sensible heat there.

So, we can say that specific heat capacity cannot be changed it will be constant here so specific
heat capacity for most substances generally varies with unit temperature values of CP value for
the range of change in temperature there so, example is given for nitrogen gas at 1 atmosphere in
the slides. These slides also earlier have shown that how specific heat capacity at constant
pressure and constant volume depending on that temperature specific heat capacity at constant
pressure depends on you know the temperature.

As you know Polynomial function but as specific heat capacity at constant volume actually
shows the functionality of temperature as a linear function there.
(Refer Slide Time: 07:07)

And the specific heat capacity for the mixture we have also discuss about that it is actually
depending on that, what is the you know volume fraction or more fraction of that components are
present in the mixture. So, it depends on the smaller fraction or mass fraction of these
components in the mixture and it can be calculated by you know, the product of that more
fraction and the specific heat capacity of the pure substances there.

559
If there are more than 1 components of course, you will be there are more than 2 components
then accordingly you have to you know first find out what truth does more fraction some aspects
and then what the you know specific heat capacity for individual components simply by product
of those you know variables and summing up you get that was specifically capacity of that
mixture.
(Refer Slide Time: 08:01)

If you know that a specific heat capacity then you can calculate that proximate the enthalpy
change. If you know that CP is constant that means specific heat capacity is constant then simply
you can calculate that you know enthalpy change by this equation
H  mC p (T  Tref )

and if you are you know having the change of specific capacity with temperature then you have
to you know calculate the enthalpy change.
T
H  m  C p dT
Tref

Based on that integral form of that you know enthalpy just by multiplying molar flow rate or
mass flow rate with this you know i integrated value of this you know specific capacity within a
certain range of temperature that temperature range can be you know defined from the reference
temperature to a certain temperature there. So, this reference temperature maybe you know that
for standard from standard condition like it may be you know 30 degree Celsius.

560
And 1 atmospheric patient or you can take that reference temperature to 73.15 Kelvin or 0 degree
Celsius there and the coefficients for that specific heat capacity which are expressed based on
polynomial function is that is, depending on that measure of substances there.
(Refer Slide Time: 09:24)

Main focus on this lecture is to you know, estimate the heat of formation they are now, change of
enthalpy the chemical reactions if you are talking about that, there is a certain reaction happens
there and that reaction is taking place between somewhere you know reactance and which will
give you some products. So, in that case you will see that there will be certain changes of you
know enthalpy during that reaction.

Now, that change of enthalpy or heat you can say that comes from sensitive heat or also diastral
being contributed by you know that heat of formation of that individual components like here
react incipit his reactions, then you have to you know considered that heat of formation for this
you know, particular you know analyzes often tell people that chemical reactions.

Now, to take account of that possible energy changes caused by a reaction in the energy balance,
the new half to incorporate in that enthalpy apiece individual constituent at operating condition
and an additional quantity term does a standard heat of formation. So, you have to you know, add

561
that the standard heat of formation with that sensible heat change with respect to temperature.
There but to find out that total you know heat up reaction.

Now, how to you know find out that heat of formation of individual components are based on
that you know, heat released or heat absorbed during that reaction once you know that amount of
heat released or amount of heat absorbed by that reaction from that, you know, heat absorption or
heat you know generation you can calculate that heat of permission of that individual constituent
or components in the reaction mixture.

So, for that, you can define that heat of formation by this you know equation here as Hfi at a
standard condition that will be close to you know delta Hi minus sensible heat because of that
temporary differences.
T
Hˆ of ,i  Hˆ i  C P ,i dT
Tref

So, this Hfi0 hat is basically the standard heat of formation at a standard condition like you know
298 degrees degree Kelvin and 1 atmospheric pressure and this Hi is, you know, basically the
heat released or absorbed by the chemical reaction that is obtain by experimentation.

And after getting these heat released or absorption by experiment, you have to subtract this
sensible heat within a certain range of temperature there. So, after getting these you know,
subtraction of this, you know sensible heat from the heat of reaction, you can regard it as a heat
of formation of that particular constituents. Now, in this case, we are not considering that there is
no phase change, so, within a certain phase that will be you know to be considered, but whenever
phase change will be there, then you have to you know consider also that sensible heat for phase
change their.
(Refer Slide Time: 13:02)

562
What is the definition of that heat of formation, standard heat of formation, the standard heat of
formation of a compound is the enthalpy change that is associated to the formation of 1 mole of
compound at 25 degrees Celsius and 1 atmosphere from its elemental constituents as they are
normally found in itself like some compounds carbon, oxygen, nitrogen, hydrogen, they are
actually necessarily occurring, you know, compounds are constituents you can say and these are
elemental constituents.

So, in this case, all these you know compounds will have that standard heat up formation of you
know, 0 because those who are necessarily you know, form that compounds, the heat release to
be you know, 0 or permission of that components requiring that heat will be equal to 0. So, that
is why you have to define that the standard heat of formation for a particular substance which are
not actually necessarily occurring substances.

So, that can be obtained from that particular you know heat release or heat absorption by the
reaction of that components with other you know, consequence there.
(Refer Slide Time: 14:27)

563
So, enthalpy change of the phase change is there. So, in that case, you know that additional terms
for the enthalpy of the piece changes to be considered to give the total enthalpy of the substance
like here the heat of formation will be physical to here that is experimentally obtained heat
released or absorption there and what should be the sensible heat that you have to subtract and
also you have to subtract that for to be the enthalpy is change because about a phase change
there.

So, this enthalpy change because of that phase change it will be difficult to here HTP we have
actually discussed about that you know that phase change like you know from solid to liquid and
then liquid to vapor there is a transition and for converting that certain moles of liquid to vapor
or vapor to solid or even liquid to solid or solid to liquid and that transition heat release or heat
requirement for that it is called you know that heat of you know phase change or a discord let it
heat up you know certain phase change there.

If suppose all it is converting to you know liquid and it will be called us you know let it heat up,
you know, phase change of solid to liquid and even liquid if it is converting to be part and it will
be let it job vaporization there. So, in this way again we can say that whenever we are having
these patients are during the formation of the compounds and also the reaction then you have to
consider that heat of formation.

564
But just by you know subtracting that you know heat up subtracting that the heat of phase change
from that heat of reaction as well as the subtraction of the sensible heat within a certain range of
temperature from the heat of reaction there. So, here one you know that systematic you know
that conversion of that or you can say that P change is shown here for you know solid to you
know vapor how it is actually changing this case.

Generally solid that if we are considering water so, water actually becomes the solid when it is at
0 degree Celsius. Then solid, you know water at 0 degrees Celsius whenever it will be you know
becoming to liquid generate that theoretically centigrade you have to you know apply some
enthalpy or heat energy there, so, that it will become that you know solid to liquid just by
melting. So, these you know converting this solid to liquid at that 0 degree Celsius it would be
you know requiring some enthalpy or heat.

So, that heat will be called as let in heat of you know that melting there and similarly, that liquid
whenever you know, changing his temperature from 0 degree Celsius to 100 degrees Celsius,
then you will see there will be you know sensible heat scenes within this you know temperature
range of 0 to 100 degrees Celsius and again at that you know 100 degree Celsius it will see that
liquid will you know become vapor.

And during this conversion of these are liquid to vapor at 100 degrees Celsius, there will be some
heat, you know required that heat requirement is called latent heat of vaporization. So, these are
you know, transition another, you know enthalpy that is latent heat of you know melting or
vaporization those are actually happened at a constant temperature there. So, this whenever
phase changing will be there, there will be certain heat requirement.

Again, if you are hitting these from hundred degrees Celsius to you know certain temperature
like T then there will be again that certain you know, heat, you know requirement and that heat
requirement is called that sensible heat within temperature is a range of hundred degree Celsius
to temperature T. Now, again you know that if you are converting this you know this vapor to
again directly to solid you will see that there will be a latent heat of you know, solidification
discord sublimation.

565
So, again there will be a huge amount of you know heat is required to you know convert this
vapor to the solid at that temperature again solid temperature to temperature or to 0 degree
Celsius there will be no releasing of heat there then there will be you know that again sensible
you know latent heat or sensible heat is required from you know converting this solid at
temperature T to 0 Celsius.

So, in this way there will be a cycle and to you know get this you know material so, solid to
vapor and vapor to solid like this. So, are these are called that a phase change to this case, how
many bargain will be required for to be the enthalpy change that you have to calculate.
(Refer Slide Time: 20:07)

Now, let us have an example for phase change from solid to vapor for you know phenol. Now,
phenol if we consider that at 25 degrees Celsius, you know, at 1 atmospheric pressure, this is a
standard condition, this phenol if we you know heat it up to 42.5 degrees Celsius, you will see
that this phenol will change its you know, will heat up because of that, you know, sensible heat
there.

This phenol basically as a solid we can say that at 25 degrees Celsius and 1 atmosphere and if
you heat it up to 42.5 degrees Celsius there will be a certain heat requirement or enthalpy
requirement at that entropy requirement is called that you know, heat of you know, sensible to

566
you know converting this material from this 25 degrees Celsius to 42.5 degree Celsius. So, here
in this case, some heat is required to you know heated up from this, you know reference
temperature to the certain temperature.

After that you will see that, at that fixed temperature of 42.5 degree Celsius at 1 atmospheric
pressure, this solid phenol will become to liquid phenol in this case, becoming that solid to liquid
at that constant temperature are some heat will be required. So, that heat is called you know
latent heat of you know melting, so, this melting latent heat will be regarded H2 here Similarly,
at that 42.5 degrees Celsius, when about this solid phenol will be becoming liquid phenol and
again it will be heated up to 181.24 degree Celsius.

And that liquid phase at atmospheric pressure for that, you will need some sensible heat opt in
phase 3 and again at that particular you know a temperature of 181.4 degrees Celsius This is
basically that boiling point of you know phenol. So, at this boiling point of phenol keeping this
temperature constant you will see that this liquid will become vapor. So, at that particular
temperature of 181.4 degrees Celsius without changing that temperature.

You have to you know supply some energy or it will require some you know energy as an
enthalpy change and that entropy change it is called latent heat of vaporization of this phenol.
And after that, if you know, want to you know, heat this vapor, you know, this vapor this panel
up to you know 300 degrees Celsius, then there will be no some heat is required that is called
sensible heat for this vaporization state from 181.4 degrees Celsius to 300 degrees Celsius.

Again at that 300 degrees Celsius if you want to you know, change this up bar up to a certain
pressure then you will have you also required some you know enthalpy or supplier P2 there. So,
for that, you know that that heat also to be you know, considered for that so totally from this
solid phenolic 25 degrees Celsius to you know converted to vapor at 300 degrees Celsius at the
atmosphere, there will be a total of H1 + H2 + H3 + H4 +H5 +H6. So, total enthalpies
declared like this.

567
Now, if you want to you know directly convert this you know solid phase to that web page
hypothetically it will require total you know enthalpy delta So, delta H will be equal to
summation of this, you know, H1 + H2 + H3 + H4 +H5 +H6. So, in this way that you
have to calculate the enthalpy change, worrying about any materials you know becoming vapor
from its solid state or becoming you know solid from its vapor state.
(Refer Slide Time: 24:59)

Let us do an example for this calculation of standard heat of formation from the standard heat up
generation or absorption by reaction that is experimentally estimated. Now, here the following
you know reactions, you know 1 to 4, there are some enthalpy changes during this section are
observed experimentally at 25 degrees Celsius in a standard state in this case you have to
calculate the standard heat of formation of you know this profiling there. So, here profiling is
you know converting into you know 4 different components there as part reactions.

Respective reactions will released or absorb some you know that heat energy that is called
enthalpy that enthalpy change is given for you know respective you know reactions here in the
slides. See, so, from this enthalpy change that is experimentally obtained you have to find out
that what should be you know standard heat of formation from this for this you know profiling
substance.
(Refer Slide Time: 26:12)

568
Now, according to this reaction, we right we considered that reaction number 1 reaction number
2 reaction number 3 and reaction number 4 and respective you know that enthalpy of you know
reaction or heat of reaction, it is there. Now, according to this law, basically we can get this heat
of formation just by you know some adding or subtracting or manipulating like by multiplying
subtraction or by addition of this, you know, equation and also corresponding you know
enthalpies.

So, in this case if you add this equation number 1 and 2 and canceling the common constituents
from both the sides, we can get this equation number 5 by you will see. So, accordingly that
enthalpy also will come like it is here delta H will be coming as here, what is you know the
condition of 1 wins here is - 29.6 plus here - 530.6 kilo calorie per gram mole. So, in this way
that enthalpy can be you know they are - 560 point 2 kilo calorie.

Now, if we multiply the reaction see and reaction 4 by 4 and 3 respectively and then adding then
we can get this equation number 6 here. Now, in this case again that enthalpy correspondingly
will be calculated by this you know equation and in this case you have to multiply the enthalpy
of this you know say 3rd equation by 4 and the you know by fourth equation by you know 3 and
then add it up you will get this final value of 555.25 kilocalorie.

569
And reaction 6 and reaction 5 if you subtract then it will you know, result this equation on 7 and
finally, you know that respective you know that enthalpy change will be coming as like this 4.85
kilo calorie. So, in this case, this equation number seven is basically the formation of violin from
this carbon and hydrogen. Now, this carbon and hydrogen are you know, that enthalpy changes,
you know that. So, ultimately, what about enthalpy changes for you know that, you know
profiling.

So, this profiling formation will, you know required this enthalpy change of 4.85 and that you
know standard condition. So, that is why this amount of 4.85 you know kilocalorie for the
formation of phenol you know profiling will be regarded as standard heat of formation for this
profiling and heat of formation here is you know 4.85 kilo calorie per gram mole and it is a
positive so, it is basically you know that endothermic reaction.
(Refer Slide Time: 29:35)

Similarly, another example you can you know do for calculation of standard heat of formation
from standard heat generation or absorption by reaction that experimentally estimated now, in
this case, an example like on the basis of data and the chemical reactions given below here in the
slides and the heat of formation of zinc sulfate from the element exactly the same way what
about we have done.

570
the previous example, we can do we can calculate that you know heat standard heat of formation
for this formation of gene south, but there in this case again these 4 reactions are given and
respective you know enthalpy you know phase change or this reactions are given here.
(Refer Slide Time: 30:22)

And in this case again solution can be you know, obtain based on that some inabilities are these
reactions as well as you know enthalpies respective enthalpies and adding or subtracting then we
can get that perspective of value of that heat of formation. Now, let us do that here first reaction
is zinc + sulfate that will give you the zinc sulfate and zinc sulfide then, it fluid up you know
enthalpy of that reaction is this given here.

Even second reactions in south by to lag in time reactive oxygen it will give you a zinc oxide and
sulfur dioxide and he talked our reaction is - 2.1 .88 kilo calorie per kg mole and this produced
sulfur dioxide again will react to toxins and it will give you the sulfur trioxide and then heat
reactions is will be you know that 46.8 kilo calorie per kg mole and then again this zinc oxide
will be reacting with this sulfur trioxide which will give you that zinc sulfate by releasing that
heat of you know 55.10 kilo calorie per kg mole.

Now, multiplying this reaction 1 by 2 and adding to the reaction to will this you know the action
of this here and finally, after you know canceling the terms and the right hand side and left hand
side, we can express this equation as zinc + sulfur + oxygen that will give you a zinc oxide +

571
Dark side and then you can get this you know enthalpy of after adding these enthalpy
accordingly, you know there. So it will be coming as - 309.88 kilocalorie.
(Refer Slide Time: 32:12)

Now again multiplying the reaction 4 by 2 and adding to reaction 3, we can get this final
enthalpy as - 157.08. In this case, the reactions are, you know zinc oxide + SO2 and + oxygen
that will give you that zinc sulfate. Again, if we consider this reaction as you know equation
number 6 then adding equation 5 and 6, we can represent this equation like this and canceling the
common terms from both sides we can get this zinc + sulfur + oxygen that will give using sulfate
there.

Now in this case this zinc is unnecessarily occurring substance sulfur is naturally occurring
oscine and also that Nestle offering compound. So, in this case the centerpiece also zero. So,
ultimately what happened this zinc sulfate will form that formation of these things help it will
give you that heat of formation standard heat of formation of the thing celebrated that standard
condition. So, this can be finally, calculated based on this you know his law of the summation of
this enthalpy here from this equation from the enthalpy of you know equation of you know 5 and
6 there.

So, this delta S is basically heat of formation of 2 mole of zinc sulfate, since it is produced to
more often self at their hands heat of formation in kg more kilo calorie per kg mole off you know

572
zinc sulfate can be often just by dividing this enthalpy by 2 then you can get this up finally - 233
point 3.8. So, in this way you can easily calculate what from the standard heat of formation of a
particular substance.
(Refer Slide Time: 34:06)

How to calculate that heat of formation including a phase change, let us consider this like, if the
standard heat of formation for you know that water liquid is - 285.838 kilo joule per gram mole
and the heat of evaporation is 44.012 kilo Joules per gram all at 25 degrees Celsius and 1
atmosphere then what is the standard heat of formation of you know, water gas as a gas. So, in
this case, first considered that 1 gram mole of water.

In this case we can proceed is as to add the unknown, you know chemical equations and the
phase transition to yield the desired chemical equation and K out the same operation on the
enthalpy changes. So, in this case standard heat of reaction can be, you know, defined as
submission of a standard heat of formation of the products and also, you know, subtracting the
summation of the heat of formation of the reactants by this equation as given in the slide.
H rxn
o
 
Products
ni Hˆ of ,i  
Reactants
ni Hˆ of ,i

Now, in this case if we consider that reaction A has here, hydrogen + oxygen that will give you
that water just by releasing that heat of reaction as you know - 285 point 838 kilo per gram old at
its standard condition. And again, this liquid water height will become that gas was water just by
changing its pace. And in that case, latent heat of vaporization at that standard condition is

573
44.012 kilo Ioules per gram mole, then we can you know edit up these 2 equations and finally,
we can have this you know hydrogen + oxygen that will be due to, you know, water, but that
water will be in the vapor stage.

So, finally, we can calculate what should be the standard heat up, you know, reaction for these.
So, we can get this standard heat up reaction for this component A and also for this you can see
that standard heat of vaporization they are now in this case standard heat up reaction for this
component A here in reaction A that will be equal to extended heat of reaction for this you know
this water formation.

And also you can see that that can be obtained you know that that that you have to add the heat
up let me to bear for addition they are then totally you will get this total amount you know, heat
up, you know, reaction for this formation of gash was water molecule. So, this is basically the
formation of you know gaseous water molecule at this, you know a standard condition. So, this is
basically opt in by this enthalpy or enthalpy of the reaction and until we have this vaporization.

Which is called latent heat of vaporization finally, you can get it by just summing up these 2, you
can get this - 240 1.826 kilo Joule per gram mole.
(Refer Slide Time: 37:36)

574
Now, let us consider another thing that enthalpy of solution how to calculate it. Now, the
enthalpy of solutions refers to the total amount of heat that is absorbed or released, when the
dissolution of a substance in a, you know, solvent at constant pressure that will result in in finite
or you know dilution. Now, this total enthalpy can be either Positive or negative, and if there is a
positive enthalpy of solution results.

Then you can see that we are endothermic reaction, if there is a negative enthalpy of solution
results, then you can see that could be exothermic reaction, sometimes you will see that in
therapy of solution is, you know referred to the enthalpy of the solution or heat up solution. Now,
this heat of solution like all enthalpy changes is expressed in kilojoules per mole or a reaction
that is taking place at standard condition there.
(Refer Slide Time: 38:34)

Now, there are you know, different processes actually considered to you know, estimate that
enthalpy of solution, there are 3 processes basically happened if there is suppose any salivate are
dissolving in a water solution. So, in this case, like sodium fluoride suppose sodium fluoride is
you know dissolving in water. So, in that case what are you know process involves there to get
this solution.

Now, that solution sometimes some heat will be required to break the solute in the solution. So,
that will be called as process 1 and for the you know breaking up of solute in this case like salt

575
like cable salt, sodium chloride is a molecule in this case because the positive sodium ion is
attracted to the negative chloride ion at its you know molecular form and for that if you were the
eristic together.

And so, to break that sodium chloride in the solution, you will have to exert a certain amount of
energy that energy is called that enthalpy of this process 1 and it is let it be H1. Similarly, the
solution you will see that portable solvent being used in this case let it be water. So, you will see
that there will be you know that dissociation of the, you know, polar ends of that solvent happens
and poured that some energy is required.

So, water molecules are partially that having negative poles that is stick to that partially positive
pulls of neighboring water molecules there. So, it takes some energy to separate them. So, we
call them in therapy of this process like you know hydrogen and hydroxyl ion there. So, there
will be you know, some energy requirement to be suited to dissociate that polar is there again
whenever solution to be made, there will be some certain mixing of that solute and solvent.

So, to you know mix that you know; solute and solvent to there will be a certain energy
requirement for that mixing. So, for that also have to consider that enthalpy contribution to that
entropy of the solution. So, energy requirement for mixing that case a solute and solvent have to
mix together by applying some energy. So, we call that in therapy for this process little bit little
tasty. So, there are 3 you know enthalpy changes are there.

when is that the enthalpy change for the breaking up of you know, salute in the solution and in
therapy change for the you know, dissociation of polar ions of the solvent, that is that H2 and
energy requirement for the mixing of solid and salute and let it be H3. So, summation of these
are you know 3 contribution of you know enthalpy will give you know enthalpy of solution.
(Refer Slide Time: 41:49)

576
Even the enthalpy of solution that may be you know different for ideal and non-ideal solution
that the enthalpy of mixing up an ideal solution basically is zero by definition, but the enthalpy
of the solution of non-electrolytes has been you know has the value of the enthalpy of fusion or
vaporization or non-ideal solution of electrolytes which is connected to the activity coefficient of
the solute and also this you know that breaking up the you know, molecules you know molecules
of solvent and solids also.

And the temperature sometimes you know derivative of the relative permittivity up to have the
solution there. So, in that case that you know that enthalpy of that total dilution of that you know
non ideal solution can be defined by this equation

here in this case,  is called activity coefficients and i is basically the surface tension of that
particular components and then, here if aslant basically the relative permittivity of that, you
know, components there.

So, this is basically change with respect to temperature. So, any activity coefficient is a factor
which will actually change that you know enthalpy of that you know valued solution. The
activity coefficient is a factor used in thermodynamics to account that deviations from the ideal
behavior in a mixture of chemical substance.

577
(Refer Slide Time: 43:26)

And here in this tables, there are some salts at 25 degree Celsius how they are molar enthalpy of
the solution, when they will be you know dissolve in water it changing these are given here.
(Refer Slide Time: 43:40)

And based on Hess’ law you will see that mala interpret the solution is equal to the sum of the
centerpiece of formation of products the act and that already given example, they are like
standard molar enthalpy of formation of sodium chloride to be you know that - 411.2 kilo Joules
per mole and steady molar enthalpy of formation of sodium ion for the dissociation that will be–

578
240.1 kilojoules per mole or a standard molar enthalpy of formation for that chloride down, it is -
167.2 kilo per mole.

So, according to that his law that the standard enthalpy of solution to be equal to - 240.1
kilojoules per mole -167.2 kilojoules per mole + 411. 2 kilojoules per mole that will be able to
3.9 kilojoules per mole, here this is - 1 is actually superscripts this - 1 is superficially per mole
here. So this is correct here this will be you know, molar per mole here kilojoules per mole this i.
(Refer Slide Time: 44:55)

So, we have so discuss that how heat of formation can we calculated from the heat of reaction
and also how heat of past and that heat of formation can be, you know, calculated from the you
know phase changing and also heat up solution how to calculate based on their mechanism of
dissociation and mixing and also you can say breakup of salivate solution. So, I would suggest
you to go further about this standard heat of formation with some other examples also from this
textbook and practice it.

And in the next lecture, we will try to discuss you know, that, about that energy balance, like
how to do that mechanical energy balance and also, other you know, energy balance is based on
the actions there So thank you for you are kind attention.

579
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 20
The Mechanical Energy Balance

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about basic laws of energy equations and basic equations how
to calculate that, you know energy balance for a particular system in this lecture under the
module of energy balanced on a nonreactive processes will discuss the problem based on that
mechanical energy balances.
(Refer Slide Time: 01:02)

So, we have discussed that basic equation for that you know energy balance and from which you
will be calculating that mechanical energy also we have discuss about the heat of formation and
the heat of reaction heat up solution all those things, you know previous lectures in this case will
try to you know that derived that mechanical energy balance and from whose will also try to
understand that model is equation with some examples.
(Refer Slide Time: 01:38)

580
So, what is that mechanical energy balance this is a basically, you know, useful for processing
which changes in the potential and kinetic energies which are primarily interest or rather than
changes you in you know enthalpy or internal energy or heat associated with the you know our
processes that is why this mechanical energy balance will be mainly used for purely mechanical
problems that is some problems increase our heat transport chemical reactions or free change are
not present in that particular processes, we have already discussed.
(Refer Slide Time: 02:24)

that is generally how that energy balance for the open system can be you know represented here
in the slides, we have given that for an open system, there will be you know heat energy to be
supplied to the system for us by this system some work will be done and in this system also there

581
will be you know some mass flow rate and also you will see that there will be a change of you
know velocity because at least there will be a change of kinetic energy.

And also the you know position of that system in a particular you know, label based on which
there will be a certain change of you know energy that will be regarded as you know potential
energy and also due to the seat energy supply to the open process and based on which you will
see that there will be a certain change of energy in the system that will be regarded as you know
internal energy and also you will see that there will be some pro and it will be working on the
system.

Because of that change of volume of the system or because of the change of pressure in the inlet
and outlet top position. So, based on whose, you will see there will be a certain change of energy
that is called that pore energy So, upon all those you know, tums considering we can you know
that right, that energy balance equation for the open process like you will know that part of the
change of internal magic what will be the change of kinetic energy, what will be the change of
potential energy.

What will be that change of you know pore energy that of course, will be equal to you know that
what will be the net energy you know supply to the system that means, you know what the heat
energy supply to the system and also what will be the amount of work done by the system if you
subtract these 2 quantities, then you will get that need energy supply to the system and this net
energy supply to the system will be close to summation of all changes of internal energy kinetic
energy potential energy even improved energy out there.
(Refer Slide Time: 04:43)

582
So, in that case when you work done by the system will be working you know that the net of
work done by that system. Actually, we be you know summation of 2 works done that will be
you know that So, what is called the shaft work and another is called flow work. So, here we can
write that the flow of work done by the system that will be equal to summation of this shaft work
and flow work.
W  WS  W fl

What is the shaft work this is basically the rate of work done by the fluid all a moving part within
the system like piston turbine and to talk us through work this is basically rate of work done by
the fluid at the system outlet minus the rate of work done on the fluid at the system inlet. So, this
will be called us flow work.
(Refer Slide Time: 05:40)

583
So, this flow work is basically rate of work done by the fluid at the system that will be at the
outlet and if you subtract that the rate of work done in the fluid at the system inlet you will get
that flow work and this will be regarded as actually
PoutVout  PinVin

what does it mean? What is the pressure at that outlet condition and what will be the volume at
that outlet condition and what is the pressure in it inlet condition and what the volume in the inlet
condition.

So, if you are considering as a rate P you cannot regard it as rate. So, in that case only volumetric
flow rate you can you know consider their outlet and also volumetric product in the inlet. So,
finally, you can say that PoutVout  PinVin if you have this then you will see that total work will be
defined by this quantity. Now, if you have that several input and output streams then flow what
can be you know regarded as this.

What would be the summation of that, you know flow work at this you know outlet condition
and what should be the upload work at you know outlet condition and input condition there. So,
subtracting the summation of that input flow work and output flow work, we can get that what
will be that total you know flow work for this several input and output streams.
(Refer Slide Time: 07:30)

584
Now, from this you know terms we can make the general energy balance equation for an open
continuous system, in terms of rate just by here in this case, we do that accumulation will visible
to you input - output. And if it is you know continuous then you can see that accumulation will
be equal to input rate - output rate and the rate of final system energy – rate of initial system
energy that is equal to rate of net energy transport to the system that is in - out.

So, based on whose we can ride that you know rate of initial system energy that will be you
know that summation of internal energy, kinetic energy potential energy and flow and are the
work at that inlet condition. Similarly, for the final system energy, we can have the summation of
internal energy, kinetic energy potential energy and you know that flow energy upload work at
that outlet condition.

So, energy transport actually basically, it will be what will be the heat energy transport and what
will be the work done by the system and if you subtract this you will get that net energy you
know transferred to the system. Now this net energy transfer to the system will be equal to here
that energy that is not just by rate of final and final system energy - rate of initial system energy
can be you know equated.
Rate of final system energy  Rate of initial system energy
 Rate of net energy transfered to the system (in  out)

585
And finally, you can get that that you are you know that difference in unit you know that internal
energy rate difference in kinetic energy rate difference in you know potential energy rate and
difference in flow work rate there are so, summation of all these you know, differences of these
you know, internal energy, kinetic energy, potential energy and flow work,
Rate of initial system energy  U in  KE in  PE in  Pin Vin
Final system energy  U out  KE out  PE out  Pout Vout
Energy transfered  Q  Ws

then it will be equal to you know that net you know energy transfer to the system that is inlet and
outlet condition that.
So, this way we can have this you know, general form of you know, this general form of this,
you know, energy balance equation for an open continuous system.
(Refer Slide Time: 09:57)

And from these, you can worried this here more concisely like that you know that rate of internal
energy change it will be equal to U , rate of kinetic energy we will KE , similarly, potential
energy rate change it to be PE and a flow work you know change rate will be equal to you
know that ( PV ) , here in this case, this is given is term what do you know the definition of that
is terms here given in this slides.
U  KE  PE  ( PV )  Q  W

586
So, remember this here this internal energy change + this you know flow energy change will be
equals to that are will be denoted by, are will be you know defined as are will be referred as are
will be you know known as enthalpy change there. So, this enthalpy basically the summation of
internal energy + you know full energy there. So, rate of change of that enthalpy will be equal to
rate of summation of internal energy + rate open you know pure energy change there.

So, these are you know equation will give you that the generally general energy balance equation
for the open conditioner at continuous more.
(Uout  Uin )  (KEout  KEin )  (PEout  PEin )  ( Pout Vout  Pin Vin )  Q  Ws
(Refer Slide Time: 11:31)

And from this general energy balance equation, at a steady state we can write these you know,
equation here from this you can write, you know this internal energy kinetic energy potential
energy and flow energy in terms of its specific energy rate there. So, in that case a specific
energy can be represented by this you know term that you had similarly here in the inlet
condition to be you, hat in.

So, we can right here, this you know, at inlet and outlet condition what will be the change of you
know that energy there we can write this equation in terms of specific terms by taking the you
know mass production as a common factor here. So, from this we can write this equation

587
  
ˆ  vout  gz  P v  -  Uˆ  vin  gz  P v    Q  W
2 2
m  U out out out out in in in in s
 2   2 

and we can then express this equation that will be Q  Ws , here in this case pore energy has 2
components 1 components is going to these sites that is why we can write these you know in
terms of that specific you know, terms there.

In this case here v (a small v) What about represented here in this case, this will be specific
1
volume that is v  specific volume  . So, this your velocity as u, so, this is u and so, what will

be the ability to change in the inlet and outlet condition that will be regarded as what is that you
know kinetic energy change and since kinetic energy is defined by that half m u squared, so, here
m is common factor m dot so, it would be you know kinetic energy change.

2
vout v2
So, similarly, in that will be in your inlet condition that will be the kinetic energy there and
2 2
so, we saw the density of the material. If it is constant for incompressible fluid we can simply
then consider that here to be you know that v you know that it will be you know that constant
there.

So only that because of pressure change that you can get that you know flow work there. So, in
this way we can write this general form equation in terms of specific you know terms by taking
the mass flow rate as a common factor.

(Refer Slide Time: 14:12)

588
Now, after you know considering that incompressible flow rate, so, that the density is constant,
so, you can right here
vin  vout  1/ 
Similarly, also let us define here that delta you had that will be able to here U you know out hat -
you add in that means specific internal energy difference of this outlet condition from which inlet
condition and P will be regarded as Pout – Pin there.

These changes the general energy balance equation can be written as here like this after
simplification like this in this case here. Similarly, this is your you know pressure work and this
is your kinetic energy and this is your potential work and this is what is that internal energy and
this is your you know that heat energy per unit mass.

So, the term this case in the absence of chemical reactions, the change or other sources large
amount of heat transfer wise generally we can represented heat generated due to the viscous
friction in the fluid in such situations this term, you know as regarded as you know, that loss and
denoted as F. So, what we can right here, these total terms that delta U hat - Q dot by m dot that
would be regarded as you know that F this F is called friction loss.

589
So, finally, you can have this equation of energy balance equation in terms of you know that
frictions this you know total and that you will be equal to here, what will be the you know, the
shaft work referred by the system on the surroundings.
(Refer Slide Time: 16:29)

Now, let us do an example with this you know, mechanical energy balance equation. So, this is
basically mechanical energy balance equation. So, in this case, if we consider that the water is
supplying from a storage tank or filtering plant of a you know common tank of house complex in
its roof by a pump at a rate of 0.2 meter cube per second after this filtering and the elevation of
the surface of the storage tank is a 410 meter.

The elevation of the tank of house complex is 450 you know meter from sea level by water
distressed pipe is located at a depth of 10 meter from the source of the storage tank of filtration
plant. The frictional losses in the water line to the plant are given by a relation 0.01 meters per
second is squared into L are L is the length of the pipeline. The water line to the supply tank has
an inner diameter of that 0.1 meter and linked up 1000 meter.

Now, how much energy must a pump deliver to the water destination tank there in the house
complex and this case basically what happened that Water to be supplied by a pump from the
water storage tank which is kept in filtration plant from whose that you know filtered water to be
supplied to house complex by this pump. Now, in this case that the distress line of this pump is a

590
certain distance from that you know water level of that you know storage tank it is given it is 10
meter you know that about this you know this line.

And also this tank this storage tank is you know it is in a you know level of 410 meter high from
the you know sea level for as the destination tank of water in the house complex it is 450 meter
above that sea level and also it does seem that the you know based on this you know level
difference you can say that the distance line from the pipe this you know, saturated you know, 50
meter below that.

You know, destination tank or you can say that the storage tank water level is 40 meter below
that, you know this tension my tank of that water in the house complex. Now, at this condition,
there are certain you know fictional losses will be there whenever water will be flowing to the
pipe, the rate of frictions is given here as 0.01 meter per second is square then you have to
multiply by the length of this you know pipe whatever required total length to get to the
frictional loss as 0.01 meter per second is current to length of the pipe there.

Now in this case, by diameter is given 0.1 meter inner diameter whereas length is given 1000
meter total length. So, at this condition what are we the energy master pump delivered to the
water so, that it will reach to that you know destination water tank there in the house complex.
(Refer Slide Time: 20:18)

591
Now, in this case how to solve this problem, we know that mechanical energy balance by this
equation here we have already described. So, based on this mechanical energy balance you have
to calculate what should be the you know energy required to you know supply that water from
that you know storage tank to the you know destination tank here. So, this
Ws P u 2
   g z  F
m  2
In this case first of all you have to find out what will be the mass flow rate. So, what is the mass
flow rate here, let us calculate here. So, m dot who can write m dot will be = mass flow rate. So,
this is basically it is given 0.2 into 1000 so, that will be equal to 200 kg per second. So, this is
you are mass flow rate and the elevation change is 50 meter, elevation changes 50 meter as for
diagram given as for diagram given here.

So, we know that this mass flow rate next we have to calculate what will be you know pressure
change. So, what should be the absolute pressure change, we can calculate as delta P here so, that
will be equal to simply P2 - P1 as per diagram this is you are P2 at that you know level of water at
the destination tank and this P1 from where this you know water is sucking by this pump or
delivering that pump.

So, this will be P  P2  P1 . So, it will be is equal to what is P2 here sensitives atmospheric
pressure P2 101 325 - what to be the P1 here, P1 is here 1000 into 9.81 into 10 this is 10 meter
height this is you are you know that pressure there of this water pressure, what is this water
pressure at this point P1by this level of this water in this storage tank + this is + atmospheric
pressure 101325 this is your atmospheric pressure this is Pascal.

So, finally, it is coming as what is that - 98100 Pascal, this is your absolute pressure change
there. So, we can write this as part equation here, we can write - then Ws dot, that will be is
equal to, here, we can right here delta P - still here delta P by rho what is that delta p here, this is
90 - 98100 Pascal divided by rho is the density of water here + kinetic energy change for to the,
you know velocity there it is given this velocity we can have this velocity from this flow rate, we
can calculate here.

592
This velocity here 15.92 that will be square - here initial velocity 0 divided by 4 is that 2. So, this
is your velocity difference so, based on which you can calculate what the kinetic energy will
come and then + potential energy, what is the potential energy term here, g is 9.81 into what is
that delta z what is the elevation change there it is I think 50 meter, it is given here. Frictional
loss as you do that, as part problem that frictional loss is you know depends on the distillation of
the water.

And the length of the pipe their solution is given 0.01 meter per second squared into length of
this pipe is given 1000 So, finally you can get this you know that delta P by rho and what is the
kinetic energy change and also potential energy than frictional energy. So, after that you have to
multiply it by mass flow rate that is here what is that mass flow rate here m dot here it is given
as, what is that 1000, 200 kg per second.

So, we can then finally, have this as what is that 105 here 124 watt that means here, joule per
second, we can right here, watt there. So, in way we can calculate what should be you know
energy supply by the pump to deliver this water to the destination tank.
(Refer Slide Time: 27:04)

Let us do another example here like suppose, a pond water is supposed to use for fire
extinguishment in an you know Institute for an emergency if any sauce case, that is the water is
to be used by a pump and then delivered to hoses it may be designed to deliver 2000 liter of
water per minute at a pressure of 15 bar gauge if there is a 5 meter elevation change between the

593
water level in the pond and the discharge of the pump that case no change in the diameter of the
pipes and hoses.

And if the pump has an efficiency of you know 70% there in this case how must work must be
supply to the pump in order to meet that pressure and specified discharge rate to you know,
utilize for the per extinguishment. So, assume that there is a negligible friction. So, based on
which we can then calculate again by this you know that general energy balance equation where
you can write here you know W s dot by m dot that will be equal to what is that pressure energy
change there you have pressure is 15 bar.

So, you have to make it an absolute since it has given us gas pressure. So, you have 15 + 1 bar -
1 that would be you know atmospheric condition. So, this is your pressure change in terms of
bar. So, what from the you know pressure change in terms of you know that here in Newton per
meter square then you have to multiply it by you know that 101325 then finally, you will get this
1 after that you have to calculate the kinetic energy.

Since, here this velocity at the inlet and outlet conditions are you know negligible or kinetic
energy is negligible in that case, we can say that this difference will be you know 0 or you can
see the same velocity of that you know inlet and outlet of this pump there of the system, then you
can see that there will be you know kinetic energy change will be 0 for has potential energy it
will come because of that elevation. So, you can calculate simply that you know g into here delta
z and then friction is 0 here it is neglected.

So, finally, we can have this calculation of this you know this W s dot that will be is equal to
here after substitution of all those values, then you can get this here like this 52.3 kilo watt. Now,
the pump has an efficiency of 70% accordingly the extra work that must be supplied to the pump
in order to meet the pressure and research rate specification, then you have to you know divide
this you know 52.3 by its efficiency factor, that is point 70 then finally, you can get the actual
work to be done here 74.71 kilowatt, so, in this way you can calculate.
(Refer Slide Time: 30:41)

594
Now, let us do another example, like water flows from any elevated container through a pipe to a
turbine at a level at a lower level and out of the turbine to a similar pipe here has given in the
picture in the slide and you will see that at a point 100 meters above from this you know turbine
the pressure is 207 kilo Pascal and at a point 3 meter below the turbine the pressure is 124 kilo
Pascal.

Now, in this case you have to calculate the water flow rate that must be if the turbine output is 1
megawatt there. Now in discuss how to calculate these things. So, again here you can apply that
you know, mechanical you know energy balance equation to calculate this water flow rate here.
So, in this case what you have to do fast as for the problem you have to see whether that is there
any kinetic energies they are not here velocity you know that will be same since we are using
that the same cross sectional area of the pipe.

So, delta u squared here that will be equal to 0 and friction loss we can you know neglect here
you know a specific fiction energy you can neglect here So, F dot it a hat that would be = 0 then,
we can write from that energy balance equation

595
So, based on this equation, we can calculate what will be you know water flow rate that is V if
the turbine output is a certain amount there. So, in this case, what would be the W s dot here, this
is given 1.00 megawatt. So, this is basically we can write 1 into 10 to the power 5 Newton meter
per second that will be = what is that this is you know there and similarly you can write here it is
1 megawatts to do I think this is you are 10 to the power 6 1 into 10 to the power 6 Newton per
Newton meter per second and delta P will be = here 124 - 207 kilo Pascal.

So, it will be a circle to - 83 kilo Pascal and here that is basically - 83 into 10 to the power 3, here
newton per meter is square you can write delta P by rho is your 1000 that is density. So, it will be
coming finally, here - 83 then Newton meter per kg and then what is that delta z accordingly to
be coming as what is that? – 103 meter and g is given here 9.81 meter per second is square. So,
we can calculate g into delta z as here, finally to come here what is that 9.81 into - 103 this will
be is equal to you know 1010 neutron per Newton meter per kg.
(Refer Slide Time: 36:07)

And then after substitution of those values in the equation m dot that will be equal to -Ws dot by
delta P by rho plus g delta z it will be coming has - 1 into 10 to the power 6 divided by this is -
83 here - 1010 So, it will be coming as finally 915 that is kg per second. So, in this way we can
calculate what should be the mass flow rate of water that is flowing through the, you know 5 and
to the turbine and based on which there will be you know energy supplied by the turbine there.
(Refer Slide Time: 37:31)

596
Now, let us you know consider another you know principle of this mechanical energy this is
called Bernoulli is principles that case in many cases you will see that the amount of energy lost
due to his cost dissipation in the fluid is a small that will be compared to magnitudes of the other
terms in the general energy balance equation. In such cases, you will see there will be a you
know loss of friction.

So, we can simply F can be, you know, regarded as you know 0. So, we can simply you know
negate that frictional energy. So, also are in very common processes fluid flow through a pipe
that do not have any appreciable shaft work that is associated to them accordingly we can write
that w because 20 suppose as frictionless flow per unit frictional you know a contribution will be
negligible that we have considered that for that amount of energy loss to discuss distribution in
the fluid will be small compared to the other terms in the energy supplied or consideration.

So, in that case we can say that the flow is that frictionless flow without you know shaft work
then we can simplify that mechanical energy balance into this you know equation here. So, we
can simply that neglect that Ws that will be = 0 and also friction, because to F will = 0. So, here
Ws that will because to 0 and frictional force that will = 0. So, after you know neglecting these, 2
terms who can then write this equation here.

597
So, this equation is called Bernoulli’s equation, and the equation has a wide range of application
despite its simplified assumptions. So, remember this when you bar this Bernoulli’s equation to
be applied to any system that initially you have to that you know assess whether that system is
ideal or not that means frictionless or not is there any you know shaft work is working on that or
not that also to be you know considered.

So, simplify form of that mechanical energy will give you this Bernoulli’s equation, what is this
you know that summation of this pressure energy kinetic energy and that potential energy that
will be equal to 0, what does it mean that change of these 3 energy summation of these 3 energy
will be you know constant there. So, based on these principles, we can you know solve some
problems are you know some process.
(Refer Slide Time: 40:42)

Like this let us do an example here. Suppose an aero plane is moving at a velocity 250 meter per
second at an elevation of approximately 8000 meters Now, the density of the air at that elevation
is considered as 0.4 kg per meter cube the air velocity at under side wing here of that aero plane
has the same velocity of the aeroplane velocity whereas, the air velocity at the underside wing is
300 meter per second.

In this case, calculate the pressure difference between the underside of the wing and the top side
of the wing that is necessary to lift that weight of that aero plane to a height. So, here basically

598
we are having that, the airplane is moving at a velocity of 200 meter per second at an elevation of
8000 meter. The density of course will be changing along to that height is given that the height is
.40 kg per meter cube whereas the air velocity, what is the air in the underside of the wing.

This is basically that same as that wing velocity there it is basically 300 meters per second there.
Now, based on the you know velocity change that elevated height you have to calculate that what
would the pressure difference there in this case we are considering that there will be a frictionless
movement of that you know aero plane and also there will be no you know shaft work done on
us done by that system and also there will be no heat energy supply to the you know, system
there.

So, based on this we can apply, that does mechanical energy balance equation here what is that
equation as per Bernoulli’s equation this is

So, according to this equation, we can write delta p that would be lower to - delta u square by 2 +
g into delta z whole bracket - so, we can make it common here into rho are you can write it here
as - u2 squared – u1 squared by 2 that is velocity difference there.

And then accordingly kinetic energy difference will be there + g into here elevation height here
z2 - z1 we can right into density after that, then we can right after substitution of respect the value
of here velocity here u2 is given 250 Square u1 is here for 300 and then divided by 2 + here + g
is 9.81 into z2 is what is that z2 – z1 is given z2 – z1 it is basically here the elevated height is 8000
meter. So, into whole bracket into density of the fluid here 0.40 after simplification or
calculation, we can have this as - 25892.

So, this is you know that pressure difference as you know pascal. So, this mass pressure
difference will be there according to you are problem. So, in this case we are applying that
Bernoulli’s equation and how to solve this equation based on this Bernoulli’s equation like this.
(Refer Slide Time: 45:50)

599
Let us do another example of this Bernoulli’s equation like here one you know that nozzle is
shown in the slide here and water is flowing through a nozzle before coming to that or before
playing to that nozzle here, this is 1 nozzle at this point 2 and before flowing through that nozzle,
the fluid is coming from a pipe at point 1. Now, the pipe diameter at point 1 it is given a certain
value whereas at this nozzle the nozzle diameter will be something different from this pipe.
Generally nozzle diameter will be very smaller than compared to this you know pipe diameter.

Now, pressure at point is atmospheric here at this point to inner diameter of the pipe or you can
see that nozzle here at 2 is 0.001 meter there and at this point in our diameter of the pipe is given
0.01 meter this is 10 times higher than you know that nozzle diameter pressure at this point is
unknown to you, have to find out whereas pressure at this point 2 is atmosphere. So, there will be
a pressure at this 2 point and there is the elevation of this 2 point is 50 centimeters there is no
friction which is considered water is flowing through this you know pipe and then nozzles at the
rate of 20 liter per minute.

Now, at that situation, you have to find out what should be the pressure at this point 1 at its 5
here. So, let us again apply that Bernoulli’s equation. So, before applying that, you have to first
calculate what would be the water flow rate in terms of you know, volumetric flow rate in you
know SI system cost meter per second then only we can calculate. So, water flow rate what is the
water flow rate here water flow rate is given here 20 liter per minute.

600
this will be equal to 20 into liter you have to convert it to meter cube into 10 to the power - 3 that
is 1000 liter that will equal to 1 meter cube divided by here 60 to be converted to second then it
will come as here to empty into 10 to the 4 - 3 by 60 here it will be meter cube per second and
velocity at point 2 this is will be equal to this is your flow rate if you consider flow rate is cube in
meter 2 per second the velocity you can calculate just by dividing it by its cross sectional area at
this point 2.

So, it will be coming as for that velocity flow rate is 20 into 10 to the power - 3 divided by 60
then you have to divide it by you know that cross sectional area what is that 5 by 4 into you
know diameter at this point is 0.001 into that is square. So, this is your cross section then it will
come finally, as u2 = 424.41 meter per second. Similarly, you can calculate the velocity at point 1
similarly, for the same product is going so, you can have 20 into 10 to the power - 3 by 60
divided by its cross sectional area, it is 5 by 4 into 0.01 here the diameter.

So, it will be as here 4.24 meter per second and what is the elevation here? Elevation is delta z
that will be = z2 - z1. This is your 50 centimeter, converting to meter to 0.5 meters. then applying
Bernoulli’s equation, we can write, applying Bernoulli’s equation Bernoulli’s equation we can
write delta P that will be equal to - u2 squared - u1 squared by 2 + g into z2 – z1 into rho.

So, based on this, we can calculate after substitution all you know values of u1, u2, z1, z2 and g all
these things and then density finally, we can have this value of pressure differences, - 90059173
this is in terms of unit as neutron per meter squared. So, this is basically pressure difference.
(Refer Slide Time: 52:37)

601
Now, as you know that this pressure difference is basically P2 - P1 that is basically is - 90059173
newton per meter squared or you can say that it is Pascal which implies that P1 will be = P2 +
90059173 Pascal which implies P1 that will be = what is the P2 value this is atmospheric pressure
as per atmospheric pressure you can say that it will be here 101325 then + 90059173 that will be
coming as 90160493 0493 is it is 930 or it is getting to be here 8.

And this will be considering as absolute why absolute because we are adding here with this
values as you know, atmospheric pressure here. So, finally to be coming as an absolute pleasure
as a P1. So, this would be = you know patient at that point 1 there. So, finally we can write it as a
bar as 90 901.61 bar, because 1 bar that will be = 10 to the power 5 newton per meter squared.

So, in this way, by applying the Bernoulli’s equation we can solve of for pressure we can solve
for velocity we can solve for even elevation height also provided other terms are they are as per
your you know problem.
(Refer Slide Time: 55:13)

602
Let us do another examples here see 1 figure is given in the slides this case water is flowing from
a tank to a you know that converging diverging, you know 5 this called you know venturing 5
and you will see that when you are this venturing pipe is let us to that tank at this location. The
diameter of this part of this density is here at this study one for us at this you know converting
section of this venturing at point 2 its diameter is d2.

Whereas again from this you know conversion section, it will be converted to diverging as for
that principle of density for getting that lower pressure at this point 3, you will see that the
diameter is d3 here at this 3 sections, you will see the diameter are you know d1 d2 and d3
whereas at this point 2 you will see that d2 is very smaller compared to that d1 and d3. This d1 and
d3 will be the same diameter whereas d2 will be the difference from this you know 2 and 1 and 2
you know point.

Now, when you got a fluid to be flowing to the dispensary meter, you will see there will change
of pressure between point 1 and 2 again you can get the pressure between 1 and 3 also again the
pressure difference between 2 and 3 will be there, because of that velocity change, whenever
fluid to be flowing through that lower cross sectional area, the velocity will be higher relative to
that higher cross sectional area.

603
So, based on these velocity sayings you will see there will be change your pressure for a constant
elevated height, even if you change that elevation there you have to consider that how much
energy will be changing. So, based on this, what will be the pressure change or velocity change
that you can calculate based on that Bernoulli’s equation. So, pressure difference between this
point 1 and 3 is given here. 0.7 bar by this manometer you can measure it cross sectional area at
point 2 is half of that in point 3 here, pressure at point 1 is 1.7 bar absolute.

So, according to these saw you no problem you have to find out what should be the pressure at
point 2 here, pressure at point 2, you have to find out pressure at .1 is given to a here you that is
here 1.7 bar pressure at .3 P3 is given that is, you know that pressure difference that you know p1
- p3 that is given here 0.7 bar. So, accordingly you have to find out what the P velocity also you
have to calculate their based on this cross sectional area.

So, let us apply that Bernoulli’s equation what is that Bernoulli’s equation you know that in this
case what would be the z elevation here since z1 that will be equal to z2. So, we can right here
delta z it will be = 0, you want to not be equal to you know that u2 of course, since the cross
sectional area is different, but u1 = 0 because the liquid is coming from that stream condition
from this tank and then we can calculate u3 as what is that from that Bernoulli’s equation as 2
into what is that P1 - P3 by P3 by rho between this point 1 and 3 then it will be equal to what half.

So, if we apply this Bernoulli’s equation between points 1 and 3 we can have this here z delta z
because to 0 and you know that u3 that can be calculated from this pressure difference and u1 is
then you know it is you know 0. So, u3 can be calculated, if you are having that cross sectional
area at this point 1 and 3 are not same and then what is that even if there is a cross sectional area
same.

You see that if the velocity at this cross section is 0. Then you have to of course calculate what is
the velocity at this point 3 there, because of that by cross sectional area. So, after substitution of
this value that means here 2 into what is the pressure difference between 1 and 3 that is 0.7 bar
you have to multiply by 10 to the power 5, then you will get the pressure in terms of Newton per

604
meter squared divided by density is here water then it will be density of water is 1000 after
substitution.

And then calculation we can get these value as 11.83 meter per second after that if you do the
mass balance between this points 2 and 3 we can have this A2 into u2 that will be = A3 into u3
what is that A2 is the cross sectional area u2 is the velocity at that point 2 that means A2 into u2
we it will give you that volumetric flow rate at that 2 and A3 into u3 will give you the volumetric
flow rate at that point 3 since these volumetric flow rate are constant, so you can write this
equation here.

And from these we can write you know u2 = A3 by A2 into u3 that will be = what here A2 by A3 is
given to you A2 by A3 is given. You know that 0.5 according to this problem we are because
cross sectional area at point 2 is half of that in point 3 So, we can write A2 by A3 will equal to 2.5
So, finally we can right here after substitution of A2 by A3 and you see value here as u3 11.83
divided by then A2 by A3 it is simply it is 0.5 then we can have this value as 23.66 this is meter
per second.
(Refer Slide Time: 1:03:51)

Now, applying that Bernoulli’s equation 1 and 2, we can get P2 - P1 as u2 square by 2 whose
implies P2 = P1 + u2 square by 2 that implies P2 = here after substitution of those values - 1.1
into 10 to the power 5 neutron per meter squared. So, that will be your absolute value this is

605
simply you can write 1.1 bar absolute. So, in this way we can apply this bottle is equation for the
different problems.

Whereas we know this you know, either of the values of these you know kinetic energy terms
and potential energy terms or you know pressure different stops there. So, we are having this
Bernoulli’s equation and solving those problems based on that general mechanical energy
balance equation.
(Refer Slide Time: 1:05:41)

I would suggest to you know read more about this you know gentle energy balance equation and
solving the problems as you know suggested this textbook here in the slides for this course. So, I
think you understood here in this lecture How to solve the problem based on this mechanical
energy balance equation and based on which you can solve more problems from this textbook, in
the next lecture. We will try to discuss more about this you know energy balance equation,
higher entropy balance will be considered without reaction and solving some problems. Thank
you.

606
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture # 21
Enthalpy balances without reaction

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about energy balances on nonreactive processes as a module
7. In the previous lecture we have discussed about the mechanical energy balance in this lecture
will try to you know discuss more about that energy balances with nonreactive processes.
(Refer Slide Time: 00:56)

Especially for enthalpy balance without you know reaction also, we will discuss more about that
the enthalpy balances when there will be a (you know) change of phase without any reaction
there.
(Refer Slide Time: 01:06)

607
So, what is the energy balance for a closed system that already we have discussed in our you
know earlier lectures in that case energy can cross the boundary of a closed system in the form of
heat and work the energy balance of a system that is used to determine the amount of energy that
flows into or out of the system for our particular process, unique and this is because, actually,
that energy of anybody to be supplied to the system, that we change its internal energy.

And how that you know, that internal energy will, you know, changes you know, that, system
environment and then accordingly how that system will be you know done work to the
surroundings or to the fluid or to other you know that you know process unit for a particular you
know operation. Now, this balance is used to calculate that Net energy requirement for the
process and assess of reducing energy requirement in a particular you know system.
(Refer Slide Time: 02:27)

608
We know that energy balance equation that is accumulation that is caused through input minus
output and particular system what is the you know, final system energy and what is the, you
know, initial system energy and this change of our final initial system and it will give you that
Net energy transport to the system or net energy transfer to the system will change this you know
energy system energy from it is initial to final.

Now, in that case we also you know told about that initial system energy is basically the you
know summation of internal energy, kinetic energy and potential energy. And similarly, final
system and it also will be as some of you know that internal energy, kinetic energy and potential
energy and to get this you know change of this you know initial to final you know system energy
that some energy to be supplied and based on which you will see there will be some, you know
work to be done by the system.

So, net energy will be you know that some amount that is represented by you know, our heat
energy minus, you know, flow energy there. So, basically the difference of these two energy that
is Uf - Ui are that is internal energy change plus you know kinetic energy change plus potential
energy change that will be equal to Q - W. So, by this equation we can say that net change of
energy in the system as an output that will be equals to net input to the system.
(Refer Slide Time: 04:18)

609
Then this energy balance for a closed system can be expressed by this equation given in the
slides that already we have discussed.
(Refer Slide Time: 04:28)

And also we you know suggested to you know remember that, if no temperature change, if there
is no phase change or no chemical reactions occur in a closed system and if the pressure change
are less than a few atmospheres, then we can say that internal energy change will be close to
zero. Now, if your system is not accelerating, then we can say that the kinetic energy will be
equal to zero and, if a system is not rising or falling, then you can see that potential energy is
equal to zero.

610
Now, if your system and its surroundings are at the same temperature or the system is perfectly,
you can see that insulated in that case Q will be equal to zero that is supplied to the system with
it is zero and work done on or by the system will be accomplished by the movement of the
system boundary. And if there are no moving parts or you can see that electrical currents or other
form of energy at the system boundary will not work, then you can simply write that W will
equal to be zero there.
(Refer Slide Time: 05:53)

And based on that we can also write that energy balance equation for an open system here it is
given in the previous lectures also we have described this you know energy balance equation.
(Refer Slide Time: 06:06)

611
And for that, you know net rate of work done by the system that is regarded by this you know
that summation of that work because to shaft work and also flow work there.
(Refer Slide Time: 06:21)

(Refer Slide Time: 06:24)

And you will see that, based on that, you know shaft work and flow work, the general energy
balance equation can be written by this equation here as shown in the slide. So, please go to the
slides also here how to represent that you know general energy balance equation in terms of you
know, change up internal energy change your kinetic energy, change your potential energy and
also change of flow work they are in the system and also want to be the input and output in the
system.

612
Because of that net energy supply of you know heat or by you know work done by your to the
system. So, finally we can write this you know, General energy balance equation even in
continuous form as the rate there.
(Refer Slide Time: 07:16)

And in concise form we can write in terms of difference we can write this equation as delta U dot
plus delta KE dot plus delta PE dot plus delta PV dot that will be equal to Q dot minus W dot.
Here, dot means rate and delta U means, basically internal energy change delta K dot means
basically kinetic energy change in rates and delta PV is basically the flow of work that is
performed on the system in order to push the fluid in or out of the system and Q dot is the rate of
heat energy in to the system and W dot is generally rate of work done by the system as an output
and summation of these internal energy and this you know rate of work done by the system or to
work that is performed on the system in order to push the fluid in or out of the system will be
regarded as enthalpy of the system, which is denoted by H. So, delta H would be equal to
basically that summation of that internal energy change and you know, flow work of change
here.
(Refer Slide Time: 08:33)

613
Now, from the general energy balance equation, we can represent that equation in terms of you
know specific terms by taking the you know mass flow rate as a common factor there. And then
finally, we can write this equation based on this, you know mass flow rate, and also specific
terms there and in this case here correction is that V and U here is basically U and this is new is
here this is U and here new is basically 1 by row is defined the specific volume and this new is U
that is velocity at different composition, and they are in inlet and outlet condition.

We can say so, finally, we can get this, you know equation has final form of equation here as that
you know their energy balance equation based on that enthalpy for enthalpy is defined as your H
will equal to U plus Pv, there.
(Refer Slide Time: 09:45)

614
And they saw if there is no shaft work no kinetic and potential energy then we can write here,
simply this equation from that general energy balance equation that is Q dot will be equal to m
dot into delta H dot and then we can write that enthalpy change will equal to here, if you are
having that enthalpy change at inlet and outlet condition then you can simply write that a
difference in the enthalpy based on this equation.
H   m Hˆ
Output
j j   m Hˆ
Input
j j

stream stream

(Refer Slide Time: 10:22)

615
Also you have to remember that for the closed system, what should the energy balance equation
for the open system what should be the energy balance equation and in terms of you know that
internal energy change for the closed system we can write this here because they are kinetic
energy and potential energy will be you know negligible. So, the equation will be coming as only
in terms of you know internal energy and enthalpy there and if there is a you know, temperature
change from its reference point or if you are hitting the system from its temperature 1 to
temperature 2, we can say that there will be a enthalpy change based on that, you know,
temperature change.

And also what is, you know, specific heat capacity for that substance at particular temperature,
because this specific heat capacity depends on the temperature, the air. So, accordingly if you are
having that constant specific heat capacity there you can easily calculate what should be the
enthalpy change on the based on that temperature difference and if you are having that specific
heat capacity changing with you know temperature.

Then of course, you have to consider that integral form of enthalpy change based on this you
know, temperature change. Again if you are having that there will be you know change of phase
liquid to vapour. So, there will be a certain change of you know energy or enthalpy that enthalpy
will be called as you know, heat of vaporization or heat up you know, melting point or you can
see that heat of sublimation like this. So, that heat you know or enthalpy because of that needs to
be considered.

And also suppose, if you are considering the enthalpy change at a particular temperature range,
they are of course, you have to consider what should be the heat you know or enthalpy change
because of its formation. So, that is called you know, heat of formation of that component. So, to
do any you know energy balance for the inlet and outlet components of the system to calculate
that enthalpy at a particular temperature. What you have to do that you have to calculate that
enthalpy change because of the temperature, because of that phase change and also because of
that formation of that component there.
(Refer Slide Time: 13:17)

616
Now, let us see that, you know enthalpy changes, there is a phase changes. Now, in that case,
you have to consider that additional terms for the enthalpy of the phase change with those, you
know, energy change of, you know, for your process. And in that case, the total enthalpy of that
substance, if you are considering any substance say. So, we can write the era you know that the
enthalpy change will be equal to here,
T
Hˆ i  Hˆ of ,i  C P ,i dT  Hˆ T , p
Tref

heat of formation of that particular component i or A and the enthalpy change because of that,
you know, temperature change.

That will be regarded as sensible heat or sensible enthalpy you can say and also enthalpy change
because of that phase change. So, these are 2 terms here, as soon here in the slide that these 2
terms basically includes the both sensitive heat up a change and this terms is basically the
enthalpy change due to its formation and this here in this terms or basically represents the
standard condition, that being said, you know, zero degrees Celsius.

And you know, that one atmospheric there, suppose, there is a you know, a phase change of the
suppose water from solid state to you know, vapor phase, so, at zero degrees Celsius, you will
see that solid liquid will try to, you know, mainly to the liquid phase. So, there will be a
temperature is constant. So, at that constant temperature, the solid water will be converting to the

617
liquid water after that, you know that this liquid will be you know heated up 100 degrees Celsius
till it boils.

What happened here during that constant temperature of zero degrees Celsius, when this solid
water will be melting so, there will be a change of enthalpy will be called as you know it is
called that melting you know enthalpy or you can see that latent hat you know melting after that
whenever liquid will be you know heated up 100 degrees Celsius there will be a change of
temperature. There will be a change of temperature from 0 to 100 degrees Celsius and because of
which you will see there will be a changeup enthalpy or heat and that is called you know sensible
heat or sensible enthalpy.

And that enthalpy can be calculated based on that you know temperature difference and also
bought to be the specific heat capacity of that water and if it is changing with temperature, then
you have to you know calculated by integrating that multiplication of specific heat capacity of
the water and you know that temperature difference and up to that, when you bought that liquid
will be converting into a vapour at that particular constant temperature of 100 degrees Celsius
you will see there will be again change of enthalpy that change of enthalpy will be called us
latent heat up, you know, on vapourization or latent heat of vaporization.

And after that, this you know vapour at 100 degrees Celsius to be you know heated up again to a
certain temperature T. So, for that again you have to calculate that you know sensible heat based
on that you know specific heat capacity and that temperature difference after that if you want to
you know convert that you know vapour into directly to solve it then you know what will be the
you know energy required that energy required will be you know that, you know will be the
summation of that you know to convert from solid to that direct vapour said that will be called
solid vapour.

So, in this way we can see that there will be an enthalpy change because of that phase change as
well as you know temperature change as well as its formation. So, all those you know, enthalpy
change to be considered for a particular component whenever you are going to you know

618
consider heat at an outlet you know components or inlet components they are for that process
and also for the you know energy balance for that particular process.
(Refer Slide Time: 18:17)

Now, let us have another example of that phase change here for phase change of your phenol will
see that the phenol will be a solid phase at 25 degrees Celsius at one atmospheric pressure. Again
if you heated up to 25 degrees Celsius there will be a sensible heat for that solid phenol and there
is some heat requirement or enthalpy change will be there that will be regarded as delta H one
per unit moles or mass you can say.

And similarly, when you bought this solid phenol will be converting to liquid phase particular
constant temperature of 42.5 degrees Celsius at one atmospheric pressure you will see there will
be you know, latent heat change that will be change of enthalpy which is regarded as H2 here
hat per unit mass. Similarly, liquid you know enthalpy to be you know heated up to you know it
is boiling point of 181.4 degrees Celsius by you know that heat up amount it is you know
sensible heat because of this temperature difference.

And then, it will be you know, heated up to you know, 300 degrees Celsius after converting it
phase change from you know liquid to vapor to that changing of liquid to vapor of this phenol
phase, you have to you know, consider that latent heat of vaporization and after that you have to

619
heat it up to a certain and other temperature from its boiling point up to 300 degrees Celsius like
here. So, in this case it will be you know H5.

Similarly, you can change these you know vapour phase of phenol x at 300 degrees Celsius at
atmospheric condition to higher pressure also at the same temperature for that also you need to
have some you know enthalpy change that can be regarded as H6. So, to convert these you
know, solid this phenol to it is vapour from 25 degrees Celsius to 300 degrees Celsius
temperature and a pressure from one atmospheric to you know 3 atmospheric pressure for that
total amount of enthalpy will be required.

That total enthalpy change will be equal to

Hˆ  Hˆ 1  Hˆ 2  Hˆ 3  Hˆ 4  Hˆ 5  Hˆ 6
respectively here as given in the, you know, slide there. So, you are having that how that
enthalpy change will be there because of that phase change. Now, this enthalpy change, because
of that phase change will be you know, at constant temperature there in that case, you know, that,
there are different types of enthalpy change it is called heat of fusion, where solids will be
converting into liquid, heat of vaporization.

When liquids to be converting into vapor heat of condensation that means, vapor will be
converting to you know that liquid phase and heat of sublimation that case solids to be directly
converting to the vapour. So, that will that will be called as heat of sublimation there.
(Refer Slide Time: 21:56)

620
Another thing that suppose if you have being a process unique without you, you know reaction
there will be some process going on and for that at the inlet condition some components like
component 1 component 2 component 3 like there are several components will be coming into
the process unit and after processing you will see that that components will be you know, coming
out as a component 1 and 2 again after having some you know, change maybe because of that
phase change maybe because of you know, some other you know, physical you know, state of
that component change, or maybe you know that, you know that mixture change also they are
being you know that, that some change of properties.

So, there will be some input, there will be some output for that components, because of some,
you know, that change your phase, you know, enthalpy now, you have to calculate that enthalpy
change for those components which are coming into the system and which are coming out from
the system based on that, if is there any temperature change if is there any phase change or not
so, far that you have to first consider what will be the you know enthalpy change because of its
formation you know in the inlet condition for all components.

Similarly, what should be the heat of formation for all components in the outlet condition again
what should be the summation of sensible heat because of that temperature if is there any heat is
supplied to the system because of heat that there will be a certain change of sensible heat,

621
because of its temperature difference, then you have to summing up all the sensible heat for all
components in the inlet and outlet streams.

Again, if you are seeing that there is a change of temperature from one to another in Celsius that
in between there will be a change of those components, then they are also you have to consider
that enthalpy change because of enthalpy change. So, according to that the enthalpy change in
the input that will be able to heat up formation for all components in the input, sensible heat
summation of all components for all those, you know sensible heat they are similar at the outlet
condition.

Also summation of all you know, heat formation for all components and summation of all
sensible heats because of that temporary change and also if is there any feature that you have to
consider. So, accordingly we can have this change of interpreted the input change of enthalpy
and the output and what do we have entropy change between these input and output just simply
you have to subtract it, then you will get that what the enthalpy change for this particular process
in this case one interesting point that if you are having the same components in the input and
output streams.

You see that heat of formation for all those components will be same, because heat of formation
for any components will not be changed anywhere in the system. So, in this case, you can neglect
this heat of formation at the inlet and outlet condition if you are having the same components and
the inlet and outlet streams. So, we can say that since there is no reaction, same component will
be in the inlet and outlet streams. So, heat of formation for the same component in both the
streams will be cancelled out. So, only you know that enthalpy change will be because of that
sensible heat because of that temperature change, because of that a phase change.
(Refer Slide Time: 26:29)

622
Now, let us do an example particular this you know energy balance equation and how it can be
used for this you know internal energy change, let us consider a cylinder which is filled with a
you know movable piston with a gas and amount of you know 5 kilocalorie of heat is you know
transferred to the gas to raise the gas temperature of 100 degrees Celsius higher the gas does 70
joules of work in moving the piston to its new equilibrium position.

As per figure shown in the slide, in this case, you have to calculate how that internal energy
change will give you these you know new equilibrium position of this piston and what will be
the amount of that internal energy they are in the system. So, in this case, we can say that there is
a difference in gas temperature that is, you know 100 degrees Celsius and we are done by the
system is you know 70 joule. And heat to the system is here it is given 5 kilo calorie.

So, according to this closed system concept, and based on that energy balance equation we can
write
U  KE  PE  ( PV )  Q  Ws
here summation of internal energy, kinetic energy potential energy that will actually will be close
to the net energy supplied to the system. In this case, since there is no change in kinetic and
potential energies accordingly we can say that delta KE and delta PE that will be close to zero.

And if you set this zero here in this equation, then you can write here

623
U  Q  Ws

So, after substitution of this value of Q and W as given in the problem then we can write delta U
will be equal to 20850 joule that is 20.585 kilojoule. In this case you have to convert this, you
know calorie to joule by this conversion factor, remember this, if all units are in joule, then you
have to convert this calorie to joule here according to the problem.

So, finally, we are getting that internal energy change of will be 20.85 kilojoule based on this
temperature rise 200 degree Celsius just because of that 70 joule work done for moving this
piece down to its new equilibrium position and also because of this temperature that are to be
that high kilocalorie of heat is transport to the gas. So, based on which we can calculate what
internal energy change.
(Refer Slide Time: 29:42)

Similarly, another example you can do to calculate this enthalpy from the internal energy like in
this case, if you know that a specific internal energy of suppose neon gas at 25 degree Celsius
and 1 atmosphere is 1.62 kilojoules per mole and the specific molar volume under the same
conditions is given us 24.45 liter per mole. So, in that case, you have to calculate what should be
the specific enthalpy of the neon gas at this temperature and pressure and the rate at which that
enthalpy is transferred by your stream with the molar flow rate of 200 kilometres per hour.

624
So, what exactly you need to find out here, this specific enthalpy and for that, you know that this
specific enthalpy is basically summation of internal energy plus you know, flow energy, that
internal energy it is if you are considering that a specific rate then here to be that specific rate of
internal energy here specific rate of flow energy.

So, here specific internal energy is given to you pressure is given to you here you know, specific
volume is here 24.45 liter per mole era, this is 0.0245 meter per mole here this is nothing but a
specific volume. This is nothing but we had we can write as H hat is basically after substitution
can be calculated based on that equation here it will come finally, 4102.46 joules per mole. So,
the enthalpy transport rate we can write it is a you know specific enthalpy that means the energy
per mole.

So to that total enthalpy transport rate you have to multiply it by molecular or molar flow rate
there, this molar flow rate is given here in H dot that is here 200 kilomole per hour. So,
accordingly, we can have this total enthalpy transport rate will be equal to 8.20 into 10 to the
power of joule per hour.
(Refer Slide Time: 32:35)

Now, let us do another example, for steam turbine in this case also, you know, you have to
calculate what should be that change in enthalpy transport rate of the process and also calculate
the internal energy change when a steam enters this steam turbine at a rate of you know 10 kg

625
per hour at a velocity of 50 meter per second and it leaves at 8.5 meter below the inlet active
velocity of 300 meter per second the heat loss from the turbine is estimated to be you know 10
kilo watt and the turbine delivers some shaft work at a rate of you know 70 kilowatt. In this case,
you have to calculate what should be the change in enthalpy transport rate of the process and also
what should be the internal energy change.

So, here see that, at the inlet condition of this turbine, as shown here in the slide, that P is given
here. At this point one mass flow rate is given velocity at this point is given and at this point 2 it
is that level at point 2 is 5 meter below that you know inlet you know stream and pressure at this
condition at the point to it is given 120 kilopascal were as velocity is 300 meter per second. Here
the heat loss from the turbine it is given 10 kilowatt and also turbine delivers work at the rate of
70 kilowatt so, based on this what should be your enthalpy change and internal change.
(Refer Slide Time: 34:44)

As for that general energy balance equation for that open system we can write
H  KE  PE  Q  Ws
here kinetic energy can be calculated from the velocity of differences to you know streams in
inlet and outlet and what would the kinetic energy change that is half you squared from that you
can calculate similarly potential energy.

626
You can calculate, then enthalpy change after substitution of that value in this equation of
general energy balance equation you can have, so, it is finally coming as minus 80.12 kilojoule
per second. So, based on this enthalpy change you can calculate what should be the, you know
internal energy change, because this internal energy change is basically that how much you know
enthalpy is exceeded from this flow energy that will be regarded as your internal energy.

So, it will be basically that delta H minus PV dot so after substitution of that, here, we can have
this value up here in V dot basically m dot by row and delta P is here and then finally, we can get
a substitution of those you know variables and then you can get to minus 80.33 kilojoule per
second. So, this is your internal energy. So, turbine based on this, you know problem that
changing that internal energy of this amount and change of enthalpy will be of this amount there.
(Refer Slide Time: 36:42)

Let us do another example of you know applying this you know, energy balance equation for
flash you know drum that case in the flash drum and among amount of 450 kg per hour of
saturated liquid vapor mixture of ammonia water at 93 degrees Celsius with an overall mass
fraction of like you know 30% ammonia and remaining 70% water is operated at you know
344.738 kilo Pascal absolute pressure now, exit saturated vapor is to be produced with a
composition of 90% of you know water vapor by weight.

627
And remaining is you know that 90% of you know that ammonia and 10% of water that you
know vapour stream from that you know flash drum then what is the composition and also you
have to find out what should be the heat added to or removed based on the calculation from the
process if the products are at equilibrium. So, in this case the liquid era liquid will be coming
from this you know bottom part with the composition of you know, that liquid ammonia and
liquid water you know will be coming as a certain fraction that you have to find out.

In this case you need to have that you know specific enthalpy of that components in the entering
mixture, the specific enthalpy of that mixture is this given and mass production is given here
exists to be a mass production is given and also enthalpies given their and liquid that enthalpy
specific enterprise given and mass production is given there so, according to that you have to
calculate this you know composition and heat added or removed from the system.
(Refer Slide Time: 38:50)

Now, material balance will give you that as per total balance 450 that will be equal to V plus L
and if you do the ammonia balance there, it will come as 450 into 0.30 that will be equal to V
into 0.90 plus L into 0.24 and after solving you will get that amount of vapour from the flash
drum and amount of liquid from the liquid drum. And then as per that energy balance we should
be reducing here Q dot will be equal to delta is H dot now, this delta H dot is basically the
enthalpy change from its you know, output stream and input streams by summing up all that you
know enthalpy change for all components there.

628
So, according to that up the substitution of all you know that we lose here, we can finally get this
enthalpy changes minus 1.67 into 10 into the power of 8 joule. So, please go through this you
know calculation again then finally, you get this you know this mass of energy they are since it is
negative, so, we can say that heat must be removed from the system for the liquid composition
after material balance, what is that ammonia from the ammonia balance we can have this this
liquid composition after substitution of those, you know composition in the vapour and liquid
phase.

Here since the liquid phase this amonia liquid is you know, unknown so, you are assuming here
that the fraction of amonia balance is W. So, after substitution of that, we are having these sub
volume fraction of ammonia in the liquid phases .23. So, remaining portion will be as you know
what that it will be you know that around 69.69 there for water. So, in this way, how that energy
balance equation can be applied to calculate that you know enthalpy change, if you are having
multiple components in the inlet and outlet system.
(Refer Slide Time: 41:19)

Another example, suppose, in a shell and tube heat exchanger steam is used to heat cold water
passing it through the tube side here, you will see that shell and tube heat exchanger the outside
it is you know that shell side this is tube side from the tube side some you know that liquid will

629
be passing maybe you know hot water to be passing or hot liquid to be passing to heat up that
you know cold liquid which is in shell side or vice versa also it can be done.

So, suppose a steam at a rate of 60 kg per hour at 200 degrees Celsius and one bar enters the tube
side of the heat exchanger. Now the steam leaves rated liquid here from the outlet neglect the
pressure drop of the steam in the tube side and the water in the shield side of the heat exchanger.
Now, based on this, how must it must be transferred from the steam to heat of this water in shell
side? So, here this is cold liquid you have to heat it up by supplying that steam in the you know
tube side that case, how much heat is to be transport that you have to calculate.
(Refer Slide Time: 42:32)

So, it can be done based on that energy balance equation now, in this case 60 kg per hour that is
a steam is supplying and inlet condition is one bar and 200 degrees Celsius enthalpy is this
condition is 2875 you can calculate or you can have it from you know that psychometrics or that
we have you know discussed in earlier lecture there so, based on that psychometric set at this,
you know temperature and pressure you can calculate what should be the you know enthalpies
there or you can calculate it from a you know, other way from that you know temperature
change.

Therefore, to the (you know) enthalpy there at outlet also since it is a saturated water one bar
again you can have this enthalpy from this you know psychometric chart and no change in steam

630
mass flow rate in the inlet and outlet condition. So, you can write what is the mass flow rate in
inlet and what the mass flow rate in outlet that will be equal and that is basically 60 kg per hour
is given and here no shaft work is done. No pump no other things is used to you know supply to
the (you know) system or system does not work as a shaft work there and no change in
innovation.

Since this is horizontally placed. So, there is no you know change in elevation. So, potential
energy it will be zero. And also you can see that since the diameter of that inlet that takes in
uniform at the inlet and outlet side. So, we can say that there will be no change of velocity of that
steam. So, we can say that kinetic energy change will be zero. So, after considering that, no shaft
work no potential energy no kinetic energy based on which you can finally, get this you know
energy balance equation into a simplified form of Q dot will be equal to delta H dot. This delta H
dot basically that what will be the total enthalpy in the output stream and total enthalpy in the
inlet streams.

So, based on that deviation to give you that enthalpy change of this particular processes. So, that
can be calculated after substitution of that mass flow rate here m dot j here at the inlet, the same
as the simply 16 into 2875 and outlet that is 60 into 417.5. So, after you know calculation we can
get this enthalpy change as you know minus 147450 kilojoule per hour. So, this is basically that
heat is supplied or heat is you know transport from this you know due to the shell side.

Since it is coming negative, we can say that the heat is applied it is our transport from this tube
side to the shell side. So, based on this example, we can then assess this energy balance equation
and we can understand this energy balance equation more, you know precisely.
(Refer Slide Time: 46:02)

631
And then you can apply this you know enthalpy balance equation or energy balance equation, but
the compressor also there also you will see that if suppose if you want to use a compressor you
know by heating up certain you know steam that is super-heated at 300 degrees Celsius and at
200 bar absolute pressure you will see that when this this steam interests this compressor at a
velocity of 20 meter per second and to this pipe of diameter of .1 meter and the discharging pipe
hotter that compressor has a smaller diameter.

And the distance velocities suppose, increased up to 170 meters per second and the exit of that
compressor is superheated steam at 350 degree Celsius and the pressure at 60 bar absolute under
this condition there will be a certain heat loss from the compressor to the surrounding and it is
seen that it is approximately 5 kiloWatt. Now, in this case you have to calculate with a
compressor power.

So, this is a simple that air enthalpy change will be there, because of that temperature change
from 300 to 315 Celsius, kinetic energy change will be there because of that velocity change at
the inlet and outlet condition outlet now, you know of this compressor there will be no change or
potential energy because of that alignment of this inlet and outlet pipe in the same level and you
know that heat loss that is you know, because of this compressor that heat loss to the
surrounding.

632
So, we can have this Q dot here as a negative value and also we can see that there will be some
power will be done by this you know compressor. So, what should be that, you know compressor
power that you have to find out So, you can write this energy balance equation here enthalpy
change kinetic energy change Q dot and W dot will be used.
(Refer Slide Time: 48:32)

For this calculation for us this potential energy because to zero now, from the steam table you
can directly calculate at a certain pressure and temperature what should be a specific enthalpy
and also what to be the specific volume and from the exit stream also at a certain temperature
and pressure, possibly the specific enthalpy and the specific Volume. Now, rearranging and
solving for this a shaft work from this energy balance equation we can have this Ws dot will be
equal to minus 49.25 kilowatts.

So, this is you know compressor power which is worked on the system worked by this
compressor to you know heat because of this energy change and to be lost the atmosphere. Let us
have an example when there will be enthalpy change because of that a change. Now if you have
that saturated air at 25 degrees Celsius and one atmospheric pressure, who says an absolute
humidity here 0.0202 kg of water by kg dry air in this case has a specific enthalpy 76.5 kilojoules
per kg dry air.

633
The enthalpy is the sum of enthalpy changes for 1 kg dry air and 0.0202 kg water that goes from
their reference condition to 25 degree Celsius. Now, how this specific enthalpy can calculate
there now, in this case, 1 kg dry air and it is saturated at 25 degrees Celsius dryer in this case this
the dry air enthalpy change you can calculate based on that you know temperature difference and
from this specific heat capacity based on this equation and will come 25.1 kilojoule.

And you will see that this water and moisture content of these 2.0202 kg and that is that liquid
condition at zero degree Celsius. It will be converting to you know vapor at 25 degrees Celsius
of the same amount of that water. Now for this what will be the (you know) enthalpy change that
enthalpy add that 25 degrees Celsius for the vapour of that water and enthalpy of water at that
liquid state of zero degree Celsius and you know difference of that in enthalpy change.

You will get that total enthalpy change of water based on this you know temperature change and
after that you will see that what will be the specific you know, enthalpy change after substitution
of this value up enthalpy change of air and enthalpy change of the water per unit you know mass
of dry air, then it will be coming up finally as 76.5 kilojoule per kg of dry air. So, this is you
know 1 kg of dry air will give you the enthalpy change of 76.5 kilo Joule.

When this liquid you know water will be, you know changing it is state to vapor at 25 degree
Celsius now enthalpy change for water at one atmosphere showing the phase transition in this
figure it is shown that the x axis is temperature, based on this temperature, you will see that how
enthalpy will be changing at a different you know phase change condition like for heat of fusion
at this condition at a temperature up to 73 you know Kelvin at constant temperature we change
our heat that is called heat of fusion.

Again if you change the temperature from 273 to here 373 that is at its boiling point there will be
a change of you know enthalpy of your sensible heat and again add that you know boiling point
temperature of water you will see that the water will be becoming before vapour and at a you
know that enthalpy change of vaporization. So, this vaporization can be you know represented by
this you know figure here as shown in the slide in this case very interesting that no accurate
simple way to estimate heat or fusion, you will see experimentally.

634
So, the heat of fusion of many elements and compounds can be roughly estimated by this
equation here as part you know, email, that is text book. They are, I have suggested to you know,
follow that textbook. So, there it is given that that enthalpy change because of this fusion at a
constant temperature that can be close to constant. It will be 2 to 3, 4 elements and to be 5 to 7 or
inorganic compounds and to be 9 to 11 for organic compounds. And in this case Tf is basically
melting point and this Hf hat which is that will be molar heat of fusion their calorie per gram.
(Refer Slide Time: 54:17)

Similarly, calculation of enthalpy change including phase transition here, it is represented by this
you know figure as shown in the slide, you will see that how you know temperature change will
give you that different enthalpy change that we have already discussed for you know that phenol
and water here for water it is shown that how enthalpy change at each different you know
temperature and how to be changing whenever temperature is constant.

They are you know solid water will be converting to you know that liquid water and then liquid
to you know, a higher temperature and up to its boiling point after the from the boiling point to
be vaporized, and then at that vaporization condition, you can you know, keep the constant at a
certain you know boiling point that at its boiling point and then you know from that boiling point
you can rise the temperature up to a certain temperature as part of your you know consideration.

635
So, accordingly that liquid solid will be you know that are solid will be converting to liquid
liquid to vapor and vapor then even higher you know superheated vapor there according to that
temperature change and because of that vapour change, there will be you know certain change of
enthalpy that can be represented by this diagram here. Now, when you know there will be
sensitive heat change because of the temperatures are you know change that you have to consider
the specific heat capacity that may be a function of temperature.

So, for that, you know, temperature dependent specific heat capacity, can be you know
calculated for basically for what are you can calculate it by this equation and similarly for vapour
you can calculate by this equation. So, accordingly you can get to these you know that sensible
heat based on the specific heat and the temperature difference also a heat fusion also can be you
know considered here and also heat vaporization can be, you know calculated or can be, you
know, used based on this balance here given in the slide.
(Refer Slide Time: 56:30)

And then up to substitution of these values of fusion at zero degrees Celsius liquid at 0 to 100
degrees Celsius, that enthalpy change and entropy change for vaporization at 100 degree Celsius
and also entropy change because of the temperatures are arising from these you know, boiling
point to that certain temperature and after substitution of that specific heat capacity as a function
of temperature here, and finally, you can get this value of 3048 joule.

636
So, per gram of you know water, if you change it is you know solid to its vapour up to 120
degrees Celsius, you need to have that enthalpy or heat it will be equal to 3048 joule per gram, I
think you have understood the problem solving based on that, you know energy balance equation
without reaction based on the enthalpy change and how to calculate the entropy change based on
that temperature variation, how to calculate the enthalpy change based on you know, a change.

How to calculate the internal energy based on that pressure change how to calculate the internal
energy based on enthalpy change, how to you know solve those, you know, problem of you
know, like turbine or you know that other examples that is given here in this lecture, it will be, I
think helpful for better understanding of that enthalpy balance for that, and I would suggest you
to follow this text to you know solve more problems up example, that is given in the textbook.

So, next lecture, we will discuss more about that energy balance, they are with multiple streams
without reaction would be considering. And so, thank you for giving your kind attention to the
lecture.

637
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 22
Energy Balance with Multiple Streams without Reaction

Welcome to massive open online course on basic principles and calculations in

chemical engineering. So we are discussing about the energy balances on nonreactive
processes under module seven. Now in this lecture of this module we will discuss
about again that energy balance with some examples where multiple streams will be
involving without reactions.
(Refer Slide Time: 00:59)

In the previous slides, we have described that enthalpy balances on nonreactive

processes and also how enthalpy can be calculated based on the phase change. So here
again, we will discuss that enthalpy balances or heat balances there with nonreactive
systems where there will be more than one you know, streams will be there in the
process like evaporation process, drying process, distillation process, even
refrigeration process, how this you know, heat energy can be calculated during the
process.

Now, before going to that, you know calculation based on that, you know principle of
energy conservation equation we should know that what is that energy conservation
equation.

638
(Refer Slide Time: 01:58)

We have already described all those equations and derivation in our previous lectures.
So still we are actually let us having this look of that equation here. Here this you
know general energy balance for an open process systems can be expressed by this
equation where U is the internal energy change. KE is the kinetic energy change.
PE is the potential energy change and PV is the you know flow work that is
performed on the system in order to push the fluid in or out of the system.

And Q dot the rate of heat energy that is into the system and Ws dot, this is the rate of
work done by the system as the output. So this energy balance is to be used for the
calculation of different you know, processes where multiple streams are involved in
there. So as we know that the summation of this internal energy change and also flow
work performed on the system that will give you that you know enthalpy change of
the you know system there.
(Refer Slide Time: 03:32)

639
So if there is no shaft work, no kinetic and potential energy you know will be there,
then we can say that canceling all those you know shaft work know that is kinetic
energy, potential energy, we can have this simplified form of this, you know energy
balance equation as


ˆ H
m H out
ˆ Q
in 
ˆ
Or Q  mH
Or Q  ΔH
Here, remember that this delta H dot is basically the rate of enthalpy change for that
particular systems.

Now, if there are more than one, you know streams there in the process, then you
have to calculate what will be the enthalpy for all components in the output streams
and also what should be the enthalpy in you know, enthalpy of that components in the
inlet stream. And from those, you know that total enthalpy of those components in the
inlet and output streams, we can calculate that enthalpy change there by this equation.
(Refer Slide Time: 04:43)

640
Now in this case, remember that for the closed system, this equation to be used where
the rate of the energy is not being considered. Whereas open system you will see that
this the same equation, but in terms of rate, at a continuous process we can say that
this equation will be you know considered.

And in terms of internal energy for multiple streams based you know processes you
will see that, that for closed system that internal energy change will be again that
summation of internal energy of all components in the final and initial states and from
which you can get the total you know that internal energy change there. And similarly
for open system that we can have this you know that enthalpy change of this on the
inlet and outlet streams.

So here it will be, there may be you know that our final or initial here that we will see
you have to subtract this. So here instead of plus it will be negative here it will be
negative there. Whereas for all you know that if there are, you know, that multiple
inlets there, then you have to sum it up in inlet there all that components for each
systems there.

So in this way you have to you know, calculate this enthalpy for particular you know
component what should be that specific enthalpy there that is specific enthalpy will be
calculated based on that what will be the enthalpy change of formation of that
components and also if there is a change of temperature from reference to other
temperature, then you have to calculate the sensible heat.

641
And also if there is a enthalpy change due to the phase change, then you have to add
up all those you know, that enthalpy change due to that you know, change of you
know phases. So in that case, the summation of all this you know enthalpy change due
to formation, enthalpy change due to the sensibly heat change and also enthalpy
change due to the phase transition then you have to get this you know enthalpy
change for that individual components in the you know system.
(Refer Slide Time: 07:15)

Now let us do an example for refrigeration process. We know that we are using
refrigerator in our daily use. Even for air condition we are using that you know air
conditioner like this how those things are actually working where we seek principle
like show here that you know that there are some components like here different units
like liquid reservoirs, expansion valve, evaporator coil, compressor and condenser.

These are the (you know), several units are generally used for that refrigeration
process.
In this case, you will see that in the liquid reservoir some you know refrigerant to be
you know kept there. So from that reservoir that refrigerant like you know that
refrigerant R-12 it is called carbon dichloride difluoride. So there you can use that
refrigerant there are generally being used.

So liquid reservoir of that refrigerant as a liquid it will be there and from that it is sent
to sent through the expansion valve and whenever it is coming from that expansion

642
valve at a certain you know that pressure, maybe you know that the pressure will be
lower than that, you know, that inlet stream of this expansion valve. And you will see
that this liquid will be you know coming out from that expansion valve as a liquid and
vapor.

And after that it will be coming through the evaporator where this you know liquid
will be evaporated and in that case by this evaporator heat from the certain article that
is stored in refrigerator area that will be you know coming into that you know
evaporator.

And after that the vapor of that you know refrigerator will be you know passing
through that compressor where the pressure will be you know again increased from
increased by this you know compressor there at higher temperature of this vapor. And
then it will go through the condenser where heat loss will be there and this heat loss
will be going that outside there, so that heat will be going to that outside by this
condenser.

And then that vapor that refrigerant again it will become that liquid refrigerant and it
will be stored in the liquid reservoir. Again from that liquid reservoir it will go
through that expansion valve and then evaporator and then compressor and then
condenser and it will be you know that continuously cycle will be going on.

So in this operation you will see that whenever liquid is coming from the liquid
reservoir and passing through that expansion valve, the pressure will be you know
reduced and temperature will be you know reduced to a certain temperature. And then
it will go through that evaporator where heat will be sucked from that you know,
substances or material which is kept in that refrigerator.

And by that heat you will see that it will be evaporated and then it will go to the
compressor and by this compressor there again that pressure will be you know
increased by increasing the temperature also there. So and it will go through that
condenser to condense it that you know refrigerator by releasing that heat to the
atmosphere. So in this way this refrigerator generally works.

643
So based on this you know principle and in the slides that if we use this refrigerant
and flows at a circulation rate of you know 18.14 kg per minute. In that case, you will
see that for saturated fluid at T you know that 258.15 Kelvin this enthalpy change, it
will be for that liquid it will be 22.33. And enthalpy of the vapor for that superheated
fluid it will be 180.96 kilojoule.

Whereas, at 303.15 K that is Kelvin this enthalpy of the liquid it will be you know
64.66 kilojoule and then enthalpy of this vapor it will be 199.57 kilojoule and for
superheated fluid at temperature 318.71 K this pressure is that is 643.28 kilopascal,
there the enthalpy of that vapor it will be 209.34 kilo joule.

So here in this slide in this you know schematic diagram of this regeneration process,
you will see that there are several you know that operating conditions or several
conditions like temperature and pressure are given in the inlet and outlet of this you
know several you know equipments which are being used there.

So if we consider that you know expansion valve there at inlet condition of this
expansion valve, it will be liquid flowing at that you know circulation rate and the
pressure is 643.28 kilopascal that is in gas pressure, where temperature is 303.15
Kelvin and after this expansion valve, the mixture of liquid and vapor will be there at
a pressure of 81.36 kilopascal and temperature of 258.15 K.

Here this is basically less than 0 degrees Celsius we can say. So here this know it will
be you know vapor form here this you know this refrigerant and then it will go
through that evaporator coil where that heat will be supplied to that evaporator and
this liquid and vapor will be you know superheated and at a temperature at a pressure
of 81.36 kilo Pascal and temperature at 258.15 K.

And it goes through that compressor where compressor outlet will have the
component of vapor of that refrigerant and pressure of 643.28 kilopascal. But
temperature will be higher than this you know that inlet temperature that is 318 point
you know 71 Kelvin and after that it will go to the condenser where inlet condition of
that condenser it will be that you know vapor and also outlet condition it will be liquid
of that you know pressure and temperature is shown here in the slides.

644
So in this condenser some heat will be lost that is to the you know that atmosphere
and based on which you have to calculate that fraction of refrigerant that evaporates
there and heat transfer rate to the refrigerant that evaporates there. So in this case what
should be the heat transfer rate in this evaporator coil and also you have to calculate
that fraction of the refrigerant that evaporates you have to calculate there.
(Refer Slide Time: 15:44)

Now in this case let us solve this problem. First here basis is that what is the
circulation rate of you know refrigerant, refrigerant here in this case it is basically R-
12 as refrigerant. This is R-12 as refrigerant. So circulation rate is 18.14 kg per minute
and if we consider first that expansion valve we can say that inlet is you know liquid
flow rate is 18.15 kg that is liquid refrigerant, R means refrigerant here.

And here pressure is 643.28 kilopascal and temperature 303.15 K and in the outlet
condition that the same circulation rate is there since it will be of 18.14 kg per minute,
but fraction of that you know refrigerant will be converting into vapor. So that will be
you know regarded as xv and 1 – xv that will remain as a liquid. Then this xv you have
to calculate here that is fraction of the refrigerant, which will be evaporates.

And in this case the heat of vaporization it is given that 180.96 kilojoule whereas heat
of you know enthalpy of that liquid is given as you know this 22.33 kilojoule per kg.
Now, if we do the energy balance over this you know expansion valve, we can see

645
that here, potential energy will be equals to 0. You know shaft work will be equals to
0. Heat supply to this system that will be equals to 0.

And then we can have only you know that kinetic energy change there. So that will be
is equal to you know enthalpy change there but this enthalpy change will be because
of that what will be the enthalpy in the outlet stream of this you know expansion valve
and total enthalpy in the you know inlet streams there. Now according to these, we
can say that if we do this material balance of this you know inlet and outlet streams,
we can see that at the outlet streams what are the components are there.

So it will be 18.14 into xv. This is basically a vapor of that refrigerant and this is xv
vapor and into 180 point you know 96 you know kilojoule since, this you know
specific heat, specific enthalpy of that you know vapor is 180.96. So we can say that
this amount of you know enthalpy is there for this vapor. And similarly, for other
components for that liquid component here that is 1 – xv.

So 18.14 into 1 – xv into kg this amount of you know liquid will be there of that
refrigerant. And here enthalpy for that liquid is 22.33 kilo Joules. You have to
multiply it. So ultimately this amount will give you that you know enthalpy of that
liquid in that outlet streams. Now, summation of these two you know enthalpy will
give you that total enthalpy in that you know outlet streams.

Basically from this equation this component will come as here okay, summation of
these two.
(Refer Slide Time: 19:42)

646
Now similarly, we can say that other components in the inlet stream since here only
one stream is here. So we can have this you know, liquid refrigerant, what it is known
enthalpy it is given 64.66 and amount is 18.14 kg of that liquid refrigerant. So we
have to multiply this 18.14 by 64.11 64.66 kilojoule per kg. Then you can have this
you know summation of this component here, we can represent this things here.

So according to this equation, we can write this you know, equation here. So from this
if you solve this problem for x v you can get this xv will be equal to 0.267 that is
26.7% evaporators there, evaporates there. So 26.7% of liquid refrigerant will be
evaporates in this refrigeration process.
(Refer Slide Time: 20:45)

647
Now, next question is that what will be the, you know that heat transfer rate to the
refrigerant that evaporates. Now, if we do that again evaporator coil energy balance
there, we can say that in the inlet streams, the flow rate of that refrigerant is 18.14 kg
per minute and the fraction of vapor in the coil it will be basically what is coming out
from the expansion valve, it is basically 0.267 you know vapor refrigerant.

And this vapor refrigerant will go to this evaporator coil and you will see that it will
be you know, again going out from this evaporation coil after getting heat, that heat is
not known to you. So that heat will be supplied here so that heat rate to be you know,
calculated. But you will see that enthalpy of that vapor which is coming out from that
evaporator is 180.96 kilojoule per kg and at a pressure of 81.358 kilopascal and
temperature of 258.15 K.

Whereas, at the inlet condition this you know enthalpy of this vapor is 180.96
kilojoules per kg whereas liquid enthalpy is 22.33 kilojoule per kg. So here this you
know fraction of that vapor will be coming to that evaporation coil as well as other
part of that refrigerant that will be 1 - 0.267 that fraction of refrigerant as a liquid it
will go to that evaporator coil.

Now in that case, we can say that here what will be the amount of you know energy
that is supplied. So accordingly again if you do that energy balance, so we can get that
you know, potential energy even shaft valve will be neglected. So we can have this
you know that Q dot will be is equal to delta H dot. Now Q dot from this we can then
have that from the enthalpy change.

So what is the enthalpy in that inlet condition of this you know evaporator coil, this
will be there. Again but in the vapor component which is here simply this. Whereas in
the outlet streams that vapor you know this is your, you know outlet conditions
whereas inlet conditions this you know this will be your liquid you know that
refrigerant.

So we can say that here, this is basically this liquid components is 0.733 this is you
know 1 - 0.267 we can say. So this you know fractions of liquid will be entering to

648
that evaporator valve which will be you know evaporated along with that, you know
vapor which is coming out from that expansion valve, so that also will be there.

So adding up all those you know enthalpy change and after you know balancing that
finally you can have this value of Q dot will be is equal 2110.11 kilojoule per minute.
So in this way we can calculate what will be the you know heat energy to be supplied
to the evaporator coil to you know evaporate that liquid refrigerant and passing
through that you know compressor at a certain pressure there, that will be calculated
in this way.
(Refer Slide Time: 24:33)

Let us do another example of you know distillation process where you will see that
several you know output from that distillation column will be there whereas one inlet
of that feed streams will be there to the distillation column. There you know as an
example here like let it be you know, acetone and acetic acid mixture. It will be you
know, passed through that you know, distillation column where it will be evaporated
based on that boiling point temperature.

And in this case, you know from the bottom of that distillation the product will be
coming as you know bottom products of you know certain percentage of acetone and
acetic acid and it will be you know recycled to that you know distillation column
certain amount that will be as boil up.

649
Whereas from the top portions, you know that evaporates or you can say vapor phase
it will be coming out from the top and then through the condenser it will be sent and
so that after condensing that vapor components it will be coming you know liquid and
some amount of that liquid will be you know sent back to the you know distillation
column as a reflux.

Whereas, other portions will be taken out as a you know, overhead product like some
percentage of acetone and acetic acid. So in the overhead product since the acetone
has you know, lower boiling point, than acetic acid. So, we can say that maximum
portion of acetic acid will be in the overhead product whereas, you know that small
amount of you know acetone will be there in the bottom product.

Whereas, maximum portion will be acetic acid as a liquid in the bottom part of the
distillation. And from this bottom part one reboiler to be used to send back to the
distillation column certain amount of that you know product for again distillation
process. So in this way it will be you know that you know continuously you know
operated this distillation column.

And in this case you have to calculate that what will be the net heat required for the
process and also heat input to the reboiler and heat removed from the condenser that
you have to you know, calculate. Based on that you know certain amount of heat like
here 100 mol of heat as basis if you consider then what should be the net heat required
for the process that you have to calculate.

So for this you need some data. So from the steam table, you can you know have this
data like this for feed if you represent it as one and for you know that feed liquid at
67.5 degree Celsius of the mixture of 65 mol percent of you know acetone and 35% of
acetic acid there. And in the overhead as a stream two we can have this you know,
that vapor of 63.0 degrees Celsius, where 98 mol percent of you know acetone and
2% of acetic acid will be there.

And in stream three, you will see some amount of you know liquid overhead product
will be sent back to the distillation column there and there you will see that it will be
sent as a reflux. So we can have this under reflux and that will be as a liquid and it

650
will be sent to the distillation column at temperature 56.8 degrees Celsius. Whereas,
the composition will be the same as that it is coming from the, you know overhead
product there.

Similarly, you can say that the overhead product from that stream four that will have
the same composition and temperature there what is sent back to the you know,
distillation column as a reflux. And bottom product we can say that in the stream pipe
here, temperature will be 98.7 degree Celsius and mol fraction of that components
will be 15.5% of acetone and 84.5% of acetic acid.

And you can say that after reboiling of those you know liquid components by that
reboiler as a boil up to be sent to the distillation column at a temperature of 98.7
degrees Celsius. Whereas, mol fraction of that you know acetic or acetone, it would
be 54.4 mol percent and acetic acid will be 45.6% of that.

So in this case, you have to find out at a different temperature of this different
streams, what will be the you know thermodynamic data like this here what will be
the enthalpy change there that you can get from it is a steam table here it is given in
this table here. So from this we can of course calculate that you know different, we
can say that we can do that energy balance to find out that you know, net heat
requirement for the process.
(Refer Slide Time: 30:10)

651
Now, we can actually you know, outline this whole, you know schematic diagram
with the different you know, temperature and mol fractions all those things here in
this picture as shown in the slide. So please go through this what will be that, you
know fraction of that components it is coming out from the top of this distillation
column as overhead and what would be the fractions of that components that is going
into that distillation column and it is coming as bottom products there.

What will be the Qr that is heat is required for the reboiler and also what is the
temperature So all these actually mentions here in this you know, this distillation
column.
(Refer Slide Time: 31:00)

Now, if we do the you know, balance now this balance may be first of all you have to
do that material balance how much you know that overhead product is coming, how
much you know bottom products is coming also to be you know calculated based on
that material balance here. Material balance and energy balance simultaneously will
be considered.

So at a you know that certain rate of that you know feed will be you know distillate
and it will be coming out from the overhead product and it will be coming out as a
bottom product. Now what will be that amount, that is not known to you. If we do the
material balance you can find it out there. Now, if we do that overall balance as a total
mol there, so we can say that here the inlet is 100 that is 100.

652
And what will be the outlet that you know that outlet is here. It is given as per this
diagram. It will be you know that 0.5 into as mentioned in the diagram and you plus
here n5, n5 is here, what is that? This is your n5 that is bottom product. So in this case,
we can do this overall material balance here by this equation and then if we do the
you know material balance for you know acetone here in this case, we can say that
0.65 into 100 then it will be is equal to 0.98 into 0.5 into plus 0.155 n5.

According to this you know, this material balance there so acetone for acetone if you
do this component material balance and solving this two equation we can get this n2
will be is equal to what 120 mol and n 5 will be is equal to 40 mol. What does it mean
that the moles of you know total moles coming out from that you know distillation
column as a vapor it will be 120.

Whereas as a, you know bottom product this amount is coming out as n 5, it is 40

mol. So we can see this here that product flow rates at the overhead stream here. So it
will be as 0.5 into 120 into 0.98. So this will be is equal to simply 58.8 mol A and B
will be is equal to 0.5 into 120 into 0.02. It will be 1.2 mol B. And at the bottom what
will be that amount of mol A and mol B here.

Here mol A means here we will see that here basically that acetone and mol B is
basically that acetic acid. So we can say here, this amount of acetone and this amount
of, you know acetic acid will be coming out from the bottom. Now, if you do the
overall energy balance here in this case again that potential energy just to be neglected
and shaft work to be neglected and also you know that delta E s some you know that
other you know phase change energy will be you know negligible.

So overall we can say that this is you know kinetic energy you can say that will be
also neglected. So overall we can say that this Q will be is equal to H. Then here it
will be
H   n Hˆ   n Hˆ
i i i i
out in
In this case what will be the inlet and outlet streams based on which we can do that
energy balance here. Now, from this energy balance we can then write directly that Q
will be is equal to here.

653
H   n Hˆ   n Hˆ
i i i i
out in
And after substitution of this value in this inlet and outlet conditions then we can have
finally this value of 2.63 into 10 to the power of 4 calorie. Now in this case
incorporate you know the value in the table whatever it is given at different
temperature that this values are there.
(Refer Slide Time: 35:15)

And after that you know you have to find out what will be the you know heat you
know loss in the condenser that also calculate by you know material balance what will
be the amount of you know that moles of acetone in you know flowing through that
condenser and also what will be the moles of that acetic acid is flowing through the
condenser.

So accordingly you can do again that you know energy balance for that condenser.
Now, accordingly, if you substitute that value of enthalpy there, you can get this you
know enthalpy change as here 8.77 into 10 to the power 4 calorie that will be heat
removed from the condenser. Now in this case assuming negligible heat transfer
between system and the surroundings other than Qc and Qr, so we can have this Qr
will be is equal to Q – Qc.

That will be is equal to here we can say 2.63 into 10 to the power of 4 minus 8.77 into
10 to the power of 5 here from which we can say that this 9.03 into 10 to the power 5

654
calorie heat to be added to the reboiler because this Qr is the you know that reboiler
heat energy supplied to that you know reboiler.

And Q is the here total, energy that already we have calculated by this equation here,
total you know heat required for the process. And if you subtract that, you know,
condenser heat what is coming out from that condenser, then you can get this what
will be the heat is actually supplied to the reboiler there. So in this way you can you
know do the energy balance for the distillation column.
(Refer Slide Time: 37:12)

Now, let us do another example of evaporation process based on this you know
energy balance equation. So in this case, if we consider that a solution that contains 5
kg salt per 100 kg solution is evaporated to 20% in an evaporator. The heat capacity
of the solution is 0.98 kilo calorie per kg degree Celsius and that of 20% solution is
0.90. Now, the feed temperature is you know that 30 degrees Celsius.

Whereas boiling point in the evaporator is 105 degrees Celsius. It requires 540
kilocalorie to evaporate 1 kg of water from the boiling solution. Now, the steam gives
up only its latent heat of vaporization as 525 kilocalorie per kg. Now, based on this
principle, you have to calculate how many kg of steam is required per kg of feed. And
also it is proposed to run that concentrated solution through a counter current, you
know heat exchanger to you know preheat the feed.

655
If the concentration solution, concentrated solution you can say is thus cooled from
105 to 50 degrees Celsius. In that case, how much heat is to be transferred to the feed
stream there you have to calculate and what percentage decrease in the steam
consumption results as per this problem.
(Refer Slide Time: 38:51)

So let us do this calculation here for this you know evaporation process. As a basis we
can take 100 kg of solution where 5% in weight percent you can say salt will be there
subjective to that evaporation. And in this case as per figure here, this is one
evaporator as shown here in the slide. F is representing here as you know that feed
solution of 5% salt which will be entering to that evaporator which is to be
evaporated.

And P is the product solution of 20% of salt and E is the you know, evaporation
amount that is in kg. S is you know steam that is used for that evaporation and C is the
condensate that is obtained from the steam chest in kg. Now, if we do the material
balance to find out all those you know, stream amount which is coming in and coming
out based on which we can get that E will be is equal to here 75 kg.

And P that is product solution of 20% salt will be coming as 25. So in this case, we
have to do the overall balance like this F will be is equal to E + P overall balance here
for the you know solution and salt balance if you do that, in this feed stream the salt
amount is 5% whereas products in salt amount is you know only 20%.

656
So according to that you know salt balance we can simply you know calculate this
you know what will be the product that will be coming out from that evaporation, that
amount is equal to 25 in kg. And hence if you substitute this product value in this
overall balance, you can get what should be the you know evaporation amount there
as E and that is 75 kg according to this calculation.
(Refer Slide Time: 41:09)

Now, you have to do the energy balance there. Now, for that energy balance you have
to consider some reference temperature. In this case we are considering that reference
temperature is zero degree Celsius. Now, we have to first calculate what are the heat
input there. Now heat with feed that will be is equal to since feed amount is 100 kg.

And you know that specific heat of that feed stream is 0.98 and temperature
difference is you know that 30 degrees Celsius. So we can say that this amount of that
is 2940 kilocalorie of heat will be with the feed. Similarly, heat with the steam that is
entering to that evaporator as here S into h plus 525 kilocalorie. Where in this case h
is sensible heat we are considering. S is the you know that amount of steam.

So we can simply that calculate the S into h, this is enthalpy that is sensible heat
change for that S amount of steam there and you know that also there will be certain
amount of that you know latent heat that will be is equal to S into 525 there also. So
this amount of heat will be you know supplied to that evaporator. And heat output that
will be come out heat with vapor and it will be simply that E into Cp dT plus lambda.

657
Again this lambda is the latent heat of you know vaporization. So here after
substitution of that C p value and temperature difference is 105 and E amount is 75
and that latent heat of vaporization is 540 kilo calorie. Then we can have this you
know that 48217.5 kilo calorie there that is heat with vapor. Similarly, heat with
product that will be is equal to 25 into you know 0.9 into 105.

This is the you know amount supplied, that is amount is coming out as a product and
0.9 is that specific heat capacity and 105 is the temperature difference and based on
which you can say that this is simply that sensible heat of that product. So it is coming
out as a 2362.5 kilo calorie. Similarly, what should be the heat with condensate, that
also to be calculated.

Here condensate here in this case only simply that is to convert that vapor into
condensing form. So for that you need some you know heat of condensation. That will
be is equal to h here. So S dot h will be the total amount of heat with condensate
there. So assuming heat losses to be negligible here, all the heat will be utilized there.
So in this case heat input will be is equal to heat output there.

So here we can say as per that balance of that heat we can write simply this equation
and from which after substitution of this you know sensible heat and also you can say
that other components they and then you can get what should be the amount of steam
is supplied to that evaporator there. So it is coming out as 90.74 kg that is you know
supplied as a steam to that, you know evaporator to you know evaporate those
solution there inside the evaporator.

Hence kg of steam required per kg of feed it will be simply that is 90.74 divided by
feed amount. That will come around 90% there. So in this way you can calculate what
should be the you know, fraction of you know feed stream as a steam that will be
supplied to the evaporator to you know evaporate those solution there.
(Refer Slide Time: 45:25)

658
And then again you have to calculate that what should be the you know, heat transfer
to the feed stream there. That is basically the heat lost by the product stream. So here
in this case from the material balance is same as that in the part A, you have to you
know calculate that you know different stream amount based on that and since we
have done it in part A, so we have to use all those you know, amount of streams of
you know, F, C, Cp, all those things are here itself in this part of this problem.

So in this case heat transferred to the feed stream basically considering as Q and that
will be is equal to heat lost by the product stream there. So this Q will be is equal to P
into Cp into dT. According to that you know sensible heat based on that specific heat
capacity at constant pressure and the temperature difference. So it will be becoming as
you know 25 into 0.9 into 105 minus 50. That is basically 1237.5 kilocalorie.

Now, let us consider that what should be the temperature of that feed after heat
exchanger there. So in this case if we consider that temperature is tF. So we can say
simply that this heat balance as FCF, CF is the you know that specific heat capacity of
that feed stream and F is the amount of feed which is supplied to that evaporator.

And the feed temperature is it is tF then from that, you know steam temperature, we
can subtract it then we can get that you know, enthalpy change of that feed stream as
here 1237.5. So in this case, what should be the you know temperature of feed stream.
So after solving this equation of this heat balance there for this feed stream then we
can say that the tF will be is equal to will be equals to 42.62 degree Celsius.

659
Now heat content of feed that will be is equal to 100 into 0.98 into then 42.62 degrees
Celsius This is your temperature difference from the reference temperature of 0
degree Celsius. Then finally, you can say that heat content of the feed will be is equal
to coming as 4176.76 kilocalorie.

Similarly, if you do the heat balance around the evaporator, then you can say that this
amount of feed that is entering and according to that what will be the energy which is
there and what will be the energy supplied by that steam and that will be is equal to
what is that it is that is coming out from that product stream there and also from that
you know vapor components there from the evaporator.

So after substitution of this value then we can solve this you know S will be is equal
to 88.38 kg. Now in this case, you will see that decrease in steam consumption you
will see that it will be coming as 90.74 - 88.38 there because in this case this steam is
88.38. So earlier that steam was 90.74. So basically the reduction in steam
consumption will be is equal to 2.6%.

So here in this way we can calculate that reduction that is what percentage decrease of
steam consumption results if that we propose to run the concentrated solution through
a counter current heat exchanger to preheat the feet, if the concentrated solution is
thus cooled from 105 to 50 degree Celsius. So in this way we can calculate also the
feasibility of that using what will be the amount of steam for that evaporator.

So before you know that just changing this you know temperature condition and also
preheating condition you will see that maximum amount of heat is required for that
evaporator. So to you know, economize that you know process what we have to do,
you have to you know, on that you know preheat the solution by a certain you know
heat exchange equipment, so that you will you know that utilizing less amount of
steam for that evaporation process.

Now, let us do another example, for you know solving the energy of balance for that
processes based on that energy balance equation. Let us do the example for drying
process.

660
(Refer Slide Time: 50:37)

Now, problem is that in a spray drier, a liquid solution of the material to be dried is
sprayed into a you know steam of hot gas. Now inlet air is given as 4000 meter cube
per hour that is measured at normal temperature and pressure and temperature is 300
degrees Celsius and 780 millimeter mercury of pressure. And there per kg of drier
contains 0.005 kg of moisture there.

Whereas inlet solution there 300 kg per hour to be supplied where 15% solids will be
there at 20 degrees Celsius. So you have to dry these you know solution of this 15%
solids that is called slurry. Now at the outlet solid, the temperature is 40 degree
Celsius, whereas outlet air, you will see that condition is 90 degrees Celsius where
moisture content will be 0.035 per kg of dry air at a pressure of 760 millimeter
mercury.

Now in this case, you have to calculate the composition of the outlet solids and the
radiation loss there. Assume that specific heat of dry solids to be you know 0.2 calorie
per gram degrees Celsius and that of gasses to be 0.24 calorie per gram degree
Celsius.
(Refer Slide Time: 52:06)

661
Let us do the solution or solve this problem here. In this case consider that one hour
operation of that spray drier. Here it is schematically represented in this slide. Here
this spray drier where inlet solution at 20 degrees Celsius, where inlet air containing
you know that certain moisture at 300 degrees Celsius to be supplied to that you know
spray drier at 300 degrees Celsius.

And after drying you will see that outlet air will be coming at 90 degree Celsius with
a certain moisture content and then solid whatever it is coming out as a dry product
you can say that it will be at 40 degrees Celsius. Now, based on this you know you
know schematic diagram and the streams, you will see that you have to do some
material balance to find out what will be the you know moles of that is air in the or
solution is coming to that you know spray drier all those things.

Now, assume that air and the accompanying water vapor behave as ideal gas there. So
in this case let n0 number of mol of air and water vapor combined is coming to that
spray drier. So in this case since it behaves as ideal gas, so you can write this ideal gas
equation here, n0 will be equals to PV/RT. So if you substitute that pressure and
volume there.

And that you know R value that is universal gas constant and then temperature of this
normal temperature. So we can say that 178.7 that is 57 kg moles of you know that air
and water vapor mixture is coming to that spray drier. Now, you know that, that inlet
condition that water moisture per kg of drier is you know 0.005 kg. Whereas, if you

662
convert it to mol then you have to you know divide this kg or mass by its molecular
weight.

And finally, you can say that 0.008 you know that moles of that air and water vapor
combined is coming to that sprayer. And kg mol of wet air by kg mol of dry air you
can get it by this here simply just adding up that 0.008 to that one mole of dry air. So
this is the ratio of that kg mol of wet air by kg mol of dry air.
(Refer Slide Time: 54:59)

After that, what you have to do that you have to find out the what will be the amount
of dry air that is entering that amount of dry air entering to that spray drier that will be
is equal to simply that you know 178.57 by 1.008. That will be 177.15 and amount of
dry air then in terms of you know mass it will be coming that since it is moles then
you have to multiply it by molecular weight then it is coming as 5109 you kg.

Now amount of water that is removed by air after drying then it will be as simply here
that 5109 kg of dry air is coming. Then what is that moisture at inlet and outlet
according to that, you can calculate what should be the you know moisture in that you
know removed by that you know drying process.

Now initial solution that contains you know that 15% solids now water in solution
that is 255 kg, solids in solution that is then 300 - 255 kg then it will be 45 kg that is
in solid solution. Now water left in the final solids this is basically 255 minus this

663
153.27, that is your amount of water which is removed. So water left in the final
solids it will be is equal to 101.73 kg.

Now accordingly you can calculate what will be the composition of that outlet solids.
Now, solids is 45 kg, weight is 30.66%, water is 101.73 kg, then weight percent will
be 69.34. Total is 146 point you know 73 kg and then you know weight percent will
be 100% there. So accordingly you can calculate what should be that you know mol
fractions also there.
(Refer Slide Time: 57:08)

Now, if we do the energy balance, so what this you know spray drier with reference
temperature of 0 degree Celsius, then we can have this you know heat with solution
here 300 into 1 into 20 at the temperature here it will be is equal to 6000 kilo calorie.
Heat with inlet air it will be you know that there as per that moisture content and it is
you know specific heat capacity and then at that temperature difference, then it will
come ultimate 369687.24 kilocalorie.

Similarly, heat output that will be calculated as per thus. Heat with solids this is this
amount and that is simply CPdT into what is that amount of that solids there. Heat
with outlet air, it will be coming as this amount. Heat utilized in the process for
vaporization of water simply this one. So this amount of heat is basically utilized
there. So what will be the loss of that heat energy there.

664
Now, you know that heat input is there, what would be the total heat input there we
have calculated. This is 6000 plus you know that heat with inlet air and also heat with
solution. This total amount will be as heat input whereas we will see that heat utilized
in the process for the vaporization of water is 42915.6 kilocalorie. Now, if you
subtract it you will get that what is that heat output there.

This heat output is basically that 1173.84 and plus 114216.80. Now, if you subtract
these all you know that heat output, heat utilized from that heat input, you will see
that this amount of heat will be you know lost by that you know radiation.

So this is you know that the basic you know calculation for this spray drier or energy
balance and what will be the amount of heat or amount of you know enthalpy to be
supplied to that sprayer with that solid solution and how that solid solution can be
dried after just removing of heat energy by evaporation process or just by changing of
you know enthalpy and also the moisture content of that drier in the inlet and at the
outlet condition.

So these examples will help you to solve other different types of problems based on
this you know concept and also we have discussed that the problem of energy balance
for the distillation, we have described the you know entropy balance calculation and
how to do this for you know refrigeration process, how to do this for evaporation
process and also this drying process.

I would suggest you to you know further you know practice on this type of problems
from this text books it is given here in the slides.
(Refer Slide Time: 1:00:36)

665
I think it will be you know more useful if you do the or if you do the practice on this
example given in the textbook there. So I also here suggest to consider the problem
whatever discussed in the slides today’s lecture, to practice again and again so that it
will be you know that useful for you to further understand the solving of other you
know, other different types of problems based on this energy balance equation.

In the next class we will try to discuss more about that energy balance with more
example there with different inlet and outlet streams and also we will discuss
something more about that energy balance with some you know, reaction processes
there. So thank you for your kind attention.

666
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 23
Energy Balance on Heat of Solution

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. So we are discussing about energy balances on reactive
processes and also nonreactive processes in our earlier lectures and under the module
seven, we have discussed about this with ample of examples. Now in this lecture we
will try to give more examples regarding that energy balance on you know heat of
solution.
(Refer Slide Time: 01:04)

And we have this we have covered that energy balance with multiple streams without
reaction, energy balance also you know with different you know streams in the
specific you know chemical engineering operation like evaporator, drier, distillation
column and also refrigeration processes. Now here also we have to find out that how
actually that enthalpy balance can be helpful to analyze the solution basically for acid
or other you know different type of solution.

Though we have discussed different aspects of that you know, mixtures and also how
to calculate the enthalpy changes of mixtures in a particular process there and based
on that, you know mixture specific heat capacity has also that temperature change,

667
how those energy you know can be calculated. Based on that you know, internal
energy change and also kinetic energy change inside the system.

So that solution also you know, can be considered as a mixture where that enthalpy
change can be calculated based on that input and output streams and as well as you
know that the different components enthalpy change based on their you know,
formation and also how that sensitive heat changing during its you know phase
change.
(Refer Slide Time: 02:51)

So we will extend this you know, enthalpy balance or energy balance equation for
analysis some other problems here with solution.
U  KE  PE  ( PV )  Q  Ws
So before going to that, we have to look back that energy balance equation like we
have actually described that energy balance equation in the form of you know,
internal energy change, kinetic energy change, potential energy change and also flow
work change based on that pressure change and volumetric flow rate change.

And those you know that energy as a sum that will be contributed by the net energy
supplied to the system. Now that net energy supplied to the system basically comes
from that heat energy supplied to the system and how much work is done by the
system there so that you know balancing of that energy would be contributed to that
internal energy, kinetic energy change and potential energy change.

668
Even if there is a pressure between these two you know streams of inlet and outlet if
is there for the process then you have to consider that flow work change there for the
energy balance.
(Refer Slide Time: 04:14)

And based on that, you know continuous operation and also the continuous supply of
mass, then how that internal energy, kinetic energy and also potential energy will be
changed because of that flow wok and heat energy supplied to the system and that
overall energy balance you know can be expressed based on that specific you know
energy terms, just by multiplying that you know, the mass flow rate as a common
factor in the common energy balance equation.
That also we have described earlier. So here in this slides also it is given that, this
how that energy balance equation can be written based on that you know, specific
energy terms with that mass flow rate.
 
ˆ  vout  gz  P v  -  Uˆ  vin  gz  P v    Q  W
2 2
m  U out out out out in in in in s
 2   2 

(Refer Slide Time: 05:09)

669
And finally, if you are considering that there is no you know shaft work, there is no
kinetic energy change, there is no potential energy change, then you can simplify that
energy balance equation as like this here


ˆ H
m H out
ˆ Q
in 
ˆ
Or Q  mH
Or Q  ΔH
and based on this you know enthalpy change you will be able to assess that what will
be the you know heat energy required to you know change that operation or what
would be the energy required for the you know actually that execute that process there
in the system.
(Refer Slide Time: 05:37)

670
So let us do an example with you know solution where that heat can be removed or
may be added to keep that final solution at a certain temperature. Now in this case
suppose in a closed constant pressure system of flask that you are about to dilute
suppose two mole of 100% sulfuric acid with enough water to produce a 30 mole
percent aqueous solution. In this case the acid and water are initially at a temperature
of 25 degrees Celsius to be considered.

Now, in this case here see that there is a you know sulfuric acid solution of it is 2
mole capacity and which is mixed with that enough water to produce that 30 mole
percent of aqueous sulfuric acid solution there. So in this case how much heat would
be actually removed to keep that final solution at that 25 degrees Celsius because
there you know that some heat energy to be removed to get this dilute solution of the
sulfuric acid.

In this case that heat of solution is required and it is given that it will be amount of
you know -44.28 kilojoule per mole of sulfuric acid at this condition. Another
condition that if you supply that a mass of 150 gram of that, you know flask with the
solution and the heat capacity of the flask is known to you and it contains its contents
is you know 3.30 joule per gram degree Celsius.

And if the flask is sufficiently insulated, so that it will be, the system will be as a you
know that adiabatic system and in that particular condition you have to find out what
will be the final solution temperature. So this is the problem based on which you have
to you know assess it by you know energy balance equation.
(Refer Slide Time: 08:09)

671
Now, to solve this problem, first of all you have to calculate, you know what will be
the amount of actually water to be mixed with that 2 mole of sulfuric acid to become
it as a diluted 30% sulfuric acid solution. So for that 2 moles of you know, sulfuric
acid to make it you have to add some water. That is not known to you. So for that if
you consider that n mole of water is required for that, then we can write that you
know, material balance for this solution as for this 2 mole of sulfuric acid that will
come from that you know that whatever solution to be made up that would be 30%.

So 30% of that sulfuric acid, out of that total amount of solution will be is equal to
here 2 moles of sulfuric acid plus n moles of water. So this is your total moles. So
total moles, out of this total moles that 30% of you know this, you know moles will be
sulfuric acid. That will be equals to 2 mole of sulfuric acid.

So if you write this equation of that mole balance of the sulfuric acid, you can you
know calculate what should be the you know, moles of water to be required for
getting that 30% sulfuric acid solution at its diluted condition of 25 degrees Celsius.
And then, if you are getting this amount of water, that is as per calculation, it is
coming as 4.67 mole of water.

In this case, then what will be our ratio of this sulfuric acid mole to the you know
water mole. And based on which you can assess what will be the amount of you
know, heat of solution to be required to get this you know of diluted solution at this

672
25 degree Celsius. So for that, what would be the ratio of that, water moles to that
sulfuric acid. That is basically that 4.67 divided by 2 here.

4.67 is the mole of water and 2 is mole of sulfuric acid. So it is coming as 2.33. So at
this ratio of the sulfuric acid and also that water here, you will see that at its 2.33
value that heat of solution at 25 degrees Celsius is around -44.28 kilo Joule per mole
of sulfuric acid. So in that case, what will be the total heat is actually you know to be
removed from that system of this diluted sulfuric acid there.

So as per that energy balance equation you can write that here simply that there will
be no shaft work. There is no kinetic energy change here. There is no potential energy
change here. So finally, we can write that this energy balance will be is equal to Q.
That will be equals to H that is enthalpy change there. So for that, that enthalpy

change for that solution at its ratio of 2.33 it is coming here Ĥ s , that is per mole of
sulfuric acid is enthalpy change.

Now since there is you know 2 mole of sulfuric acid then total you know enthalpy
change will be is equal to n of sulfuric acid into specific heat of solution at this 25
degree Celsius and the ratio of water to the sulfuric acid mole. So according to this
finally after calculation you can get this -88.6 kilo Joules of heat is to be you know
removed from the solution.

Now this much heat is actually produced during that you know, addition of that
sulfuric acid in you know water there. That is for making that solution, you will see
there will be a heat generation and that heat should be removed by that you know, to
the removed to the atmosphere so that certain dilution at a certain temperature it
would be reached there.

So you have to then calculate what will be the final temperature of that solution there
if you are you know removing this amount of heat from that solution. So for that you
have to calculate what will be the you know mass of solution of that 30% sulfuric acid
solution. So in this case you have to then add up of that what will be the mass of
sulfuric acid and also what will be the mass of water in a solution.

673
So mass of sulfuric acid can be, you know calculated just by multiplying this 2 mole
of sulfuric acid by a molecular weight of sulfuric acid. So it is coming as 2 mole of
sulfuric acid into 98.08 gram of sulfuric acid per mole. And then what will be the
mass of water that can be calculated again just by multiplying that mole of water by
its you know that molecular weight.

So it is coming as here 4.67 mole of water multiplying by 18.0 gram of water, which
is molecular weight of water. So finally after adding this, you can get this 280.2 gram
of total solution. Since here again doing that enthalpy balance there in a solution, it is
true that that in a net that enthalpy change will be is equal to zero. So finally, we can
say that, at this 25 degrees Celsius, we can say that enthalpy change will be is equal to
you know zero.
So what is the enthalpy basically, that is actually what will be the amount of sulfuric
acid and what will be the heat of solution at that 25 degrees Celsius of the diluted
solution. Plus, there will be a certain change of you know that temperature that is
sensitive heat will be changed because of that change of temperature there. So that
temperature you do not know, you have to find out.

So let us you know consider that temperature as T which is to be you know found out.
So here if we multiply this mass of that solution and also that specific heat capacity of
the solution at constant pressure and the temperature difference then you can get this
you know sensible heat change there.

So what will be the heat of solution and what will be the sensible heat change there
that you have to add it up to get that you know, total enthalpy change will be equals to
zero. So we can write this equation here shown in the slides to you know balance that
heat at its diluted solution of that amount here 280.2 gram. So after substitution of this
value of here enthalpy this is you know simply what is that this value is already
calculated here in part A.

So this is -88.6 kilojoule and this part here m is calculated as 280.2 and plus here 150
you know gram there total amount of this solution as well as there you know extra
water is supplied for the dilution. For that you have to add it up So this is your total

674
mass of that and then what will be the specific heat capacity that you have to multiply.
This is basically 3.3 joule of the solution.

And temperature is you know changes T-25 because the initial temperature was 25
degree Celsius and when final temperature is you know that T. So T-25 degree
Celsius, this will give you that you know, temperature change based on which that
what would be the sensible heat change there. So finally, you can get after calculation
that T will be is equal to here 87 degrees Celsius.

So you can say that if you add some water there you will see that solution temperature
will be you know changed there. So accordingly you can say that, that how
temperature will be changing because of the dilution or concentrating that solution
also, accordingly you can calculate here as per this enthalpy balance equation.
(Refer Slide Time: 17:47)

Now let us do another example, for assessing that energy balance equation with this
example here. Let us consider that water is added to pure sulfuric acid in a well-
insulated flask initially at 25 degrees Celsius and 1 atmosphere to produce a 4 molar
sulfuric acid solution where specific gravity is given to you. The final temperature of
the product solution is to be 25 degrees Celsius.

So that the water added must be chilled liquid at temperature less than 25 degrees
Celsius or a mixture of you know liquid water and ice. Now in this case you have to
consider a basis of calculation one liter of you know the product solution and assume

675
Q will be is equal to delta H that is heat energy supplied that will be is equal to
enthalpy change for the process.

Now if you need to know the heat capacity of ice and you can take it to be half that of
a liquid water. Now in this case if only water is added what masses of sulfuric acid
and water should be mixed and what should be the initial temperature of the water
that you have to find out. And also if a mixture of liquid water and ice is added, then
how many grams of each should be you know fed to the process.
(Refer Slide Time: 19:21)

Now to solve this problem basically you have to consider that basis of that, you know
problem your basis is one liter of 4 molar sulfuric acid solution is considered and
specific gravity of that solution is 1.231 it is given to you. So one liter means here
1231 gram you have to multiply to this one liter so that you can get total you know of
1231 gram because the specific gravity is 1.231.

So what should be the density of that solution it will be simply 1231 gram per liter. So
here in this way, you can calculate the mass of that solution is 1231 gram. Now, in
this mass there will be 4 moles of sulfuric acid. That means here 1231 – 392.3 that
will be your total amount of water. Here 392.3, this is basically that 4 moles of
sulfuric acid how much it will give you that weight.

So in that case, if you subtract this amount of sulfuric acid from the total solution then
you can get this what will be the amount of water there. And you can say that this

676
water moles will be is equal to 46.57 mole of water because if you divide it by you
know molecular weight of water you can get this you know, moles of water there.

So in this one liter of 4 molar sulfuric acid solution contains this gram of sulfuric acid,
that is 392.3 gram of sulfuric acid and 46.57 mole of water or you can say 838.7 gram
of water. In this case what will be the ratio of that water to sulfuric acid. It is simply
as per this calculation here. 11.6 mole of you know water by mole of sulfuric acid
here just by you know dividing this 46.57 mole of water divided by 4 moles of
sulfuric acid then you can get it simply 11.64 mole of water per mole of sulfuric acid.

This is your ratio. Now, this ratio will give you the you know heat of solution. So this
heat of solution is coming as -67.6 kilojoule per mole of sulfuric acid. So you can get
it from a table what is given in your you know textbook there in the appendix that
how heat of solution can be changed to the ratio of you know, solid to you know
solvent there.

So, in this case as per reference here it is given that water and sulfuric acid based on
which that heat of solution can be calculated. Now if you consider that in the solution
that on the water as a liquid substance then what will be the amount of this water is
coming into the you know system as it is 46.57 that we have calculated here, this
mole. So will be the enthalpy in the inlet?

That is simply you know that 0.0754 into T – 25, T is the temperature that you do not
know, that you have to find out there for that solution. Whereas, you know that what
will be the moles of water in the outlet condition. It is not known, because here this is
a simple you know, best process. There is no continuously supplying or that is
continuously outlet of that mole here, it is considered there.

So here in this case n out and H out to be you know nil. Similarly, sulfuric acid that
will be 4 mole and also you can say that here enthalpy will be is equal to zero. Now,
question is that why this 0.0754 it is coming because this is the mole ratio that you
have to consider there. And then what is that here sulfuric acid this ratio that n of
sulfuric acid nil and enthalpy change of that sulfuric acid is nil.

677
Whereas in output, there will be a sulfuric acid out at 4 mole and here this enthalpy of
this outdate stream is -67.6. So finally, if you do that you know enthalpy balance
based on that earlier equation that we have given then we can have this you know
temperature as -52 point minus 52 degree Celsius as per after you know simplification
of this balance equation by substituting this various variable.
(Refer Slide Time: 24:43)

Now at this you know, condition two whatever it is, you know given in the problem
that water as a liquid that is coming in that will be is equal to n 1 that is not known to
you that you are considering here it is n 1. Whereas in you know enthalpy at this inlet
condition it is given as this. And in the outlet there will be no water. Similarly, for
water solid in that case what will be the amount of solid there.

It is not known to you that you have to consider here as unknown and also enthalpy
change for that solid water you can calculate by this simply you know that this
amount, what is the heat of formation and then what will be the enthalpy of that you
know or sulfuric acid because of this temperature change.

And then sulfuric acid as a liquid that is given to you that is 4 moles whereas in you
know that sulfuric acid at 25 degree Celsius where this ratio of as per ratio here it is
11.64 at this ratio that you know that in total output of the sulfuric acid is 4 moles and
enthalpy change at the outlet condition it will be is equal to -67.61.

678
So again you know that from the table of that solution, enthalpy of solution you can
get this specific heat of solution for that amount of solution that you can calculate
from that table, which is coming as 6.01 kilojoule per mole. Then total amount of
liquid and solid that will be coming as you know as a material balance you can have
this you know balance equation for this liquid and solid in inlet and outlet condition.

So finally, you can get this nl + ns that will be is equal to 46.57. So as per enthalpy
balance that heat of solution will be equals to zero there. So accordingly that enthalpy
change if you calculate it from the inlet and outlet streams. Then finally, you can get
after solving this equation as n1 will be equal to 16.18 mole of liquid of water and n s
solid that is ice that will be you know 30.39 mole of ice.

So based on this equation you can also solve this whenever the solution will be you
know cooled down to a certain temperature by you know by supplying some you
know sink heat sink like you know ice like that to what will be the amount of ice to be
supplied and also what will be the water to be mixed with that you know acid solution
to get its final temperature of you know T temperature like this.

Here in this case, this final temperature is considered as 25 degree Celsius.

Accordingly, what will be the amount of heat is required that you how you can
calculate and also from that heat balance and material balance you can calculate what
will be the amount of liquid and also ice required for the making of solution.
(Refer Slide Time: 28:16)

679
And another example let us do here. In this case an 8-molar hydrochloric acid solution
the specific gravity of the solution is 1.12. And specific heat capacity at constant
pressure is given 2.76 joule per gram degree Celsius is to be produced by absorbing
hydrogen chloride as a gas in the water and liquid water enters the absorber at 25
degrees Celsius and gaseous hydrochloric acid is fed at 20 degrees Celsius and a
pressure of 790 torr. That is one torr means one millimeter mercury pressure.

This is absolute pressure and in this case, you have to you know remember that, that
all of the hydrochloric acid fed to the column is absorbed in the liquid system. And
then take one liter of product solution as a basis of you know calculation here. So
based on this you know problem you have to estimate the volume of hydrochloric acid
that must be fed to the absorber.

And also you have to calculate the heat that must be transferred from the absorber if
the product solution to emerge at 40 degrees Celsius. And also you have to estimate to
the final solution temperature if the absorber operates adiabatically.
(Refer Slide Time: 29:44)

So to solve this again you have to take that basis of one liter product solution and
whose specific gravity is given and also you know that specific heat capacity is given.
So as per that you can get this 1120 gram solution of that hydrochloric acid. Now,
based on this you can calculate what will be the you know gram of you know
hydrochloric acid there since here 8 mole of hydrochloric acid.

680
So if you multiply it by its molecular weight, then you can get what will be the mass
of hydrochloric acid. So remaining amount will be you know that water that can be
calculated here. It is as per this problem it is 828 gram of water. So in this case what
will be the mole of water just dividing it by its molecular weight then you can get this
mole of water.

And what will be the then ratio of that water to hydrochloric acid solution. It is
coming as 5.75, this is as here, n or sometimes it is represented by r as ratio. Now
assume all hydrochloric acid is to be absorbed in the absorber. So in this case, volume
of gas that will be is equal to you know 8 mole of this you know hydrochloric acid
hydrogen chloride gas to be absorbed.

So in this case 8 mole of hydrogen chloride at this temperature of you know 293 K as
per problem and also the pressure of 790 millimeter mercury. Accordingly what will
be the volume of that because per mole of gas will give you that 22.4 liter at STP
condition. So as per that and also from the equation of state of gas, you can calculate
that this 185 liter of gas feed per liter of hydrochloric acid solution which is to be you
know, absorbed in the absorber here as shown in the slide.

So we can then calculate this amount of you know gas to be you know absorbed by
this you know absorber there.
(Refer Slide Time: 32:17)

681
Now, if we consider that reference temperature, what should be the enthalpy for that
individual components in this absorber. What are the you know inlet and outlet of
course, as per this schematic diagram, this is the amount of hydrochloric acid which is
you know are going to that absorber and this is here aqueous you know hydrochloric
acid solution.

So finally, you will see that you know this amount of hydrochloric acid aqueous
solution of hydrochloric acid to be made if you absorb this you know, hydrochloric
gas at 20 degree Celsius of 790 millimeter mercury there. And from this you know
initial solution of 46.0 mole of water there. So accordingly what happened here this
mole of water will be absorbing some hydrochloric acid gas and finally, you will see
that one liter of hydrochloric acid to be made.

Now, in this case what will be the inlet what will be the outlet very interesting that
this amount of hydrochloric gas or hydrogen chloride gas it will be in and this amount
of water to be in and this is your outlet condition. So here two inlet and one outlet is
there. So accordingly that inlet you will see that water inlet is 46 moles and enthalpy
is zero.

Whereas hydrogen chloride gas inlet at 8 moles and also enthalpy change is -0.15.
And in the solution you will see that heat of solution at this ratio that you can say that
inlet condition there will be no you know hydrochloric acid solution at the inlet
condition at this ratio. So that enthalpy and moles will be zero. Whereas it will come
from this outlet whereas moles of that hydrochloric acid will be n out will be 8 moles
and this enthalpy change will be -59.07.

Now according to that what will be the you know enthalpy specific enthalpy of the
solution at this 25 degrees Celsius and how then you know sensible heat will be
changing out of this hydrochloric acid from the temperature from 25 to 40 degrees
Celsius. So if you substitute those values here, then finally you can get you know this
value of you know 0.15 kilojoule per mole of this you know hydrochloric acid at 20
degree Celsius.

682
And then you know that according to that you know enthalpy balance or you can say
that heat energy balance. So we can get this you know total enthalpy change will be is
equal to if you multiply this minus you know 15 point kilojoule and the total mole of
you know that hydrochloric acid solution there, then accordingly you can calculate
here, this will be your amount of kilojoule or heat energy that is to be removed per
liter of that hydrochloric acid solution.

So in this way you can calculate the enthalpy balance or you can do the enthalpy
balance equation to calculate that what will be the amount of heat that is to be
removed for its dilution or by absorption of even some gases by other liquid also.
(Refer Slide Time: 36:01)

And from this you know heat balance or energy balance equation, you can say that at
what temperature that solution will be you know reached there. So since the final
solution will have that enthalpy change will be equals to zero. So accordingly if you
consider that temperature is T then if you substitute that respective term here in this
balance equation, you can get the final temperature of 192 degrees Celsius.

So we can solve this status of solution based on this energy balance equation for the
assessment of you know what will be the amount of heat should be added or heat
should be removed for making a certain you know, extent of dilution of that solution.
So I think this problems will be helpful for you for further you know solving the
problems related to this problem there.

683
And for this, you have to you know sometimes you know use the you know data that
is given in you know tabulated for in appendix of this textbook. You have to consult
that data otherwise the data to be given for your assessment in the problem so that you
can solve the problem different you know problems related to this solution.
(Refer Slide Time: 37:41)

And its heat energy input and output to make this you know solution at its particular
condition of temperature and pressure. So in the next lecture, we will start the you
know new module where we will discuss more about that you know material balance
and you know energy balance there. But that material balance or energy balance will
be basically for the process where unsteady state you know operation will be there for
chemical engineering processes.

So next lecture we will discuss the portion on unsteady state material balance. So
thank you for your attention to this lecture.

684
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 24
Energy Balance with Heat of Reaction

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. We are discussing about that basic principles based on
material balance and energy balance equation.
(Refer Slide Time: 00:46)

So in the previous lecture we have discussed about the energy balances with multiple
streams without reactions and also the analysis of this energy balance equation based
on the examples on evaporator, drier, distillation column, etc. So in this lecture we
will try to again discuss about that energy balance with heat of reaction.

So in this lecture, we will discuss the heat of formation, standard heat of reaction and
also how to analyze those standard heat of reaction based on the heat of formation and
also with some examples.
(Refer Slide Time: 01:32)

685
Now you have to know what is that standard heat of formation because one of the
important you know aspect of energy balance when reactions will be involving in a
particular process. So for that you have to know that, how that chemical compounds
to be formed and during that formation, what will be the energy released or what will
be the energy you know are required to form that particular you know compound.

Now that will be actually regarded as standard heat of formation and here standard
means that is at a you know standard temperature and pressure what will be the heat is
actually required to form that particular compound it is called standard heat of
formation. Now this standard heat of formation you can actually estimate based on the
you know enthalpy or energy required for a particular reaction.

And by which that you know reaction is carried out and in that case the heat of
formation of you know each individual constituent that take part for that reaction at a
particular operating condition. If you know that enthalpy released or energy changes
caused by that reaction, then you can find out what should be the you know,
formation of that particular you know condition like, if it is at a standard temperature
and pressure then it will be called as standard condition.

So at that standard condition, what will be the you know energy required to form that
particular constituents which are actually taking place, which are actually participate
for that particular reaction. If I consider that there will be a certain change of enthalpy
due to the temperature change. So that will be regarded as sensible heat.

686
So if you know that sensible heat for that particular enthalpy change and if you know
that you know heat of reaction for that particular you know reaction then from that
heat of reaction if you subtract that you know sensible heat, you will get that you
know heat of formation of that constituent. So here in this slide it is shown that here
that heat of formation of any constituent which will be denoted by that delta H f i 0
hat.

Here see that this hat is basically that specific you know heat formation and 0 here
denotes the standard condition, f for formation, i for you know constituents or you
know that species there.

So Hˆ of ,i , it is basically that standard heat of formation of a constituent i but at the

specific you know condition that is a standard condition and also at specific you know
terms like per unit mass or per unit mole what should be that you know energy
required or energy released for that formation of that constituent. Now this Hˆ of ,i , if I

consider that the you know it is the heat released or absorbed by that chemical
reaction there.

Then we can have this standard heat of formation just by subtracting this you know
enthalpy change or you can say that sensible heat change by the change of
temperature from its you know standard condition if is there. Then you have to
subtract this. So from this subtraction of this you know energy from this heat of
reaction, you can easily calculate what will be the heat of formation there.

So to find out that heat of formation basically you need first to you know allow
reaction and then measure the that heat of reaction that is released. That should be
find out experimentally. So from that experimental value, then you can find out what
should be the heat of formation by this equation. And in this case, if you are changing,
you are seeing that, that is there any phase change there, then you have to include all
that enthalpy change because of that phase change.

687
So that is heat of you know vaporization, heat of sublimation, heat of you know
melting. So all those terms to be included also if there is a phase change there. If there
is no phase change then you have to easily you know omit those terms there.
(Refer Slide Time: 06:39)

Now, basically how you will define that standard heat of formation. So it is basically
defined as the enthalpy changes, which is associated with the formation of one mole
of the compound at 25 degrees Celsius and one atmospheric condition. This is called
standard condition from its element constituents as they are normally found in nature
like you know carbon, oxygen, nitrogen, hydrogen.

They are you know most important element constituents which are naturally occurred.
Now the heat of formations to be you know zero in this standard state for each
element of this carbon, oxygen, nitrogen hydrogen at 25 degrees Celsius and one
atmosphere. So which constituents are naturally occurring substituents or constituents
those you know heat of formation to be regarded as 0.

Whereas if any chemical compound is formed based on some other element then you
have to you know consider what should be the heat of formation for that particular
compound. We will do some example for this understanding.
(Refer Slide Time: 08:01)

688
Now before going to that, also you have to know at a standard condition, what should
be the heat of reaction and how to estimate that heat of reaction from the standard heat
of formation there. The standard heat of reaction is calculated as the difference
between the product and reactants enthalpies or you can say that heat of formation
when both reactants and products are at a standard conditions.

That is at 25 degrees Celsius and one atmosphere. Now suppose, there is a reaction
like here aA +bB which will give you the products of C and D. With this you know
that stoichiometric coefficient as shown, you know the reaction equation here in the
slide. So in this case, you can find out the heat of reaction at this standard condition
by this explanation here given in the slide like here
H rxn
o
 
Products
ni Hˆ of ,i  
Reactants
ni Hˆ of ,i

This is basically that enthalpy change or you can say that heat of reaction at a standard
condition, zero means here standard and rxn means reaction. So H rxn
o
this is basically
standard heat of reaction. And this can be calculated based on the difference of total
heat of formation of the products and the total heat of formation for the reactants.

So total heat of formation for the products can be you know calculated by this you
know terms here. This is basically a summation of all heat of formation of the
products components. Now here ni is the number of ith components in the products
and here Hfi. This is basically the heat of formation for that ith component. So in the
products if there are n number of components there.

689
So we can have this you know total you know heat of formation just by multiplying
this you know standard heat of formation of each components by the number of that
components there. And similarly, you can get that total enthalpy of formation just by
you know multiplying that heat of formation that is specific heat of formation with the
number of moles in reactants.

Now, if we consider this reaction equation where you will see that the reactants are A
and B as given here in the slide and products are C and D. Whereas they are you
know stoichiometric coefficients are a, b, c and d. Now in this case, you will see that
heat of reaction for this reaction, it will be as you know number of moles for products
here c and d for C and D respectively here.

Then we can calculate the heat of formation for the c as cHˆ of ,C . This will give you

the heat of formation for this component c. Similarly, heat of formation for the
component d in the products that will be your d Hˆ of , D and then you have to subtract

this enthalpy you know enthalpy of that reactants a and b as per this aHˆ of , A  bHˆ of , B

So what these up to this here, this is the you know total enthalpy of formation for this
products and this is basically the you know total enthalpy for you know that you know
reactants for the formation at that standard condition. So just by subtracting this total
heat of formation of the reactants from the products, you can get that heat of reaction
at standard condition.
(Refer Slide Time: 12:38)

690
In this regard if you have more than one reaction, then you have to apply you know
Hess laws. According to Hess law, it is basically if a set of reactions can be
manipulated through a series of algebraic operations, which will give you the desired
reaction, then the desired heat of reaction accordingly can be obtained by performing
the same algebraic operations on the heats of reaction of the manipulated set of
reactions.

That means here if you have more than one reactions like reaction one, reaction two,
reaction three, reaction four like this. And if you are having the respective heat of
reactions, like heat of reaction one, heat of reaction two, heat of reaction three, heat of
reaction four and so on.

Then, you can find out the you know the total or desired heat of reaction just by
performing just by manipulating by the heat of reaction by subtracting those or either
one from another one in this way. So this is called Hess law.
(Refer Slide Time: 14:10)

691
Let us do an example first giving only one reaction. This is not Hess law as per that
from the standard heat of reaction how to calculate the standard heat of reaction. In
this example, it is given calculate here the standard heat of reaction for the following
reaction given where this reaction ammonia is reacting with oxygen which will give
you that you know nitrous oxide with water.

Now in this 4 gram mole of ammonia is participating to react with oxygen to give the
production of nitrous oxide and you know that water. In this case, heat of formation at
standard condition in kilocalorie per gram mole is given as for ammonia -11.04, for
oxygen it is given 0, for nitrous oxide it is given 21.60 and for you know water it is
given -57.80.

Now as for you know that heat of reaction according to that principles of finding out
the heat of reaction from the heat of formation. So we can find out what should be the
heat of you know formation for this product side. It is basically here since the product
side is nitrous oxide and water. So here 4 moles of nitrous oxide that will require, that
will you know require that heat of formation is you know per mole it is 21.60.

So for 4 moles it will be 4 into 21.60. Similarly, for you know that for water, it is
given per mole that heat of formation is -57.80. Then what should be the total heat of
formation for six moles of water it will be 6 into -57.80. This is for simply you know
product side. Similarly, in the reactant side this you know ammonia, 4 moles of
ammonia there since it is naturally occurring.

692
So we can say that since oxygen is as naturally occurring so for that the heat of
formation for naturally occurring you know compound it will be zero. So we can say
right here 5 into 0 that will be your heat of formation for this oxygen. Whereas for
ammonia, 4 moles of the ammonia, heat of formation will be is equal to 4 into -11.04
as per mole of ammonia formation, it is required -11.04 you know kilocalorie heat.

So after simplification, we can say that the heat of reaction just by subtracting this you
know product side to the reactant side. So here we can get this amount minus 216.24
kilocalorie per 4 gram mole of ammonia. So in this way we can calculate the standard
heat of reaction from the standard heat of formation.
(Refer Slide Time: 17:38)

Let us do another example here to calculate the standard heat of reaction from the
standard heats of formation. Now in this case, if you consider that if production of
metallic manganese that 10 kg of manganese oxide are heated in an electric furnace
with 3 kg of amorphous carbon that is coke. In this case, it will give you the results as
a products which will contain 4.8 kg of manganese metal and 2.6 kg of manganese
oxide as a slack.

The remainder you know of that products consists of here unconverted charge of that
you know manganese and carbon monoxide gas which is actually produced during
that you know heating or there is a you know combustion of that manganese oxide

693
with that carbon. Then carbon will be you know producing carbon monoxide which
will be in oxidized based on that oxidation process in the furnace.

And then, according to this problem at a standard you know condition there you will
see that what should be the standard heat of reaction of this process for the entire you
know furnace charge you have to calculate. In this case it is given that 0.0413 kg mole
of manganese oxide used for the production of one mole of manganese and one mole
of manganese oxide.

As a data we can say that heats of formations at standard conditions are required. It is
given here the standard heat of formation for this manganese oxide it is given -331.4
kilocalorie per gram mole. Similarly, other you know heat of formations for
manganese oxide, manganese, carbon monoxide and coke are given here in the slides.
(Refer Slide Time: 19:48)

And based on this heat of formation of all those you know components you have to
you know calculate what should be the heat of reaction for this whole processes. Now,
in this case basis we can consider that since here 10 kg of manganese oxide and 3 kg
coke is used for this production of different components of you know that manganese,
manganese oxide, even carbon monoxide there.

So you have to first you know convert this you know in unit which will be consistent
in all cases. Now since it is given in terms of you know mole here in this case for
heats of formation at standard condition, but your charge is given in kg so you have to

694
convert it to moles first. So, initial amount of manganese oxide in you know it is
given in kg that is 10 kg it is given. So you have to convert it to moles or kg moles
just by dividing this 10 kg by its molecular weight. So it is coming as 0.0437 kg mole.
Initial amount of carbon it is 3 kg.

Then after conversion or it will be 0.25 kg mole just by dividing its molecular weight
and then manganese formed it is 4.8 kg. You will get 0.0874 kg mole just by dividing
its molecular weight. Similarly manganese oxide formed it will be 0.036 kg mole.
Now these are the you know components which are formed from this manganese
oxide.

You will see that there will be no hundred percent conversion of this manganese
oxide. There will be some unconverted manganese oxide to be remained in that
furnace. So what is that unconverted manganese oxide? Since this you know one mole
of manganese and manganese oxide formed you know has like this here, this amount
and this amount, that is 0.0874 and 0.036 mole there.

So for that, this 0.0413 kg moles of manganese oxide is required. Whereas, the
manganese oxide supplied as here 0.0437 kg mole. So what will be the unconverted
manganese oxide there? Just subtracting it you will get that 0.0024 kg mole. Now, for
this oxygen of this manganese oxide which is associated with that carbon to give you
that carbon monoxide which will be coming out from that furnace can be calculated
by this what will be that?

That that will be you know 4 into 0.0413 here. Here 4 means here 4 moles of oxygen
is required for that one mole of you know that manganese oxide conversion and then
you can say that 4 into 0.0413 and then minus here what will be the you know
manganese oxide form and here from that you can subtract this amount then what will
be the you know oxygen for that manganese oxide actually is required to you know
oxidize that carbon to carbon monoxide.

So here please correct it here 0.1286 kg it will be kg mole and since the you know that
0.0366 kg you know mole of oxygen is as manganese oxide. So we can say that this
amount will be subtracted from this total amount of you know that manganese oxide

695
and remaining amount will be you know used for conversion of carbon to carbon
monoxide.
(Refer Slide Time: 24:23)

Carbon monoxide form that will be is equal to then 0.1286 kg mole based on that
amount of oxidized oxygen and carbon and converted it will be simply subtracting
this you know conversion of carbon monoxide to that you know supplied carbon
there. So it will be you know 0.1214 kg mole.

Now as per that material balance of the process we can write this amount of you know
material is supplied or entering to that furnace, that is manganese oxide 10 kg, carbon
is 3 kg. Whereas materials that are leaving it will be as manganese is 4.8 kg,
manganese oxide 2.6 kg, manganese oxide here you know 0.55 kg, carbon monoxide
3.60 kg whereas carbon will be 1.45.

So this will be leaving from that furnace or you can say these are you know at the
outlet stream of that process unit. Now heats of formation of that reactants simply
here what will be that, manganese oxide. This is your heat of formation of this
reactant of manganese oxide and similarly heat of formation of this coke it will be you
know this amount.

So total heat of formation for this you know reactants it will be your -13.352 sorry
13352.6 kilocalorie.
(Refer Slide Time: 25:58)

696
And heats of formation of that production then this manganese oxide it will be you
know 3367.2 kilocalorie and then carbon monoxide it will be you know that 3397.1
kilocalorie and manganese is zero. So finally, total heat of formation for this product
side it will be -6764.3 kilocalorie.

Now as per that you know equation of that standard heat of reaction from that heat of
formation of that products and reactants, you can get this value of 6588.3 kilocalorie
after substitution of the values of that, you know heater formation for the products and
the reactants there. So in this way you can calculate you know heat of reaction from
the heat of formation of the constituents.
(Refer Slide Time: 27:01)

697
Now example based on Hess law, let us do this example here. In this case you have to
calculate heat of reaction for this C 2 H 6 from the following reactions. Here, you will
see that this first reaction that heat of, standard heat of reaction for this first reaction is
given to you. And the standard heat of reaction for the second reaction it is given to
you. Similarly, for third reaction this heat of reaction is given to you.

Now based on this, you know reaction one, two, and three you have to calculate the
heat of reaction for this ethylene to form this products of this here along with this
water, carbon dioxide and this.
(Refer Slide Time: 27:48)

So in this case, we can manipulate this you know reaction just by subtracting and
accordingly that heat of reactions just by adding, subtracting according to that Hess
law. So here also we can do the same fashion based on that Hess law that subtracting
the second reaction from the first reaction on one more basis, then we can have this
here just subtracting this equation from this first equation, then we can get this.

So here whenever you are subtracting this equation, accordingly you have to subtract
that heat of reaction also. So finally, we can get this here for this subtraction. Again,
this resulting reaction is to be added with the third one. This is why convention, you
have to think about how to do this to get this final equation for this ethane for
conversion.

698
Now in this case, you will see that again if you, you know add this third you know
reaction, you know with this resulting reaction, then you can have this final reaction
as C2H6 + 3.5O2, which will give you that carbon dioxide and water and accordingly
then you have to add this you know that is heat of reaction and finally you can get this
you know this heat of reaction like this.

So it is coming as 1558.3 kilo Joule. Now, accordingly heat of combustion of this you
know C2H6 then it will be -1558.3 kilojoule.
(Refer Slide Time: 29:39)

So here from this lecture, we understood that what is the heat of formation, how heat
of formation can be you know calculated based on the heat of reaction which is
obtained experimentally and also from this heat of formation how to calculate that
heat of reaction, whether it is single reaction or here multiple reaction.

Now for the multiple reaction by Hess law, you can manipulate these reactions along
with that heat of reactions just by manipulating according to your you know problem
and also convenience and then finally, you can get that total heat of you know
reaction based on this you know heat of formation at a particular condition. In this
lecture, we have described only at standard condition.

In the next lecture onward we will try to give some other examples, which are actually
not in standard condition. There will be a you know that heat of reaction at a certain
condition where you can get that there will be a change of you know enthalpy because

699
of that temperature change as well as you will see that there will be a enthalpy change
because of Hess change.

And based on that enthalpy change due to that temperature effect and also Hess
transformation, how that heat of reaction can be calculated at a particular operating
conditions. So we will be discussing all those things in the next lecture. Thank you.

700
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 25
Energy Balance With Heat of Reaction (Contd..)

Welcome to massive open online course on basic principles and calculations in

chemical engineering. We are discussing about energy balances on reactive system
under module eight. Now in this module, the lecture 8.2 we will discuss about energy
balance with heat of reaction, which is continuation of the previous lecture.

There we have described about different you know aspect of energy balances on heat
of reaction based on heat of formation and also we have described those heat of
reaction based on heat of formation with different examples.
(Refer Slide Time: 01:20)

Now in this lecture we will describe more about that energy balances with heat of
reaction and this heat of reaction will be based on that at operating conditions with
some examples there.
(Refer Slide Time: 01:33)

701
Now let us look back of that you know standard heat of formation based on which you
can calculate the standard heat of reaction, which is very important for calculation of
heat of reaction at any operating condition. Now what is that standard heat of
formation?

This is basically the formation of that constituents which are taking part in a particular
reaction and at the standard condition how these constituents are formed by you know
absorbing energy or releasing energy. So those amount of energy which is released or
adsorbed by formation of that constituent is called heat of formation at the standard
condition.

Now that heat of formation can be calculated based on that reaction, you know
enthalpy change or energy changed due to that reaction and which can be obtained
experimentally and based on that experimental data this heat of formation can be
calculated for that individual components which are actually taking part in that
particular reaction.

So we have described already this you know equation to calculate that heat of
formation for particular constituents.
(Refer Slide Time: 03:07)

702
Now since this is the enthalpy change which is associated with the formation of one
mole of the compound at 25 degrees Celsius and one atmosphere from its elemental
constituents. Now in the nature you will see that some components will be you know
occurring automatically or you can say that just in nature in an you know elemental
forms or some molecular forms like that oxygen, nitrogen, hydrogen etc.

Even some elemental forms like carbon there. So for those cases that standard heat of
formation will be considered as a zero there. So you have to you know, consider that
enthalpy change because of this, you know elemental constituents or this you know
molecular you know form in the nature that will be you know considered as a heat of
formation of zero.

But other compound which are formed during the reaction based on these elements
and also other you know naturally occurring compounds. For that, you have to you
know find out what should be the heat of formation at that particular operating
condition as well as what will be the you know heat of formation at standard
condition that you have to consider.

And based on that heat of formation, that heat of reaction to be calculated and also
this standard heat of reaction to be added whenever there will be a certain process and
if you have the change of enthalpy or energy change because of that you know
production of that some substances by the reaction.

703
And considering that reactants there and based on that enthalpy change of that
reactants and products, what should be the you know energy change along with that,
you know a standard heat of reaction that you have to consider for that standard heat
of reaction at a particular operating condition.
(Refer Slide Time: 05:24)

Now since we have described that to how to you know calculate the standard heat of
reaction at that 25 degree Celsius and one atmospheric condition, we have you know
given this equation here like you know H rxn
o
. This zero means here that denotes
standard conditions and rxn means reaction.

So this standard heat of reaction is basically what will be the change of you know
enthalpy of formation of each constituents in the products and reactants. And this
already described in the previous you know lecture that this heat of reaction can be
calculated based on this equation when there is a reaction is aA + bB that will give
you that products of you know C and D with that stoichiometric coefficient of you
know c and d.
(Refer Slide Time: 06:20)

704
Now in this case, what should be the heat of reaction other than that standard heat of
standard heat sorry standard you know condition like at operating condition other than
standard you know temperature and pressure. So in that case, if there is an effect on
heat of reaction, the heat of reaction or enthalpy change of reaction at that operated
condition to be defined by this equation as given in the slides here.
Q  H rxn
o
 
Products
ni Hˆ of ,i  
Reactants
ni Hˆ of ,i

So that heat of reaction will be released as Q and that is basically the change of you
know enthalpy during that reaction. And that is actually calculated based on this you
know enthalpy change in the you know product as well as you know reactants at that
operating conditions along with that you know standard he talked reaction.

So this component here in this reaction, you will be able to you know calculate that
summation of you know all enthalpy change at that operating condition for that you
know product components and this will be that you know enthalpy change for all
components in the reactants. And the subtraction will give you that enthalpy change
because of that reaction at that operating condition.

But you have to add what will be the standard heat of formation that with this change
of this enthalpy. So if you add this standard heat of reaction finally you know you will
get that net you know enthalpy change due to this you know heat of due to this you
know operating condition for this reaction.

705
Now here H rxn this is basically heat of reaction at operating condition. H rxn is

basically heat of reaction at standard condition and also H i , this is basically specific
enthalpy of components at operating condition. Now for adiabatic condition, this Q
should be equals to zero.

For such cases this summation of ni H i is calculated in terms of temperature here.

Here T is called that adiabatic flame temperature or temperature of reaction. So at a
certain temperature you will see that the change of this you know enthalpy for this
you know component i then you have to find out at which temperature this will
happen then that temperature to be found out and it is to be actually considered as a
flame temperature.
(Refer Slide Time: 09:17)

And overall if you have that heat of reaction at that particular operating condition as
negative, it will actually reflect that reaction will be as exothermic and in that case
energy must be removed from the reactor to prevent that temperature from the
increasing based on this reaction.

And if this enthalpy change is positive, that will you know refer to that reaction will
be endothermic. In that case, energy must be added to the reactor to prevent the
temperature from decreasing. Now the heat of reaction is nearly independent of
pressure at that particular you know temperature and pressure you will say.

706
The value of the heat of reaction depends on how the stoichiometric equation is
written and on the phase of the reactants and products are there. So based on this you
can calculate what should be the heat of reaction.
(Refer Slide Time: 10:20)

Now let us do an example for this theory. In this case we have given that a standard
heat of combustion of normal butane vapor as per this you know reaction equation
here C4H10 that is in gaseous form. That will you know be burned with that oxygen
here and after burning you will see that the carbon dioxide and moisture will be you
know coming out.

So in that case, the standard heat of reaction is found that -2878 kilojoule per mole.
Now you have to calculate the rate of enthalpy change if 2500 moles per second of
carbon dioxide is produced in this reaction and the reactants and products are all at 25
degree Celsius. So how to solve this equation here? Let us solve this equation.
(Refer Slide Time: 11:27)

707
In this case, we know that here the Hrxn that is heat of reaction, that is

H rxn  
Products at
ni Hˆ i  
Reactants at
ni Hˆ i  H rxn
o

operating cond. operating cond.

This is in you know that reactant side reactants and these are all products and then you
have to add the standard heat of reaction that is H rxn
o
.

For standard condition it is zero. So enthalpy change at the standard condition for
products and reactants are zero. We always you know consider these things that
therefore, per mole of carbon dioxide production, the rate of you know change of
enthalpy will be H .

This is specific terms, that will be equal to you know that this is zero, then minus zero
minus here 2878 divided by 4. Why it is coming because we know that reaction is
what? In this case C4H10 that is in you know gaseous form and plus 13 by 2 O2 here in
gas. That will give you 4 moles of carbon dioxide in gaseous forms plus you know 5
moles of water in liquid form.

So based on this reactions we are getting that since here product side is carbon
dioxide and water. So in this case, you will see that this product side here all are you
know naturally occurring substance. So here this enthalpy change will be equals to
zero for these components and for these components it will be zero.

708
So finally, what is that you will see that summation of all these you know product
components enthalpy at that condition will be equals to zero. That is why here this
zero is coming. Similarly for you know that this reactants, similar for reactants you
will see that here it is coming that this oxygen is naturally occurring.

And this is also butane, naturally occurring that is in gaseous substance that then
enthalpy change will be equals to zero. That is why it is coming as zero. Now another
terms is here heat of reaction is given that is -2878. So if you add it then it will be
coming this.

Now this is basically based on that one mole you know per mole if you are
considering that specific enthalpy change then you have to divide it by the
stoichiometric coefficient of carbon dioxide. So it is that is why here 4 there. So based
on this you can say that here it is coming after calculation -719.5 kilojoule per mole.

Therefore, we can say that since 2500 moles per second of carbon dioxide there the
rate of enthalpy change will be here it will be there, what will be the rate of carbon
dioxide production this is given 2500 moles per second of carbon dioxide. So we can
say therefore, for 2500 moles per I think in second that is of carbon dioxide flow or
production you can say the rate of enthalpy change will be it will be 2500 that is
moles per second.

Whereas, this enthalpy change is given here -719. So into -719.5, this will be your
you know kilojoule. So this is in terms of you know second. So here finally it will
come as it will be here 1.80 into 10 to the power 6 kilojoule per second. So this is
your you know final answer that how that you know enthalpy change that is specific
enthalpy change for moles of carbon dioxide will be there.

And if that carbon dioxide production rate is 2500 moles per second then total amount
of enthalpy change per second that will be is equal to 1.8 into 10 to the power 6
kilojoule per second. So in this way we can calculate that heat of reaction and then
you know finally, at a certain rate what should be the you know enthalpy change
there.
(Refer Slide Time: 17:19)

709
Now let us consider the system for enthalpy change you know for a mixture in a
process unit. In that case suppose a mixture enters and leaves the system after a
reaction taking place. So in that case, suppose component one and component two
enters and after reaction components three and four are left there as per you know
flow diagram given in this slide.

So here in this process unit, the component one and component two are coming as
input in this process in unit and after reaction in this process unit, you will see that
there will be some formation of components and you will see that components will be
leaving from this process unit as component three and component four as output.

Now based on this you have to calculate what should be the enthalpy change from this
inlet and outlet portion. So in that case you have to calculate what will be the enthalpy
change in output and what will be the enthalpy change in the input. So thus Hout
minus Hin that can be calculated based on that formation of that components in the
inlet and outlet.

Now in this you know outlet condition what will be the components that is component
three and component four and for that component three and component four what
should be the enthalpy change. Now that enthalpy change can be calculated based on
their you know heat of formation of that components.

710
Now heat of formation for this component three that is Hf. Now in specific form that

is Hˆ f 3 that is in zero that means in standard condition. So if you multiply it by n3

that means here suppose moles of components three there is n3.

Similarly, for component four similarly we can calculate it for that enthalpy change in
that you know total enthalpy in the inlet condition as here Hˆ f 1 and Hˆ f 2 and that

can be actually obtained from that you know that heat of formation of that respective
component one and two.

After that, you have to you know calculate that how that enthalpy change based on
that operating condition. Now if your operating condition is not that of standard
condition that is 25 degrees Celsius and one atmosphere, if it is changed at a certain
temperature and pressure then you have to calculate that enthalpy change because of
this temperature change.

So what is that enthalpy change or sensible heat change because of that temperature
that you have to calculate form this equation here. Here basically you have to know
that specific heat capacity for individual components in the inlet and outlet and what
is the temperature difference from that the standard condition or difference from the
reference condition up to that you know operating condition.

And then you have to integrate it based on this you know specific heat capacity if that
specific heat capacity depends on the temperature. If it is constant then is not required
to integrate here. Simply you have to multiply that specific capacity with the you
know moles as well as the temperature difference.

Similarly, you have to calculate it for you know, reactant or input you know
components and then output components along with that. So here these two terms will
be cancelled out if all components are at a standard condition. That you have to
remember that if you are considering only standard you know condition that means
your reference temperature and then T out or you can say that T in that will be your
reference.

711
So that is why here integration limit will be there at the same temperature. So here in
this case this dT terms will be zero. So basically this sensible heat will be you know
zero and this also will be zero. So accordingly we can say that at you know reference
temperature or standard condition, standard temperature, this sensible heat terms will
be cancelled out.

So other than this you know standard condition of course, you have to consider these
two sensible heat. Again, there if there is a phase change during that temperature
change, then you have to consider that enthalpy change during the phase change also.
(Refer Slide Time: 22:05)

Now let us have an example for this you know theory here. Now in this case it is
given that a you know magnetite ore you know that in different you know naturally
occurring different you know compound conjugated in a particular you know soil
form or stone form where it is called that you know ore and from where this ore after
processing we can get different you know valuable mineral particles.

Now in this case this is a magnetite ore, that is one important ore from which you can
you know separate that you know iron and from which we are getting different you
know product of that iron. Now during that you know ore processing there, a
magnetite ore that will contain you know 100% suppose Fe3O4 now it is to be
subjected to reduction by pure carbon in an externally heated you know, retort there.

712
So in that case this you know magnetic ore or magnetite ore is generally is bond with
carbon at a certain temperature and then you will see that after bonding you will see
that this you know this iron ore will be you know separated into a different products
after reduction. And it is seen that 95% of that iron ore present in you know is reduced
to the metallic state while the remaining that is 5% is converted into you know,
ferrous oxide.

So according to that, according to this following equations given here as one and two
in the slide, you see here that this iron ore Fe3O4 with carbon, it will give you that
metallic form of you know iron as and also you know that carbon monoxide. And
again this you know ore also will give you that ferrous oxide and carbon monoxide
there as equation number two.

Now the amount of carbon to be charged is 400% in excess of that required according
to equation one. Now the reactants enters at a temperature of 200 degrees Celsius and
the products both the solids and gas leave at a temperature of here 950 degree Celsius.
Now calculate the material balance for the process on the basis of 100 kg magnetite
that is charged into the you know retort.

Also have to estimate that heat requirements for the process based on 100 kg of
magnetite ore that is charged. Now following data are given to you like a specific heat
capacity of that you know compound here, Fe3O4 it is given as 0.18 and ferrous oxide
it is given to you. Even iron it is given to you. Carbon it is given to you.

Carbon monoxide also it is given to you. So all are specific heat capacity. And
similarly, standard heat of formation of all those compounds also given at standard
condition that is at 25 degrees Celsius and for that for iron you know oxide that is ore
the standard heat of formation it is given, -267 whereas ferrous oxide it is given is -
64.3 and carbon monoxide it is given as -26.4.

We have to solve this problem to estimate the heat requirements for the process based
on 100 kg of magnetite ore that is charged into the retort. What to do here, you have
to write first what is the basis for this.
(Refer Slide Time: 26:21)

713
So the basis of this you know problem to be considered as know 100 kg of magnetite,
and your reaction is Fe3O4 plus 4 moles of carbon, which will give you the 3 moles of
iron plus 4 moles of carbon monoxide as reaction one and the second reaction again it
will be Fe3O4plus carbon one mole, which will give you the 3 moles of ferrous oxide
plus 4 moles of carbon monoxide.

And here we can say that this equation, these two equations will be used to you know
calculate first in terms of you know moles what is charged and what will be the most
of that products are formed there. So from equation one, from equation one we can
write 232 kg of Fe3O4 requires 12 into 4 kg of carbon.

Why 12? 12 is the molecular weight of carbon and here since 4 moles of carbon is
required, so here 4 into 12 kg of carbon is required. So here 232 is basically that
molecular weight of this Fe3O4. So we can say that, since 100 kg of this ore is
charged, so 100 kg of Fe3O4requires then 48 divided by 232 into 100. That will be
equals to 20.7.

This is you know kg of carbon. So this amount of carbon to be you know required to
you know bond this you know 100 kg of iron ore there. So carbon charged will be
equals to 20.7 into 4. That will be equals to here 82.8 kg. Now Fe3O4converted we
know that by this reaction one, by this reaction one will be equal to 95 kg.

714
So Fe3O4 converted by reaction two will be equals to 5 kg. So we can write here
carbon required by reaction one. So carbon required by reaction one will be equal to
48 by 232 into here 95 kg. So it will be coming as 19.66 kg. Similarly, carbon
required by reaction two that will be is equal to 12 by 232 into 5.

So it will be coming as 0.26 kg. So this amount of carbons are required for this
respective reaction one and two. Then what will be the total carbon used.
(Refer Slide Time: 32:00)

Therefore, total carbon used in this two reactions that will be is equal to first one is
19.66, second one is 0.26 kg. So total it will be coming as 19.92 kg. And then carbon
excess here, will be is equal to what is carbon supplied, what is the amount of carbon
supplied? It is 82.8. Whereas, required amount is 19.92.

If you subtract this amount then you will get that carbon in excess. That will be is
equal to here it will be coming as 62.88 kg. So this amount of carbon will be in excess
in the retort. Now we have to find out what will be the iron is produced based on this
reaction one and reaction two.

Iron produced based on reaction one, that will be is equal to, you know that 3 kg is
produced out of 232 kg of that iron ore into here it will be 56. Here 3 into 56 means
molecular weight of iron is 56, 3 to 56. This amount of you know iron will be
produced out of 232 kg of you know magnetite ore that is you know as per reactions.

715
You have that you know total 95 kg of iron you know there. So it will be here iron
oxide there. So total iron produced based on this 95 kg of magnetite ore, it will be
here 68.8 kg. Similarly, iron produced based on reaction two it will be is equal to 3
into 72 divided by, this is iron oxide FeO, ferrous oxide is produced.

Based on reaction two it will be here 3 into 72 divided by 232 into what will be the
amount of here you know, iron ore there in the reaction two this is 5. So it will be
coming as 4.66 kg. And carbon monoxide produced based on reaction one that will be
is equal to 4 into 28 divided by 232 into magnetite ore amount is 95 in reaction one.

So it will be coming as here 45.86 kg as per calculation. Similarly, we can say that
carbon monoxide produced based on reaction two it will be here simply 28, since here
is one mole. So this is 28 by 232. This is molecular weight of magnetite ore into what
will be the amount of you know magnetite ore is taking part in that reaction two, it is
5 kg.

So total amount will be equals to 0.60 kg of carbon monoxide that is produced based
on the reaction two. Therefore we can say that total carbon monoxide produced, total
carbon monoxide produced based on two reactions that will be is equal to 45.86 +
0.60 that will be as 46.46 kg. So this amount of total carbon monoxide will be
produced.

So we are getting different components that are produced based on that reaction as
well as what are the you know that materials that is entering into the retort that is iron
oxide ore or magnetite ore and carbon.
(Refer Slide Time: 38:00)

716
So we can summarized here as here material entering, and material leaving. So we can
say here the material entering as Fe3O4, this amount is 100 kg. Carbon, this amount is
82.2 kg. Then total 182.2 kg. Similarly, material leaving iron as a metal that is 68.8
kg. FeO that is ferrous oxide, it is 4.66 kg.

Carbon monoxide it is coming 46.46 kg. Similarly, carbon it is 62.88 kg. So here total
amount that is leaving the retort it will be after summing up, it will be coming as
182.2 kg. So here we can say that as per material balance input and output will be
same.

Whereas as output, we are getting different components based on that you know
reaction conditions or reaction, you know component material balance. Next we have
to do the energy balance. Now in this case you have to first consider that what will be
the enthalpy of reactants at reference temperature.

So we say that here enthalpy of reactants reference temperature is 25 degree Celsius.

Reference temperature is 25 degree Celsius based on which we can say enthalpy of
this you know inlet condition delta H sorry HFe3O4 for this component. This will be is
equal to this amount is 100 kg and specific heat capacity is given as 0.18.

And then temperature difference is here at 250 degrees Celsius this is burning
reference temperature is 25 degrees Celsius. So this enthalpy for this you know
magnetite ore at its you know inlet condition as a reactant, this will be coming as

717
4050 kilocalorie. Similarly, you have to calculate the enthalpy for carbon for the
change of temperature of 250 degree Celsius from this reference temperature.

Whereas this carbon amount is given 82.2 kg at its inlet as a reactant. What is the
specific heat capacity? It is given 0.3 and the temperature difference is 250 – 25. Then
it will come as 5589.0 kilocalorie. So summation of this enthalpy for this reactant that
will be is equal to you know enthalpy of reactants, it is called enthalpy of reactants.

So it will be equals to here 4050 + 5589. So total amount will be is equal to 9639
kilocalorie. So this is your total enthalpy in the reactant side. Now similarly you have
to calculate what will be the enthalpy of product.
(Refer Slide Time: 44:04)

So enthalpy of product. Enthalpy of products based on this reference temperature is

25 degrees Celsius. So you can say that here, product side as enthalpy of this iron
metal that will be is equal to amount is 68.8 as per material balance into you know
specific heat capacity is given 0.13.

And temperature difference is here at the outlet condition temperature is 950 degrees
Celsius and the reference temperature is 25. So finally it is coming as you know some
amount that is what is the amount that you can calculate it here. Similarly, HFeO you
can get it 4 point similarly 66, into 0.18 specific heat capacity, the temperature
difference again 950 - 25 here.

718
Similarly enthalpy for carbon monoxide, total amount of carbon monoxide is pound
as per material balance is 46.46 kg into specific heat capacity is given 0.27 and the
temperature difference is 950 – 25. So what will be the amount that you have to
calculate.

What will be the, so enthalpy of remaining that carbon, which is not you know taking
part in the reaction that is which is in excess that can be calculated as here, that
amount is 62.88 kg. And specific heat capacity it is given 0.3 and the temperature here
950 minus reference temperature 25. Then what will be the amount.

Then total enthalpy of this you know product we can get here simply enthalpy of
products that will be is equal to HFe + HFeO + HCO + HC. So it will be coming as total
amount after substitution of all these values here it will be coming as 38091.5
kilocalorie. So this much of enthalpy will be for the total product components for the
change of temperature.

Next, you have to calculate based on this what will be the heat of reaction. Heat of
reaction we have to then calculate heat of reaction. Now for first reaction, for first
reaction, we can say that HR1, R for reaction, 1 for reaction one.

So this will be equal to

H R1   H f , P   H f , R

summation of Hf,P for product, f for formation p for product minus summation of
Hf,R for reactant here, here f for formation and R for here reactant. So it will be
coming as 4 into Hf of CO (carbon monoxide), this is for product minus here Hf, f
for formation for Fe2O3.

So this will be coming as 4 into -26.4. This is given to you minus -267.0. So finally it
is coming as 161.4 kilocalorie per gram mole. Similarly, for reaction two. We can say
delta HR2 that will be is equal to 3 into -64.3 of this product iron oxide that is FeO
plus -26.4 that is for carbon monoxide.

719
This one for product side minus reactant side there it will be you know minus of 267.0
this amount. So finally it is coming as you know 47.7 kilo calorie per gram mole. So
heat of reaction for the first reaction it is coming 161.4. Whereas for second reaction
it is coming here 47.7 kilocalorie per gram mole.
(Refer Slide Time: 52:04)

Since we can have this in terms of mole we can say that here Fe3O4 converted by
reaction one is equal to 95 kg this is basically 95 by 232. This is 0.409 kg mole.
Similarly, we can say that for other components also and accordingly H that is
enthalpy change for reaction one, it will be is equal to 161 point 161400.

Since it is you know kilocalorie per gram mole, so kg mole it will be here into here it
will be 0.409. Then it is coming as 66012.5 kilocalorie. And Fe3O4here converted by
reaction two that is amount is 5 kg. This is basically 5 by 232 kg mole. Then it will be
0.022 kg mole.

So enthalpy change for this reaction two that will be is equal to then if you multiply
moles of this you know conversion of Fe3O4then it will come as here 47700 into 0.022
that will be 1049.4 kilocalorie. So total enthalpy change for these two reactions HRxn
that will be equal to or we can say summation of HRxn for reaction one and two.

So we can say that HR1 + HR2. So it will be coming as here as first one is 66012.5
plus for reaction two it is 1049.4. So total amount is coming as 67061.9 kilocalorie.

720
Therefore, heat requirement as per problem, heat requirement that will be is equal to
q.

This is basically summation of Hp plus summation of HR minus summation of H

reactant. This is reactant and this is product and this is heat of reaction. Now finally it
will be coming as, what is that product side enthalpy, summation of that.

This is earlier we have calculated this is 38091.5 plus here heat of reaction is 67061.9
minus summation of enthalpy change because of that reactant components formation
that is you know that 9639. So finally it is coming 95514.4 kilo calorie.

So this mass of heat is required to bond that magnetite ore to get that metallic iron
along with other you know gaseous components. So in this way, we can do the
material balance as well as energy balance to find out the materials required or
materials supplied which are taking part to the reactions.

And based on that reaction you know enthalpy change we can have what will be the
total heat is actually required for the complete combustion of that ore to find out this
metallic form of that metals as per reaction.
(Refer Slide Time: 58:35)

Now these are all about that open process okay based on that reaction. Now suppose if
reaction is going on in closed process and the reaction is taking place in a system
where the volume will be kept constant and in that case the change in the internal

721
energy of the reaction will happen and you have to find out that change of internal
energy based on that reaction.

Now the change in that number of moles during that you know combustion of that,
you know moles from its reactants to the product in that closed system, there are
different components will be formed. Now the change of that you know reactant
moles will be there.

And you will see that the change in that number of moles will be equivalent to the
change in the number of stoichiometric coefficient between the product and the
reactant. So in that case, we can write that what will be the internal energy change,
because of that reaction in the specific terms like here specific heat of you know
internal energy.

Then in that case that internal energy change will be is equal to what will be the
enthalpy change for that reaction and in specific form. And then you have to you
know calculate due to that temperature change and because of that you know closed
system you will see that there will be a stoichiometric ratio changes because of that
you know change of that you know pressure.

So based on which you can say total that you know that pressure and you know
volume inside that reaction in the inside that you know closed system will be
changing and that will change because of that you know what will be the you know
stoichiometric coefficient of that product and stoichiometric coefficient of the you
know reactants.

And based on which that net you know amount of moles change because of that
reaction in the closed system. There will be a you know change of that you know
pressure and volume because of that temperature change there. That can be calculated
by this term here it is given.

So internal energy change can be calculated by this equation here based on that
reaction where here you will see that this nu i is the stoichiometric efficient of the

722
gaseous reactants or products components that is positive for the product and negative
for the reactant to be considered.
(Refer Slide Time: 1:01:44)

Now let us have an example here based on this concept. Now in this case you have to
calculate the specific internal energy change of reaction of the following given at a
standard conditions at 25 degrees Celsius and at one atmosphere. The reaction is here
C2H4 + 2Cl2, which will give you that C2HCl3 as a liquid and hydrogen and hydrogen
chloride gas.

In this case the specific enthalpy change of reaction at standard conditions is 25

degrees Celsius and one atmosphere is given here -420.5 kilojoule per mole. Let us
solve this problem here again based on that concept.
(Refer Slide Time: 1:02:42)

723
Now here apply this equation of internal energy change like U hat that is for you
know reaction. This is basically enthalpy change,
 
U rxn  H rxn  RT  vi   vi 
ˆ ˆ 
 gaseous 
 products gaseous 
 reactants 

So based on this equation, we can then write here Uˆ rxn that will be is equal to, it is
given that enthalpy change for this minus 420.5 minus RT, R value is 8.314 that is in
joule by mole K into here you have to convert it to kilojoule. Here 1000 joule. This is
basically one kilojoule.

Then temperature is here 298.15 Kelvin into here you know that product side
stoichiometric ratio as per reaction, what is that reaction? Let us write this reaction
here again. C2H4 that is in gaseous form plus 2Cl2 that is chlorine gas in gaseous form.
Here it will be forming as chloroform C2HCl3 (l) and plus H2(g) and then hydrogen
chloride in gaseous form.

Now here in this product side the stoichiometric is one plus one plus we can see that
here we can write here 1 + 1 plus here what is that? We have not to consider that here
the liquid form. So only 1 + 1 that is gaseous forms to be considered. And then, what
will be the here we can say this is basically this is 0 + 1 + 1.

724
Then here minus and the product side it will be here C2H4it is one and then minus. It
will be chlorine is I think 2. So finally, you will get this much and after simplification
and calculation we can say that it will be -418.02 kilojoule per mole. So this is your
internal energy change because of this reaction in a closed vessel where you will see
only temperature can be changed.

But if it is you know that adiabatic you know chamber or closed vessel, there will be
no change in temperature. So at constant temperature you have to consider that. If you
are having that temperature change, then you have to consider also at what
temperature you are going to calculate this internal energy change that temperature to
be considered there.

I think we have done enough example for understanding the you know enthalpy
balance or energy balance with you know heat of reaction calculation and also in open
systems also if there are several you know components as a reactants and in the
product side also there are several components as a product side components and how
their enthalpy changing whenever temperature will be changing from its reference
temperature.

So I think you understood this you know this energy balance with this reaction in
open system and closed system. So in the next lecture we will try to discuss more
about that energy balances of you know, heat of combustion. During that combustion
how you can calculate that you know enthalpy change based on that product and you
know reactant side components and their formation. So thank you for your giving
attention.

725
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 26
Energy Balance with Heat of Combustion

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. So we were discussing energy balances on reactive systems
with examples. So in this lecture we will try to discuss about the energy balance with
heat of combustion with some examples.
(Refer Slide Time: 00:56)

In the previous lectures we have described the energy balance with heat of reaction
and analysis with different examples. Now previous lecture, we have given that
equation for calculating that heat of formation from the heat of reaction that is
experimentally obtained for the case where there will be no phase change.

Also, we have described the heat of reaction based on you know heat of formation for
the compounds which are taking part in particular reactions. We have also you know
described about the heat of reaction, how it can be calculated based on their operating
condition in a particular systems.

That means when temperature is changing from reference temperature to a certain

temperature, how to calculate that heat of reaction that we have given and that heat of

726
reaction to be actually calculated based on the you know heat of formation of reactant
and products components also sensible heat change for that reactants and products for
changing the temperature as a sensible heat.

And then along with this differences in enthalpies you have to you know add that heat
of reaction at standard condition.
(Refer Slide Time: 02:41)

So based on these principles we have already described all these things and analyzed
based on different experiments and different examples there in the previous lecture.
(Refer Slide Time: 02:53)

In this lecture we will try to discuss about that standard heat of combustion. You
know that there are several combustion reactions are there to you know, you know

727
obtain the products as you know carbon dioxide, carbon monoxide along with
valuable products after combustion. So in that case, how to calculate that standard
heat of combustion there at a standard condition.

Now this is basically the enthalpy change when one mole of reactant completely
burns in excess of oxygen under standard thermodynamic conditions and the standard
heat of combustion of the species suppose if there is a species i,

So we can say that this standard heat of combustion can be you know represented by
this delta H c i will be the enthalpy change which will be associated with the complete
combustion of one mole of species i with oxygen at standard condition of 25 degrees
Celsius and one atmosphere. Now what is the complete combustion actually?

For complete combustion, you will see that there will be a conversion of all carbons
into a carbon dioxide gas and all the hydrogen that is in the you know main
components which is to be combust which is to be burnt will be converted into you
know water.

And all the sulfur if it is there in the you know, feed components which are actually to
be burned, it will be you know converted to sulfur dioxide after complete combustion.
And all the nitrogen similarly, will forms nitrogen dioxide. So in this way, you can
say that when there will be a complete combustion of any you know compounds then
you will see that what should be the heat of combustion and how to calculate there.
(Refer Slide Time: 05:11)

728
As we know that standard heat of reaction that is actually obtained based on that heat
of you know formation of that constituents, which are taking part in the particular
reactions.

So in that case we have described that standard heat of reaction is calculated as the
difference between the product and reactant enthalpies that is heat of formation where
both reactants and products are at standard conditions that is at 25 degrees Celsius and
one atmosphere. So according to that, you know principles we are actually calculating
that standard heat of reaction by this equation.
H rxn
o
 
Reactants
ni Hˆ co,i  
Products
ni Hˆ co,i

Here, standard heat of formation for all products components and standard heat of
formation for all reactant components and subtracting that will give you the standard
heat of reaction. Now standard heat of combustion can be actually again that
estimated or calculated from the standard heat of combustion and based on this you
know reaction.

So here standard heat of reaction that is here can be calculated here like this here if
you know that reactants components which are taking part in the reactions. Now for
those components what should be the standard heat of combustions there and then the
standard heat of combustions for that reactants, what will be the total amount of that
enthalpy change because of that combustion for that constituents in reactants.

729
Similarly, what will be the total amount of enthalpy change for the constituents of
products when you know that, that specific enthalpy of combustion is there. So from
this actually, you can calculate that heat of reaction from the you know standard heat
of combustion.

So, this is basically the same way, how you are calculating the standard heat of
reaction from the standard heat of formation. Here also that same way same fashion,
that you can calculate the standard heat of reaction from the standard heat of
combustion of the constituents. But in this case, you have to remember that, you are
going to subtract this you know that enthalpy change from the reactants of you know
there.

But whereas, the standard heat of reaction whenever you are calculating from the
standard heat of formation there you are subtracting the you know standard heat of
you know formation of that reactants from the you know product side.

So basically here we can say that standard heat of reaction will be is equal to negative
of standard heat of reaction from the standard heat of combustion. So from this you
know equation you can easily calculate what should be the standard heat of reaction
from standard heat of combustion there.

So you have to remember this format. Only thing is that you have to know what
should be the standard heat of combustion for individual components or individual
constituents of that reaction there. So simple way to calculate that standard heat of
reaction from the standard heat of combustion.
(Refer Slide Time: 08:41)

730
So let us do an example here like carbon, solid carbon is you know
reacting with you know, a hydrogen gas, which will give you that C5H12 here as
liquid. Now from this reaction, we can say that carbon, hydrogen and pentane you
know can all be burned and their standard heat of combustion can be you know
determined experimentally.

Now the standard heat of you know reaction from that standard heat of combustion
can be then calculated here. So H you know Rxn at standard condition that will be is
equal to here what will be the in this case here reactants minus you know products
that you have to remember here.

So 5 into you know standard heat of combustion. For combustion we are writing c,
whereas for formation we are writing f. So Hc here at standard condition for the
constituents here reactants is c that is carbon as here solid and plus other constituents
in the reactant side is hydrogen.

So your stoichiometric coefficient is here 6, so 6 into H here of combustion of

hydrogen gas at the standard condition minus what will be the standard heat of you
know combustion for this you know product of this pentane that is C5H12 in liquid
form.

So from this you know equation you can calculate what will be the standard heat of
reaction from this standard heat of combination of all these constituents. Now if any

731
reactants, suppose if any reactants or products are combustion products. Let us have
example here.

Like suppose carbon dioxide, water, sulfur dioxide, then their heat of combustion, are
equal to zero. As what we have discussed earlier also for naturally you know existing
any gas or substances you will see that heat of formation will be equals to zero.

Similarly, here also we can say that this you know products of combustion here like
carbon dioxide, water and sulfur dioxide all will have their heat of combustion will be
equals to zero. Now the standard heat of formation as like this here according to this
here c instead of c it will be coming as f there.

But here you will see that standard you know heat of reaction in this case here we are
considering first reactants and products. And but standard heat of reaction in that case
in case of you know that formation, we have to write it in just negative of this heat of
reaction by combustion here.

So if we represent it as per combustion, so we can write here standard heat of reaction

of as for you know formation f, so we can write here this s you know that H here f
instead of c. Here product side will come first.

Then it will be C5H12 as liquid, then minus it will be 5 into delta H formation of this
you know carbon solid minus here 6 into H at standard condition for this formation
of this you know hydrogen gas there. So in this way we can calculate. So here this is
basically the you know reactant and here this is product for standard heat of reaction
from combustion.

But here in this case, it is you know that this will be this, this is actually this one will
be you know that product where this to this will be your, you know reactant. You can
subtract it here like this also. Here in this way also you can represent. So this is the
you know standard heat of reaction which are obtained from heat of combustion and
heat of formation.

732
And how they are related? Simply since here Hrxn this is combustion, we will be is
equal to negative of H. Here rxn that is reaction at standard condition based on
standard heat of formation, okay.

Next, we will do another you know example for this like here suppose you have to
calculate the standard heat of reaction as follows from the standard heat of formation
and standard heat of combustion for this you know reaction given in the slide.
(Refer Slide Time: 16:02)

In this case ethanol will be you know reacting with oxygen which will give you that
carbon dioxide and water after complete combustion. Now in this case the heat of
formation of ethanol, carbon dioxide and water are respectively given as -277.63, -
393.51 and -285.84. And heat of combustion of ethanol is given as -1366.91.

So based on this you have to calculate what will be the standard heat of reaction based
on this standard heat of formation. Since it is you know that combustion reaction so
first of all we have to find out what will be the standard heat of reaction based on this
value given for standard heat of formation of all constituents here for the reactants and
product sides.

So as a solution we can write here we can first calculate that from the standard heat of
formation, from the standard heat of formation we can write Hrxn at standard
condition in kilojoule per, it is given kilojoule per mole. That will be is equal to here
what should be the first we have to consider here product side.

733
The for the product side we can write here this 3 into for water what is the standard
heat of formation it is given. This is -285.84 plus here 2 into for carbon dioxide it is
given -393.51. Then minus in your reactant side or specific heat of you know that
standard condition of heat of formation for those components are like this.

So accordingly what is the stoichiometric component or coefficient for this reactant

side here. For ethanol it is one. So we can write one into for ethanol this standard heat
of formation is given -277.63 and then minus the stoichiometric coefficient of oxygen,
it is 3. So 3 into what is the specific heat of combustion at standard condition for
oxygen it is given or not.

It is not since it is a naturally occurring compound, so you have to consider it as zero.

So finally, we can get after you know calculation then you can have this -1366.9
kilojoule per mole. So in this way, you can calculate what will be the standard heat of
you know reaction based on the standard heat of formation.

Similarly, we can then calculate the standard heat of combustion from the you know
reaction as like this.
(Refer Slide Time: 20:12)

Here in this case the standard heat of reaction for combustion that will be is equal to
what negative of you know that Hrxn at standard condition of formation. So like this
you can get it or otherwise

734
you can get the standard heat of you know combustion based on the standard heat of
you know combustion of individual constituents.

Now if we consider that standard heat of actually combustion for ethanol delta H you
know combustion at standard condition for C2H5OH. This is basically you know -
1366.9 kilojoule per mole. And also you can say that standard heat of combustion for
other components in this reaction here Hc of degree here oxygen since it is naturally
occurring substance this will be equal to zero.

Similarly Hc for you know carbon dioxide it will be 0. Similarly, Hc that will be for
water, that also zero. So based on the you know formula for standard heat of
combustion reaction, So Hc of reaction that is you know that we can say here rxn for
combustion, that will be is equal to here H is summation of delta Hc of combustion
in of i minus, this is in product side.

Sorry this is reactant side, reactant and minus summation of Hc standard heat of the
combustion into you know ni. This is actually for product side. So based on these we
can say that since here we are getting these reactant or like you know that methanol.
Okay let us write this equation first. C2H5OH that is liquid plus 3 oxygen that is gas
that will give you to 2CO2 here gas plus 3 water, liquid.

Now in this case what are the reactant side? These are the reactant side. So according
we can write here, it will be basically number of moles of that ethanol is according to
this reaction is one. So it will be here and standard heat of condition for this ethanol is
given to you. This is -1366.9 and then plus other components here.

Then 3 into oxygen here it is zero minus here it will be, what is that combustion for
product side. This is 2 into then carbon dioxide here again zero plus here 3 into for
water it is zero. So here we can say finally after simplification, it will be coming as -
1366.9 you know kilojoule per mole. So this one in this way you can you know
calculate the standard heat of reaction based on the combustion reaction.

735
But since we have calculated earlier the standard heat of formation and its value was
here minus you know 1366.9. So accordingly we can say that this value will be
coming as here standard heat of combustion will be is equal to this simply here again
the 1366.9 kilo Joule per mole.

So you can say here in this way you can simply calculate what should be that standard
heat of combustion and standard heat of formation based standard heat of reaction. So
both are, in both cases we are we are having the same results for standard heat of
reaction.
(Refer Slide Time: 25:43)

Let us do another example. In this case, calculate the standard heat of reaction from
the you know dehydrogenation of ethane using the standard heat of combustion. This
reaction is given to you here in this case dehydrogenation of ethane giving you that
here ethane and hydrogen.

Now standard heat of combustion for this you know ethane and ethane is given to
you, ethylene is given to you and hydrogen also is given to you. So ethane is given to
ethylene and hydrogen gas and their respective heat of combustions are given like
this. So based on this you know standard heat of combustion you have to calculate
what will be the standard heat of reaction.

So again you can then write the same principle of calculating standard heat of reaction
for this combustion reaction. It will be is equal to Hc for this you know ethane C2H6

736
and this is your you know reactants minus here it will be Hc you know combustion
at standard condition for ethylene C2H4 plus here Hc here combustion for you know
hydrogen gas.

So in this case if we substitute the value of this standard you know heat of combustion
for its constituents, then you can right here, this will be is equal to minus here 1559.9,
this is for ethane, minus here for ethylene it is given -1410.99 and plus here for
hydrogen it is given -285.84 like this.

So after calculation, we can have this heat of reaction as -136.93 kilojoule per mole.
So in this way you can calculate what will be the standard heat of reaction based on
the standard heat of combustion, okay. And then we can have another example for
this.
(Refer Slide Time: 28:48)

Like you have to calculate the heat of reaction of the following reaction from the
standard heat of combustion data. Here ethyl alcohol will be you know, reacting with
acetic acid which will give you that ethyl acetate and water. In this case one gram
mole of ethanol is considered.

And based on this your standard heat of combustion for each components at 25 degree
Celsius and one atmospheric condition is given as for ethanol it is given. For acetic
acid also it is given. Here ethyl acetate is given. For water it will be zero of course. So

737
based on this example, how to calculate the you know standard you know heat of
combustion.

So here again as per same principles you can you know calculate this as here then
standard heat of reaction that will be is equal to here as per combustion, it will be is
equal to what this minus of this is you can say that minus here 1366.91. This is for
reactants and plus here -2274.48. Here this is your reactant side.

And then minus of minus you know that 871.69. Then here you can say that minus of
again 0 for water and we can say that here within a bracket and then finally, third
bracket closed. So after substitution of this, you know constituents value in the
reactants and product side.

And finally we can get after calculation it will be coming as positive of 35.9 kilojoule
per gram mole. So in this way you can have this value of heat of reaction from this
standard heat of combustion.
(Refer Slide Time: 31:22)

Now we will discuss about that heat of reaction at constant pressure versus constant
volume. In this case whatever you know condition for standard heat of reaction,
standard heat of combustion, that will be a certain you know pressure and certain
volume there.

738
If it is suppose closed vessel or if it is open condition or open vessel system, open
process unit system there accordingly how to calculate that standard heat of reaction,
standard heat of you know formation, standard heat of you know combustion, that we
have described. And also based on that you know operating condition how to
calculate the standard heat of reaction based on the standard heat of formation.

Even a standard not only the standard condition you can calculate heat of reaction at
other operating conditions also if there is a temperature change. So based on which
we have calculated also, because of that sensible heat change by you know
temperature change.

Now the condition is that in this case what should be the standard heat of reaction at
constant pressure and also what should the standard you know heat of reaction or heat
of reaction at constant volume. Now sometimes this will be you know applied for a
certain you know, chemical engineering operation like for you know proximate
analysis.

Or some other analysis of you know particles in a closed system at constant

temperature and also constant you know volume, constant pressure. So how to find
out that heat of reaction when it is done in a closed you know volume at a constant
volume and at a constant pressure there.

Now considered the heat of reaction of a substance that is you know obtained in a
bomb calorimeter. It is basically you know that a constant volume system, but there
pressure is not keeping constant and it is a closed vessel where there will be a certain
you know, combustion reaction is taking place.

Now for such process in this case, material in the bomb as shown in the figure here,
see this is a totally you know sealed you know volume here as shown in the diagram.
That you will see that inside that you know bomb, there is you know crucible is kept
and then in this crucible some solid particles to be burned by you know supplying
some heat energy there.

739
And then also according to that supplying energy and also the you know in presence
of oxygen, otherwise the burning will not be there. So oxygen will be you know
supplying from inlet of this closed system there. And there will be a airtight sealing of
this you know bomb calorimeter system where you know that outside this system
some you know water to be there.

And a certain temperature to be maintained in that water bath. And based on that at
constant temperature and constant volume what should be the heat of you know
reaction that you have to find out by this bomb calorimeter. Now for such systems
then I can say that the general energy balance will be reducing to here you know delta
U that is total you know internal energy change that will be is equal to Ut2 – Ut1.

Here at a certain time interval this you know reactions will be you know allowed to do
there. So in that case total heat energy will be changed between during this time
interval and as per that general energy balance equation. Of course some other terms
will be there like shaft work, even here also kinetic energy, potential energy will be
there.

Since it is a closed vessel, there will be no flow of the you know materials there and
also there will be no energy or work done on this system externally by any you know
pump or some other you know, mechanical device. So in that case we can consider
that there will be no work done there and there will mass flow rate also here since it is
a batch wise process.

And there is no kinetic energy change because there is no flow and there is no
potential energy effect also because this crucible is you know or material is kept at a
certain position and there will be no you know positional effect and gravitational
effect on that at a particular position there.

So ultimately we can say that neglecting all other that you know shaft work, flow
work and kinetic and potential energy terms there. So the final energy balance
equation will be giving you like this simple that total internal energy change because
of that you know heat supply and changing the temperature inside the bomb with
respect to time.

740
And accordingly what should be the heat energy released there or heat energy you
know produced based on this reaction that you have to calculate. So here Qv is
basically the heat that is transferred from the bomb at a constant volume.
(Refer Slide Time: 37:37)

And then let us assume that the heat of reaction is determined in steady state flow,
you know calorimeter with you know entering fluid at position one and the exiting
fluid at position two at an open you know process unit system and there if no shaft
work is supplied to that system. And if it kept horizontally then potential energy will
be negligible.

Or you can see zero and kinetic energy will be also considered as zero there. So in
that case, if the process takes place at constant pressure, the general energy balance
will be reducing to you know H will be is equal to Qp. Here Q p is in suffix. So it is
H will be is equal to Qp. Here Qp designates you know the heat transferred from the
flow calorimeter at a constant pressure.
(Refer Slide Time: 38:46)

741
Now if we subtract this you know Qv from Qp and use the relationship of enthalpy
with this you know internal energy as like this
H = U + pV.
Then we can find out that what should be the Qp – Qv. That pV will be is equal to
H – U.

Now this H is basically H2 – H1. And that is state 1 to state 2. Similarly, here this
flow work from this you know at this you know time two here H – pV at t2 and H –
pV at t1 at this condition of you know t2 to t1.

Now furthermore, we can say that the enthalpy change for the you know batch
constant volume process is made identical to the enthalpy difference between the
outlet and the inlet in the process by a suitable adjustment of the temperature of the
water baths, that is surrounded to that you know bomb calorimeter.

So in that case we can say that this Ht2 – Ht1 that will be is equal to H2 – H1 if that
temperature is kept constant. And again we can write Qp – Qv, this v is in actually
suffix which represents this heat at constant volume. So here Qp – Qv will be coming
as pV at t2 – pV at t1 between this interval of t2 and t1.

So from this equation, we can calculate from the flow work at condition two to
condition one what should the change of you know heat energy based on that constant
pressure and constant volume.

742
(Refer Slide Time: 41:00)

Now to analyze that right hand side of this you know equation, this flow work. Here
in this case, we can assume that for solids and liquids here delta pV change is
negligible and can be ignored there. So for such cases, the only change which will be
taken into account is for gases that is present as product and or reactants.

And if for simplicity the gases are, you know assumed to be ideal, then at constant
temperature we can write this pV will be is equal to nRT and then what will be that
gradient of that pV that will be basically based on that gradient of what is that moles
there. So it is represented by delta n.

So delta pV will be is equal to delta n into RT where this temperature is kept constant
and R is universal gas constant. So based on this you know equation, we can write
that Qp – Qv that means change of heat energy based on constant pressure and
constant volume, we can write simply n into RT.

Now this equation will give you the difference between the heat of reaction for the
constant pressure experiment and the constant volume experiment.
(Refer Slide Time: 42:34)

743
Now let us do an example for such cases. Here in this case, you have to find out what
should be the you know the difference between the heat of reaction at constant
pressure and constant volume for the following reaction at 25 degree Celsius
assuming that it could take place here as per reactions here.

This carbon particles will be bond with oxygen, which will give you that product as
carbon monoxide in the bomb calorimeter. So in this case how to calculate this first
heat of reaction at constant pressure and constant volume that you have to calculate.
In this case, let us consider the basis as one mole of carbon solid.

So as par the figure here the you know system is bomb here and Q let us see what will
be that Q value. It should be positive since it is you know absorbed by the bomb. And
we can say that from the equation like Qp – Qv we know that this is delta n into RT.
So based on this equation, we can have what should be the value of Qp – Qv.

Now before going to calculate that you have to know what should be the delta n. So
this delta n will be is equal to here what will be the you know product side that is you
know 1 and minus here you can say that it will be half this, this is carbon. So it will be
you know simply as we can say it will be half.

Now we can say that since c is you know solid, since c is solid we can, we cannot
consider here this you know coefficient there. So based on which we can say that Qp –

744
Qv that will be is equal to then here what is delta n, this is half into R, R value is
8.314. This is basically joule per you know mole.

That is K here and into here R here into t, t is here at 25 degrees Celsius. So it will be
298 Kelvin, you have to convert it. Then finally, it is you know coming as 1239 you
know joule per gram mole. So this is your Qp – Qv. This is the difference of this heat
based on this constant pressure and constant volume.
(Refer Slide Time: 46:26)

Now if the measured heat, let us considered that if the measured you know heat
evolved from the bomb was 111 point sorry 111759 joule, this total amount of this
heat is evolved from the bomb. Then we can say Qp will be is equal to Qv plus this
1239 here as per this equation.

So it will be coming as here minus, you know that -111759. This is reverse that is
why negative plus here 1239. So it is coming as -110520 joule. So this much of heat is
you know released at constant pressure. Since you have this value of heat energy that
is released or evolved as per constant volume is 111759 Joule.

Now if we consider that the size of this correction you know is relatively insignificant
compared to either the you know quantity that is Qp and Qv. Basically what should be
the heat of reaction based on this you know Qv and Qp that you have to calculate.

745
So in any case, let us in any case, the heat of reaction, calculated form the bomb
calorimeter experiment is delta H rxn at a specific condition at constant volume. That
will be is equal to Qv/n. So it will be here -111759, that is a constant volume by
divided by n, n is here 1.

So it will be is equal to simply -111759 here joule per gram mole of that carbon, that
is solid. And similarly, we can calculate what should be the you know heat of reaction
based on constant pressure that is experimentally obtained.

So since the reported value of heat of reaction from this combustion reaction we can
write here since reported value of reaction, heat or heat of reaction at constant
pressure process the value of that heat of reaction as Hrxn hat at specific condition
that will be is equal to Qp by n. So that will be is equal to here -110521 divided by 1
mole of carbon.

So this will be is equal to -11052 here joule 521 sorry 521 joule per gram mole of
carbon solid. So this is at constant pressure. So this value is actually obtained
experimentally when there is a you know heat released from that burning of coal at
constant pressure and the specific heat of that reaction at constant pressure then can be
calculated as like this.

Now this value, now if you know this you know or if you can experimentally obtain
the value of reaction or heat of reaction at constant pressure from which you can
easily calculate what will be the you know value of heat evolved at constant volume.
So those are related based on that you know, ideal gas equation at constant you know
temperature there.

So from which we can simply you know relate these things based on that you know
constant volume and constant pressure system. And once you know either one of this
you know value, you can calculate other value of this heat released by that reaction.

746
So it is interesting that here that constant pressure system you know always to be you
know referred in any process instead of constant volume system because you know to
maintain that constant volume system and doing the experiment it is very tough.

Whereas you know that constant pressure system to be maintained it will be you know
easier relative to that constant volume system. So if you are having that value of
constant pressure based you know heat released by that reaction, then from the
relation of this equation represented by this equation, you can easily calculate what
should be the heat evolved by the reaction at constant volume there.

So it is sometimes required to know the heat of reaction at constant volume condition.

So we have described the heat of combustion based on the heat of reaction that is
experimentally obtained by you know by combustion reaction and also heat of
combustion reaction can be you know calculated based on that heat of you know
combustion of individual constituents.

Also heat of reaction can be calculated once you know that heat of reaction based on
the heat of combustion. So all are related to each other and some examples are given
to you. I would suggest you to go further to practice with some examples given in the
textbooks.
(Refer Slide Time: 55:31)

And it will be helpful to better understand of this heat energy balance concept and
further calculation based on this concept. And next lecture we will discuss something

747
more about that material balance and energy balance based on that you know transient
condition like at unsteady state condition how you can calculate or you can do the
material balance and you know energy balance there.

So we will be discussing from next module onward those things. So thank you for
giving attention in this lecture.

748
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 27
Material Balance of Transient Process

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. Here we will discuss about the balances on transient processes
as a module 9. Now under this module 9 in this lecture we will try to discuss about the
material balance of transient processes.
(Refer Slide Time: 00:52)

In the previous lecture we have discussed about that energy balance with heat of
combustion reaction, analysis with examples. But those you know balances were you
know steady state process. But here I will try to do some material balance where the
process will be unsteady state and also will describe with examples here.
(Refer Slide Time: 01:17)

749
Now what is that unsteady state process? The term unsteady state process basically
refers to the process in which quantities or you can say that dependent variables or
operating you know variables as a dependent variables within the system changes
with time and the unsteady state process is sometimes called as transient process.

So transient means here unsteady state process, you have to refer it like this. Now let
us consider this chemical engineering process where we will see that the process will
be based on you know time consumption like in this case here one steel at a you know
that certain condition and inside this steel some amount of you know liquid mixture.

Let this liquid mixture is you know that propane and butane mixture and in this
mixture certain you know amount of propane will be there and certain amount of
butane will be there with a mole fractions of like Xp and Xb. Here Xp means mole
fractions of propane and Xb means mole fraction of butane.

We will see that if we you know heat this steel of this mixture of propane and butane
you will see that the you know higher boiling point liquid will be remaining in the
steel whereas lower boiling point liquid will be you know vaporized and it will be
coming out from the top portion of this you know steel.

And after that if we you know condense it through a condenser and it will be you
know taken out as a you know liquid butane because here butane will be coming out

750
as it has the boiling point is less than that is propane. And the boiling point of butane
is -1 degree Celsius whereas propane boiling point is -42 degrees Celsius.

So here in this case you will see that, so, this vapor will be coming out, butane vapor
will be coming out here or higher boiling point instead of you know that propane and
butane mixture, any mixture of this you know different boiling point component if it
is there.

So higher boiling point, you know that liquid will be coming out as a vapor whenever
it will be heated and then it will be condensed out and then it will be taken out as a
you know that x d that is a distillate product after separation.

Now, in this case you will see that in this steel whatever you know butane
composition will be there inside this steel during that heating process, you will see
that this composition of this butane will be you know changing. Now that change will
be you know with respect to time.

If you boil for you know for a certain time, you will see that accordingly that
composition of that, you know butane in the distillate product will be there. Now in
this case that means here with respect to time, this composition in the steel will be
changing. So this type of process is called that unsteady state process.

Now how long it will take to you know that condensed or you can say that separate
this butane vapor from its initial concentration to a certain final concentration. So that
can be obtained by this you know energy sorry material balance equation. But that
material balance equation will be as per you know unsteady state condition.
(Refer Slide Time: 05:30)

751
So let us look back into the general material balance equation. We have discussed it in
module 3 in lecture 3.1 where lecture serial number it is 7. So there we have discussed
that this general material balance equation as accumulation within a defined system.

That will be equals to input through system boundary minus output through system
boundary plus generation within the system minus consumption within the system.
That means, in short we can write here accumulation will be is equal to input minus
output plus generation minus consumption.

Now positive contribution to this system will be input and generation and negative
contribution to the system is output and consumption. So here it is seen in the figure
that if this is a process unit, you will see that in this process unit input will be coming
and whereas output will be like this in this stream.

And you will see that this input and output this will be you know that stream. So input
stream and output stream there will be a certain amount of that you know components
will be there at a certain flow rate.

And during this process in this process unit, if is there any you know generation there,
like in reaction certain you know at a certain condition, there will be you know some
product that will be produced with the reactants. So there will be certain generation of
the components. So that components also will be coming out as a output there.

752
And then during that reactant you will set up during that reaction some reactants will
be consumed and it will be you know that will be you know that consumed so that
amount to be considered as a consumption terms. So in any process there this you
know accumulation input, output, generation and consumption terms will be
considered for the overall material balance there.
(Refer Slide Time: 07:40)

Now in this case, if I consider that, that unsteady state material balance. In unsteady
state processes the accumulation term in the mass balance equation cannot be
neglected and must be accounted for. So if suppose there is a steady state process that
means there is no accumulation.

In that case input and output plus you know generation minus consumption will be
there. Whereas, in case of unsteady state process there you will see that input rate and
output rate will not be same. So in that case some amount of you know materials will
be deposited or accumulated in the system with respect to time.

So that will be called as accumulation. So in that case accumulation you cannot

neglect there. Here suppose in this flow process, some amount of you know that
materials will be coming in as you know that mass flow rate of you know m1 .

Similarly, another component m2 and another component m3 .

753
Those are coming into this flow process unit and they are coming out here as m 4 dot
and m 4 dot 5 and you know that m 6 dot there as a mass flow rate there. Now in this
case you will see that overall if this output, total output is greater than this you know
that input then what will happen?

You will see that there will be a you know that amount in the system will be
decreasing. Whereas, if output is less than this input you will see there will be an
accumulation. That means here in the system the mass will be increasing with respect
to time. So in this way, this will be you know considered as unsteady state process
where accumulation terms to be considered.
(Refer Slide Time: 09:32)

Now let us write this unsteady state material balance in symbol. Here, if we consider
that the accumulation of mass in the system will be there with respect to time. So
what will be the change of that accumulated amount with respect to time that can be
represented by this dm/dt.

And where we will see that m dot you know in that will be your mass of you know
material that is coming into the system as a flow rate here m dot in. And similarly, m
dot out that is rate of you know mass of that material, which is coming out from the
system at a rate that will be regarded as m dot out.

Similarly, at the same time if is there any material is generated in the system, then you
have to consider that will be as you know m dot generation. Whereas if is there any

754
mass is consumed during that processes that also you have to consider here as a rate
of m dot consumption here.

Now this here m dot in there maybe you know more than one inlet. So total inlet mass
flow rate will be considered as summation of that you know mass of you know
several you know inputs that you have to consider as a sum. Whereas at output also
you have to consider what will be the you know total amount of out based on the
summation of all the output mass flow rate.

So in this way you can calculate. If there are suppose more than one components also.
So separately for that individual components also you have to consider and adding up
all those component’s mass flow rate you will get that total amount of mass that is in
will be coming into the system as an input.

And if you are considering the flow rate of that individual components, which will be
coming out from the outlet that also to be considered as a total you know, mass out for
that summation of all components that will be regarded as summation of m i out and it
will be total output rate of that mass there. So similarly, generation and consumption
to be considered.

Now this is regarded on report that multiple inlet and outlet condition. So here m is
the mass accumulated in the system and m dot in is the inlet mass flow rate that is
mass per unit time. Even m dot out is outlet mass flow rate that is mass per time; m
dot generation it will be you know generated mass flow rate that is mass per time.

Similarly, m dot consumption it will be is equal to consumed mass flow rate that is
mass per time. Now you can express in terms of moles also not only that only mass. It
will be considered as a mole also as a rate. So that will be mole per time there.
(Refer Slide Time: 12:38)

755
Now let us do an example for this unsteady state process here. Let us consider this
small steel is you know used to separate propane and butane mixture at 135 degree
Celsius and initially contains 10 kg moles of mixture in that steel whose composition
is you know that x is equal to 0.3 mole fraction of butane.

And additional mixture here xF that is mole fraction of butane as 30% is fed at the rate
of you know 5 kg mole per hour. Now if the total volume of the liquid in the steel is
remain constant during that operation and the concentration of the vapor from the
steel which is coming out as xD is related to that you know concentration of the butane
in that particular steel will be you know expressed as xD will be is equal to x s by 1 +
xs.

So based on this you know composition of you know distillate product, you can
calculate how long will it take for the value of that concentration of that butane in the
steel to change from its concentration from 30% to the 40% that you have to find out.
(Refer Slide Time: 14:10)

756
So this okay let us solve this problem here. So as for this problem we can have this
steel here and in this case feed here composition is 0.30 as xF and composition of
propane and butane mixture here it is given as propane it is 70% and butane as 30%
and initially the steel is filled of 10 kg mole of you know propane butane mixture.

And after that, that feed will be you know supplied as a you know 5 kg moles per
hour rate to this steel and then heating it and during this heating you will see that, that
butane vapor will be you know coming out from that you know steel and accordingly
you will see that there will be you know that concentration of that butane inside the
you know steel will be changing with respect to time.

Now that you know that distillate whatever will be there inside that you know steel
that will be coming out as a vapor and it will be after that condensed it will be you
know taken as some D amount and where this butane concentration in that distillate
you know amount would be xD.

Now this is xD change that is x with respect to you know time that will be you know
changed and accordingly you can say that this xD basically how it will be related to
that you know concentration of the butane in that steel. So it will be you know related
by this equation here xD will be is equal to xs by 1 + xs.

What is xs here; xs is nothing but that you know concentration of that butane in the
steel at a time t. So in that case how to solve this you know problem to find out that if

757
suppose butane concentration is changing from 30% to 40% how long it will take to
have such you know change of this mole fraction from 30 to 40%.

Now in this case we will do that you know material balance first, unsteady state
material balance like we know that material balance as
 ACCUMULATION  INPUT   OUTPUT   GENERATION  CONSUMPTION
This is your you know material balance equation.

Now in this case, since there is no reaction is going on and there is no generation of
the you know components. So we can neglect it as zero and also there is no
consumption of this you know any materials for reaction. So in that case we will also
neglect that consumption terms. So we can neglect it.

So finally you can have this material balance equation as accumulation will be is
equal to in minus out. Now what is the accumulation there? Now if we consider only
that you know butane you know material, so if you do that material balance for this
butane so we can right here initially butane concentration was you know, there will be
some amount.

That is there 30% and 70% all the time it will be you know that they are in this steel
30% but with respect to time, you will see that it will be changing because there will
be a you know that amount of butane will be changing and it will be vaporized and it
will be coming out from that steel.

Now, the total volume of that steel inside that, that is steel will be remaining constant.
So that is I think 10 kilo mole, sorry 10 I think it is given as per problem it is you
know 10 kg mole of mixture will be you know kept constant there inside that steel. So
accordingly we can say that accumulation will 1.

Now, during that you know vaporization process the concentration of that steel that is
in butane concentration will be changing. Now what is that change? That we do not
know. Let us have this change is xs; s is the here steel concentration here butane
concentration in that steel.

758
Now the change with respect to time, time maybe you know that with respect to time
delta t, that change of that concentration will be xs. Now since the volume of this
steel is remain constant, it is 10. So we can multiply this with 10.

Then it will be your that total amount of butane at a particular time and there will be a
change of butane with respect to delta t time. It will be 10 into xs. So this is your
accumulation and then what will be the inlet of this you know butane in this steel.
Now there is a flow rate of that you know as per problem this flow rate is given, the
feed flow rate is given 5 kg mole per hour.

Now in this 5 kg mole per hour flow rate what will be the amount of that is xs there or
you can say that xF that is butane vapor in that feed. So we can write here then since it
is 5 kg mole per hour flow rate and concentration is xF there. So we can write 5 into
xF and since we are considering within a period of time that is t, so we have to
multiply it like this.

So it will be coming out at this, this amount of you know material is in the steel and
then out will be is equal to then again out at the flow rate of 5 of that xF so that, that
total volume of that steel will remain constant 10. So 5 into your outlet concentration
is basically xD here and the time is t. So in this way you can write that outlet you
know material for this short period of time t.

And generation is zero and you know consumption is here zero. So finally, this
equation you can get. Now dividing by t and taking the limit of you know at a process
to zero. So we can write here d into x s by d t that will be is equal to 0.15 - 0.5 into xD.
Why 0.15 here? Here xF is basically here 30% that is 0.30. So 5 into 0.30 it will be
coming as here.

I think it is here 5 into zero point, this is 1.5 here it is 1.5 sorry this is 1.5. 1.5 – 0.5
into xD. Now after that, we will see that we can write this final equation as we can
write here as what is the value here? This is yeah, what is that here 5 into xD here. So
we can write this. So finally, we can write dxs/dt.

759
That will be is equal to here if we divide it by 10 then we can write here it will be is
equal to 0.15 - 0.5xD. So this is your final equation. This is one differential equation.
From this, you know material balance that is unsteady state material balance. Now in
this case, since we know that the xD will be is equal to xs by 1 + xs. So if we substitute
here this xD value finally then we can write this equation as xs, dxs by 0.15 you know
that -0.5 xs divided by one plus here xs.

That will be is equal to dt. So in this way we can have this equation in terms of xs and
dt. Now this x s that is steel concentration will be changing with respect to time and
you have to integrate this equation within a certain limit of that as per condition given
in the problem.

So we can write here, integration of here concentration is changing from 0.30 to 0.40
of this dxs by 0.15 - 0.5 xs by you know that 1 + xs. So xs that will be is equal to 0 to
here you can say tdt.
(Refer Slide Time: 24:33)

Now after that after getting integration within a limit at you know that t is equal to
zero, initially steel concentration is 0.30 where you have to find out the time at t is
equal to t. This xs to be 0.40. So based on this, you know limit we can have this you
know integration of this 0.30 to 0.40 of dxs by 0.15 - 0.5 xs /(1 + xs).

760
That will be is equal to 0 to t here dt. So from this we can have that t will be is equal
to zero point sorry, it will be as 5.85. This would be in hour. So total 5.85 hour time
will be required to you know vapor this you know mixture to get this you know
composition of butane from its initial to the final of 0.40 there.

So in this way, we can say that it is 5.85 hour will take to change the concentration of
steel from 30% to the 40%. So this you know unsteady state material balance, I think
it would be helpful to do further this material balance in unsteady state condition.
Now let us do another example for this.
(Refer Slide Time: 26:46)

Let us consider a liquid tank of 1.0 meter square here. Cross sectional area is here 1.0
meter square and it is filled with water at a rate of you know a meter cube per second,
a certain amount. Let us consider a general a meter cube per second. Now when the
height of the liquid is h1 meter in the tank a control valve installed on the exit stream
at the bottom of the tank, that opens up.

And the liquid flows at a rate proportional to the head of the fluid as b into h meter
cube per second, where h is the height of the liquid in meters. Now in this case, you
have to express height of the liquid as a function of time, what is the steady state
height of the liquid in the tank; a and b are constants here.

So basically you know that, initially there will be certain amount of liquid. Now if
you allow some liquid here in this tank at a certain flow rate of a meter cube per

761
second and you will see to keep this initial you know volume inside the liquid
constant, then you have to you know allow it to you know flow out from this outlet
stream.

So there you have to maintain that output rate there so that the liquid inside the you
know tank will be constant. So that will be your steady state. But here in this problem,
it is not there. You will see that initial volume will you know that gradually you will
see that either increasing or decreasing as per you know that input and output flow
rate there.

If suppose input flow rate is you know lower than this output flow rate, you will see
that the liquid whatever initially was there inside the tank it will be decreasing and
accordingly height of that liquid will be you know decreasing with respect to time.

If suppose inlet flow rate is higher than the output flow rate, you will see that liquid
will you know that liquid level will increase in the tank with respect to time, because
that volume will be increasing because inlet flow rate will be higher than the outlet
flow rate. Now in this case you have to you know if suppose a is higher than this you
know outlet flow rate of b into h.

So in that case liquid flow rate will increase. And again if suppose here outlet flow
rate is here you will see that greater than that input flow rate what will happen that
liquid level will be decreasing at a certain flow rate. Now in this case what is the
steady state here what should be the you know that height of the liquid as a function
of time, that you have to calculate here. You have to find out or you have to express
this.
(Refer Slide Time: 29:59)

762
Now, this tank you know cross-sectional area is given 1 meter square, whereas the
you know inlet flow rate is given a meter cube per second. Now how to solve this you
know problem here. Now how to express this you know height of this liquid that is
changing with respect to time there.

Now what to do here again we have to do here material balance which is unsteady
state. Now if we do that unsteady state material balance, unsteady state material
balance we have to consider in this case in this problem, in this case we can say that
generation will be equals to zero. Consumption will be is equal to zero.

So we can write dm/dt that will be is equal to in minus out where m in as a rate minus
m out that means output flow rate of that mass. So here this is accumulation and this
is input rate, this is output rate. Now according to this material balance, what we can
write here. In this case first of all what is m here; m is nothing but density into
volume.

So it is basically rho into volume is what? Cross-sectional area into height of the
liquid; h is height, A is the cross-sectional area. So here A is basically pi into D
square by 4, D is the diameter of the tank and m dot that is mass flow rate here
m  V .
What does it mean? That is mass that is per unit time.

763
What is accumulated inside the you know tank that will be based on that volume rate
that is increased or decreased inside the tank. So that can be obtained just by you
know V where we can write here, rho is the density where  is equal to density and

V is equal to volume V is equal to volume flow rate, volumetric flow rate.

And m dot is equal to mass flow rate, mass flow rate or you can say that mass
accumulation rate. Now simplifying this you know material balance, now simplifying
material balance we get d (  Ah) / dt .We have just substitute the value of m here as
 Ah .

That will be is equal to rho into v dot in minus rho into v dot out which implies dh/dt
that will be is equal to what a – bh, why? Here see rho, rho and rho. This is constant.
That is here incompressible flow. So rho will be you know constant and it can be you
know omitted from this left hand side and right hand side just by dividing the both
sides.

And then here you will see that v in is given as a and the outlet of b is given as bh and
in this case you can then write here this you know that dh/dt will be is equal to this
here one important point here it will be coming Ah here so A will be remain here in
this case. So we are getting this you know equation here as per this.

Now per unit cross-sectional area, we can write A is equal to 1 since it is given as per
problem A is equal to 1. So we can write A will be equals to 1. Next what we have to
do?
(Refer Slide Time: 36:18)

764
You have to that integrate this you know differential equation of this dh/dt that will be
is equal to a – bh. Now integrating this equation here in this case, now how to do this
here; dh/(a – bh) as integration here that will be is equal to integration of dt.

Now as per you can say that you know that initial condition as at time t is equal to 0.
The height of the you know liquid inside the tank, it will be as h is equal to h1.
(Refer Slide Time: 37:11)

That is given in this picture here, initially up to this height was there, that is at h1. At
any time that height will be h. Now in this case we can then write here, we can write
here h1 to h as dh/(a – bh). That will be is equal to 0 to t as here dt.

765
Now after integration, we can write after integration within this limit, we can write
after simplification,
a a
h  (  h1 )e  bt
b b
So this will be your solution of this integration. So this you know that height at any
time t, how is it related?
a a
h  (  h1 )e  bt
b b
So this will give you that with respect to you know time that height will be changed.
Now that depends on this you know input and output you know that flow rate and also
that coefficient a and b here or constant a and b.

Here you know that this a is that input flow rate and b is here the coefficient at this
outlet flow rate. How that output rate depends on that height of that liquid inside the
tank at any time t. So that b there. So initial height is h 1. Now the last portion of this
problem there, suppose what is the steady state height of the liquid in the tank a and b
are constants here.

Steady state condition, at a steady state condition we can say we can write here that
dh by dt that will be is equal to 0. Therefore, we can write here the steady state height
as hs that will be is equal to what will be the value here because dh/dt, what we got
here, this is basically dh/dt.

That will be is equal to a - bh. That means here a – bh will be is equal to 0 at steady
state condition. So which implies h will be is equal to simply you know that a by b. So
this is your you know at steady state condition what should be the height. That means
here if suppose inlet and outlet you know flow rate will be you know same.

So in that case this steady state height will be is equal to a/b here. So if you consider
that a is equal to suppose you know 1 meter cube per second and b is equal to suppose
here coefficient is 2, then steady state height will be is equal to 1/2 here. So it will be
simply you know half, that is h is half meter there.

766
So in this way you can calculate at steady state condition what will be the you know
that steady state height of the liquid inside the column. So this is one example of this
unsteady state you know material balance equation. Let us do another example here.
(Refer Slide Time: 41:59)

Dilution of salt solution. Now the average here ocean water of salinity is 35 ppt that
flows into a 100 liter of tank that containing 1.5 kg of salt let us considered at a rate of
5 liter per minute. Now the salt solution overflows out of the tank at 5 liter per
minute. Now how much salt will remain in the tank at the end of 15 minutes. That you
have to find out.

Now assume the fluid in the tank is well mixed and the density of the salt solution is
constant and equal to that of water. Now in this case, you have to remember if 1 kg of
salt in 1000 gram of water the salinity will be is equal to 1 ppt. So 1 ppt how it is
related that is given here. Now basically this is ocean water.

That salinity is 35 ppt, that is flows into a 100 liter of tank that contains 1.5 kg salt
and it flows at a rate of 5 liter per minute. Now the salt solution also overflows out of
the tank at a 5 liter per minute. Now in this case you will see that the salt will be you
know leaving from this tank. Now how much salt will remain in the tank at the end of
15 minutes that you have to find out.
(Refer Slide Time: 43:31)

767
So let us do this problem here again as per you know unsteady state material balance
equation. Now in this case, we can write this general unsteady state material balance,
general unsteady state material balance equation as here dm/dt. That will be is equal
to m dot in minus m dot out plus m dot generation minus m dot consumption.

Since there are you know no reactions, so we can neglect this generation and also you
know consumption terms. So the final general material balance will come as dm by dt.
That will be is equal to m dot in minus m dot out. Now if we replace this you know
mass flow rate in terms of concentration we can write here d(vc)/dt, v is the volume c
is the concentration by dt.

That will be is equal to then in terms of flow rate inlet condition into c in, that is
concentration of the inlet stream minus again v dot out flow rate and the outlet stream
with a concentration of c out there. So this you can write here in this way.

Now assuming the solution in the tank is well mixed that as per problem and the
outlet salt concentration you know that equals the concentration in the tank. Assume
here outlet, the outlet concentration equals the concentration in the tank. So we can
write here d(vc)/dt.

That will be is equal to VinCin  Vout Cout ( C)

768
c out is basically as you know that c. So here we can write again if we consider that v
in that is inlet flow rate and outlet flow rate of this stream is equal then we can write
here, we can write here as, we can write vdc/dt.

That will be is equal to here we can write here what it is given that okay let it be here
VinCin  Vout Cout ( C) and in this case, then we can you know omit all those things
here, here in this case, then we can omit all those you know v terms here. And after
that we can get that you know integration of c inlet and c outlet.
(Refer Slide Time: 48:33)

And solving that equation we can get solving the then solving the resultant differential
equation as per as per problem given we can write c then at t t is equal to 0. It will be
is equal to 1.5 kg per 100 liter of solution. This is 0.015 kg per liter there and c in that
will be is equal to 35 ppt.

That will be coming as ultimately 0.035 kg per liter. So this is your c in there. Then
after integration the concentration of the salt, okay here we can say that the
concentration of the salt then as per integration then the concentration of salt in the
tank after 15 minutes that is 90 second.

Let 15 minute no that is what 900 second is approximately will be is equal to 0.035
here kg per liter since the tank is 100 liter. And accordingly the amount of salt is 3.5
kg. So this will give you that after 15 minutes this amount of salt will be there inside
the tank okay.

769
(Refer Slide Time: 51:54)

So let us do another example this type of you know problem to solve this like example
for sewage treatment there. Now in a sewage treatment plant you will see that a large
concrete tank initially contains here 4,40,000 liter liquid and 10,000 kg fine
suspended solid.

Now to flush this material out of the tank we will see water is pumped into the vessel
at a rate of you know 40,000 liter per hour and liquid containing solids leave at same
rate. Now in this case estimate the concentration of suspended solid in the tank at the
end of four hour. So here the input and output flow rate of this tank is 40,000 liter per
hour.

Now because of this stirring and irrigation process you will see that fine suspended
solids you know that it will be you know coming out from this outlet and there you
will see there exchange of concentration of that suspended solids inside the sewage
treatment will be there with respect to time that will change.

Now in this condition after 4 hour what should be the you know that concentration of
that suspended solids that you have to find out. Now again according to this problem,
if we do the general material balance here since there is no reaction here, we can also
neglect here that generation and consumption terms and then finally we can write that
you know, material balance equation.
(Refer Slide Time: 53:45)

770
Your material balance equation as here dm/dt that will be is equal to m dot in minus
m dot out. Now replacing mass flow rate, in terms of concentration we can write
d(vc)/dt.

That will be is equal to VinCin  Vout Cout or since here Vin and Vout is equal 40,000 liter
per hour we can write the same amount here in this equation or you just keep here and
finally you can substitute that value. And in this case, the outlet concentration of the
suspended solid will be considering that the concentration will be in the you know
tank itself at that particular time.

So we can write here d(vc)/dt. That will be is equal to VinCin  Vout Cout will be is equal
to simply c, we can consider here. That means this concentration is at a certain time t
in the tank. Now here this since water is flowing into the vessel at a rate of 40,000
liter per hour as input rate and also if we consider that only water balance accordingly
we can write here this as dv, v we can keep it as constant.

So we can write here v into dc/dt and here inlet here concentration you know that of
solids in the inlet pure water is 0. So we can write here 0 minus Vout that is at a certain

flow rate it is given there that is Vout that is 40,000 liters per hour and in this case here
we can say that this c will be c at that outlet condition.

771
Now what is that initial condition that time t in the you know tank that solid
concentration, we have to find out first. To solve this you know resultant you know
this differential equation of this concentration change with respect to time. So for this,
so here we need to have this initial condition.
(Refer Slide Time: 57:30)

Initial condition which is the concentration, which is the concentration of solids in the
sewage tank at time t is equal to 0 where you can write c at t is equal to 0. That will be
is equal to what 10,000 you know kg of solid in 4, 40,000 liter of water. So it will be
coming as 0.023 kg per liter. So this amount of solid will be initially in the sewage
tank.

Now do the analytical solution of the differential equation that obtained as dc/dt. That
will be is equal to minus dc/dt; dc/dt will be is equal to here (Vout / V )C . So from

which you can write dc/c. That will be is equal to (Vout / V )dt .

So from this after integration we can have the c at time t and initial condition suppose
c0 that will be is equal to (Vout / V )t . This will give you your after integration or we

can represent it as ct will be is equal to c0 into exponent of (Vout / V )t . So this is your

equation or you know concentration at time t okay as a function of time t.

In this case you can find out the consideration t at any time t here, concentration c t at
any time t provided c0 and Vout and also initial volume inside the reactor known to

772
you. Now substitute the known quantities here. Substituting the known quantities as
per problem we can get ct will be is equal to, initial concentration is 0.023 that we
found.

This is kg per liter into exponent of here what is the v dot out? This is you know
40,000 liter per hour divided by that is v is 4,40,000 that is four lakh forty thousands,
this is liter. But here as per equation it is minus. So finally after simplification it will
come as 0.016, this is kg per liter. So this is your concentration for the time 4 hour.

Here it will be is equal to like this. So it will be zero point sorry 0.016 kg per liter.
This concentration will be there in the outlet condition at time t is equal to 4 hour. So
in this way we can calculate by the material balance what should be the outlet
concentration of this you know solution at a time t.
(Refer Slide Time: 1:03:07)

Let us do another example of unsteady state chemical reaction. There in this case a
material dissolves in water as per following law it is given that is
Rd  kd nud (Css  Cas )
where Rd is called rate of dissolution. kd is equal to constant of you know dissolution,
nud is the undissolved quantity of time t.
Css is given as concentration in the standard solution. And C as is the concentration in
the actual solution at any time t. Now the saturated solution of compound contains 40

773
gram per 100 gram of water in a test run starting with 20 kg of undissolved compound
in 100 kg of pure compound is found that 5 kg is dissolved in 3 hour.

Now if the test continues how many kilograms of compound will remain undissolved
after 7 hour. Assume that the system is isothermal. So here in this case you will see
that there will be a dissolution of material in water that will follow a certain laws, that
is dissolution rate laws. So that dissolution rate laws is given as per this equation.

Now in this case the saturated solution of compound always contains 40 gram per 100
gram of water. Now in an experiment it is seen that for a test run starting with 20 kg
of undissolved compound in 100 kg of pure compound is found that 5 kg is dissolved
in 3 hour in that solution, in that liquid. If the test continuous there for a certain time.

Now you will see that after 3 hours that how many kilograms of compound will
remain undissolved if you consume that time at 7 hours. So assume that the system is
isothermal in this case, there will be no heat input output there at a constant
temperature it will be there.
(Refer Slide Time: 1:05:26)

So to find out that you know kilograms of compound will remain undissolved after 7
hours that you have to calculate. Now in this case what we have to do that first of all,
you have to consider that undissolved quantity at time t. So assume that the
undissolved quantity at time t is equal to n.

774
Therefore, as per problem, we can write the material balance as
dm
 min  mout  mgen  mcons
dt .
In this case you will see that there will be a generation here with respect to time there.

So at a time t the undissolved quantity will be there and it will be generated and it will
be n. So we can write here this generation time or accumulation time of that molecule
here dn/dt. That will be is equal to here there will be input. There will be no output as
per problem, but generation is there.

That depends on that rate laws, that rate laws as per that constant is K. And here what
is that rate laws equation
Rd  kd nud (Css  Cas )
Based on this equation we can write then k into n into here 40 by here 100 minus 20
minus n by you know 100. So this is your generation that is initial minus final minus
here consumption is zero.

So finally we can write here dn/dt, that will be is equal to kn into 20 plus n to K in
into 20 plus n by 100 after simplification, which will give you dn by here n into 20
plus n. That will be is equal to k by 100 into dt. Now we can simplify it as, or
rearrange it as dn by n minus dn by 20 plus n. That will be is equal to K by 5 into dt.
So in this way we can rearrange it.
(Refer Slide Time: 1:08:48)

775
After that we can write dn/dt here that will be is equal to kn that means here for Kn
into 20 plus n by 20 sorry 100. From this dn by n into 20 plus n. That means minus dn
by this is I think, no no we can write here dn/dt. That will be kn into 20 plus n by 100
from which we can write here we can write, dn by n that is plus minus dn by 20 plus
here n okay.

We can write it finally as more simplified form. That we have written earlier also dn
by n minus dn by 20 plus n. That will be is equal to k by 5 into dt. Now this is your
equation. Now you have to integrate this equation with boundary conditions. What is
that boundary condition?

Boundary condition as per problem as t 0 that is a time t, t 0 is equal to 0, n 0 is equal

to 20 at time t 0. And then t1 is equal to 3. We can say that n 1 will be is equal to 15 at
time t2 is equal to 7 hours. Then n you know 2 will be is equal to at s 1 here what is
that t 0 is equal to 0, n 0 is equal to 20 and t 1 at 3 that you know, n 1 will be is equal
to 15.

At t2 is equal to 7. Then n2 will be is equal to what? So if we do this integration within

this limit of here 20 to 15 as per you know boundary condition. So we can write dn by
n minus integration 22 15 as you know dn by 20 plus n. That will be is equal to k by 5
here 0 to 3 as you know dt which will be given as here n2 will be is equal to 10.7 as k
is equal to - 0.257.

So finally we can get this at t2 is equal to 7, n2 will be is equal to 10.7. Why because
from this here 0 to 3 in this case you can get k will be is equal to minus you know
0.257. So after substitution of this k value again here for this limit of this you know
time here, 3 to 7 and within a limit of this here 22 15 you can get this you know n2
will be is equal to here something 10.7.

Here in this case final concentration is n2 this. So we can get this here at a you know 7
hour time this you know final concentration of this undissolved solid will be there
10.7 here kg of this amount of total n2. In this case, the total amount of here material,
we can see that here compound will remain undissolved after 7 hour will be is equal
to n2 will be is equal to 10.7 kg.

776
(Refer Slide Time: 1:13:41)

So we have solved different problems with unsteady state material balance. I would
suggest you to further go through the example problems given in you know the
textbook in example problem and solved by that authors. Then you will understand
more you know there and also you can solve the problems with this unsteady state
material balance there that is given in exercise also in the textbook and you practice it.

I think you can do. In the next lecture we will try to discuss something more about
that unsteady state process, but that will be energy balance equation. So thank you for
giving attention for this lecture.

777
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 28
Unsteady State Energy Balance

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. So in module 9, we were discussing about balances on
unsteady state processes. And in the previous lecture we have described about the
unsteady state process for material balance.
(Refer Slide Time: 00:52)

And also we have discussed those unsteady state material balance with examples. In
this lecture we will try to extend those lecture, but it will be with the unsteady state
energy balance and we will try to solve some problems where this unsteady state
energy balance are involving. Now what are those you know unsteady state processes
that already we have described in our previous lecture.
(Refer Slide Time: 01:24)

778
We know that the term unsteady state process that refers to processes in which
quantities or opening conditions or operating conditions within the system that change
with the time and in that case, another one important terms like transient state, which
also applies to such processes. This transient state is basically unsteady state process.
(Refer Slide Time: 01:58)

And general unsteady state energy balance equation how we can write. We know that
general energy balance equation where there is no accumulation terms, we have
already described in our earlier lecture. So if we consider that accumulation terms in
you know general you know energy balance equation, then you can you know write
this final form of you know unsteady state energy balance equation.

d (E)   u2 
ˆ
   m  H   gz    Q  W
dt   2 

779
Where you will see that this dE/dt is basically the energy you know that accumulated
or energy loss with respect to time or change of energy with respect to time that we
can have. So this energy change with respect to time we can calculate form the
enthalpy change of that you know process as well as if there is a flow in open system
then what should be the kinetic energy change.

And also if there is the elevation you know of the you know process you need and the
flow is with the elevation then we can say that there will be some potential energy
change from the you know batch potential energy. So based on which there will be a
summation of that you know potential energy change, enthalpy change and kinetic
energy change.

And also you will see that this energy change of course will be coming based on that,
you know what will be the heat energy supplied to the system and also work done by
the system there. And based on that, if there is suppose overall change of that energy
with respect to time, based on this change of this enthalpy, kinetic energy, potential
energy and even heat supplied to the system, work done by the system.

And based on which we can say that the change of that you know energy with respect
to time, which will be regarded as that you know unsteady state energy balance. So
that unsteady state energy balance equation, we can write by this format. Now in a
closed system, the rate of change of energy inside the closed system is nothing more
than the rate of change of internal energy.

So in closed system we know that there will be no you know flow work, there will be
no potential energy, there will be no kinetic energy change and also since there will be
no you know flow work then we can say that there will be only energy change with
respect to time will be based on that internal energy change.

So which in turn is essentially the same as the rate of change of enthalpy here. Since
we can say that this flow work rate that is d(pV)/dt equals to zero.
Since, d ( pV ) / dt  0; dE / dt  dU / dt  dH / dt

780
And hence we can say that dE / dt  dU / dt  dH / dt upon that you know kinetic
energy and potential energy is negligible.

So finally, we can say that this you know energy change will be based on that internal
energy change and if there is no flow work, then simply we can say that the enthalpy
change based on that no flow work down on the system.

So that is why we can write here this you know rate of energy change that will be is
equal to rate of internal energy change and that will be is equal to rate of enthalpy
change if there is a condition of no flow work.
(Refer Slide Time: 05:58)

Now if we write that energy balance on unsteady state processes, we can simply write
based on that this internal energy change with respect to time that will be is equal to
dU/dt. Then what should be the enthalpy at the inlet condition and what will be the
enthalpy at the outlet condition or outlet streams.

And what will be the heat energy supply to the system and also what will be the shaft
work done by the system. So from those components, we can write this internal
energy change based on these enthalpy change in the inlet and outlet streams and also
energy supplied and work done by the system at a rate.

So here from this equation,

781
d (U )
  min Hˆ in  mout Hˆ out  Q  Ws
dt
we can calculate what should be the internal energy change. If you know that what
will be the energy you know change, enthalpy change at the inlet and outlet streams
provided that heat energy supplied to the system and shaft work done by the system.
(Refer Slide Time: 07:13)

And for liquid and solid we know that this specific heat capacity at constant volume
and at constant pressure will be equals to zero, sorry will be same to each other. That
d ( pV )
means Cv will be equals to Cp. Because in that case, the flow work that is 0.
dt

Therefore, from the relation of enthalpy that is equal to internal energy plus the
product of pressure and volume. We can write then
dH dU d ( pV )
 
dt dt dt
So here the rate of change of enthalpy that will be is equal to rate of change of internal
energy in addition to the change of flow work with respect to time which yields this
dH dU

dt dt
That means here enthalpy change will be is equal to internal energy change with
respect to time if there is no flow work. That means here d(pV)/dt will be equals to 0
if it is there.
(Refer Slide Time: 08:43)

782
Now let us do an example for a closed system where heating is done. Suppose a pan
of water containing 5 liter of water at 30 degrees Celsius, which is placed on an
electric heater as shown here in the slide where the heat is supplied by this heater to
the system as Q which is about 2500 joule per second. Now it is this heat is supplied
to boil the water.

Now you have to find out what is the time required at which the water begins to boil.
So you can solve this problem based on that unsteady state energy balance equation.
In this case you are going to boil this water at 100 degrees Celsius. So the normal
boiling point of water you have to know to boil this.

If instead of water other liquids are there, you have to consider there what should be
the boiling point of that liquid. Now the general energy balance equation is we know
that write that general energy balance equation here. The general energy balance
dU
equation can be written as for this unsteady state operation, that will be is equal
dt

to m in Hˆ in here.

That is specific enthalpy at the inlet, since we are using at minus m out Hˆ out at the

outlet condition plus heat supplied to the system here in this pan at a rate Q minus

work done by the system here as a shaft work Ws . Now the pan is batch system. In
this case inlet and outlet, outlet mass flow rate will be equals to 0.

783
There is no flow at the inlet and outlet condition. So in that case, we do not need any
shaft work to, shaft work by this system to be considered.
(Refer Slide Time: 12:20)

So we can write no shaft work. Therefore, Ws that will be is equals to zero and also we
know that for liquid and solid this Cv that will be is equal to Cp. So the general
dU
balance equation can be written as .
dt

That will be is equal to

d (U )
  min Hˆ in  mout Hˆ out  Q  Ws
dt
So we can delete this Ws and also we can delete this inlet enthalpy and outlet
enthalpy. Since there is no flow at the inlet and outlet since it is a batch process.

So from this we can write d(mCvT). This is basically internal energy. This is
d(mCvT)/dt. That will be is equal to here simply Q . Now we can write m that is
basically V. So we can write from this energy balance equation as dT/dt. That will
be is equal to Q / ( VC p ) . Cp and Cv both are same.

So we can write Cp instead of Cv here. Then we can get this final equation as per this
energy balance equation.

784
dT
 Q / ( VC p )
dt

Now if we do the analytical solution of this equation, we can get, after analytical
solution we can write
T2  30  [Q / ( VC p )]t

V is the volume of that system, here t is the time.

So from this we can calculate what should be the temperature at this boiling point
here for a certain time t. Since we know that temperature is 100 degrees Celsius, since
we have to boil this water at 100 degrees Celsius, so here T2 will be is equal to 100
degrees Celsius. Whereas, this initial temperature is 30 degrees Celsius.

So in that case you can find out this time t after substitution of the T2 at 100 degrees
Celsius and Q it is also given to you what will be the heat energy supplied to the
system by this heater. It is given as 2500 joule per second and specific heat capacity is
also given to you.
(Refer Slide Time: 17:12)

So if we substitute T2 is equal to 100 degrees Celsius and Q that is 2500 joule per
second and Cp specific heat capacity of water is here, this is 0.0418 0 here, this is you
know that zero point, I think it is 0.00418 kilojoule per second. This is simply we can

785
write 4.18 Joule per, here this is Joule per gram degree Celsius here, Joule per gram
degree Celsius.

So this is your Cp value and volume of pan that will be is equal to V. This is simply
given 5.0 liter and density of the water is equal to let it be 1000. This is gram per, this
is 1000 kg per meter cube. That means here we can say simply 1000 gram per liter,
because kg 1000 gram and then what is that, meter cube means 1000 liter.

1000s, 1000s will be cancelled out. So ultimately it will be 1000 gram per liter.
Therefore, we can substitute this value in the previous that energy balance equation as
shown here in the slide. And then we have 100 will be is equal to then 30 plus here
2500 divided by 100 into 5 into 4.18 here. So it will be coming as, this is into t.

So from this t will be is equal to what; t will be is equal to ultimately 668.8, this is in
second. So it will be coming as 11.14 minute. At 11.14 minute you know that your
water will be starting to boil.
(Refer Slide Time: 20:38)

Let us do another example here, in this case heating of a stirred tank. You know that
in chemical engineering process where in a reaction sometimes you need to you know
stir the solution to execute the reaction at a certain temperature and pressure.

786
And if it is done at a continuous mode, then there will be a certain you know flow rate
at which the stream will go into the reactor and at a certain rate the product will be
coming out and at a temperature to be maintained for that reaction.

Now let us consider this problem here where are we will do this you know energy
balance to find out certain expression of you know this process based on which you
can calculate what should be the time required to reach the liquid temperature at a
certain temperature or what should be the profile of the equation for the temperature
change with respect to time inside the reactor.

Now let us consider an organic liquid which is at initial temperature T0 degree Celsius
is being heated in a stir tank. The liquid enters the tank at a rate of suppose m 1 kg per
hour at this temperature of T0 degrees Celsius. And the stream leaves out at
temperature T from this reactor at time T.

The tank holds this m 1 kg of liquid which is initially at T0 degree Celsius. The heat is
provided by steam considering at temperature Tsteam degree Celsius in coils which is
submerged in the tank. The rate of heat transfer is given by Q will be equals to here
some expression is given that heat transfer will be actually basically based on that
temperature difference of steam and the temperature of that liquid inside the stir tank.

So if there is a temperature difference and that heat transfer basically will be based on
that temperature difference and this heat transfer will be proportional to that heat
transfer, heat differences or temperature differences. So that proportionality constant
of that heat transfer based on that temperature difference will be called as heat transfer
coefficient.

That we have already described in our lectures that very beginning of this course,
where we were discussing about the rate of you know transfer or transfer equation or
rate of processes, where we have described this heat transfer rate, mass transfer rate,
even some other you know fluid flow rate systems that we have described.

So accordingly we can say that here the rate of heat transfer is proportional to that
temperature difference of this steam and the liquid inside the tank. And since this heat

787
rate is proportional to the temperature difference, the proportionality constant will be
regarded as that heat transfer coefficient.

And that heat transfer coefficient is denoted by this h here. That units are joule per
second degree Celsius. Now heat capacity of the liquid is given by Cp and in this case
the shaft work of that stirrer is Ws watt is given to you. So at this rate this, you know
that bubble will you know stirring that, you know that liquid inside the reactor.

Now in this case you have to write the final differential equation from which you can
find out the time to reach the liquid temperature at T degree Celsius and also express
the final form of equation for temperature as a function of time.
(Refer Slide Time: 25:23)

So let us solve this problem here. Based on that general energy balance equation for
unsteady state, we can write dU/dt. That will be is equal to
d (U )
  min Hˆ in  mout Hˆ out  Q  Ws
dt
Now rearranging this equation and separate variables, separating variables we can
write d(miCvT), this is basically internal energy change with respect to time dt. Inlet
flow rate is zero.

Whereas we can write output flow rate as a certain you know rate of that heat you
know transfer there. Here it will be simply minus, what is that m out. It is let it be here

788
m dot into Cp and temperature difference is T minus basically T0 and then plus heat
energy supplied to the system as Q .
d (mi CvT )
 0  mC p (T  T0 )  h(Tsteam  T )  Ws
dt
That will be simply h(Tsteam  T )  Ws which implies the final form of equation like this
after separation as dT/dt. That will be is equal to

dT mC p (T0  T )  h(Tsteam  T )  Ws

dt mi C p

Since it is rate, so we are giving a dot there and divided by mi initial mass into
specific heat capacity of the fluid.

Here you can write Cv also no problem, because Cv and Cp will be same for liquid.
Now after integration, what we can write?

(Refer Slide Time: 29:16)

After integration we can write

 (a  b)T  d 
ln    (a  b)t
 (a  b)T0  d 
T0 is the initial temperature plus d. That will be is equal to a – b into small t, small t is
the time. In this case we have brought here a, b and d. These are coefficients from that
equation of that integration. After integration, we have simplified as this.

789
Where we have defined this
mC p h W
a ; b ; c  s ; d  bTsteam  aT0  c
mi Cv mi Cv mi Cv
So after substitution of this a, b, c, d here in this equation you can have this final form
of equation for the temperature as a function of time. So if you know this mi value
initial mass, if you know that Cv value, if you know that heat transfer coefficient, if
you know that shaft work, if you know that you know that m dot that means here at
you know outlet condition at a certain rate, then we can easily find out what should be
the temperature for a certain time.
(Refer Slide Time: 32:24)

Let us do another example, with this you know unsteady state energy balance
equation. There again if we consider that an adiabatic stir tank is used to heat 50 kg or
a 48% glycerol solution in water. Here mass capacity, mass heat capacity is given as
3.54 joule per gram degree Celsius and electrical coil which delivers certain amount
of power, here it is given 3 kilo Joule per second of power to the tank.

And it is seen that 90% of the energy delivered by the coil goes into hitting the vessel
contents and remaining 10% will be lost to the atmosphere. Now the shaft work to
rotate that you know stirrer is 600 watt. The glycerol solution is initially at 15 degrees
Celsius. Now you have to find out how long will the solution take to reach its
temperature to 90 degrees Celsius.

790
So here interesting that mi value is given to you, initial amount 50 kg and temperature
also given to you 15 degree Celsius. Shaft work is given to you to heat that solution
this 3 kilojoule per second. This amount of heat is supplied to that system where 90%
will be utilized, other 10% will be lost.

Now at this condition you have to find out how long it will take to reach this solution
to a temperature of 90 degree Celsius. So, again we will do it by general energy
balance equation. What is that general energy balance equation?
(Refer Slide Time: 34:23)

We know
d (U )
  min Hˆ in  mout Hˆ out  Q  Ws
dt
In this case again this inlet and outlet streams to be neglected because there is no
stream. This is batch wise process so simply we can write this equation as here
d (mi CvT )
 Q  Ws
dt
which implies
dT Q  Ws

dt mi Cv

In this case Q net that means net energy supplied to that solution to heat that solution

to 90 degrees Celsius is Q net. It will be basically what is that Qe that is you know
entered to that solution plus what is the heat energy lost to that surroundings.

791
Since the system is adiabatic, system is adiabatic, that means no heat energy is lost is
you know is going to that surrounding from that. So Q surrounding here will be

equals to zero. So, we can say that Q net that will be is equal to Q entering to the
solution. This is basically 90% of that utilized there which is added to that solution.

So here we can write it will be is equal to that is Q which is supplied into 0.90. This
is basically zero sorry 3.0 into 0.90. So, this is basically 2.7 kilojoule per second. So,
this amount of net heat to be supplied to the solution to heat up that solution to 90
degrees Celsius.

Now if we substitute this value we can write here dT/dt that will be is equal to Q is
27, since it is kilo Joule, so we can convert it to joule here 2700 minus here Ws is
what? It is given 600. So we are substituting here in this equation. So divided by m i it
is given here 50,000 50 liter means 50,000. I think, here it is given 50,000 yes there
into what is that?

No this is 50 kg it is given, am I right? This is m i so 50,000 gram and into Cp is

given, what is the value of Cp it is given 3.54 Joule per gram per degree Celsius. So
finally it will be coming as 0.012.
(Refer Slide Time: 39:11)

So from which we can write T – T0. It will be is equal to 0.012 small t, this is time
from which we can calculate t will be is equal to T – T0 divided by 0.012. Which

792
implies t will be is equal to this is 90 degree Celsius, your final temperature minus
initial temperature is 50 degrees Celsius and then this 0.012. It will be coming as 6312
sorry 621 6321.0 this is second.

So finally, we can say that the time required to reach the temperature of solution at 90
degree Celsius is 6321 second, which is equals to 1.76 hour. So 1.76 hour time will be
taking to reach the solution temperature to 90 degree Celsius.
(Refer Slide Time: 41:00)

So we have given different, you know examples to understand the unsteady state
energy balance equation and how to solve those equations even in general form and
also we have given some examples numerically. So I think you understood this, you
know the energy balance and how to apply it to the chemical engineering processes.

I would suggest you to go further and solve some problems given in examples in the
textbook even in exercise. So it will be you know easier to understand based on this
concept and it will be you know more useful for you.

In the next lecture we will try to start another module of that you know computer
techniques and based on which we will discuss about the degree of freedom and
analysis for that processes and thank you for your attention for this lecture.

793
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 29
Least Square Method Linear Equation Fitting

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. Today we will start module 10, which is about the
computational techniques and in this lecture we will try to discuss about the least
square method by which how to fit the linear equation graphically based on the
experimental data.
(Refer Slide Time: 00:57)

And for that we have actually discussed that how to fit that or how to make a
differential equation or you can how to make the energy balance equation, material
balance equation based on the chemical process and to solve those you know material
balance equation or energy balance equation, whether it is linear or nonlinear, you
need to solve those equations.

Now there are several, you know way to solve those equations. Basically, to solve
those equations either you can do numerically or by you know that analytically. Now
to solve that analytically, you know that you have to you know manage those
equations, either by multiplying or dividing the coefficients and eliminating some
coefficients from one equations and comparing to other equations.

794
After that either subtraction or addition, you will see that you can eliminate some
variables and those variables after that, you can you know get just by you know
solving, if it is coming one single equation based on which you can solve that single
variable from those equation.

You will see that since there are you know various chemical engineering operations
where you need to sometime you know predict that dependent variables like you
know that suppose, any fluid is flowing through the pipe then there you will see that
there will be a frictional pressure drop will be changing based on the you know that
variables like velocity like diameter of the pipe.

Even you can say that fluid proprieties. Now you need to sometimes predict those you
know a change of pressure drop based on that variables just by you know just
proposing an equation. Whether it may be linear or nonlinear that will be you know
based on that you know experimental data on that particular you know results, in this
case like fictional pressure drop.

Like other also you can say that like suppose you want to you know predict some
output of the process like process efficiency or yield or you can say that suppose heat
transfer coefficient, mass transfer coefficient, those you know variables are called the
dependent variables, why? Because these variables depends on different operating
variables.

Now in that case, suppose heat transfer coefficient will be depending on the you know
Reynolds number and how that dispersion coefficient will be you know changing with
the Reynolds number, even other variables that also can be predict based on the
experimental data.

Now to you know make that one you know empirical equation or any you know that
linear equation based on that experimental data you need to sometimes you know
estimate the coefficient of that equation based on which you can say that this equation
will be you know predicting that experimental data.

795
Now in generally if we consider that, that dependent variables will be you know a
function of some independent variables like in case of suppose fluid is flowing
through the pipe, their frictional pressure drop will be you know varying with that you
know fluid properties like viscosity, density, even surface tension and also pipe
diameter and also you can say that velocity of the fluid.

So this velocity, pipe diameter, viscosity, density, surface tension those are
independent variables based on which you can say that, that pressure drop, friction of
pressure drop which is dependent variables will be changing.

Now let us consider that how to actually fit that frictional pressure drop or suppose
any in general dependent variables depending on that independent variables, how one
can you know develop an equation and how that equation can be fitted with that
experimental data. For that you know dependent variables based on that independent
variables.

Now to find out those you know or make that equations you need to solve that
equation coefficient either by least square method or numerically based on other you
know computational programming method. Now let us consider that least square
method here by which you can you know develop an equation to predict that
experimental data.
(Refer Slide Time: 06:37)

796
Now what is that you know least square method? Sometimes we need to express that
experimental results of any dependent variable by an equation. Now let us consider
that equation which will be you know expressing by dependent variables and
independent variables.

Let us consider that dependent variables as y and independent variables are x0, x1 like
this. Now if we propose an equation based on this dependent variable and independent
variables like then

Now here this is an equation, which is only one variable here x, whereas this b0 and b1
these are coefficients.

And these coefficients you know can be you know estimated if you fit this equation
with the experimental data. But whenever you will be fitting these experimental data
with this equation you will have some error, because this equation will not give you
that 100 percent correct data of that experimental data.

Or you can say that there will be a sudden deviation of this you know predicted
equation or proposing equation based on that experimental data from that
experimental results. Now how to estimate this b 0 and b 1 coefficients and what will
be the goodness of feat of this equation with that experimental data you need to know.
(Refer Slide Time: 08:17)

797
Now let us find out these things here in this lecture, suppose that if epsilon the error
between the experimental value and you know that propose you know equation. So
this experimental value is capital Y and this y dependent variables will be obtained
based on that equation

Now error between these two you know values is representing by you know epsilon.
Now this epsilon of course, there will be a certain error between this. This is deviation
or epsilon you can see in this figure here. This is your experimental data. These are
your experiment data and this dotted line is representing that data which can be
obtained by that equation

.
Now if you consider this experimental data, and the data obtained by this equation
here, there will be a certain error. So this error is represented by epsilon. Similarly, for
other points also there will be an error. Similarly, here also there will be another error.
Here also there will be another error.

But all those error, if you consider individual data of that experiment and individual
data obtained by that equation, they may not be same. There may be you know that
some small error maybe bigger error maybe even that all the values of this error will
not be uniform in value or you know that number.

So in that case, you know that you have to optimize this error so that you can get that
less percentage of you know deviation of this experimental this proposed equation. So
you have to optimize this you know error there. And based on that optimization in this
case you have to minimize this error.

So the best way of estimation of the coefficients, here b0 and b1 can be obtained if you
minimize this error there. Now by minimizing the sum of the squares of the error or
between these y’s, capital Y and small y for all the i set of experimental data, you can
write here minimize of this f function.

798
That will be is equal to here basically that epsilon i whole square and this is for ith
component. So for all components you have to sum it up. So summation of all square
of these errors if you can minimize then you can get that you know best value of this b
1 and b 0 from the experimental data.

So that you can get least error so that you can get less percentage error of this
experimental data with the proposed equation. So here let it be considering here this
epsilon i which is to be minimized. Now this epsilon i is basically Yi – yi. What is this
yi? yi is basically a function that we have considered here,

.
So this equation to be minimized here.
(Refer Slide Time: 11:51)

Now consider that model linear equation in the coefficients with one independent

variable x that is as a function there. So here the objective function will

be is equal to here that F will be is equal to summation of i to n of Yi – yi whole
square. That will be is equal to here simply Yi means here, this one this function.

So

Here in this case, we are getting two unknown coefficients. There may be more than
one and more than two unknown coefficients. There also you have to do in this way,

799
what should be the error which is to be minimized. Now there are two unknown
coefficient in this case b0 and b1.

And also we can have that there will be a certain pairs of experimental values of Yj
and xj. Here you have to minimize this F with respect to that b0 and b1 there.
(Refer Slide Time: 13:00)

Now if we apply that necessary conditions for a minimum error, that means here

That should be is equal to zero because to minimize that this differentiation will be
equals to zero as per necessary conditions. So we can express this equation here

Similarly, that error with respect to coefficient b1 that can be expressed like this. Now
for minimum error, this will be equals to zero and this will be equals to zero. Now
rearrangement of these two equations, we can write a set of linear equations in two
unknowns, here b0 and b1. So we can write here from these two equations here,

800
Similarly from this equation 2 here, let it be this equation,

these equation 1 and this equation 2. So from these two equations, you can write this
two linear equations as a

So from these two equations, we can solve for b0 and b1 just by elimination techniques
or either way or other methods.

(Refer Slide Time: 14:27)

801
Now from those equations we can write after simplification or rearrangement like this
in this way this and this. Now the two linear equations here above as shown here in
the slides, here two unknown so two linear equations we are getting. So we can solve
this equation and we can get the solution for you know b0 and b1.

And now this b 0 and b 1 coefficient is basically intercept and the slope, if you are
considering that equation as a straight line equation, so in that case b 0 will be
intercept and b 1 will be is equal to slope.
(Refer Slide Time: 15:10)

Now after solving these two linear equations, we can express the coefficients in terms
of that independent and dependent variables here by this here. So we can write here b0
is equal to here this based on this equation.

Here p is this number of datas or you can write here n also instead of p here n. So it
will be n number of data n also you can write.
So b0 can be calculated by this equation and b1 can be calculated by this equation.

802
So the model equation will be is equal to

.
Now this b0 and b1 will be you know calculated based on this you know equation,
which is basically as a function of that experimental data of that variables.
(Refer Slide Time: 16:10)

Now how you know good this you know equation to be fitted with the experimental
data with list error that you have to assess there. Now to access this equation, you
have to find out one coefficient that is called correlation coefficient. This correlation
coefficient is significant because this will give you that how or what extent of
goodness or fitness of that equation with the experimental data.

So this is basically represented by the notation R square. So this R square is called

correlation coefficient. This is defined as by this equation here. Now this R square
value if it is coming near about to 1, not greater than 1, then you can say that the
equation will be well fitted with the experimental data.

But if it is coming below, you know 0.90 we will see that there will be a huge
deficient of the experimental data with the data given by this equation. So in that case
you have to find out that goodness of fit of that equation. If your equation is not
giving that R square value near about 1 you cannot propose that equation to predict
the experimental data.

803
Now how to find out this correlation coefficient. Now to find out this correlation
coefficient, you need to you know sum squares of you know variables there. Now
what is that sum square of variables here? We will see we have defined here you have
given here in this slide some equations for that.

You have to calculate first this SSxx. What is this sum squares for x values, that is
independent values. What is that? This is basically defined as

What is the xi? xi is the independent variables or x bar is the average of that
independent variables.

That average of that independent variables can be calculated based on this equation
here simply you have to sum it up that independent variables and divide it by number
of here data. So you can obtain this x bar here.

Similarly, SSyy you can calculate based on this equation which is defined as

Here Yi is the you know dependent variables whereas Y bar is the average value of
that dependent variables based on that experimental data and then SSxy is basically
that

804
and then you have to sum all those data. So product of this deviation of xi from mean
and deviation of Yi from its mean and then sum.

So it is called SSxy. It is called sum squares of xy. Now after that if you get this value
up SSxx, SSyy and SSxy, you just substitute that value here in this equation, you can get
this R square value. Now you will see there will be a sum standard error of this you
know b0 coefficient and b1 coefficient here.

So that standard error or that b0 based on that b0 you can obtain based on this sum
square and this average value of dependent variables and also how many numbers of
experimental data is there. So in this case it is defined as like this

So from this equation, you can obtain what will be the standard error of b0. And
similarly standard error for b1 it will be

whereas S is defined as this

Here n is the number of experimental data.

So in this way you can find out if you propose any equation to predict your
experimental data, how or what extent of goodness of fit that you know experimental
data with your proposed equation.
(Refer Slide Time: 21:15)

805
Now let us do an example here to you know clarify this you know theory, of least
square method. Let us consider that some experimental value in general we are
considering that experimental value as you know independent variables like x where x
values are like suppose 1, 2, 3, 4, and 5.

And this x value will you know effect this dependent values like y which will be
valued as 2.5 for x1. Similarly 3.5 for x2 and it will be you know here 5. Let it be 5 for
x3 and then it will be 6.5 for x4 and 7 for value x5. Now in this case you have to find
out you have to fit this you know data and proposing that equation

Now based on this experimental data, you have to find out this b0 and b1x value. Now
we have to use those you know equivalent to calculate this b0 and b 1. So what is that
equation? We know that b 0 that will be is equal to what?

Summation of yi, summation of you know xi square and then minus summation of xi
summation of xiyi divided by you know that n into you know summation of xi square
minus of summation of xi whole square. This is your b0.

Whereas b1 will be is equal to n into summation of xiyi minus summation of xi into

summation of yi divided by in into summation of xi square minus you know
summation of xi whole square. So in this way you can calculate what will be the b0.

806
So as per this first of all you have to find out what will be the summation of y, what
will be the summation of xi square, what will be the summation of xiyi.

So let us find out those you know values. Here let it be x, here let it be y, here let it be
xy value and then x square and then here you can say after that you can easily
calculate. So what is the x value here 1, here 2, 3, 4, 5. These are the x values and y
values are here 2.5, here 3.5 and 5 and 6.6 and 7. And then xy that is x into y it will be
coming as 2.5.

And then 7 here and then it will be 3 into 5 15, then 4 into 6.5 it will be coming 26
and then 5 into 7 35. And then x square it will be coming as what is the value of x
square here. This will be 1 here then 4 this 9 and then here 16 and then 25. Now we
have to find out the summation of this x.

This will be coming as 15 and summation of y it is coming as 24.5 and summation of

xy it is coming 85.5 and summation of x square it will be coming as 55. After that,
you just you know calculate what should be the value of this b 0 and b 1. So what
should be the b 0? After substitution of this value here in this equation, we can get b 0
is equal to 1.3 and b 1 is equal to 1.2.

So from this you know example we can say that from this experimental data of x and
y we can find out what will be the b0 and b1. Now final equation then it will be
coming as here y. That will be is equal to 1.3 + 1.2x. So this will be your proposed
equation based on your experimental data and by this equation you can calculate what
will be the y value once you know that x value.

Suppose that you know that x value is 1. Then what should be the y value. So it will
be coming what is the value? Let it be 1, so 1.2 + 1.3. Then it will be simply 2.5. So
as per this equation as per this equation of predicted value, so it will be coming as 2.5.
Whereas if you consider that x is equal to 2, you will see that this value will be
coming as per this equation, it will be coming as 3.7. Whereas, here y value is 3.5.

So we are getting from this equation it is coming 3.7. There will be a certain
deviation, very small deviation will be there. Whereas the first point, it is exactly the

807
same as with the experimental data. Similarly, if suppose x is equal to 3, you can get
this value or the value it is coming 4.9 whereas, experimental value is 5. So there is
also small deviation.

Similarly, if you are considering that x is equal to 4, experimental value is 6.5 but
your predicted value by this equation it is coming 6.1. Similarly, for x is equal to you
know 5 we are getting this y value as 7.3 whereas its value as per experiment, it is 7.
So there is a deviation.

So we can say there will be a certain deviation for each value of this experimental
value comparing with that, you know predicted value. So those errors in this case first
point this error is coming 0, second point it is coming -0.2. Third point it is coming
0.1 this error and fourth point is -0.3 and last point it is coming almost what is that 0.

And you will see that error is coming almost you know that here is 0. So you are
getting here zero error and equation what is proposed it is exactly giving the same
value of experimental data without you know that considerable you know error.

So we can say that we can predict we can propose an equation, where we will be
considering there will be a certain you know that coefficients that is to be found from
the experimental data and how to find out that experimental data you can use this least
square method.

Now how you know what is the extent of goodness that is R square value what should
be that value, you have to find out based on this experimental data now for that you
need to calculate as per discussion that what should be sum squares.
(Refer Slide Time: 29:36)

808
So sum squares if you consider here sum squares, let us see what is the sum square are
here. First of all SSxx to be calculated thus will be equal to what? This is basically xi
minus x bar what should be the value here? But for that you need to know that x bar
where x bar this is basically that 1 by n into summation of know that xi.

So it is coming as per that data it is coming 3and then SS xx after substitution of this x
bar and subtracting that x bar from that individual data of x i and then whole square of
this data and then summing up it will be you know giving the value n. Similarly, SSyy
to be estimated. This will be basically defined as Yi minus Y bar again whole square,
this will be coming as what?

But before calculating you have to first calculate what will be the Y bar. So this is
basically 1 by n into summation of Yi. So it is coming as here 4.9. So after
substitution of here, this SS yy it will be coming as 14.7. And then you have to
calculate what should be the R square value. So R square value that is correlation
coefficient it is basically, what is that, defined as SSxy square divided by SSxx into
SSyy.

So for this SS xy also it is required to know. So SS xy can be obtained based on this

you know definition here, that is x1 minus x bar into Yi minus Y bar. So after
substitution of this value, you can get this value as 12. Now after substitution of this
value of SSxy is nothing but 12. So 12 square divided by SSxx it is basically 10 and
SSyy it is 14.7.

809
So it is coming as 144 divided by 147 it is coming 0.98. So it is very near about to 1.

So we can see that this equation y is equal to that means 1.3 + 1.2 into x is fitting very
well. very well with the experimental data. So this is your final you know proposed
equation here. So in this way we can obtain what should be the you know goodness of
fit there that is R square value correlation coefficient.

And then you know what will be the standard error based on that b 0 value, standard
error that will be is equal to as per that b 0. So it will be basically s into square root of
1 by n plus x bar square divided by SSxx. So it is coming basically 0.332 after
substitution of this value and SE based on b1 it is coming s by root over SSxx.

It is coming 0.1 where S is basically square root of SS yy minus SS xy whole square

divided by SSxx divided by n minus 2. So after substitution of this value, it is coming
0.316. So we can obtain this standard error based on these coefficients b0 and b1 based
on this equation.

So we you know that, then consider an equation like in this format of Y is equal to b0
+ b1x and if you know that experimental value of x and y then you can easily hone
that or propose that equation in the form of Y is equal to b0 + b1x just to and also
obtain that b0 and b1 from this experimental data.
(Refer Slide Time: 35:27)

810
Now another important point that for different chemical engineering operation, you
may get different forms of you know experimental data and you will see that that
experimental data may come you know based on different you know dependent
independent variables.

Now that dependent variables maybe in terms of frictional pressure drop, maybe you
know some you know combined form of frictional pressure drop and with other you
know variables and as a whole one dependent variables would be formed based on
you know combination of other variables.

And also you will see that the independent variables maybe of different forms. So you
need to sometimes correlate to those independent and dependent variables and to
predict those dependent variables based on independent variables, you can you know
rearrange those variables or you can propose those, you know experimental data
based on that equation of the form that is linear form of that is Y is equal to here b0 +
b1x.

But sometimes you will see that some general you know principles, general equations
that are coming from that basic laws. There also you will see that some laws will be in
other forms of that you know b0 + b1x function. There may be like you know the
format like y is equal to a x square plus b.

There may be you know that some other forms y square is equal to a by x plus b.
There may be you know that some forms will be coming as 1 by y is equal to a into x
plus 3 plus b. This type of form. Maybe you know sin y will be equals to a into x
square plus 4 or x square minus 4. Sometimes you will see some forms will be
coming as y is equal to 1 plus x into m x square plus n whole to the power 2.

Or sometimes you will see that some equation will be coming as you know power law
likewise equal to a into x to the power b. So those equations are you know that
nonlinear form it may be but single equation nonlinear form. So to fit those nonlinear
form of equation with the experimental data, what we have to do?

811
You have to first convert this nonlinear equation into a linear form. After that you just
follow this least square method to find out that unknown coefficients based on those
equation. So let us see here, what are the different types of equation you may expect
there. Like here Y is equal to aX square plus b.

If suppose this type of equation is coming, and you have to find out what should be
the value of a and b here of this equation. Here x square or x is you know independent
variables and y is dependent variables. So this is nonlinear equation. You have to you
know rearrange this nonlinear equation into a linear equation. How to do that?

If you consider that this equation will be is equal to Y = aX + b or you can say that Y
will be is equal to what? b1x + b0. So in this case, what we have to do this Y to be
considered as capital Y as a dependent new equation, new variables and x square will
be considered as X here. So here in this case, you can get this Y = aX + b.

Now comparing this equation of Y = b1x + b0. So as per least square method, you can
easily find out this here b1 and b0 based on your experimental data of x and y.
Similarly, y square will be equals to a by x plus b. You just you know rearrange this
as y = aX + b where in this case capital Y would be is equal to simply Y square.

And here X will be is equal to what 1 by x. So this then again you have to compare
with this equation and then follow that least square method that what we have
discussed here. Similarly, suppose if you are having this type of equation or you want
to propose this type of equation with your experimental data and fit this equation with
your experimental data.

Now to find out this unknown variables of a and unknown coefficient of a and b here,
what you have to do? You have to make it linear form as Y = aX + b. Like in this case
you have to consider here 1 by y would be is equal to Y and x + 3 will be as X. And
then you just fit it with your experimental data and follow this least square method.

Similarly, sin(y) that will be is equal to a into x square plus b or x square minus b. So
in this case again sin(y) to be considered as capital Y here and x square minus 4 will

812
be considered as X and then simply it will be coming as Y = aX + b. This is basically
that equation. Similarly, y = 1 + x into mx square plus n whole to the power half.

This is basically again you can write in this form Y = aX + b where very complicated
here in this case, y minus 1 whole square divided by x square will be as in Y whereas
x square will be as X. Here see important thing is that dependent and independent
variables combinely you know that they can form one dependent variables here as Y.

So here see Y and X here both as a combined they are forming one dependent variable
as y – 1 whole square by x square. And it will be regarded as here Y. And then x
square will be as X. So again, if you are having this type of form and then follow this
least square method as discussed here, you can get what will be the value of a and b
there.

And once you know that a and b and then you can consider that here m should be as a
and n should be as b. Here again if suppose, if you want to you know fit this equation
of Y is equal to aX to the power b. This is you know power law model. What you
have to do to make this you know linear form you have to take the logarithm on both
sides of this equation like here ln y that will be is equal to b into ln x plus ln a.

This will be simply Y = aX + b where Y will be is equal to here ln y and X will be

here ln x. And a and b are as accordingly they are a will be is equal to b here, b will
be is equal to ln a. So in this way you can calculate or you can say that here b will be
is equal to here b 1 and ln a will be is equal to b 0. So accordingly you can calculate
here.

So in this way you can you know make that nonlinear to linear and then comparing
with this you know equation of y = b1x plus b0 and then apply that equation of least
square method to find out this b1 and b0 value. Now let us consider one example here
based on this you know nonlinear equation
(Refer Slide Time: 43:40)

813
Where we can consider here one example of like let us consider there is an operation
like oil is flowing through pipe. Now during the flow there will be some frictional
pressure drop and from that frictional pressure drop you have to calculate what will be
the friction factor there, friction factor as part principles of fluid mechanics there.

That whenever there will be frictional pressure drop now you have to you know,
know what should be the friction factor based on which you can say that, that flow
will be how viscous and all those things. Now this friction factor is basically a
function of Reynolds number.

What is that Reynolds number we have discussed at the very beginning of this course
that Reynolds number is a dimensionless number, which is defined as you know
ud/. Rho is the density of the fluid, u is the velocity of the flow and also d is the
diameter of the pipe and mu is the you know viscosity.

So whenever pipe is there and through the pipe is fluid is flowing like oil, water
whatever it is. Then you will see that there will be some frictional pressure drop
between these two points, point 1 and point 2. So this frictional pressure drop, from
this frictional pressure drop, there will be some factor, friction factor it is called.

That friction factor it is coming basically this frictional pressure drop is

depending on the you know that kinetic energy of the system and then the factor of
that you know kinetic energy to be you know that, you know resulted from this

814
friction factor and will be equal to that kinetic energy for which you have to you know
multiply some factor it is called friction factor.

Now that friction factor, you know more about that frictional pressure drop, friction
factor improved mechanics course there. We have already, you know developed one
course that MOOC course that is fluid flow operations. There you I think will know
more about this friction factor and frictional pressure drop.

There we have already you know floated you know you can also have those you know
lectures in you know in YouTube also there. Or you can you know register for this
course in future also if it is coming then there. And you will know that more about
that frictional pressure drop and friction factor.

Now this frictional pressure drop or friction factor, that friction factor is basically is
defined as what is that this friction first friction factor, this frictional pressure drop
first it is basically you know 2f into rho u square L by d okay. So from this you can
calculate what will be the f. This is basically delta P f d, d is the diameter of the pipe.

This is d, d by 2 rho u square L. From this, this is basically L, this distance is L and
diameter is d and density of the you know fluid is rho and you know that viscosity is
mu. So you know now this friction factor is basically depending on the Reynolds
number.

Now you will see that, if Reynolds number is value is less than 2300 you will see this
you know flow will be laminar, very slow flow of this you know there and highly
viscous manner will be there and because of which there will be a flow is very, you
know slow and it is called laminar flow and if Reynolds number is greater than 4000s
it will be called as you know turbulent flow.

So basically this friction factor depending on the you know Reynolds number. For
laminar flow Reynolds number is you know you know for laminar flow, this friction
factor is 16 by Reynolds number. Whereas for turbulent flow, this friction factor is
you know 0.079 into Reynolds number to the power -0.25. So this is your friction
factor.

815
Now this 0.079 and 0.25 those values are actually unknown values. Those are
obtained based on the experimental data. Now let us consider this type of you know
correlation. Let us consider that this f will be is equal to here some value of a into
Reynolds number to the power you know b. Now in this case, this friction factor is a
you know function of Reynolds number and it is correlated by this equation.

So this is nonlinear equation, you have to find out this a and b from your experimental
data. Now how to do that experiment? First you have to do this experimental to find
out this frictional pressure drop and from that frictional pressure drop, you have to
calculate what should be the you know friction factor and then Reynolds number.

You will see that based on that Reynolds number this friction factor will be changing.
Now let us consider those values here. Now if you have this Reynolds number and
friction factor like this, for Reynolds number of 4000s this friction factor is coming
0.01 sorry 0.01, this is your friction factor for this Reynolds number.

And for Reynolds number 4496 this friction factor is 0.01 whereas 4999 this friction
factor is coming 0.009. Whereas for Reynolds number 5497 it is coming 0.009 and
then for Reynolds number 5997 it is coming 0.009 up to here three digit we are
considering. Now based on these you know experimental data you have to establish
this equation f is equal to a into Re to the power b.

You have to find out what will be the a and b, this coefficient based on this
experimental. So you have to you know follow that least square method. Let us do
this here.
(Refer Slide Time: 50:58)

816
What you have to do first, you have to convert this equation a into Reynolds number
to the power b to a linear form by taking logarithm on both sides of this equation as ln
f. That will be is equal to ln(a) plus b into ln you know (Reynolds number). In this
case we will consider here this ln f will be is equal to Y and then ln Re will be is equal
to x and here b we will be considering as b1.

And ln a we will be considering as b0 and here thus plus. So we are having Y = b0 +

b1x where this y is equal to ln f and x will be is equal to ln Re and here b will be is
equal to b1 and ln (a) would be is equal to b0. Now we are having this equation of
linear equation from this nonlinear equation.

Now you have to solve or you have to fit this equation with your experimental data to
find out this b0 and b1. So in the same way you have to calculate all the values. As per
that you have to calculate first what is the x value? This is basically ln Re. You know
Re, so what should be the ln Re; y this is basically ln f.

You know that f value and accordingly it will be coming us ln f. And then what is
that. Here xy and then x square, like this and also epsilon a, epsilon here like this and
accordingly you have to calculate also what is that you know that x minus x bar here
whole square and then y minus y bar whole square and then here also x minus x bar
into y minus y bar.

817
So for all those values here you can get different values of this xy, x square, epsilon,
this and this.
(Refer Slide Time: 53:48)

So after getting this xy and xy you can obtain this value of b 0 from that equation of
here what is that summation of yi, summation of xi square minus summation of xi into
summation of xiyi divided by what is that n into here summation of xi square minus
summation of xi whole square. So after substitution of this value, it will be coming as
- 2.5436.

Similarly, you can get after substitution of different value of xy summation in you
know this equation of definition of b1 it will be coming as -0.24938 and you can get x
bar will be is equal to here 8.5066 and then y bar that will be is equal to minus here
4.665 and then SS xx you can get this value as you know that 0.10.

SSyy you can get this value of 0.006384 and then you can get a SS xy that will be is
equal to -0.02558. And then you calculate S that will be coming as 0.001 and then
finally after substitution of this some squares in the definition of R square then it will
be coming as R square will be equals to here this is SS xx square, sorry this is xy
square divided by here SSxx into SSyy. So it will be coming as 0.999.

So this is your correlation coefficient. So from this correlation coefficient you can
obtain what will be the degree of fitness of this equation with your experimental data.

818
Since it is coming very near about to 1 we can say that this equation will be you know
fitted exactly with that experimental data.

So finally we can get what will be the coefficient of you know a and b value and then
what will be the final equation there. There in this case we can write then f will be is
equal to simply what is that equation? F will be is equal to a into Reynolds number to
the power b whereas a is coming as what is the value of a is coming?

It is coming as zero point you know that what is the value it is coming. This a is
coming what is the value of this you know a value? A value will be is equal to what?
Here a will be is equal to here exponent of b 0. This is exponent of b 0. This exponent
of b 0 that means exp of b 0 that will be is equal to a. That is basically here you will
get 0.0788 something.

So we can write 0.079 here into Reynolds number to the power. And b is basically
here b 1. So it is coming -0.249. It is exactly -0.25. So it is coming as -0.25. So in this
way you can have this equation. So we can develop this equation for f as here 0.079
Reynolds number to to power -0.25. So this equation is developed by Blasius when
you know 1964.

So there they have developed this equation based on the experimental data. So how
they have developed this equation basically, based on the experimental data and then
following that least square method, what we have described here, exactly the same
way.

So in this way you can also fit that experimental data and proposing that equation,
linear equation like y is equal to b0 plus b1x and you know fitting that equation with
the experimental data, you can obtain unknown coefficients of b0 and b1in this way.
Now this is the simple way to you know fit the experimental data with the linear
equation.

Now these things are basically for single equation. Now if there are more than one
equation involving in a particular chemical engineering process, what we have to do.
Like material balance, there are several units will be there in your chemical

819
engineering process. Now if you do the material balance you will see that there you
may get more than two equations, they are even you know that with different you
know unknown variables.

So there you may get that n number of linear and nonlinear equations. Let us consider
first that material balance equation where you can get only linear equations, set of
linear equations.
(Refer Slide Time: 1:00:04)

That set of linear equations can be expressed by this equation here given in the slides
where this you will see that a 11, this is coefficient x1 is one variable, x2 is another
variable and dot dot like n number of variables will be there.

Now all those variables like suppose in a particular chemical process like distillation
process.

So there are suppose you have to you know separate suppose, that propylene and
benzene by distillation process. Now there are two components propylene and
benzene. You have to heat it then in the vapor phase there will be some percentage of

820
propylene and benzene and in the bottom phase, there will be a some percentage of
benzene and propylene.

And you will see that there will be some total material balance will be there, like here
what will be the you total amount of feed is coming into the distillation column and
what is the output of that distillation column as overhead and bottom product. There
you can get you know one total material balance equation.

And then if you consider individual components of suppose propylene and benzene
and if you do the material balance for benzene and propylene in that distribution
column, you will see that you can get two you know again equations. So you can get
three you know equations there. All those equations will be linear equations.

So here simple equations, but in this case, you are having set of three equations with
some unknown variables. So that you have to solve. Not only like this simple you
know example you can get you know more than one unit distillation column along
with you know that condenser, boiler, pumps.

Even other you know sometimes separation unit like adsorber, absorber, all those
units, even sometimes reactor also can be used, like reactive distillation column.
There separately reactor and distillation will be there. So in that case you will see that
there are more than you know one units will be involving in a particular chemical
engineering process.

So for that what you have to do? You have to do the material balance for all the units
and then you can get the set of linear equations by balancing out those materials of
that components in each you know unit. And you will get set of linear equations there.
Now you have to solve those set of linear equations for unknown you know
coefficients.

Like this if we express those you know equations by material balance as this format,
okay? And then you have to you know solve this equations for this, you know
unknown coefficients of like this a 11 to a mn. Now in this case, these are all you
know linear equations here n number of you know variables involving there.

821
Like distillation there two variables here, what is that two components here propylene
and benzene, here two unknown variables maybe there, they are fractions there you
know more factions there. May be you know more than two variables also will be
involving. Let be n number of variables like x1, x2, x3.

Now you can get after material balance maybe more than two equations more than
one equations and there may be considering there n number of equations can be
formed by material balance. So you can express those set of linear equations after the
material balance by this set of linear equations.

And in compact form you can express this set of linear equations by this aX = b.
Where a will be a set of what is that a11, a12, nn and up to this a mn. And b will be like
this these are the you know amount that is coefficients in this case. Like total material
balance for the propylene or benzene or some components there.

So there it will be total what will be the amount in the inlet or outlet based on which
this b1, b2, bm to be defined. So there is a unique set of this x’s that satisfy this
equation number one for which you can get the solution. So let us have an example
for this you know concept.
(Refer Slide Time: 1:04:43)

Let us have one chemical engineering unit here. In this case suppose in this unit some
feed is entering as 100 kg as F and their composition is you know 50% you know

822
ethanol and 40% water and 10% methanol. And they are after separation of this, you
know component by you know either distillation process or other separation process
let it be a general unit here, this is a separation unit.

And in this case we will see that some amount will be coming out as overhead that
overhead will be you know as w which will contains that composition as ethanol as
you know 5.0% and here water will be as 92.5% and methanol here, it will be suppose
2.5%.

Whereas from the bottom product of the separation unit, it will be coming as P and
composition as 80% you know ethanol and 5% water and remaining 15% will be you
know methanol. Now in this case you have to you know write the set of linear
equations for unknown variables here and express that, you know equations by
material balance.

So if you do that material balance here, if we consider suppose ethanol first, we can
write the ethanol balance here. Here one is input two outputs are there. Here we can
write then input will be is equal to output since there is no reactions. So we can write
for ethanol 0.80 as here as a product, this is 0.80 P plus 0.05 w that is output.

That will be is equal to input is simply 50% since 50 here. Similarly for you know that
water balance if we do it will be coming 0.05 P plus 0.925 w. That will be is equal to
amount of water entering. That will be 40 and similarly for methanol we can write
0.15 p 0.025 here w. That will be is equal to what, 10.

So these are the set of linear equations by the material balance. So we can simply
express this material balance as a you know format of a, b that is matrix form here
that will be is equal to like this 0.8, 0.05, 0.15 and then 0.05, 0.925 and then 0.025 and
then here 50, 40, 10 this one. So this is called matrix form. It is called augmented
matrix.

So in this way any chemical engineering process, you can represent the material
balance equation a set of linear equations and after that you can solve either by you

823
know computers by programming or you know software that is already given that you
know programming language is their tools is there, so you can solve.

Or you can solve by manually also. You can use that Cramer's rule to solve that linear
equation as a you know matrix format and you have to find out for the determinants
and then how to find out that solution based on that Cramer’s rule you can use okay.
So I think you understood this you know computer techniques to you know how to
solve this to find out that you know nonlinear equation as a form of you know linear
equation.

And then finding out the coefficient by least square method and also how to represent
the, you know material balance equation for a particular chemical engineering process
unit as a set of you know linear equation. And I would you know suggest to further
reading of this know text books given here in the slides and practice it for
understanding this you know this least square method.

And then you can try also with other y is equal to some you know some values of
suppose a plus b x or y is equal to mX plus c format of equation just by having the
values of you know x and y and then finding out the b 0 and b 1 as per that equation
based on this least square method. So thank you for your attention.

Next lecture we will consider some nonlinear equation system and how to you know
solve that nonlinear equations based on other you know principles.

824
 Basic Principles and Calculations in Chemical Engineering
Prof. S. K. Majumder
Chemical Engineering Department
Indian Institute of Technology-Guwahati

Lecture - 30
Non-Linear Algebraic Equation System

Welcome to massive open online course on Basic Principles and Calculations in

Chemical Engineering. So we are discussing about computational techniques in
module 10. And under this module in this lecture, we will discuss about nonlinear
algebraic equation system and how to solve those nonlinear equation.
(Refer Slide Time: 00:55)

In the previous lecture we have described the least square method how to fit a linear
single equation with experimental data and how to analyze the error of that fitting data
with the you know that proposed equation we have discussed with example. So here
also we will describe about that, how to solve that nonlinear equation system.

If suppose any nonlinear equation is coming based on the material balance equation or
energy balance equation for a particular chemical engineering process, how to solve
those. First of all you have to know the basic principle of that solving nonlinear
equation.
(Refer Slide Time: 01:34)

825
You know that there are you know several nonlinear equations will be coming based
on that, you know material balance of chemical engineer processes. There you will
see a set of a nonlinear equation like this here as shown in the slides here like
f1 ( x1 ,....., xn )  0 . This is one nonlinear equation as a function of variables like x1 to

xn.

And another equation like f 2 ( x1 ,....., xn )  0 as a function of again those you know
independent variables of x1 to xn. And we can see that similarly there may be more
than two equations will coming in the you know chemical engineering process for its
analysis based on the material balance equation and after that we can you know
recognize these set of nonlinear equation as a you know f(x) that will be equals to 0
like this.
f1 ( x1 ,....., xn )  0 

f 2 ( x1 ,....., xn )  0 
 f(x)  0
....................... 
f n ( x1 ,....., xn )  0 

Now each function here in the slides that f as a function of that independent variables
of x1 to xn that corresponds to a nonlinear function. Of course, that will contains one
or more of the variables whose you know values are unknown which will be you
know calculated by a certain principle.
(Refer Slide Time: 03:08)

826
Now there are you know major general you know methods of solving those nonlinear
equation systems like you know some are you know successive substitution
techniques, some are you know differential homotopy technique, some are Newton’s,
you know mostly used that method like Quasi-Newton, Newton-Raphson method,
even Secant method, even Levenberg-Marquardt you know method.

Some other techniques also available like you know graphical solution even Regula-
Falsi method you know spreadsheet solution like this. So here we will discuss about
that Newton method which are mostly used to solve that nonlinear equation.
(Refer Slide Time: 03:56)

So here solving a single variable nonlinear equation how to solve first we have to
express. There you will see that if we have the spreadsheet solution like this here,

827
based on that you know nonlinear equation function. In this case, let us consider that
you have to you know estimate the solution of equation like x  exp(2 x) using a
spreadsheet.

Now in this case, you will see that the equation here x  exp(2 x) is totally you know
that nonlinear equation where you will see in the both sides of this equation you know
having this unknown variables like x here, you have to find out what should be the
value of x so that this equation will satisfy based on that you know unknown variables
there.

Now in this case you have to you know solve this equation based on spreadsheet like
what is that you have to assume you know that variables here x and after substitution
of that variables of that assumption value and what should be the value in you know
that in left hand side and the right hand side will be coming based on which you will
see that if you keep on changing that value of variables.

This you know deviation of this left hand side and right hand side will be you know
coming to reduced or maybe increased. Now whenever you will see that there will be
increase then you have to change the variables x in such way that so that your you
know deviation from this left hand side to right hand side will be reduced.

So in that direction you have to go. Like this here shown in this you know slide that if
you are considering here, the x value as 0.1 and accordingly what should be the
function f (x) will come. That will be is equal to it will be expressed as like
x  exp(2 x) . That will be equals to zero. This is very simple that it will be
x  exp(2 x) .

This is basically the you know deviation of this left hand side to right hand side. Or
you can express this as a function of x  exp(2 x) so that your x value, corresponding
x value will give you that function of this you know x  exp(2 x) will be equals to 0
or very near about to 0.

828
Now in this case you will see that if you consider this x is equal to 0.1 you will get
this function f(x) will be equals to - 0.7187305 you know 753 like this. Similarly, if
you increase that value 0.2 its value is coming like this here. This you know it is not
coming to exactly 0 as f(x) is equal to 0, but if you change this value of 0.3 you will
see that this you know deviation is coming to reduced here. Here 0.7 to 0.2 it is
coming.

Whereas if you keep on increase that value of x here 0.32 suppose if you assume here
0. 4 26156 you will see that this value of f(x) will be is equal to you know that is -2.73
into 10 to the power – 4. This is you know very near about to zero you can say. So in
this case you are getting this f(x) for this corresponding value of x here.

If you again increase the value of x here, here 0.5 you will see that this value is
coming to increase again 0.132120556 here. Again if you increase that value 0.6 it
will again it will increase to 0.29 and if you keep on increasing this value, you will
see there you know function of x that is f (x) will you know gradually increased.

So here initially it is decreased and then increased then it will be seen it will come
here at 0.426153. It is seen that this you know function’s value is coming almost
equals to zero. So we can consider here the value of x will be equals to 0.426156
which will give you that function f (x) will be near about to zero.

So in this way we can you know find out what will be the solution of this you know
nonlinear equation. So this is called spreadsheet solution but it is trial and error. It will
take a lot of time to you know find out this you know a solution of this nonlinearly
equation.

But you can do by you can use other computational you know programming or you
can use that you know computer program by which you can you know solve this
easily. Or otherwise you can you know do a graph x versus f (x) versus know x. There
you will see that where this minimum value of x will be coming or what will be the
value of x will be coming where that f (x) will be minimum.

829
So in that way you can also find out what should be the solution of this nonlinear
equation.
(Refer Slide Time: 09:40)

Now we will then do that Newton's method to solve this nonlinear equation which is
mostly used and this is actually one of the most popular numerical methods and this is
basically originates from the Taylor's you know series expansion of the function about
the point suppose x1 initial point.

And in this case, if we write that you know Taylor series here for the expansion of this
function f (x) at this point x1, we can write here,

(Refer Slide Time: 10:42)

830
After that if we take the first two terms of the Taylor’s series expansion then we have
f ( x)  f ( x1 )  ( x  x1 ) f ( x1 )
Now we then set equation two here to 0. That is f (x) will be equals to 0 to find the
root of the equation which gives us like this
f ( x1 )  ( x  x1 ) f ( x1 )  0 .

as shown here in the equation number 3. Now if we rearrange this equation number 3
we can get the next approximation to the root given as you know x will be equals to
then x2. That will be is equal to
f ( x1 )
x  x2  x1 
f ( x1 )

So from this basically what we did here, we took that you know two terms of the
Taylor series expansion there.

And after that we are considering that f(x) will be equals to 0 and then from which we
can find out what should be the value of x. So this x will be basically the initial value
of the next step that will be is equal to x2. So this x2 will be is equal to
f ( x1 )
x  x2  x1 
f ( x1 )

So here basically what will be the initial value of this x and minus then function of
that x at the value of x1 and also what will be the first derivative of that, you know
function at point x1 that you have to you know take a ratio for that and then you have
to subtract this ratio from that initial value of that x.

831
(Refer Slide Time: 12:56)

So in this way keep on that assuming that what should be the you know next value of
x just by taking that function at point x and also ratio of this function to which the first
derivative at that particular point. So if we generalize this you know condition of that
finding the successive x then we can write here

f ( xi1 )
xi  xi 1  ,i  N
f ( xi1 )

Where i will be you know that 1, 2, 3, 4 like this. And since here
f ( xi )
Since xi 1  xi 
f ( xi )

and if xi  xi 1 , then

then we can write here

f ( xi )
xi  xi 
f ( xi )

So this implies that

f ( xi )
0
f ( xi )

What does it mean that at any point x that function will be equals to 0. So this is the
main principles of this you know Newton's method by which you can solve the
nonlinear equation. So in this case xi is the ith estimate of the root and successive

832
estimates are then generated with a test of convergence, when that function will come
to 0.
(Refer Slide Time: 14:35)

Now if we represent it graphically, we can then have this you know diagram or figure
here like this, the y axis we can, you know consider f(x) and in x axis that is x
successes value of you know x here. If you consider that initial point of that x then x1
then this is your function simply f (x).

So at this function profile at point x1 what should be the function value it is f1.
Similarly, at this point x1 if you make a tangent at this point you will see that tangent
will you know intersect this x axis at point x2. Now at this point x2 if you go to that
profile here f (x) then corresponding f (x) will be is equal to here like this. So this will
be your f2.

Similarly, again at this point x2 at this, you know on this, you know profile if you
make again the tangent of this profile then this tangent will you know intersect the x
axis at point x3.

Now at this x3 point again you will see that if you consider what should be the value
of function here and if it is represented by f3 then we can consider here at this point f3
again if you make a tangent, you will see there will be a you know intersection at x
axis x at x star and this at this point of x star you will see that this f (x) will be coming
almost equals to 0. That means here x star, f (x) star will be equals to 0.

833
So in this way you will see that at different point of x whenever you are making any
slope or tangent and when it intersects to that x axis that will be your next you know
successive point of x and at when this you know functions will be coming zero at that
particular successive points that will give you the root or solution of that nonlinear
equation.

So here we can write that

here we will see that, when it will intersect that x axis and at that particular point, if
this function x function f (x) will comes to zero, then you will get that final root of
that nonlinear equation.
(Refer Slide Time: 17:45)

Let us do an example here for this. Now you have to determine the root of the
equation here. Suppose x is equal e to the power -x using this Newton's method. Now
f ( x)  x  e  x
This is your f(x). Now what should be the derivative of this first derivative of this
function.
df
It will be equal to f ( x)   1  e  x as shown here in the slide. Now when x is equal
dx
to zero, f(x) is in negative, whereas when x is equal to 1, f(x) is coming positive,
therefore, we can say that the root x* must be between 0 and 1.

834
So in this case, if we assume that the initial value of x as x1 is equal to 0.2, then first
iteration by this x1 is equal to 0.2. We can write then f ( x1 ) that means first derivative

of that function at this point x1 is equal to 0.2. It will come 1  e0.2 . That means here
1.8187. So what should be the successive point of this x1?

It will be coming x2. This x2 will be becoming as per this Newton’s method. It will be
x1 minus f (x1) divided by f dash x1. What is the x1 value? It is given 0.2 and f (x1) that
is basically what is that after substitution of x1 in that function you know x it will be
coming as whatever value and then divide it by this f dash x then it will becoming us
finally 0.5402.

Now this x2 value of 0.5402 it will be your first or initial guess of that second
iteration. So in the second iteration the initial value is x2. That will be is equal to
0.5402. And then f (x2) will be is equal to what 0.5402 minus e to the power -0.5402.
Then it will be coming as -0.0424 and then what should be the first derivative of that
function at this x2 value?

It will be 1  e 0.5402 . Then it will come 1.5826. Now with this values of f (x2), f dash x
2 and initial value of x2, we can calculate the successive value of x3 which will be the
initial value of the third iteration.
So thi.
f ( x2 )
x3  x2 
f ( x 2 )

This is basically based on the principle of Newton's method.

Then after substitution of this value, we can get this value of x3 as 0.5670. Now see
the third iteration, this x3 will be equals to your first guess of that x value. So x3 is
equal to 0.5670 its initial value of this third iteration, and then find what will be the
f(x3) that will be coming as 2.246 into 10 to the power minus 4.

And then first derivative of this function at this x3 point it will be as 1  e 0.5670 . It is
coming 1.5672. After that to find out the next point of x that means x4 here, it will be
as per principle of Newton's law, it will be

835
 f ( x3 )
x4  x3 
f ( x3 )

After substitution of this value of x3, f (x3) and f ( x 3 ) it will come 0.56714.

Now see, at this value of x4, you will see that 0.56714, the function f (x) is very nearly
equals to 0. This will give you the value as -5.15655 into 10 to the power minus 6. So
it is very near about to 0. So that is why we can say we can stop the iteration here and
we can consider that solution of this equation will be equals to here 0.56714.

So in this way you can solve the nonlinear equation by trial and error method as per
this you know Newton's method. Now let us now consider the solving a set of
nonlinear algebraic equations involving multiple variables.
(Refer Slide Time: 23:10)

So till now we have described how to solve single nonlinear equation by Newton's
method. Now in this case we will describe how to solve the nonlinear algebraic
equations, there will be a set of nonlinear algebraic equations. There multiple
variables will be there. So in the, we can also use here the same Newton's method that
will be used for that multiple equations by modifying this Newton's method.
(Refer Slide Time: 23:52)

836
And in this case, you have to consider some other you know some matrix, it will be
called as Jacobian matrix for this modification of this Newton's method. So in this
case, the nonlinear system is to be expressed as a matrix with that corresponding
vector as
x ( k )  x ( k 1)  J (x ( k 1) )1 F(x ( k 1) )
So in this case k will be equals to 1, 2, n which will represent the iteration. Now so we
can say that
x ( k )  x ( k 1)  J (x ( k 1) )1 F(x ( k 1) )
So this is your iteration procedure based on which you have to find out the solution.
Now this F is a vector function and J (x) 1 is the inverse of the Jacobian matrix.

This equation represents the procedure of Newton's method for solving nonlinear
algebraic equation.
(Refer Slide Time: 25:16)

837
Now let us see what should be the function and also Jacobian matrix. Now instead of
solving the equation F(x) is equal to 0 whatever we have described earlier, we are
now solving the system of F(x) equals to 0. In this case, there will be a set of
nonlinear equation instead of single nonlinear equation.

So we will now go through the equation and define each component like here, let F be
a function of this here
 f1 ( x1 , x2 ,....., xn ) 
 
f ( x , x ,....., xn ) 
F( x1 , x2 ,....., xn )   2 1 2
....................... 
 
 f n ( x1 , x2 ,....., xn ) 
and this you know function will be a set of nonlinear equation like f1, f2 and up to fn
where x here represents the vector as a set of this x1, x2 up to xn.
 x1 
x 
x   2
....
 
 xn 
(Refer Slide Time: 26:14)

838
And J(x) is the Jacobian matrix, which is defined as here, you know first here that
means first derivative of you know that function that is by which that set of that
function is formed. So it will be
1
 f1 f1 f1
 x  x  x . .  x 
x2 xn
 1 
 f 2 f 2 f 2 
 x  x  x2
x . .
xn
 x 
J (x) 1   
1

 . . . . . 
 
 . . . . . 
 f n f n f n 
 x x  x 
 x1 x2 xn 

So and this is called Jacobian matrix and inverse of this it will be regarded as inverse
of Jacobian matrix.
(Refer Slide Time: 27:32)

839
Now if we consider that steps of Newton’s method based on this, you know nonlinear
set equation, then we can say that as a first step what you have to do that, here let


x (0)  x1(0) , x2(0) , x3(0) ,..., xn(0) 
And it will be the initial vector of those variables x1 to xn.

And the next step what you have to do you have to calculate the Jacobian matrix at
that x(0), that is initial of value, initial guess there, and also what will be the F(x0). And
then after that as a step 3, we have to calculate the vector y0 where y0 will be defined
as
y(0) =  J(x (0) ) 1F(x (0) )

So you can replace this J(x (0) )1F(x (0) ) formula with y(0) here. Then

x ( k )  x ( k 1)  J (x ( k 1) )1 F(x ( k 1) )  x ( k 1)  y ( k 1)

So this step 3. In this way you have to calculate.

(Refer Slide Time: 29:12)

840
And then in step 4, once y0 is found, we can now proceed to finish the first iteration,
by solving for x1 thus using the result from the step 3, then we can get x1 will be
equals to x0 + y0. This
 x1(0)   y1(0) 
 (0)   (0) 
  2    2 
x y
x (1) = x (0)  y (0)
.... ....
   
 xn   yn(0) 
(0)

And then once we have calculated this x1 based on this x0 and y0 we have to repeat the
process again until xk converges to x. And this indicates we have reached the solution
to f(x) is equal to 0 where x is the solution to the system. Now when a set of vectors
x( k )  x( k 1)  0
converges, the norm is like this , and then it will be defined as this
here

x   
2 2
x ( k )  x ( k 1)  (k )
1  x1( k 1)  .....  xn( k )  xn( k 1) 0

So in this way we can calculate what should be the or we can get what should be the
root of that or solution of that set of nonlinear equation just by converging to x, the
value of whatever guess we are considering as a step by step and successive value of x
as per that Newton's method will give you that convergence of that x and which will
be considering as the solution of the set of you know nonlinear equation.

Now advantages and disadvantages of this Newton's method to solve this, you know
nonlinear equation like this.

841
(Refer Slide Time: 31:36)

Advantages of Newton's method is that it is not too complicated in form and it can be
used to solve a variety of, you know problems. The major disadvantage is that, this
here Jacobian matrix as well as its inversion has to be calculated for each iteration. So
it will take you know a long time to finish and also calculating both the Jacobian
matrix and its inverse can be quite time consuming that depending on the size of your
system.

Another problem is that it may fail to converge. If Newton's method fails to converge
this will result in an oscillation between points there. So there will be a issue for that.
So otherwise, it is advantageous because it will not be too complicated system to
solve the equation.
(Refer Slide Time: 32:39)

842
Now let us do an example based on this you know Newton's method for a set of
nonlinear equation to solve. Here is example given in the slides here. Here one
equation is like this
3x1  cos( x2 x3 )  0.5  0

3x1  cos( x2 x3 )  0.5  0

x12  81 x2  0.1  sin x3  1.06  0
2

10  3
e  x1x2  20 x3  0
3
Here one equation, this is nonlinear equation.

Another equation is given

x12  81 x2  0.1  sin x3  1.06  0

2

And then third equation is given

10  3
e  x1x2  20 x3  0
3
This is another equation. So here three you know nonlinear equation given to you and
you have to find out the, you know solution of this x1, x2 and x3.

Now consider the initial approximation is here x(0) is 0.1, 0.1 and - 0.1. So based on
this, you have to solve this nonlinear equation to find out the solution for x1, x2 and
x3.
(Refer Slide Time: 34:06)

843
Now first of all, that you have to follow that step 1, what should be the initial, you
know vector. Since it is given that you have to assume this initial vector as x0 is equal
to 0.1, 0.1 and - 0.1. This is basically x1 is equal to 0.1, x2 is equal to 0.1 and x3 is
equal to - 0.1 at its initial guess. Then, step 2 you have to define F(x) and J(x).

That means function set of you know function and also Jacobian matrix. So F(x) is
here, simply this is
3x1  cos( x2 x3 )  0.5 here.

And then here

x12  81 x2  0.1  sin x3  1.06

2

And then third equation here given.

10  3
e  x1x2  20 x3 
3
So these actually made this you know function F (x).
 
3 x1  cos( x2 x3 )  0.5 
 2 
F(x)   x1  81 x2  0.1  sin x3  1.06 
2

 
e  x1 x2  20 x3  10  3 
 3 
And then Jacobian matrix simply the derivative of this you know function F(x) based
on that variables there. So it will be coming as

844
  3 x3 sin( x2 x3 )x2 sin( x2 x3 ) 
J(x)   2 x1 162( x2  0.1) cos x3 
  x2 e  x1x2  x1e  x1x2 20 

So in this way, you can find out what should be the Jacobian matrix for that initial
value.
(Refer Slide Time: 36:08)

Now for this initial value of this function, F(x(0)) and Jacobian matrix zero will be
equals to here, after substitution of value of x(0) here in the F(x) it will be coming as
like this, and then here Jacobian matrix here, it will be like this as a transport here. So
it will be coming as this after substitution of this value, this will be your Jacobian
matrix.
(Refer Slide Time: 36:38)

845
And then, to solve this you have to consider that Jacobian matrix x(0) into y(0). That
will be is equal to minus F(x(0)). Now then, using Gaussian elimination method, we
can have this to solve after that finally we can get this here for this
 y1(0) 
 (0) 
 y 2  here.
 y (0) 
 3 
Then we can get here y(0) as will be equals to here as per this matrix it will be coming
 0.40003702 
y (0)
  0.08053314 

as  0.42152047 

And then y3 will be equals to -0.4215047. So here this will be your, you know y(0) as
per that Newton's method whatever we have described earlier.
(Refer Slide Time: 37:34)

And then next guess of you know initial value of x that will be equals to x(1), this is
basically x(0) + y(0), then it will be coming as your as per that matrix rule that will be
equals to here 0.50, 0.0194 and -0.5215. So this will give you what is that x(1) value.

Again then you have to use this x(1) value to find out what will be the F(x) at that x(1)
and Jacobian matrix at that you know x(1) value. So we can use this results of x(1) to
find our next iteration x(2) by using the same procedure.
(Refer Slide Time: 38:22)

846
So if we continue to repeat this procedure, we will get the following results here for
you know k here 0, 1, 2, 3, 4 that means here iteration number. Here for this first
iteration it is you know it is given here and then second iteration we have found that
this value and then the third iteration here, what will happen?

After that x(1) plus you know y(0) it will be coming like this and then keep on
continuing the repetition of the process based on that, you know Newton's method we
can have at different k value we can get different value of x(1), x(2) and x(3). And then
you will see that at this fifth iteration of this you will see that the value of x1 will be
coming as 0.5 and x(2) will be equals to almost 0 and x(2) will be equals t0 -
0.5235987.

And finally, you will see that this deviation x(k) - x(k – 1) will be equals to 0 where you
have to stop the iteration. So parallel you have to find out what should be the you
know deviation of this x(k) - x(k – 1). And if it is coming almost equals to 0 then you
have to stop your iteration.

And that you know iteration will give you the corresponding value of x(1), x(2) and x(3)
and those value will be you know treated as the solution of that set of nonlinear
equation. So here x will be at that point it will be equals to 0.50 and -0.52359877. So
this is an approximate solution of those you know nonlinear equation.

847
Here we have 3 nonlinear equation 3 unknown variables and those 3 unknown
variables are 0.5, 0, and 0.523 like this. So in this way you can you know calculate or
you can estimate the solution of nonlinear equation and this is the best way to find out
the you know solution of nonlinear equation if there are more than one nonlinear
equation.

Even you can use that, you know single equation to find out that solution for its
nonlinearity based on that, you know Newton's method. So we have given here two
examples and two you know procedure of that Newton's method. One is simple
Newton's method just by guessing this initial value and successive value will be
coming based on the, you know function value, and its first derivative.

And then what should be the second guess that according to that, you know principle
of that, you know subtracting that ratio of that function value to the you know first
derivative from the initial guess then you will get the second guess. So in this way,
keep on you know repeating that you know that solution of that equation until this
function will come to 0 that will give you the solution of single nonlinear equation.

But for the set of you know nonlinear equation to find the solution here, in this case,
you have to you know modify that Newton's method just by you know incorporating
the that is Jacobian matrix. And from that Jacobian matrix you have to you know
calculate the next guess of that or next iteration of that x value just incorporating that,
you know Jacobian matrix with those you know function value.

And you have to you know continue this iteration in this method until there is a
deviation of this you know initial guess to the final or previous that means, successive
guess, it will be if that deviation is coming 0 for those you know values of you know
x(k) - x(k – 1)then you have to stop there that iteration and respective value of x(1), x(2)
and x(3) will give you the solution of that set of nonlinear equation.

So I think it will be helpful to solve any nonlinear equation based on this method.
(Refer Slide Time: 43:14)

848
So I would further request you, you know follow some you know example of this
Newton's method to solve the nonlinear equation there. And next lecture we will
discuss more about that computation techniques. There we will discuss about the
numerical integration, how to integrate the you know scattered data based on some
principles that will be discussed. So thank you for your attention.

849
 Basic Principles and Calculation in Chemical Engineering
Prof. S. K. Majumder
Department of Chemical Engineering
Indian Institute of Technology-Guwahati

Module-10
Lecture-31
Numerical Integration

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So, we are discussing about the computational techniques under the module 10. And
in this lecture of module 10 I will discuss about numerical integration with examples.
(Refer Slide Time: 00:50)

In the previous lecture we have described nonlinear equation and how to solve that nonlinear
equation with examples also you have described in our earlier lecture that how to you know free
to that linear equations with experimental data by least square method. So, here this lecture is
basically continuation of that, you know, computational techniques. In this case, how to actually
calculate the integration from the, you know discrete data of some you know, variables.

And what will be the integration of those profile of discrete data and what will be the area under
that you know profile based on the integration value how to estimate that and how to calculate
that, what are the different you know, rules are there to calculate that, you know area under the
curve by you know numerical integration. So, we will discuss here.

850
(Refer Slide Time: 01:48)

So, the numerical integration of the you know definite integrals, you know is of great importance
in many cases where the algebraic form of integral is difficult to sometimes integrate there. So,
in such cases we need to use numerical process. This is usually how software like you know
mathcad or graphics or calculator perform definite integrals there. So, we can use 1 of the 2
methods here like trapezoidal rule and Simpson’s rule.

The problem is to evaluate such an integral of the form like this here

.
So, we can see that this how this you know, integration within limits of x1 to x2 can be you know
numerically calculated.
(Refer Slide Time: 02:47)

851
Now we told that there are 2 methods to calculate the you know, integrals here from the data
within range of x1 to x2 is called trapezoidal rule. Now, based on these the area under a lines
through here x1, y1 and x2, y2. So, this is the you know line between these 2 points. Now on the
plot of this y versus x axis, you can calculate what should be the area under this line like this, this
area how to calculate you know here.

So, this you know area under a series of points from that, you know x1 to xn here, here up here in
this picture it is x1 to x2, but you may have you know x1 to xn value and it can be obtained by
summation of such terms here.
(Refer Slide Time: 04:00)

852
In this case let us see that thinks now we will see that in this case this integrals can be you know,
obtained by this formula as per trapezoidal rule. So, this will be equal to you know, here x1 to x2
here function is y into dx. So this is your integrals. So, from this you know we can you know
from this limit of the x1 to x2 data and corresponding value of y1 to y2 data we can obtain this area
under this you know grabbed by this, you know, definition of the integral says like here it will be
you know that x2 - x1.

This is here
 y  y2 
I 0   y dx   x2  x1   1
x2

x1
 2 
So, by this equation you can get this you know that what we the area under the curve, here x1 to
x2 this is the limit of this you know x value whereas y1, y2 is this is basically functions value at
this x1 and x2 and then you have to take it an average. So, from this you can get what should be
the integrals there. Now area suppose under the series of points, from x1 to xn that can be
obtained by summation of such terms like here that can be written as here I as these.

So that will be is equal to here we can write

1
I   x2  x1  y1  y2    x3  x2  y2  y3   .....   xn  xn 1  yn 1  yn  
2
So, from this equation you can obtain of what will be the you know, area under a, you know you
know line within you know point here, where x1 to xn. So, this is called trapezoidal rule.

Now, if the abscissa values of the data points are you know spaced at equal intervals then the
trapezoidal rule can be simplified like this here, we can write this
h
I  y1  y2    y2  y3   ......   yn 1  yn  
2
So, from this if abscissa value of the data points are spaced at equal intervals, then this
trapezoidal rule will be simplified to this.

Now, if you are having that you know equal intervals, so, we can write this integral as here
suppose,

853
 x2
x1
y ( x) dx

So, that will be is equal to

h n 1 
y ( x) dx   y1  yn  2 y j 
x2
x1 2 j 2 
So, this is your generalized form or h is the distance between the x values of at just in data
points. That means here we can write here, what is the difference between these 2 points x there
like s that will be is equal to if there is an equal intervals you can write x2 - x1 divided by 2 this is
your, you know h value.

So, here h is the distance between no this is h by 2 that will be x2 - x1 by 2 that means here h will
be equal to simply x2 - x1. So, this h is the distance between the x values are adjusting data points
that you know observed to use the trapezoidal rule. Now, in this case you need to plot anything
simply to substitute tabulated data into the equation there. So, in this way you can calculate.

So, by this equation, you can calculate what should be the integrals here, in this case, we can
write that this limit will be x1 to xn instead of x2 here. So, because here we are considering that n
number data whereas for 2 points x1 and x2 we have discovered that this will be equal to simply
this equation by this equation that 2 points you can get this integrals, but n number of points that
you have to use this equation and in general you can write this equation here.
(Refer Slide Time: 09:57)

854
Another method is called Simpson’s rule. Now, in this case, you know, this is, you know, more
widely used, you know techniques to you know estimate that integrals within a certain limit, it is
applicable only to an you know, odd number of equally spaced data points and is based on fitting
parabolic functions to successive groups of 3 points there, like here we will see that one you
know parabola, 2 points here, 1 to here 5 like this.

And in the left side 0.123 and right side to be parabola at 2.32 and in this case, you will see that,
if we you know, divide these x axis into equal intervals, like this like h here x2 – x1, and here
again, h is x3 – x2, x4 – x3, x5 – x4, this will be your h value. Whereas the y axis you will see that
for each value of x1 you will get that function value as y1 and similarly y2. y3 like this and based
on this you know that you know parabola.

And under this parabola what will be the area that can be obtained by this you know integrals
and that integrals can be calculated based on this you know Simpsons rule.
(Refer Slide Time: 11:32)

Now, what is that Simpsons rule it can be actually shown after a you know fair amount of
algebra that the area under a parabola through equally spaced points of (x1, y1); (x2, y2) and (x3,
y3) can be actually expressed as here,
h
I0   y1  4 y2  y3 
3

855
if you are having 3 points here, so, it can be represented by this you know equation. In this case h
is the interval between that successive x values consequently the area under the series of such
parabolas you know fitted on that on the value of that x1 to you know xn.

And n number of values will be there, those are equally spaced points and that can be expressed
by this integral as
h
I  y1  4 y2  y3    y3  4 y4  y5   .....   yn 2  4 yn 1  yn  
3
and then after that here again, the same, you know, pattern will be starting from y3 like this y3 +
4 y4 + y5 like it will be continued up to a point you know n here then final point will be coming
as here like this,  yn2  4 yn1  yn  .

So, this is your general term to express that integrals, if they are you are having n number of you
know of data for this you know functions as far that the number of data of x1 to xn. In this case
here you have to find out as far in the h value and then successively you have to you know,
consider this pattern here  y1  4 y2  y3  and then other points like this y3 to y5 which will be

 y3  4 y4  y5  .

And then you know up to nth value you can consider by this you know general value. So, we can
write this the Simpsons rule here as a general form like this integration of your suppose x1 to xn
xn
for the function x1
y ( x) dx . So that can be written as

 
h
y1  yn  4  y j  2  y j 
xn
x1
y ( x) dx 

3 j  2,4..., j 3,5...,

 n  1 n  2 
And then plus, then 2 into we can write summation of here you can write j is equal to you know
3, 5, dot dot dot here n - 2 and then here it is yj. So, based on these, you know, formula you can
calculate what should be the integral you know or area under that n functions that is represent in
the graphical form. So, this way you can you know obtain the integrals based on The Simpsons
rule.
(Refer Slide Time: 15:35)

856
Now, let us have some examples here to calculate based on that theory. Now, one example is
given that the heat capacity of a gas is terminated at a series of temperatures like this T in degree
Celsius like 20, 50, 80, 110, 140, 170, 200 and 230 and specific heat capacity is given like where
at 20 degrees Celsius it is 28.95 and at 50 degree Celsius it is 29.13 and at 80 degrees Celsius it
is given 29.30 and 110 will be 29.48, 140 it will be this, and 170 up to 230 you are having these
saw you know specific capacity value.

Now you are having here the data like 20 to 230 degree Celsius within this range this specific
capacity data you know are having. Now, you will see that this temperatures are a difference that
is successive temperature differences, you know on the 30 degree Celsius. So, with us you are
getting that you know 20 to 50 then 50 to 80, 80 to 110 and 110 to 140 like this, everywhere you
are getting that interval is same.

So, equal intervals is there and here number of points are like 1, 2, 3, 4, 5, 6, 7, 8 point. So, here
even number of points are there. So, how to solve this problem to find out the change in enthalpy
for you know 3 gram moles of this gas that is going from 20 degrees Celsius to 230 degree
Celsius. So, here enthalpy can be calculated based on this equation here given that is equal to n
into integral of 20 to 230 degree Celsius into Cp into dT.

857
Now, this n is you number of moles here it is given that 3 gram moles of this gas and also here it
is given that the integrals value will be you know Cp into dT. So, total enthalpy change will be n
into here, like this 20 to 232 into CpdT. Now this part is your integral that you have to obtain
based on this you know data given in the table. Now, how to actually apply that you know
trapezoidal rule or Simpsons rule to calculate this, you know enthalpy based on this.
(Refer Slide Time: 18:14)

Now, in this case remember this since there are even number of points the trapezoidal rule must
be applied to what the first or last impressive interval, this you have to remember, because,
where Simpsons rules in early applied for you know that you know that odd number of data and
to get that similar pattern of that you know successive 3 points to find out that you know that
integrals and here since we are having you know, 8 points, so, here even number of points.

So, the trapezoidal rule first you have to apply over the first or last in intervals and for the race to
Simpsons rule can be applied there. So, according to this, you know, we can then write here this
according to trapezoidal rule what we can write here for first you know 2 you know points that is
here 20 to 50 within this range of temperature we can write that integrals here x1 to here x2 + 2
points we can write here y into y as a function of x into dx that will be is equal to

h n 1 
y ( x) dx   y1  yn  2 y j 
x2
x1 2 j 2 

858
So, this is your basically trapezoidal rule. So, and for Simpsons one third rule we can write here
x1 to here xn we can write y as a function of x that will be is equal to
 
h
y1  yn  4  y j  2  y j 
xn
x1
y ( x) dx 
3  j  2,4..., j 3,5...,

 n 1 n2 
So, this is you know Simpsons rule. So, as for this problem we can write here then the limit here
T1 to T you know that final that is your T0 that means here Cp into dT.

So, in this case we can write delta T by 2 here delta T here, this is h that means here temperature
difference, then we can write here Cp here 1 that is first value of Cp1 + similarly, Cp2 second point
here specific capacity, this is your trapezoidal rule as for that and plus then, you know delta T by
3 this part will be applied for Simpson rule. So, it will be here, like Cp here we can write 2 + Cp,
you know who that Cp2+ here we can write Cp8 here then plus 4 into Cp3+ Cp5+ Cp7.

Then we can write + 2 into here, Cp4 + Cp6. So, this is your final equation as per this you know,
combination of this you know trapezoidal rule and Simpsons rule. Now, substituting the value of
this, you know, here delta T and then Cp1, Cp2, all those values then we can get this will be
around 6207.7 Joule per mole. So, this is your you know that integral forms of that equation for
this enthalpy here, that is delta H that will be is equal to n into this.

Now, total enthalpy can be calculated based on these as then we can calculate delta is H that will
be is equal to here given n what is the you know temperature here at 22 to 30 20 to 230 into
CpdT, so, that will be is equal to here n is given to you, that is 3 moles and then integral value is
opted here as 6207.7. So, finally to becoming as here 1.86 into 10 to the power 4 that means here
joule. So, this is your final answer for this.

So, by this you know point we can then calculate what should be the integrals and then what will
be the enthalpy. Now, let us do another examples here.
(Refer Slide Time: 24:29)

859
Let us consider that water is flowing through a you know a pipelines that is 6 centimeter in
diameter and the local velocity at various you know radial positions are given below here like as
per this tabulated form here at radial position of despite suppose this is your pipe and the fluid is
that is your water is flowing. Now at different radial position you will see that velocity will be
changing .

Because here this velocity to be like this, this velocity profile will be like this. Now, at the center
that velocity will be higher, whereas at this you know adjacent to this wall the velocity will be
lower. So, whenever this radial position will be there, according to this radial position this
velocity of this you know water will be changing. Now, according to that, we can have this data
experimental data like this.

At you know r = 0 that means, at this wall, this velocity will be equal to what this will be equal 2
or as this at 0.5 this r that is 1.94. And here, you know set at r = 1 is 1.78 at 1.5, 1.50 and then r =
2 it is 1.11 and 2.5 it is 0.61 and at 3 it will be again 0. Now, based on this, we can write here
this, you know average velocity and that average velocity can be you know calculated, you know
based on this, you know, new r value within integral of 0 to you know r radius they are here.

860
This total radius is some that, it will be to this r. So, at this radius what should be the average
velocity that you have to calculate. Now, you have to use this trapezoidal rule and Simpsons rule.
Now, how to solve this. Now, to find out that average velocity.
(Refer Slide Time: 26:57)

This average velocity actually given by the average here is velocity can be obtained by your
means, here

So, based on this formula you can calculate what should be the average velocity, within this you
know radius that is 0 to R are despite. Now, for this you will see now, you have to then find out
first what will be the integral of the 0 to R ur dr.

Based on that, you know tabulated data given, now values of ur for the different values of R2 first
calculated. So values of ur for different values of r can be tabulated as here like this first point of
that is r, what should be the ur, this is ur and r first values of r r = 0 then ur will be able is equal
to of course 0. Second point is given 0.5 r 0.5 r value and velocity is given here. Velocity is
given there according to that what should be the ur value it is coming 0.97 whereas this at r = 1
that ur will be is equal to 1.78 at r = 1.5 this you know that ur will be is equal to 2.25.

861
And at r = 2 this you know ur will be is equal to 2.22 and at 2.5 this ur will be is equal to 1.52
whereas, r = here 3 that ur will be is equal to again 0. Now, based on this data you have to apply
what should be the you know integrals based on that, you know trapezoidal rule and then what
should be the average velocity. Now applying by trapezoidal rule we can write for n = 6 here
total number of point is here no it is n = 7 1 2 3 4 5 6 7.

So n = 7 here, data point and h h will be equal to r final that is 3 - initial is 0, divided by number
of points here 7. So, it will be simply 0.428 and then we can write as per equation we can write

h n 1 
y ( x) dx   y1  yn  2 y j 
x2
x1 2 j 2 
And then we can substitute here as like this here 0 to 3 ur dr that will be is equal to 0.428 divided
by 2 here y1 is 0 + yn is 0 and then + 2 into remaining is 0.97 + 1.78 and then plus, this is + 2.25
and then + 2.22 and then + 1.5 these are the remaining points. Then we can close this bracket
here, and then finally to becoming as 3.74. Therefore hour is velocity u = 2 by r square 0 to r ur
dr that will is equal to 2 by here r is given 3 then 3 square into then this integral value is 3.74.

So, finally to be coming as 0.832, this will be centimeter per second as per problem. So, in this
way, we can calculate this, you know average velocity based on trapezoidal rule. Similarly, for
you know average velocity if we apply the Simpsons rule what we can write here.
(Refer Slide Time: 33:53)

862
So, we can write here by Simpsons rule. By Simpsons rule here for n = 7 h = 0.428 and here
 
h
y1  yn  4  y j  2  y j 
xn
x1
y ( x) dx 
3  j  2,4..., j 3,5...,

 n 1 n2 
So, based on this we can write here 0 to 3 ur dr. According to the tabulated data you have 0.428
divided by 2, here y1 is 0 + y n0 + here 4 into this up to n - 1 data to be 0.97 and then + 2.25 +
1.52.

This is your remaining data and then other parts of this data we can write as per equation of
Simpsons rule n 2 into 1.78 + 2.22. So finally to becoming as 5.77 and then average velocity as
per Simpsons rule can be written as you bar that will be is equal to 2 by r square integrate 0 to r,
ur dr, so it will be coming as 2yr is given to you that is 3 square into this integral value is 5.77,
then finally it will be coming as 1.284 is a centimeter per second as per problem.

So, based on the Simpsons rule you can estimate what is the average velocity based on the
velocity versus radial position of despite data. So, we have learned here how to calculate that you
know integral values are based on that you know numerical integration proceed ur of trapezoidal
rule and Simpsons on third rule or Simpsons rule simply and you can also have practice other
you notability data, or you can find out that differently, you know that variables of chemical
engineering processes like here 1 problem.

It is given if water is flowing to the 5 what should be the average velocity whenever it will be
flowing to the 5 that can be calculated based on this integral value, but this integral value cannot
be you know obtained, you know analytically because there is no certain you know equation that
is represented by that you know average velocity. Even if you know that you know integral or
you can see that particular function then you can easily calculate that integral value by analytical
method.

But somewhere you will see that some integral or some equation will be so complicated that you
may not had that you know analytical solution of that integration. So, for that you can apply this

863
Simpsons rule or trapezoidal rule directly according to that you know that is equation and also
that integral values based on that function.
(Refer Slide Time: 39:08)

So, in this case, we have learned this trapezoidal rule and Simpsons rule. Now, the trapezoidal
rule is that if the function to be integrated is in effect linear is interval between data points and
Simpsons rule is exact if the real function is parabolic or cubic in each intervals. Even you can
get these integrals if your function is not exactly that parabolic with some other complex you
know nonlinear function there.

You can get that integral value of that nonlinear function based on this Simpsons rule. In the next
lecture will try to discuss about the analysis of process degrees of freedom. So, we are here you
know stopping that, you know, computational techniques, because these things is very important,
this is the basic understanding of this, you know computational techniques, because you have to
know that these 2 square meter to feed that you know linear equation.

And in many you know chemical engineering process even other engineering processes
sometimes the experimental data to be predicted by performing an equation that is linear
equation or nonlinear equation whatever it is and that nonlinear equation will have some you
know parameters and that parameters can be obtained just by fitting with the experimental data.
So, that can be obtained by least square method.

864
Even for nonlinear equation, you can simply use that you know Newton's method and also for
integral values that you can use the Simpsons rule and trapezoidal rule, so it will be helpful for
your further understanding of the you know process and also that variables how to calculate
based on that linear and nonlinear equation and also how to feed that linear or nonlinear equation
based on that experimental data.

In the next module will try to you know discuss more about that chemical engineer process and
based on that process, how to analyze the degrees of freedom based on that variables, how many
variables will be there with that variables how many equations will be performed and those
equations whether will be you know, giving the unique solution or not that can be you know
access by the degrees of freedom. So, it will be discussed in the you know next module in the
next lecture. So, thank you for your giving attention.

865
 Basic Principles and Calculation in Chemical engineering
Prof. S. K. Majumder
Department of Chemical engineering
Indian Institute of Technology-Guwahati

Module-11
Lecture-32
Process Degrees of Freedom

Welcome to massive open online course on basic principles and calculations in chemical
engineering. In this lecture we will start to discuss about some basics of computer aided balance
equations. And in this lecture mainly will be focusing on the process degrees of freedom.
(Refer Slide Time: 00:52)

And how to analyze that process degrees of freedom with examples will be you know discussed
here.
(Refer Slide Time: 01:00)

866
So, you know that in the previous module we have described something about the computer
basics based on which how to calculate the numerical integration for a function. And also we
have describe something about that least square method also we have described about solution
methodology for linear and nonlinear equations. So, all those actually phenomena or you can say
that topics that we have described those are computer based you know calculations.

Here also we will try to do something about some calculations, how to do the process, analysis
based on modular based you know computer analysis as well as how to actually express the
different codes based on the flowsheeting of the chemical engineering processes. And this will
be very basic of this based on these you may be you know that able to analyze different process
and how to you know handle the tools of different softwares based on this module.

Because there are various you know softwares they are actually developed based on the module
based you know analysis of the chemical engineering process. And for that they have developed
you know different codes based on that flowsheeting of individual units of that particular
chemical engineering processes. Now based on that you know flowsheeting that is analysis of
that chemical engineering process.

You have to first what should be the degrees of freedom of that you know process because it will
give you the you know basis of that idea. Whether the you know solution of that chemical

867
engineering process can be you know assessed based on that you know set of linear equation or
nonlinear equation based on the material balance or energy balance equation or not.

If you know that there are n number of variables for a particular process and also you are getting
that some numbers of equations that is form based on that material balance equation. Now based
on that number of equations and number of variables whether these you know equations can be
you know solved or unique solution or not. Or how to actually manage those equations based on
that variables.

So that you can get a particular solution maybe unique solution maybe more than one solution
also there. But to get that unique solution of individual variables you have to know the degrees of
freedom of that you know process. And also based on that degrees of freedom you can assess
whether that equations can be solved or not. And also whether that variables to be specified for
that particular process or not in that particular flowsheeting codes.

Also it may be helpful for analysis of that you know process based on that process variables
whether it will be you know validated or not for that process analysis there.
(Refer Slide Time: 05:36)

Now when attempting to solve a material balance problem that is aided by computer code you
will see that typical questions that may arise. Like how many equations are needed and where do

868
these potentially come from. The degrees of freedom analysis is used to address these questions,
it is a highly useful tool for systematic analysis of block flow diagrams. And it provides rapid
means of you know assessing if a specific problem is solvable or not.
(Refer Slide Time: 06:18)

So that is why you have to know the degrees of freedom to do the process analysis. Now, to
carry the analysis you need to draw a flow diagram. And also you have to label on the flow
diagram for each stream with the components that are present in the stream. You need to make a
list of you know additional information such as flow rates even compositions ratios. And also
you can say if there any conversions or not that you have to know.
(Refer Slide Time: 07:00)

869
Now 2 important points that to be remembered in this case the past has to do with drawing, now
balanced boundaries that is the number of systems. However you can write the material balance
equation. There are 3 rules for drawing system boundaries, first of all that you have to draw the
boundary around is process unit. Secondly you have to draw the boundary around junction
points, and third a boundary will be drawn around the entire process unless there is only one
boundary there.

It is a second point has to do with the with how many questions you can write for each drawn
boundary there. And then you have to write as many as possible the equations where there are
unique components passing through the boundary.
(Refer Slide Time: 08:03)

Now for a reacting system then after mentioning all those you know boundaries even processes
streams specifications there. The number of degrees of freedom to be calculated based on this
you know definition like here.
no. of  no. of 
no. of    other 
  molecular   
 No. of  independent    
NDF      balances on   relations 
unknowns  atomic species  independent  relating 
balances     
nonreactive species   variables 

870
The number of degrees of freedom that will be equal to how many numbers of unknown
variables are there and number of independent reactions is happened or not there.

Number of independent material balance equations that you have to know, number of useful
auxiliary relations or they are not that also you have to know. So from those number of
unknowns, number of independent reactions, number of you know independent material balance
equations. And also number of useful auxiliary relations you can calculate what should be the
degrees of freedom for the process.

Now that number of degrees of freedom can be defined as number of unknowns plus number of
independent relations minus number of independent material balance equations minus number of
useful auxiliary you know relations. Now in atomic balance case the degrees of freedom analysis
can be expressed as like number of unknowns minus number of independent atomic species
balances minus number of molecular balances on independent non reactive species minus
number of other relations relating variables.

So from these you know equations you can calculate what should be the number of degrees of
freedom. And that can be you know based on the moles or that can be based on the atoms also.
(Refer Slide Time: 10:09)

871
Now what is the significance of that degrees of freedom analysis, why we should do these things.
Now in this case from this definition of degrees of freedom if you are getting suppose number of
degrees of freedom musical to 0. In that case you can say that the system is completely defined,
in that case you can get a unique solution for the system where is there any unknown variables
and that unknown variables to be you know to be 1 as a solution for that particular system.

Now if number of degrees of freedom is greater than 0 what will happen. In that case, the system
is under defined that means under specified. In that case there are an infinite number of solutions
will be there, more independent equations for that will be needed to solve the unique solution. If
number of degrees of freedom is less than 0, in that case the system will be over specified, there
are too many actually restrictions will be there.

Now in that case you have to check whether you have too many questions or too many
restrictions are there or not. Over-defined problems cannot be solved to be with all the equations
there. So, you have to select some equations which will be equals to the number of unknown
variables. So if there are over specified you can neglect some equation, if it is under specified or
under defined then you have to add some other independent equations to get it is unique solution.

Now, if NDF is equal to that means number of degrees of freedom equals to 0 then system will
be completely defined, there is no more equations required even no more you know unknown
variables will be considered there. So like this in this way we can you know say whether the
system is you know well defined or not whether it is over specified or under specified, if it is
under specified what to do and if it is over specified what to do, so based on which we have to
solve the problem.
(Refer Slide Time: 12:42)

872
Now to calculate that number of degrees of freedom you need to have some independent
equations, that independent equations to be formed based on that material balance equation or
energy balance equation. Now when it will be called that independent equation, a set of
equations are said to be independent if you cannot derive one or by adding and subtracting
combinations of the others, so that equations will be called as independent equations.

Now sources of equations that unknown process variables include, now these equations whatever
independent equations to be formed that may come from material balance for reactive and
nonreactive processes. And that equations may come from energy balances, that equation may
come from processes specifications, that is given in the problem statement. That equation may
come from physical properties and laws like you know density relations, gas laws like pressure
vapor pressure relation with the you know composition of the you know materials in the liquid or
gas.

Physical constraints, like you know that summation of more fractions or mass fractions of the
you know compound should be equals to one. And then what is that stoichiometric relations for
the systems with chemical you know reactions. So these are the source of generating of those
independent equations based on which you have to calculate what should be the number of
degrees of freedom.

873
And based on which you have to assess whether the system is well defined or under defined or
you know over defined or not. And accordingly, you have to solve for unique solution of those
system.
(Refer Slide Time: 14:53)

Now for independent equations let us have this the following set of equations here given in the
slide, that is derived from a material balance of unit process. Which is independent because we
cannot derive anyone by adding or subtracting combinations of the others. Like here you will see
that these equations

Here m1, m2, m3 are the you know that stream’s amount whether it is income or incoming or out
coming that accordingly it will be coming that material balance will give you this equation.

Similarly the second equation also based on that input or output amounts that equation can be
formed similarly third equations. Now if you look at these 3 equations you will see that no
equations are dependent, no equations is dependent on others. Like you cannot generate the

874
second equation from the first one or first one cannot be generated from the second one or third
one like this.

So all these equations are independent to each other, while if you look at these second set of
equations you will see that there also there are 3 equations. And in this case you will see that the
third equations can be generated from the second equation. If you multiply the second equation
by 2 you will see that third equation will be generated. So in this case you cannot say this set of
equations are independent to each other.

Only these 2 equations first equations are independent whereas the third and second equations
are not independent. So you have to you know be careful for generating that independent
equations based on material balance equation. And for calculating degrees of freedom you have
to be very careful whether those equations formed are independent or not, only independent
equations to be counted to calculate the degrees of freedom.
(Refer Slide Time: 17:26)

Now let us have an examples to calculate the degrees of freedom for binary separation process.
Now, let us have this problem like if you have the feed stream to a distillation column that flows
at rate of 200 mole per hour and contains 40 mole percent of component A and 60 mole percent
of component B. The distillate flow is at a rate of 400 mole per hour and contains 65 mole
percent of component A and remaining is 35% of component B.

875
Now in this case you have to draw the label of this you know our process flowchart you have to
you know also perform the degree of freedom analysis.
(Refer Slide Time: 18:21)

Now let us solve this problem to calculate this degrees of freedom what is that. We knew that
degrees of freedom NDF, that is we calls to number of unknowns plus number of independent
equations minus this is sorry number of independent here reactions here reactions minus number
of independent equations then minus number of useful auxiliary equations or relations.

Now for this what to do, first of all we have to draw an label the process flowchart, what is that.
This process flowchart is one is distillation column and there will be input and this distillation
column through streams one let it be here through streams one. And in this case feed is given to
you that is 200 mole per hour and mole fraction of components A in this feed it is given 0.4
whereas mole fraction of B in this feed stream it is given 0.6.

And from this separation by this distillation column we are getting from this stream to we are
getting distillate, it is amount is 100 mole per hour. And mole fraction of component A in this
distillate it is given 0.65 and mole fraction of component B in this distillate it is given 0.35.
Whereas from this bottom part of this distillation column as is extreme 3 it will be coming out
with a bottom amount that is unknown to you that is let it be B, this is in mole per hour.

876
Whereas this component A, in this bottom product B that is also unknown to you and then
component B in this bottom product also unknown to you. Now based on this problem we have
to calculate what should be the degrees of freedom. Let us have this in tabular format like this, it
is here number of degrees of freedom analysis here number and here let it be ok justification like
this.

Now if you consider here like as a serial number suppose 1 number of unknowns here what will
be the number of unknowns here. It will be like 2, because here one is bottom product it is
unknown to you and the composition xB at bottom product, xB only here. Because if you know
the x sorry this is x, xB then you can obtain what will be the xA,B.

Or if you know that xA,B here will be able to know what should be the xB,B. So, in that case xA,B
will be equal to 1 – xB,B, so by this. Similarly what should be the number of independent
equations how many number of independent equations can be formed here. Here it will be 2
because one will be overall and another will be one of the component material balance either A
or B.

And then you have to calculate number of relations here number of relations I think it is not
required. Because there it is not suppose any equilibrium conditions or any density or any you
know viscosity relations it is not required at all. So, in that case it will be 0, no auxiliary relations
are required here. And then number 4 what will be the number of independent reactions, here
there is no reaction, so you can write it will be 0.

Therefore, number of degrees of freedom will be is equal to as per that definition. So number of
unknowns is 2, number of independent reactions is 0 minus number of independent equations is
2 and then minus number of relations is 0, so it will be coming as finally 0. That means here
number of degrees of freedom it is 0, what does it mean, the system is well defined you can get
the unique solution of this problem. So, since NDF is equal to 0 system is completely defined
like in this way we can analyze what should be the process degrees of freedom ok.
(Refer Slide Time: 27:35)

877
Let us do another examples, suppose a problem let us have this problem here again one
distillation column. Where in this distillation column the feed will be entering at a rate of 200
mole per hour where composition at this feed as xA,F that will be close to 0.4. And xB component
B in this feed is equal to 0.6 and bottom product here B is unknown to you xA at this B it is also
unknown to you, xB,B it is unknown to you.

Whereas from this top product as a distillate you can say that distillate amount is known to you
as 100 mole per hour. And it is composition here for component A in this distillate is unknown to
you. Whereas in the previous example we have given that is known to you, in this case it is
unknown to you and also xB,D is also unknown to you. But you can find it out from this unknown
variables of xA,D as 1 minus xA,D.

Now in this case you will see how many you know unknown variables will be there, how many
unknown equations can be formed that can be also calculated. Now let us do all those things
here. First of all what is the number of unknowns variables, this is basically 3 because here one is
B another is xA you know that D another is xA,B this 3 unknowns are there.

Number 2, number of independent reactions that is 0, because there is no reactions taking place
in this separation process. Number 3, number of independent equations that will be is equal to 2.
Again you can do this material balance one is for overall material balance plus one of the two

878
component material balance. And then what will be the number of relations, is there any
auxiliary relations or not, that will be equals to 0.

Because here it is not required to consider any you know relations between you know that
variables like it is a temperature dependent or viscosity dependent or something is there or not,
so it is not required. So, you can write here at 0, therefore as per definition of number of degrees
of freedom NDF, that will be equals to here number of unknowns is 3 plus number of reactions is
0 minus number of independent equations is 2 and plus sorry minus number of auxiliary relations
is 0.

So finally, we are getting here number of degrees of freedom is 1. In this case, since number of
degrees of freedom is greater than 1, we can say that what is the discussion that we have given
here.
(Refer Slide Time: 33:03)

If number of degrees of freedom is greater than 0, the system is under defined, that means under
specified, there are an infinite number of solutions. In that case you know that more independent
equations are needed. So, for this we can say this is under defined, the system is under defined,
you may get more than one solution. So, for that you need more equations to get unique solution.

879
So, in this way we can solve this type of problem for number of degrees of freedom analysis.
Now let us have another examples with multi component separation process, degrees of freedom
with multi component separation process.
(Refer Slide Time: 34:52)

Let us considered this here, degrees of freedom with multi component separation process. In this
case again let us consider that distillation column for your separation process your one input,
there will be 2 outputs for this. In the input there will be a feed there will be a you know that
moles of you know stream here let it be 1 stream 2, here stream 3.

So nA1 means component A in stream 1, so here number of moles of component A here it is

given instead of mole fractions let it be 100 and n B 1 that will be unknown to you, nC here 1 that
will be unknown. Here 3 components are there that is why you are considering that here multi
component separation process. Three components are there, A, B, C components are there. Now
in stream 1 this 3 components are there but the amount of only one components A is given to
you, others are unknown to you.

And from the stream 2 as a distillate, let it be distillate here, distillate is given here 100 kg per
second. And nA2 is given 60 kg per second and nB2is given 40 kg per second, and in the stream 3
here it is you know bottom product, it is not given to you. But here component wise it is given as

880
moles of A in this 3 it is also not given to you, it is unknown nA3 that is unknown to you, nC3 that
is also unknown to you.

So, total here B is unknown, bottom product is total, the unknown even what will be the amount
of this component also unknown to you. Now in this case you have to consider that 40% of
component A in the feed ends up in the bottom, distillate also will have this 40% of that, that
means here 40% of A in the feed. So you can say that bottom and distillate rate are same.

So, based on which we can say that number of unknowns are here one is A, another is nB here in
1, another is nA in 3, another is nB in 3 and also you do not know what will be the amount of B
there. So from this we can say that these are unknown but other unknowns like here nC3. But you
can obtain these unknown nC3 from these 2 unknowns of this nB1 and nB3 if you know the total
amount of bottom B from that stream 3.

So, we should not consider that nC3 here based on because that others are known to you. And also
you are considered that in the stream 1 that nB1 is only unknown to you why mC1 is not unknown
to you. Because if it is unknown here nB1 then you can obtain this nC1 from this any nA1 and nB1
because nA1 is already known to you. So from this you can easily calculate from the total amount
of feed what should the nC1, so we have not to consider this nC1here also.

And then what should be the number of independent reaction that will be equals to 0 because
here there is no reaction taken place. And the number of independent equation can be formed
from the material balance that will be equals to here 3. Because it will be one overall balance + 2
of the 3 components material balance. And then what should be the number of relations, this will
be equals to 2, why.

Because one is given as 40% of A in the feed ends up in the bottom comma D comma B sorry in
the bottom and D and B are equal. So, from these 2 relations you can say that there will be a
number of relations will be equals to 2. Now we know that number of unknown variables are
here that is F, nB1, nA3, nB3 and B total is here 5, so total unknowns 5. Now from these you know
data who can calculate what should the NDF.

881
So here NDF would be equals to number of unknown is 5, number of reactions is 0 minus
number of independent equations is 3 minus number of relations is 2, so it will be equals to 0.
So, here also you can say that with this multi component separation process, we can calculate the
number of degrees of freedom. Based on this flowchart flow diagram and flowsheeting we can
say that the number of degrees of freedom will be equals to 0. And hence we can say the system
is well defined to get it is solution.
(Refer Slide Time: 44:38)

Let us consider another examples as per this diagram here like this in this case like one
separation process by distillation here. Here again distillate here xA2 is unknown to you xB2 is
unknown to you, xC2 is unknown to you whereas here in the bottom it is also unknown to you.
And then what is that xA3 = 0.1, xB3 that will be equal to 0.7 and xBC that will be equals to 0.2.

Whereas in the feed F is given to you 100 and xA1 it is 0.2, xB1 it is 0.3 and xC1 it is unknown to
you. And one important relation is given here like this 80% of stream 1 ends up in distillate and
50% of stream 1 or feed you can say that feed ends up in bottom. So based on this what should
be the degrees of freedom. So in this case again we can say that number of unknowns = 4, why
one is D, one is xA2, one is xB2 another is B and then number of reaction = 0, number of
independent equation is equal to here it will be 3.

882
Because 1 is for overall and others, 2 will be from 2 of the 3 components. And the number of
relations = 2 here as per problem therefore NDF number of degrees of freedom will be equals to
here 4 + 0 – 3 here – 2 that will be equals to – 1. Here it is you know that again it is less than 0
what does it mean, that system is not well defined you cannot get the you know unique solution
for this system.

So it is you know over specified since the number of spaces number of you know unknowns of
the information given is more than you know the number of you know unknowns also. So, we
cannot this problem and for that you need to get the either you know reduce that equations or you
can consider the other unknowns there to solve this equation and also to get to the unique
solution for the system ok.
(Refer Slide Time: 49:21)

Let us analyze the degrees of freedom for multi unit processes. Now in this case the degrees of
freedom whatever we have described for a single unit process can be easily extended it to multi
unit process also. In that case also you have to label a flowchart completely with all the relevant
unknowns for all units and streams. And then perform the degrees of freedom on each unit
separately for that unit operations. And also, accordingly you have to calculate what should be
the number of degrees of freedom.
(Refer Slide Time: 49:58)

883
Now, let us do an example like this here an absorber stripper system which is used to remove
carbon dioxide and hydrogen sulfide from a feed that consists of 30% carbon dioxide and 10%
hydrogen sulfide and also nitrogen. In the absorber a solvent selectively absorbs hydrogen
sulfide, carbon dioxide, the absorber overhead contains only 1% carbon dioxide and no hydrogen
sulfide is there and nitrogen is insoluble in the solvent.

The rich solvent is streams leaving the absorber is flashed and the overhead stream consists of
20% solvent and contains 25% of the carbon dioxide and 15% of the hydrogen sulfide in the raw
feed to the absorber. Now based on this you know problem draw and completely label a
flowchart of the process and perform the degrees of freedom.
(Refer Slide Time: 50:57)

884
Now, let us have this you know problem with the flowchart like this here shown. Here absorber,
stripper and flash units are given for whole you know process. And in the absorber here C some
input will be coming an output also will be there. And there will be a some recycle from the flash
and it will be sent to the absorber and some portion will be again send to the stripper. And the
flowchart you will see that all you know knowns and unknowns’ variables are mentioned there,
now you have to you know perform the degrees of freedom.

Now see this number of unknowns if you consider individual you know equipment. Like if we
consider here absorber number of unknowns will be 8, number of independent equations will be
4, number of relations will be 0, so in that case degrees of freedom will be equals to four.
Similarly, if you consider that flash you know that unknowns are there, so number of unknowns
will be here 7, number of independent equations will be 3, number of relations will be 2 and then
number of degrees accordingly it will be 2.

Number of unknown you know variables will be for stripper as 5, number of independent
equations for stripper it will be 3 and there is no relations given for stripper. And then
accordingly number of degrees of freedom will be there. Similarly, you can calculate the number
of degrees of freedom for stripper splitter, number of degrees of freedom for mixer, number of
degrees of freedom for overall you know system.

885
So, in this case the lowest degrees of freedom first you have to find out and it is coming is for
overall processes it is coming as 1. So, which specifies that a basis will be reduce it is number of
degrees of freedom to 0. So, you have to you know control the system, you have to manipulate
the system with some relations or variables or independent equations making from the material
balance considering other you know unit.

However, you will see that the last degrees of freedom will be converting to 0 there. And then
you can say that the whole systems will be well defined and accordingly the number of degrees
of freedom for the overall system will be equals to 0. And then accordingly we have to solve the
problem and you would can get the number of you know degrees of freedom will be equals to 0
and unique solution.
(Refer Slide Time: 53:48)

Like here if we consider another example with reaction what will be the degrees of freedom like
methane oxidation process. In this case the feed to a plug flow reactor contains equi molar
amounts of methane and oxygen. Assume a basis of 100 moles feeds per second, the fractional
conversion of methane is 0.1 and the fractional yield of formaldehyde is 0.855, methane and
oxygen react in the presence of a catalyst form this formaldehyde.

886
In a parallel reaction methane is oxidized to carbon dioxide. So, here we are getting these
equations and the system is specified to it is known variables and unknown variables with the
streams.
(Refer Slide Time: 54:41)

So in this case number of unknowns will be close to 7, one is methane moles, one is oxygen
moles, one is formaldehyde and water and carbon dioxide moles like this and + 2 here unknowns
for you know extent of reactions for this 2 reaction. So total unknown variables are 7 and number
of independent equations are here that is number of your components, that would be equals to
here 5 and then number of auxiliary relations is given 2, so number of degrees of freedom will be
equals to 0 accordingly.

Here number of unknowns variables as per that equations here, we can say the number of
unknowns is you know 5 and then number of reactions will be equals to 2. So, according to we
have taken this number of unknowns will be equal to 7 + 2. So, here accordingly that number of
degrees of freedom will be equals to 0.
(Refer Slide Time: 55:37)

887
Similarly another problem here methane production.
(Refer Slide Time: 55:40)

Here this flowchart is given and in different you know inlet and outlet streams for different you
know units there all knowns and unknowns’ variables are specified. And accordingly, what will
be the number of unknowns, number of independent equations and number of auxiliary relations
are given. And then according to what should be the number of degrees of freedom that is
analyzed based on individual equipment, it is shown in the slides.

And then we can say that none of the process systems here carries, in number of degrees of
freedom of 0 here. And then lowest values of 1 corresponds to the reactor here, that is 1 and this

888
means that the one of the unknowns should be specified here and or additional information to be
needed for the problems to be you know potentially solved. So, in this way you can analyze the
degrees of freedom.
(Refer Slide Time: 56:38)

Similarly, another example is given for ammonia reactions with recycle stream.
(Refer Slide Time: 56:44)

And here all the you know knowns and unknown you know variables specified in this flowchart
in it is you know respective you know flow streams and respective you know units. And they are
respective you know degrees of freedoms are analyzed for individual units like this. Here also
you are getting that overall process this degree of freedom is 0, so we can say that these systems

889
can be you know well defined well specified. So, you can solve this equation to get the unique
solution.
(Refer Slide Time: 57:17)

Another example, methanol combustion process how to analyze the degrees of freedom. Here
also you can get this degree of freedom as 0 with this known and unknown variables in the
flowchart.
(Refer Slide Time: 57:31)

Similarly, turbine power plant how to do the degrees of freedom analysis it is given. Please go
through this again the basic concept is to that use that you know definition of degrees of freedom
and to find out that number of unknowns, number of independent equations and relations and

890
accordingly what should be the number of degrees of freedom. So here it is given these examples
please go through these examples and try to understand how to calculate these degrees of
freedom there.
(Refer Slide Time: 58:00)

So, I would suggest you to go further reading for this analysis of degrees of freedom this
textbooks is given here even you can follow the reference books also for this analysis.
(Refer Slide Time: 58:12)

So, we will discuss more about this computational flowsheet based on you know our material
balance equations analysis. In the next lecture we will describe about flowsheeting and
flowsheeting codes there under this same module. So, thank you for your attention here.

891
 Basic Principles and Calculation in Chemical Engineering
Prof. S. K. Majumder
Department of Chemical Engineering
Indian Institute of Technology-Guwahati

Module-11
Lecture-33
Process Degrees of Freedom

Welcome to massive open online course on basic principles and calculations in chemical
engineering. So we are discussing about the computer aided balance calculations under module
11. Now this module we will continue that discussion on computer aided balance calculations.
(Refer Slide Time: 00:48)

And in this lecture will try to discuss about process flowsheeting and it is principles and what are
the different types of process flowsheeting and flowsheeting codes. Now for this flowsheeting
based calculations you need to know about that process degrees of freedom. We have described
in the previous lecture about that process degrees of freedom and it is analysis with various
examples. And also, we have described how to you know make a process flowsheet and just by
mentioning different components and there that specifications of different variables.

And also, how to you know analyze that number of degrees of freedoms, they are based on
different variables and even different independent you know equations that is developed based
on material balance and energy balance. Now based on those material balance or energy balance

892
equations you can make it flowsheet. And that proceed maybe you know in terms of spreadsheet
in computers screen where you can mention all those variables.

And those variables to be you know mentioned in such a way that what is the actually material
balance equation, what is the energy balance equation. Based on which you can note down in
that you know spreadsheet for the solving of that linear equations or nonlinear equations
whatever it is coming based on that material balance. And also, after you know pointing out or
you can say that specification of those you know process you know equations and you know
variables.

And then you can solve those equations by you know of some codes or by you know that
computer programs, so it will be called as flowsheeting code. So, we will show here that what
are the different types of you know flowsheeting codes are being used for solving linear and
nonlinear equations also or process optimization, you will see that there also there maybe some
you know linear and nonlinear equations which is to be solved for optimization of the process.

Based on that you know material balance and also energy balance equation and for those you
know solving of that optimization problems. Also, there are several you know algorithms and
you know codes are being used to solve those equation. And we will also show those codes also
here. Now before going to that in details you have to what is that process flowsheeting.
(Refer Slide Time: 04:03)

893
Now it is generally a component of process designed to perform the computer based you know
calculations of steady state energy and material balance. And also, you can assess by this flow
sheeting, what is the size of that you know chemical process, equipment and also what are the
costs or economy for that particular chemical process based on that optimization problems. You
know that computer solved the problem that you know described the mathematically of a series
of that operations.
(Refer Slide Time: 04:45)

And you can say that some logical decisions or theoretically for the optimization of the process.
And the computer uses some you know balance equations to solve those equations by certain you
know course or like you know some other you know solvers like that.

894
(Refer Slide Time: 05:10)

Now, the computer uses this following you know to solve material energy balances here you will
see as given in the slides. Here some you know equation solvers can be used to solve that you
know material and energy balance equations. Some generic codes can be used to solve that
material and energy balance equation. Even you can solve that material and energy balance in a
spreadsheet even some flowsheetings codes also available to solve with this material and energy
balance equation.
(Refer Slide Time: 05:41)

Now the essential problem in you know flowsheeting is to solve a large set of linear and
nonlinear equations. And of course, this you know solution to be an acceptable degree of

895
precision just by iterative procedure. And in flowsheeting in that case you must make sufficient
specifications to take up all the degrees of freedom. Once the process flowsheet is specified with
process degrees of freedom and also processes specifications inlet outlet even specific
specification of this inlet and outlet.

Streams, they are with different you know variables like thermodynamic variables even dynamic
variables there. The solution of those you know specified flowsheet you know streams in that
case you will see if you are considering steady state operation then you have to solve that steady
state material and energy balances of that processes. And that can be obtained by computer code
who is known as a flowsheeting package.

Now this computer code is basically an equation solving programs there and it is based on
actually that energy and material balance equation. And some programs is made which is
actually used for that solution.
(Refer Slide Time: 07:12)

Now what is that equation solving programs, the equation solving programs can be use to solve
linear and nonlinear material balance. The equation solving programs may contain several sets of
you know, library models of programs that you can use as it is or change for using modified
versions. Sometimes you will see that code whatever is available commercially that you can use
for solving that linear nonlinear equation.

896
But if you are having different type of you know linear equations or nonlinear equations for a
specific problem there. So, in that case you can modify those you know, existing you know
programs or models which is available in a library. So, in that case, you can you know
conventionally change that models and make a you know new you know modified versions of
that programs.
(Refer Slide Time: 08:11)

Now what are the you know existing library models generally available of commercially like you
know that the roots of equations there is some programs available to solve these roots equations.
And also, some you know the library models are for differentiation and integration, differential
equations you know special functions, complex of variables like optimization problems, matrix
calculations, arbitrary length integers even you know interactive tables, graphics, statistics and
curve fitting etc.

So, these are the library models that are available, you can use this library models to solve your
you know linear or nonlinear equations. And also, you can modify these models based on your
problems. Now what are the techniques to solve that equations.
(Refer Slide Time: 09:12)

897
Now you will see that there are several techniques to you know accomplish to solve this linear
and nonlinear equations using general computer programs. Two major categories are here like
direct method and interactive method.
(Refer Slide Time: 09:26)

In the case of direct method, you will see that for linear equations the methods come for most
part from the well-known Gaussian elimination algorithm. And these methods need considerable
memory in order to store the entire matrix and the right-hand side both of which are constantly
modified in the course of calculations. You will see that if you are having set up linear equations
or nonlinear equations you will see that as per variables you can you know average you know
those equations.

898
And you can write a you know a linear equation forms there as a matrix forms and then you can
you know solve that matrix form of those equations by you know this Gaussian elimination
techniques. There is the algorithm is available also, you can use that algorithm to solve those you
know set of linear or nonlinear equations there. But Gaussian elimination algorithm is basically
used for linear equation solving.

Whereas, you can use that Newton Raphson method or Newton's only methods to you know
solve that nonlinear equation there. You will see that whenever you are getting that material
balance equation or energy balance equations for different components in a particular process
even for overall process also. You have to arrange all those equations as a matrix forms and then
you have to solve that you know by computer codes.

Furthermore, if suppose no approximate solution if it is you know obtained from your you know
set of equations. Then you know that you have to modify that equations with some other you
know auxiliary equations. So, that you can get that solution of there but sometimes you will see
that without using that you know Newton's method or Gaussian elimination method you can
solve that equation theoretically to get that exact solution there.
(Refer Slide Time: 11:43)

899
And iterative methods are basically if the system of equations is written in a matrix form like AX
= b here A or here you know that coefficients and X is that set of you know variables, they are
unknown variables and b is again that some coefficients there. So, if you are expressing this you
know material balance equations as a matrix form then you can use this concept to produce you
know of that solution just by an initial guess of that like X0 a sequence of vectors Xk that
converging towards the desired solution reasonably and also rapidly.

Now substitution methods are one way to implement this concept also. So here, so in this form of
matrix you can you know solve just by you know assuming that initial guess of that X value.
And then successively you just you change that you know guess values based on that initial
guess and then coming to that you know desired solution by conversing that you know
assumptions there.

So, in that way you can solve these linear equations by iterative methods, even you can solve this
by of you know computer programs there. And this can be used for linear and nonlinear
equations but for only nonlinear equations there we have described earlier that you have to use
modified you know Newton's method there just incorporating that inverse of your Jacobian
matrix there, that we have described earlier.

Then another important points here that whenever you are expressing all those linear and
nonlinear equations in a spreadsheet then you have to make a spreadsheet programs to solve all
those you know equations there.
(Refer Slide Time: 13:50)

900
And that can be you know represented you know based on different you know aspects like you
know whether it should be you know user friendly or not, whether it should be you know easily
understood or not or whether it can be used for general utilities or not. Though there, is there any
other you know tools can be used to reduce you know spreadsheet programs or not, all those to
be actually considered there.

Now a spreadsheet program can be applied to solving only material balance problems without
knowing a programming language. Here this is one of the important points here, a spreadsheet
generally represents and easy to use and iterative you know interactive visual program with user
friendly manners. And to enhance the capabilities of spreadsheet programs, numerous add on
products such as you know word processors, 3-dimensional graphics, general utilities and
communications links can be used.
(Refer Slide Time: 15:00)

901
Here see that the spreadsheet displays a portion of a large 2-dimensional matrix or array on the
you know monitor screen. As shown here in the slides that here how the spreadsheets are
actually of seen in a monitor there. So, if you are getting here a set of linear equations and then
how these set of linear equations can be expressed in a spreadsheet.

And how that is spreadsheet you actually being executed to solve this linear set of equation. So,
in that spreadsheet generally consist of numbered rows and columns that identified by sequential
parameters here. Like this here parameters or variables also parameters like here 12, 6, 9, 3, 15,
4, 4, 4, 6 like this, these are the you know coefficients here. Whereas you know that variables
like here X1, X2, X3 like this.

So, in a spreadsheet you have to mention all those you know variables like here these variables
X1, X2, X3 and also what is that, that coefficients there. For a number of iterative procedures, you
will see that that you can solve this linear equation in a spreadsheet. Now a spreadsheet codes
commonly used a method called the Gaussian Seidel you know iterative you know method to
solve a set of linear equations there.

So as per this here it is shown that here these equations are given, so as per this Gauss Seidel
iterative method how to solve this linear equation in a spreadsheet it is given there. Like this here

902
so how this you know linear equations can be expressed in a spreadsheet and how to solve this is
shown here.
(Refer Slide Time: 17:03)

Now what is the advantage of spreadsheet, one advantage of spreadsheet is that the creation and
execution of spreadsheets usually involves significantly less effort than writing and running a
user-friendly program. Other advantages like in engineering practice where you know that a low
cost of execution and ease of execution reasonable speed and a specific knowledge of the
equations used in the calculations. For those cases this you know spreadsheet programs or
spreadsheet codes can be used for solving that set of linear equations.
(Refer Slide Time: 17:44)

903
But here some disadvantage also there, in this case the spreadsheets cannot handle very complex
material and energy balance equations. And also, this spreadsheet actually is more suitable for
maintenance and minicomputers. That is why it is of you know very tough to you know get the
solution for you know very complex material energy balance in a simple computer. So, in that
case you have to use some you know of minicomputers no that you know minicomputers, and it
cannot be you know used for this you know complex material and energy balance equations.
(Refer Slide Time: 18:39)

And flowsheeting programs, what is that actually in 1960s, the chemical process industry
initiated the use of large-scale programs for computer aided process design. And such programs
accept information about a chemical process at the flowsheet level of detail and make
calculations that provide data about not only material energy flows. But also, about cost, even
pipe layout, time, even effects and other you can say that useful information for design and
operation.
(Refer Slide Time: 19:13)

904
You can get the generic flowsheeting code based on that common structure like this here. If you
are considering that user interface you know flowsheeting code. Then in that case you need that
here input data, known values of stream variables, output report graphics and then process flow
diagram. So, from this user interface you can get these 3 components and these 3 components
basically based on that physical property data, and also that equipment unit or operation
subroutines there.

And then you can you know interconnect this physical property data and equipment unit
operation subroutines by executing that you know input and output calculations, order, files,
lists, stream connection, tests for convergence like this. So, all those things will be you know
incorporating here whenever you are using any physical property data for you know assessment
of some equipment or process just by you know conjugating that subroutines of that you know
individual equipment or process unit.

And after that you will see that based on this you can get that user interface to get that you know
input data known values of stream variables. And also, what would be the output report graphs
there. And also process flow diagram based on which you can get that user interface
incorporating with those you know of that calculation based on this subroutine of that process
equipment.

905
Now 2 methods of flowsheeting here equation-oriented method of flowsheetings are there and
also modular method of flowsheetings are there. So basically, under these 2 you know
flowsheeting you know method you can you know do the flowsheeting codes and based on
which you can solve that you know process input and output variables based on their material
and energy balance equation.
(Refer Slide Time: 21:30)

Now what is that equation-oriented method of flowsheeting, you will see that in this case you
know of the entire set of equations and inequalities that representing the process which is
employed there. And the equations can be solved in a you know sequential fashion which will be
analogous to the modular representation or simultaneously by Newton's methods or other
methods.
(Refer Slide Time: 21:59)

906
The modular method of flowsheeting is basically it is a collection of modules in which the
equations and other information representing is a subsystems or piece of equipment are you
know collected together. And the subsystems are coded, so that the module may be used in you
know that isolation from the rest of the flowsheet and also it can be used as a you know portable
from one flowsheet to you know another by interconnecting the streams there.

Now, interconnections must be you know set up for the module, so that information can be you
know transferred from module to module and concerning the streams, compositions flowrates,
coefficients etc and so on. So basically, here in this case, there should be some modules this
modular method of flowsheeting there. And in that case that modules basically subsystems will
be there and those the subsystems as a module will be interconnected.

And that interconnections will be in such way that information can be you know transfer from
one module to another module. And in that case, you have to incorporate that information of the
test streams, compositions, flowrates, coefficients etc. there.
(Refer Slide Time: 23:35)

907
And each module will content that you know equipment size, the material energy balance
equations, even rate equations when you will see that what are the allocated variables for that
component flowrates that also will be there. And the temperature and pressures that is called
thermodynamic variables. The phase conditions whether you know that at a particular condition
whether page will be that is converting into you know solid to you know liquid or liquid to solid
or liquid to vapor like that.

So, in that case that phase conditions of each stream that enters and leaves the physical
equipment that will be you know represented in the module. So that is why each module to be
you know well arranged by this information, so that these informations would be you know
transferred from one module to another module. Now other ways also you can analyze this
module based flowsheeting.
(Refer Slide Time: 24:35)

908
In that case you know that most chemical processes can be represented by different combination
of you know that mass, energy and momentum transfer phenomena. Like you know that mixing,
heating, cooling, even reaction, phase contract you know that phase transition, phase separation
and also you can say that dividing up the streams like this. So, these are some you know
phenomena based on which you can make a block diagram.

And based on this block diagram you can arrange this module and then you can you know assess
that you know module and also you can solve that module by is particular module-based codes.
(Refer Slide Time: 25:31)

909
And this you know phenomena-based process flowsheet, in that case most process can be you
know represented by using the following 8 phenomena-based process blocks. Like this you know
mixing here including two-phase mixing, even three-phase mixing also be there if there is a multi
phase flow systems in your chemical processes. Even heating one should be one module there or
you can see that blocks.

And cooling reaction like phase contact, phase transition, phase separation and dividing. These
are the you know different 8 phenomena-based process blocks which are being you know
incorporated to solve those you know linear and nonlinear set of equations that is based on your
process problems. And also, you can you know optimize those process based on this you know
different you know phenomena-based process blocks.

And then computers actually no computer codes are or you can say that phenomena based
flowsheeting codes can be made based on these you know phenomena-based process blocks.
(Refer Slide Time: 26:49)

Now, an executive routine calls the modules in the you know proper order transmits information
from a library of subroutines and picks out information on physical properties from an associated
database. So, if you have that data of that streams and modules or you can say phenomena-based
blocks from those you know associated database you can you know make a you know routine or
programs.

910
And based on which you can transmits that information from a library of subroutines and picks
out information on physical properties from the associated data and then execution of the of you
know codes to solve that equations. Now either the program and or the user must select the
decision variables to solve those for recycle and provide estimates of you know certain stream
values to make sure that convergence of the calculations will be occurs.

Especially in a process with many recycled streams will be there. So, it is very important, so
interconnections of those information whenever you are using you know the process with
recycled streams it would be required. Because in that case the informations from one output will
be you know connected to another input of another you know process unit.

So, in that case all the informations to be you know wisely you know selected and also what
should be the you know of decision variables for that recycle or you know you can say that how
that you know decision variables will be you know making that conversions of that calculation
there. And it is important and it the code should be you know written in such a way that there
will be some convergence of that you know solution whenever you are considering that
transferring of that information from module to module.
(Refer Slide Time: 29:08)

911
Now typical course that are used to execute that flowsheeting here given in the slides like
ASPENPLUS you know CAPES, CHESS, CONCEPT, even PROCESS you know SIMMOD
SPEEDUP, even SYMBOL. These are some you know commonly used that codes to execute the
flowsheeting calculations there.
(Refer Slide Time: 29:27)

Main features of the flowsheeting program is that here given that information flow in a typical
flowsheeting code is given here. Like flowsheeting functions that you have to first decide and
then you have to do the manager and material balance equation and select those equations and
write that equations there. And then it will be connected to that numerical subroutines, so that
you can solve this energy and material balance equations.

For all the streams and unit is that you have to do this here and then sizing data to be
incorporated for that equipment sizing. And then you know that cost data also to be you know
incorporated for this cost estimation after that equipment sizing. All these you know energy
balance equation when material balance equation, and then equipment sizing, and then cost
estimation are interconnected with link information there.

And then after that you have to analyze that economic there, so that this process know that
economically viable or not and then you have to analyze the profitability. So, all for this finally
this you know our feasibility of that process whether it will be economic or not based on that you

912
know energy and material balance equation. Now you have to solve that energy and material
balance equation sand for that you have to use some numerical subroutines.

And after solving those also you have to you know incorporate that equipment sizing, analyze
that equipment sizing based on that sizing data. And then cost estimation based on that cost of
data and then you know evaluation of the feasibility of that process based on that data. Now in
this way you can say that how that you know flowsheeting programs can be made based on that
you know raw materials data and also other informative of this process.
(Refer Slide Time: 31:37)

Interconnections of the information how it can be done, suppose there is a module here, so in that
case some says subsystem module will be there. So, you have to use some you know subsystem
model that contains equations, inequalities, you know listed data, calls of database. And then you
know that you have to you know, know that inlet information there, what will be the variables,
what will be the coefficient, what will be the streams and energy flows there.

In the outlet also that information should be there, variables coefficient streams and energy
flows. Now this inlet and outlet will be interconnecting by this you know subsystem model and
with those equations’ inequalities and listed data.
(Refer Slide Time: 32:26)

913
Of course, you will see them some difficulties will be there with modular codes relative to
equation-based codes there. Now the output of one module is the input to another here in this
case basically for modular based codes. The input and output variables in a computer module
are fixed, so that you cannot arbitrarily introduce an output and generate an input.

The modules may require a fixed you know precedence order of solution that is the output of one
module must become the input of another in this case. Hence convergence may be slower than in
an equation solving code and the computational cost maybe high in that case. Now to specify a
parameter in a module as a design variable you have to you know place a you know control you
know block around the module.

And adjust the parameter such that design specification will be met there. And this arrangement
of course will be creating a loop and, in that case, if the values of many design variables are to be
determined, you have to you know end up with several you know nested loops of that
calculation.
(Refer Slide Time: 33:51)

914
Now the concept of tearing is one important you know phenomena who is involved in
connection with the modular flowsheeting codes to solve material and energy balance equation.
In that case tearing will be involves for the decoupling the interconnections between the
modules. So that you know sequential information flow takes place and also it is required
because of loops of information created by you know recycle streams.
(Refer Slide Time: 34:26)

Now, let us have an example for this simultaneous equation and modular techniques of solving
material balances. Now suppose a 2-step process with 1 recycle stream is shown in figure by the
total material balances for the process to calculate the amount of the recycle stream r as a

915
function of small r here. Now the fraction of a recycled use r = 1 by 4 and r = 3 by 4 for a
comparison.

Now in this case you have to calculate the amount of the recycle stream r as a function of small r
here. Now see here there are 2 models 1 and 2, 2 stage process here, so from this second stage
there will be some recycle amount. Now that recycle amount will be you know that some
fractions of this output of this process 1. So, in that case you have to find out the what will be the
amount of that recycled streams r as a function in that case.

And also, you have to calculate that the fraction of A that is recycled, now in this case you can
consider that fraction of A recycled is r = 1 by 4 and r = 3 by 4 for a comparison.
(Refer Slide Time: 35:45)

Now in this case if I considered that the material balance here for the unit 1 that will be 100 + R
that will be is equal to A. And for unit 2 that material balance will be balance A will be equals to
R + P. And the fraction recycled will be is equal to Ar that will equals to R. Now in this case if
we write that you know linear equation set here. Like here we can write A – R will be equals to
100 and then A - R – P will be equals to 0 as per that unit 2.

And then from this rA - R that will be equals to 0, so these are 3 questions you can write.

916
And if we express this linear set of equations as a matrix forms, we can write this matrix form
here,

Here this 1 1 1 these are basically the coefficients of that you know streams here of R A P like
this. Then one can use Gaussian elimination method to solve and successive elementary
operations that results in the matrix.

Like this here we can you know use this Gaussian elimination method and finally we can write
these results as a matrix here. Like this here in this case 1 0 0, 0 1 0, 1 00, you have to make like
this as for Gaussian elimination method. And accordingly, what will be this you know matrix of
this write part of this you know formulation then it will be

(Refer Slide Time: 37:41)

917
So after that to get the solution what you can say that resolving this we can simply say that here

(Refer Slide Time: 37:57)

So here and then we can say that

918
So, in this way we can solve this equation just ask for that formation of matrix from that linear
set of material balance equation. Now for the 2 given values of R what will be the value of A
what will be the value of R and what will be the value of P for that streams that can be obtained
here.

Now for you know A if R is equal to 1 by 4 we are getting here 133, if suppose fractions is 3 by
4 A will be is equal to 400. And for r is small r is equal to 1 by 4 it will be recycled stream will
be 33. And for fractions r is equal to 3 by 4 that recycled streams will be 300. And for products
we can say that for the fractions r is equal to 1 by 4 this products streams will be of 100 and
similarly for that fractions of r is equal to 3 by 4 it will be 100.

So here we are getting this solution for different fractions there, but for all cases we are getting
that here same value of these products which is coming as 100 here. Because as per this you will
see that overall material balance which will be giving as the heat 100 will be is equal to what is
that output 100 here. Another examples of this modular approach to the solution of the problems
like this.

It would be involved solve the unit 1 for A first assuming a value for r, the tear variables then
you need to would be solved. Now the value of R calculated and the value calculated compared
to the assumed value here. If the error is not small enough the new value of R from the unit 2
would become the you know assume value of R for unit 1. And unit 1 solved again for A and
you need to solve again there the sequence of solutions would be repeated until the error in R
becomes sufficiently small.

Because R is initially not known, suppose that we start with R is equal to 0 here and A is equal to
100 as the initial guesses. So, in that case for unit 1 we can right here Ak will be equals to 100 +
Rk and unit 2 Rk take is equal to Ak into r.

919
So, based on that you know initial guess how we are getting that different values of you know A
and R there based on different iterations starting with initial guess.
(Refer Slide Time: 41:03)

That is given here tabular format have of that successive calculations result. In that case if you
are considering that r = 0.25 and initial case at you know first iteration here R = 0. And then A
will be is equal to 100, and then for iteration 2 R is equal to you know 25, 125 it will be then,
capital R is recycle will be accordingly there. So, if we you know change the iteration here and
changing that you know r value as per that you know this relationship.

Then we can have this you know a successive you know iterations just by guessing that initiation
of the you know final value of the previous you know iterations. So, in that case finally we can
get to that at R = 33.33 we are getting A is 133.33 and then capital R will be is equal to what will
be that 33.33. And in this case, you will see that this recycle streams are changing based on that
iterations and it is changing from 25 and then 31.25 and 32.81, 33.20.

Once you will see that it will be not changing significantly, in that case we can stop that
iterations there and we can select that final value of that R and respective A value and P value
there. So here we are getting that this at R = 33.33 this you know the change of this R will be is
equal to you know almost negligible. So, in that case we can decide that this R at this 7th

920
iterations we are getting that final value of R and then A and then what is that capital R is equal
to this.

Similarly, for R = 0.75 that is 3 by 4, we can simply consider that iterations here and accordingly
we can calculate. And you will see that infinite value of that you know iterations there. So, we
can say that there will be a you know R value of like this here where there will be no change of
that you know of R value there accordingly. So, in this way we can say that just by guessing that
initial guess and successively if we calculate that you know R k value.

And if you think see that there will be no sufficiently you know change of that iterations then
you can stop that you know iterations and you can select that value of that particular that streams
value there. So, in this case since recycles we are considering that iterations based on these R
value iterations value we are getting that at infinite you know iterations we are getting that
almost negligible change of that R value.

So, we can select that you know respective value of that R value and also respective for that
stream other stream values.
(Refer Slide Time: 44:44)

In this way we can solve this modular based approach to solve this type of problem. And
equation based flowsheeting there, in that case you have to consider sets of linear and nonlinear

921
equations which will be solved simultaneously using an appropriate computer code. Whatever
the code used to solve material and energy balance problems, you must provide certain you know
input information to the code in an acceptable format.

All the flowsheeting codes require an information flowsheet, like in the information flowsheet,
you use the name of you know mathematical model maybe subroutine for modular based
flowsheeting. That will be used for the calculations instead of name of the process unit there.
(Refer Slide Time: 45:33)

Now once the information flowsheet is set up then the determination of the process or topology
will be easy. And you can immediately write down the stream interconnections between the
modules or subroutines that have to be included in the input dataset. The interconnections
between the unit modules may represent information flow as well as material and energy flow.
(Refer Slide Time: 45:59)

922
Now in the mathematical representation you will see of the plant the interconnection equations
are the material energy balance flows between model you know subsystems. And equations for
models such as mixing, reaction, heat exchange and so on must be listed, so that they can be
entered into the computer code use to solve the equation.
(Refer Slide Time: 46:24)

Now you will see that there will be a certain table which is shown in the next you know slides
like this.
(Refer Slide Time: 46:30)

923
Some common type of equations that might be used for a single subsystem. In general, similar
process units repeatedly occur in a plant and can be represented by the same set of equations
which differ only in the names of variables, the number of terms, in the summations and the
values of any coefficients in the equations. Now there are several equations that are actually
being used, some are you know material balance, some are you know energy balances.

Here it is given some material balance in general forms, in energy balance in general forms and
component material balance also and summation of you know molar mass fractions to be there.
So, for a particular flow process what will be the incoming material streams, what will be the
outgoing material stream that you have to know. And based on which you have to do that
material balance and energy balance and also some other equations that you have to note down
(as shown in the slide).
(Refer Slide Time: 47:34)

924
And also, some other equations like you know vapor liquid equilibrium distribution is there or
not, equilibrium vaporization coefficient or not how it will be related. And total mole balance,
total you know component mole balance, molar atom balances, mechanical energy balance, all
those equations to be incorporated there in equation based flowsheeting.
(Refer Slide Time: 47:56)

Now, what are the general computer codes to solve the sets of nonlinear equations, there are
several you know codes that are available thereof they are like this. Here in this slide it is shown
here like Co5NAF in a deeper you know HYBRD SOSNLE and Various even you will see that
ZSYSTM, these are some you know, popular codes that are being used for solve the set of
nonlinear equation.

925
(Refer Slide Time: 48:32)

Typical process modules are given in the slides here in sequential modular base flowsheeting
codes with their subroutine names here like mixer you know splitter, valve even flash drum when
you will see that are furnace, exchanger even compressor, turbine, process pump, absorber,
extractor, striper. These are you know commonly used chemical engineering process module
there also distillation column, complex column there, simple reactor, equilibrium reactor, you
can say that plug flow reactors, CSTR like this.

So, these are the common you know process modules that is being used in chemical engineering
process. And based on this there are you know flowsheeting codes are available with their
subroutine’s names.
(Refer Slide Time: 49:25)

926
Now computer aided tools for this process optimization is also important there after you know of
solving those equations and then you have to optimize also with a certain constant there. Now,
different computer aided tools can be employed for performing and evaluating process that
optimization. Now for the selection of process feasibility, model based economic and
sustainability, indicator based, environmental you know evaluations are perform to assess the
process viability. Now it provides the rapid investigation of the process you know feasibility.
(Refer Slide Time: 50:05)

So, in that case you have to use some method-based tools there, there are several methods are
available and based on which respective tools also are available to you know assets that
optimization problems. Now some methods like you know property model-based methods there.

927
And based on that property model there are some tools are available like it is called ICAS utility
tools or analysis tools.

Here ICAS it is called integrated computer aided systems there, they are you will see that group
contribution, based property models used for you know vapor liquid equilibrium, liquid-liquid
equilibrium and solid liquid equilibrium even you know distillation boundary, residue curve etc.
For those things you know to analyze this you know codes are being used. Now, it is generally
used for you know, phase diagrams for reaction separation and reaction separation process like
this.

Like CAMD database search also one method based on which you know proCAMD or selection,
computer aided tools of each you know developed. And in that case, you will see that based on
these CAMD tools you can you know search and you know select the solvents for various types
of solvent based separation processes. And in this case the selection of environmentally friendly
solvents that affect the separation of the compounds.

That is why you have to select that suitable solvents and various types of solvent which is useful
for the separation process.
(Refer Slide Time: 51:59)

928
Another important method like driving force-based equilibrium of you know based methods.
They are computer you know tools or they are like here PDS you know design analysis tools are
there, generation of phase and driving force diagrams for the design of distillation column it is
being used. And in that case how to use that driving force diagrams for the optimal design of the
hybrid and intensified unit operations there.

Other tools like you know model heuristic based tools there, it is called ECON in that case
economic calculation and evolution is being done based on this ECON.
(Refer Slide Time: 52:46)

Other like model based here like this SustainPro or analysis it is generally used for you know
environmental evaluation of process for identifying design targets for achieving process
intensification. Another important model based it is called ProPred, this is generally being used
for pure component property prediction. So, for that particular process how to predict that
property of that compound based on this tool.
(Refer Slide Time: 53:18)

929
Equation oriented problem solution tool also available like Aspen, Custom Modeller there. In
that case model-based evaluation and design of intensified or hybrid unit operations are being
done based on this tool. Even model-based calculations also one method, in that case the tool is
Aspen Plus or Pro II there. And based on this you know tools you can assess the model-based
simulation and analysis of multiple intensified process alternatives.
(Refer Slide Time: 53:54)

We have described the different aspects of that flowsheeting, even modular based flowsheeting
and also equation based flowsheeting. And also, how to you know solve that equation based
flowsheeting, based on that codes. And also, what are the other different computer based

930
flowsheeting codes are available it is shown here. So, these are very basic and fundamentals of
this flowsheetings.

And further understanding of this you know flowsheeting codes there, you have to you know do
another course for this you know optimization course where you can learn different codes by
which you can solve that you know optimization problem based on that different tools and how it
can be done it is the there. So, this you know course only this much of scope is there to learn.

And I think it will be helpful for further understanding of the you know optimization problem
based on these different codes, so it will be helpful for you. I would suggest you to go further for
basic of this you know flowsheeting things from this you know textbooks. It will be you know
more informative for you there.
(Refer Slide Time: 55:21)

And in the next module we will try to you know discuss the case studies of chemical processes
with simultaneous material energy balance equations. So, whatever we have learned till now that
energy balance equation, material balance equation, even how to solve the equations they are.
So, based on which we will describe one you know industrial process with multiple units, the
complete processes.

931
And we will show that how to do that material balance and energy balance and based on which
you will be able to understand that complete set of chemical process and it is material and energy
balance. So, thank you for giving your attention here.

932
 Basic Principles and Calculation in Chemical Engineering
Prof. S. K. Majumder
Department of Chemical Engineering
Indian Institute of Technology-Guwahati

Module-12
Lecture-34
Case Study:Cumene production

Welcome to massive open online course on basic principles and calculations and chemical
engineering. So we will describe here a case study for a process under module 12 and in this
module will describe a case study of Cumene production from you know benzene and propylene.
And we will focus on only material balance of this you know this Cumene production process.
(Refer Slide Time: 00:56)

And in the successive lecture we will try to describe about to that energy balance equation and it
is solution. And in the previous lecture, we have described the flowsheeting codes information
flow in flowsheeting codes process module with information flow connection like this. So, here
is we will describe about that cumene production from benzene and propylene as a case study
with whatever we have learned earlier.
(Refer Slide Time: 01:27)

933
Material balance and energy balance and other you know solution method of those process, even
also how to solve that material and energy balance whether it is linear or nonlinear equations.
And also what are the different codes are there that we have learned. Now let us consider here on
schematic of this cumene production process, see here this cumene is produced from the reaction
of benzene and propylene.

There are several units are actually being used for this particular cumene production industrially.
Here the complete you know process diagram or you can say schematic diagram of the processes
given. Now the main process unit for this cumene production which are used or like you know
that vaporizer, reactor, separator and distillation column. Other small you have process units also
are required and you know accessory of those you know equipment, many equipments there.

So let us describe first this you know cumene production process here. You will see that in this
flow diagram here you will see that on STB and here STP, STB is basically the storage tank for
benzene and STP is the storage tank of propylene. Now these benzene and propylene from this
storage tank is you know send to you know a furnace to raise it is temperature for the reaction in
a tubular reactor here.

Now it will be sent through vaporizer, benzene will be passing through the benzene vaporizer
and propylene will be send to the propylene vaporizer. And then these 2 streams should be mixed

934
in a you know mixer and then it will be send to a you know furnace to raise it is temperature.
Now you will see that whenever you will be sending or as per process you know industrially that
benzene .

The fresh benzene from this storage tank it will be mixed with some recycled benzene which is
basically coming from distillation where this cumene and also it is byproducts along with the
benzene is separated. And after separation the benzene components will be you know recycle to
this, you know fresh this benzene. And then mixer of this fresh benzene and recycle benzene it
will be you know send through it is vaporizer.

And then it will be mixed with that propylene and then it will be going through that furnace.
After furnace you know that it will go through the reactor where this benzene and propylene will
be reacting at a certain temperature and pressure in this reactor. And after reaction you will see
some products will be coming out like you know that cumene, you know di isobutyl, you know
isopropyl benzene.

And also you will see that unreacted benzene unreacted propylene will be you know coming out
from that reactor as a you know outlet stream. And then it will be passed through the you know
benzene vaporizer where this you know heated up of this product will be used to you know raise
the temperature of that you know benzene feed by this vaporizer using these outlet streams of
reactor.

And then it will be you know again sent through that propylene vaporizer, where this you know
temperature will be you know or heat will be used to vaporize this propylene at a certain
temperature. After that it will be again heating and then cooling and then you know it will be
sent to a separator. And in the separator you will see that unreacted propylene and propane where
propane is actually basically coming with that propylene.

Because propylene is not 100% pure some fractions of that propane will be there along with that
propylene. So those propane and then propylene will be separated by the separator and from the
top part this you know this propane and propylene it will be used for heating up that you know

935
mixer of benzene and propylene in a furnace. And from the separator you know other part of this
product like.

You know that benzene unreacted benzene and cumene and byproduct di isopropyl benzene
isopropyl you know butane . It will be you know that separated in the distillation column. So this
distillation column can be named as benzene distillation column because here the benzene will
be you know separated out from that benzene column and it will be recycled to you know mix
with that you know fresh benzene.

And from this benzene distillation column this cumene and DIPB, it will be sent to you know
that again another distillation column this distillation column is called cumene distillation
column where this mixer of cumene and you know DIPB will be separated. And in the over heat
product that cumene will be separated, there will be certain percentage of cumene of product as
per that you know requirement of that you know process.

And from the bottom part of that cumene distillation column, this DIPB will be you know taken
out and it will be used for you know preheating that output of that separator of that cumene and
DIPB mixer. And then DIPB would be you know taken out as a product there. Now in this whole
process we are seeing that several you know process units are required and in each process units
you will see that there will be some inputs and outputs.

And some also units will have that recycle stream along with the fresh stream and then after that
mixing up that recycle stream and it will be sent to another stream and it will mixed and then
process further. So this is your whole process actually for the production of cumene. Now in this
case you will see that there will be a certain reaction will be going on for the production of this
Cumene.
(Refer Slide Time: 10:02)

936
The raw material basically the propylene and you know benzene, main reaction here it is given
like propylene will be reacting with that benzene and it will be produced there you know
cumene. And as a byproduct there again that produced cumene along with that you know
propylene there will be a reaction and then byproduct like isopropyl benzene will be you know
produced. Now, these reactions can occur in liquid and gas phases here.

But high conversion is obtained at the gas phase reactions, the catalyst like solid phosphoric acid
are actually replaced by zeolites and catalytic conversion reactions are held in shell and tube
reactor rather than packed bed fixed reactors. Now this is interesting that for this reaction, you
are using that solid phosphoric acid instead of zeolites. Because of that you know increasing the
efficiency of that reaction and there will be some catalytic conversion reaction here in this
reactor.

Now there are several different type of reactors are there but generally you know packed bed
reactors are being used for this type of reactor to get the contact between gas and liquid. But here
since there will be sorted temperature to be maintained there. So it is better to use that shell and
tube reactors there where in a tube side that mixture of you know that benzene and toluene will
be benzene and propylene will be you know passed through that reactor in presence of
phosphoric acid catalyst.

937
Whereas in the shell sides there may be you know streams will be supplied for changing the R
you know that controlling that temperature there.
(Refer Slide Time: 12:09)

So this is the background here, now different sections of the plant or like you know storage
section, preheating section, vaporization section, pumping sections there. In the storage section
you will see that benzene it will be 99.9% purity and propylene it is 95% purity whereas
remaining 5% maybe mixed with propane are stored in a liquid state in a storage tanks. Now
from storage tanks by pump it is sent to respective unit of processes.

Preheating section where benzene and propylene are mixed with the you know 2 : 1 ratio and it
these are fed to preheating section where a continuous series of heat exchanger is used to heat up
the feed mixer by the effluents from the cumene reactor. And the vaporization section after the
heat exchanger, a fired heater is used to vaporize and raise the temperature of the mixer to the
reaction condition temperature.

And in the pumping section, the pressure is maintained by the compressor from the pumping
section. So that at a certain pressure that liquid mixer or gaseous mixers to be sent to the process
unit.
(Refer Slide Time: 13:36)

938
In the reactor section you will see that a tubular reactor is used to withstand the pressure to 25
atmosphere and 350 degree Celsius. The reactor tubes are filled with catalyst and the feed is
charged from the top. The feed gas reacts and pass over the catalyst bed with 99% conversion of
propylene and outlet stream is sent to the recycle and purification section. However they are you
know different type of separators or distillation columns are used.
(Refer Slide Time: 14:12)

Now in that separation and purification section unreacted benzene which is separated in a
distillation column from the effluent obtained from the reactor. And the recovered benzene by
the distillation process in the separator is recycle to the feed stream. As per you know side
reaction, there will be a byproduct this called di isopropylbenzene which will be produced as a

939
byproduct and it is generated. And then it is separated by distillation from the product mixer. The
byproduct that di isopropylbenzene is separated in a sieve tray distillation column which is of
99% pure.
(Refer Slide Time: 15:04)

Now what is the process description for that you have to first of all know that how this process is
going on. In this case raw material propylene and benzene are stored in the respective storage
tanks. In the storage yard and then pump to the unit by the centrifugal pumps, benzene pumped
into the feed vessel which mixes with the recycled benzene. And benzene stream is pumped
through the vaporizer with 25 atmospheric pressure and vaporized to the temperature of 243
degrees Celsius.

And then mixed with the propylene which is of same temperature and pressure of benzene
stream. Now this reactant mixer passed through a fired super heater where reaction temperature
350 degrees Celsius is to be obtained.
(Refer Slide Time: 15:58)

940
Now the vapor mixer is then sent to the reactor tube side which is packed to the solid phosphoric
acid catalyst supported on the kieselguhr. The exothermal heat is there recovered by the
pressurized water which is used for stream production and it is passed through the shell side of
that reactor. The effluent from the reactor that is cumene and byproduct p-DIPB, unreacted
benzene, propyl and propane which are not taking part in the reactor for reaction with
temperature 350 degrees Celsius is used as the heating media in the vaporizer which is used for
the benzene vaporizing.
(Refer Slide Time: 16:55)

After that the effluent is cooled to 40 degrees Celsius in a water cooler, propylene and propane
are separated from the liquid mixer of the cumene DIPB, benzene in a separator that is operated

941
slightly above atmospheric pressure. The pressure is controlled there by the vapor controlled
valve of the separator. The separated fuel gas that is a mixture of propylene that is unreacted and
propane is used as a fuel for the furnace.
(Refer Slide Time: 17:40)

However the mixture of propylene and benzene to be you know fired or vaporized to a
temperature of 350 degree Celsius. Then the liquid mixer is sent to the benzene distillation
column which operates that 1 atmospheric pressure where 98.1% of the benzene is obtained as
the distillate. And this distillate from the benzene distillation column is then recycled and it is
mixed with the fresh benzene.

The bottom liquid mixer from the benzene distillation is then pumped at bubble point to the
Cumene distillation column. However distillate will have 99.9% cumene and bottom products
will have pure you know para di isopropyl benzene. And then bottom product of this p-DIPB is
used for pre-heating the benzene distillation column. For each preheating of heat all the utility
they are water being used like cooling water, electricity stream from the boiler, pneumatic air are
supplied from the utility section.
(Refer Slide Time: 19:06)

942
Now then you have to do the overall material balance for this whole process there. Now all
material balance calculations, whatever we have described earlier, what is the principles that
same principles to be used here. And those material balance calculations will be based on the
principles of conservation of mass which states that matter can neither be created nor be
destroyed but they may undergo physical or chemical changes.

In that case, according to that material balance equation, we can say that rate of mass input that
will be equals to rate of mass output + rate of mass accumulation. For steady state operation
where accumulation is constant, the rate of mass input that will be equals to rate of mass output.
The material can refer to a balance on a system for total mass, total moles, mass of chemical
compounds, moles of the chemical compound or mass of an atomic species and also volumes.

So based on this you can do the overall material balance. Now in this case, for the whole process,
you will see there will be a some data assumption. Our main objective is to produce 500 tons per
day of cumene production this is our goal.
(Refer Slide Time: 20:35)

943
So in that case as per reaction, it is seen that there will be a 99% propylene conversion and
product molar selectivity of cumene to para di isopropyl benzene is 31 : 1. And propylene purity
in the feed is 95% remaining is propane, benzene purity in the feed is about 99.9% remaining
maybe other components there. Like you know whatever benzene streams is coming as a recycle
they are some small amount of cumene maybe will be mixed with that.

So that cumene will be there in the benzene streams, molar feed ratio benzene to propylene it
will be 2 : 1 top product of benzene column will be 98.1% benzene and 1.9% of cumene. Top
product of cumene separation column there will be 99.9 mole percent of cumene whereas
remaining will be byproduct, bottom product of cumene separation column it will be 100% you
know byproduct it is assumed.

And the propane whatever is assumed as a tie substance here as a you know in our material
which is not taking part in the reaction does not participate in the reaction and it is generally
being used as a fuel for the furnace.
(Refer Slide Time: 22:19)

944
So in this case, basis is that you have to produce 99.9% pure cumene at a rate of 500 tons per
day. Now as per calculation you can say that 500 tons per day means 500 tons divided by 24
hours of day. So it will be coming as here 500 into 1000s that is kg divided by 24 into you know
120.19 it will be converting that is 24 hours in a day and into 120.19. This is basically the
molecular weight of you know cumene.

So you can get in terms of unit of kilo moles per hour, but since you have to produce 99.9%. So
actually this as per calculation 173.16 kilo mole per hour of pure cumene is to be used for
reaction, what is the primary reaction that already we have described in our previous slides there
will be propylene that will reacting with benzene and it will give you the cumene as per this
reaction.

And parallelly there will be a side reaction like this propylene again with produced cumene
would be reacted and it will give you that, you know byproduct of the DIPB. In that case as per
reaction 1 mole of the DIPB will be produced based on 2 moles of propylene used for the
reaction.
(Refer Slide Time: 24:01)

945
Now propylene used for the Cumene and DIPB as per that you know assumption of that
selectivity. We can say that the propylene required is 173.16 kilo mole per hour, for that target
amount of Cumene production. And as per selectivity it is given the 31 : 1, we can say that
conversion of propylene if it is 99% then what should be the amount of DIPB to be produced
based on that you know reaction.

Let x kilo mole of DIPB is formed then cumene formed will be as 31 into x as per selectivity,
whose implies that 31 x will be equal to 173.16, that means x will be is equal to after calculation
5.59. So the amount of DIPB formed is simply 5.59 kilo mole per hour.
(Refer Slide Time: 25:06)

946
And then you have to do that propylene balance, now propylene required for cumene is as per
you know reaction stoichiometric is 173.16, propylene required for DIPB this is 2 times of that,
it will be is equal to 5.59 into 2 that will be 11.17. Now total propylene then required if you sum
it up, you will get it to 184.34 because this propylene give you the cumene and also DIPB. So
total amount will be required this 184.34 kilo mole.

Now since the propylene conversion is 99%, we can say that the propylene in feed will be this
amount, you have to divide this you know 184.34 which is taking part for reactions divided by it
is purity that is 99%. So if you divide it you will get that what will be the propylene in feed was
there. And then unreacted propylene will be there if you subtract this you know 186.20 and
184.34 then you can get what would be the unreactive propylene.

So this is basically 1.86 kilo mole, now as per propylene feed since it is 95% pure and rest of
propane, you can see that total propylene feed that is pure propylene + propane that will be is
equal to to here 186.20 divided by 0.95 it will give you 196.0 kilo mole. Then remaining amount
will be you know that propane which will be you know calculated as this is your total amount of
propylene pure + propane.

If you subtract this 186.20 which is a fed there for this propylene if you subtract it then you will
get the remaining amount of 9.80 as a propane.
(Refer Slide Time: 27:22)

947
Then you have to do the benzene balance, benzene required for the cumene as per reaction it is
173.16 kilo mole. Benzene required for DIPB it is 5.59 total benzene then required if you sum it
up you will get and it is given that benzene to propylene feed ratio should be 2 : 1. So you can
say that benzene to be feed total propylene required into 2 that will be to is equal to here 368.37
kilo mole.

Now, unreacted benzene will be then remaining whatever you know there after you know useful
for the reaction, now it will be here 189.92. Then you have to do the material balance for the
individual unit like feed vessel here one important unit. So in the feed vessel there you will see
that fresh feed of benzene is coming in and recycle feed of benzene along with cumene that is
1.19% of recycle that will be 3.68 kilo mole as per calculation.

So total amount of benzene feed is 178.75 plus here recycle amount 3.68, so it will be coming as
here, you know that 193. you know 60. And you know that mixed feed of benzene that will be is
equal to 178.75 + 193.60 that will be you know that 372.35.
(Refer Slide Time: 29:10)

948
Now balance around the reactor, in the reactor feed will be mixed feed of benzene + feed from
STP. That mixed feed of benzene, it is generally that is 372.35 as per calculation here in the
slides. And then you have to add that what is coming from the you know STP that is propylene
storage tank, so this total moles of this you know feed will be as per reactor. Now from the you
know reactor after reactions, what will be the you know output stream, what will be the amount
of that.

Now output of the reactor can be calculated based on that, you know material balance, in that
case you have to consider that generation and consumption since in the reactor there will be a
reaction. Now as per that, you know material balance equation, we can write output of reactor
will be is equal to input + generation – consumption. So for that, if we considered that only
propylene here, so for propylene output will be is equal to 186.20 + 0.

Here there is no generation of this propylene and then consumption will be 184.34 that will come
1.86. Now the for benzene similarly you can do it will be as 189.92, for cumene it will be
176.84, in the same fashion if you do the balance for DIPB it will be as 5.59. And for propane
since there is no reaction or consumption or generation there. We can say that for DIPB and
propane output will be like this, so what will be the total amount of output of that reactor.

949
If you sum it up all those components of this propylene output, benzene output, cumene output,
DIPB output and propane output you can get this 384.01 kilo mole.
(Refer Slide Time: 31:28)

After that you have to do the balance around you know separator. Now in the separator what will
be the input and output of the reactor. So you will see that whatever you know input of the
separator that of course will be output of the reactive. Because same amount of reactor as a
output it will be coming to that separator as an input. So it is 384.01 and in the top of this you
know separator it will come as unreacted propylene and propane compound.

So, it will be 1.86 + 9.80 total amount will be 11.66 kilo mole and in the bottom there will be
output of separator other than propylene and propane. So that separator output as a propylene and
propane amount other than that is you know propylene and propane amount will be then 384.01 -
11.86. You have to subtract that, you know propylene and propane amount there, then you can
get 372, your 35 kilo mole for this, you know separator from the bottom.
(Refer Slide Time: 32:49)

950
Then you have to do the balance around benzene distillation column. Now in that case, input of
this benzene distillation column will be the output of the bottom of the separator. So, as per that
it will be 372.35 kilo mole. Now in this case it is given that top product will be containing 98.1
mole percent of benzene. And in that case all the benzene is to be collected in the top and it will
be sent as a recycle to the fresh feed.

Now, as per that material balance if you do the benzene balance here, then 189.92 which is
unreacted in the reactor, it will be basically the same amount for the distillate of that benzene
distillation column. So according to that, we can write this balance equation here, where D is
called distillate that is called top product of that benzene distillation column and after calculation
it is coming as 193.60 kilo mole.

And then what will be the amount of cumene present in the top product as per that condition,
since there 98.1 mole percent of benzene will be there in the you know top product, remaining
amount of course will be the cumene. So that cumene can be you know calculated as here 193.60
into 0.019 that will come 3.68 kilo mole. So, this amount of cumene will be along with that
benzene and it will be going to that you know vessel where fresh benzene will be mixed with this
you know stream of this benzene and cumene product from this benzene distillation product
column.

951
And what will be the bottom product of that benzene distillation column it can be obtained just
subtracting that top product from the feed then it will be coming as 178.75 kilo mole.
(Refer Slide Time: 35:07)

After that, you have to do the balance around cumene distillation column, in that case the feed
will be 178.75 kilo mole and this is basically what will be the cumene produced as per reaction
that is 173.16 + what will to be the byproduct there that is 5.59. So this total amount of this
cumene and di isopropyl benzene. It will be you know going into the Cumene distribution
column as a feed.

Now since your product will be of 99.9% cumene whereas remaining amount will be as you
know that DIPB from the top and from the bottom 100% of that DIPB will be there. So as per
that balance equation, if we consider cumene balance, then you can simply write this 173.16 will
be as distillate as a top product. So you can write here top product will be 173.16 kilo mole and
bottom product will be basically it will be you know that 100% of p-DIPB.

That can be obtained by subtracting that top product from the feed of that cumene distillation
column and it will be coming as 5.59 kilo mole.
(Refer Slide Time: 36:52)

952
This you know DIPB will be sent to preheat the output of that you know separator to you know
send it to the benzene distillation column. Now overall plant then material balance, we can
summarize as what will be the input and what would be the output. Now for benzene, what will
be the input it is 178.75 kilo mole and output is here 0, whereas propylene there is input is
186.20, output will be here 1.86 kilo mole.

Propane it will be 9.80 output is again same amount and cumene in the input there will be no
cumene, here as output whatever target we are fixing that amount that is 173.16 kilo mole will be
produced per hour. You can make it in you know mass flow rate also in kg per hour just by
multiplying this molar flow rate by their molecular weight respectively. So according to that we
can get this total kilo mole per hour for the input is 374.75.

Whereas output it will be total 190.41 kilo mole per hour and as a mass you can say that will be
22,193.91 kg per second and then output will be here the same amount.
(Refer Slide Time: 38:39)

953
Now, if you consider that what will be the yield of that process, as 1 mole of cumene is produced
from 1 mole of propylene, the stoichiometric factor is here 1. So moles of cumene produced here
173.16 kilo mole, moles of reactant feed here 184.34 kilo mole. So the yield of the cumene based
on propylene, we can calculate here based on the definition of this yield here, moles of product
produced into stoichiometric factor divided by moles of reactant fed to the process. So after
substitution, we can after calculation as 93.93% yield of the process.
(Refer Slide Time: 39:32)

Now we can you know summarize all this material balance equipment wise, there are several
equipments that we have seen here for the production of this cumene. Now if we summarize this
you know this material balance and it is the amount as per that equipment. We have already

954
described, but still we can summarize here as like this, what would be the kg or mass fraction or
what would be the mass flow rate or you know more mole molar flow rate like this we can you
know represent here in this figure.

Now if we consider that benzene feed pump and benzene fresh feed propylene feed pump
benzene distillation column and there then in phenyl benzene feed also feed vessel what should
be that you know balance equation balance amount there for the benzene, propylene, propane,
Cumene, DIPB and then total amount we can get this here. So if we consider the benzene feed
pump there benzene fresh feed it will be 178.75 that means 13942.44 for benzene.

Similarly for here propylene what will be the amount, propane what will be the amount and
cumene DIPB and total what will be that. And similarly you can summarize it based on that you
know propylene feed pump, what will be the you know amount of propylene propane mixer and
what will be that input and output for respective you know compound that you can get from this
table, it is given here.
(Refer Slide Time: 41:25)

Similarly for reactor input reactor output flash drum that is separator you know what will be the
you know input and output there that you can get it from this you know table it is summarized
here as per this you have to do the you know summary for that after calculation for material
balance and energy balance equation.

955
(Refer Slide Time: 41:50)

Now equipment wise material balance also for this you know benzene distillation column, even
cumene distillation column, what will be the input and what will be the output, what is the top
product, what is the bottom product it is given like this.
(Refer Slide Time: 42:05)

So we have described here for this whole process of this you know cumene production with a
target of 500 tons per day and for that, what will be the schematic you know process diagram,
what are the different types of equipments are being used. And what will be the you know
process variables for that, what are the you know process input, what will be the process output
that has already been you know described here.

956
And what will be the amount of process input, what will be the amount of process output there.
After each equipment you know what would be the output for that, what will be the temperature,
what will be the pressure all these things here you know described. And accordingly we have
you know done the material balance and then you can you know solve this material balance
equation, and then get the you know input and output unknown variables there.

You can represent all those things in a you know that sequence of you know linear equation set
for each equipment even you know combining all equations there and then solving, you can also
be present in that way. So I think it will be helpful to you know calculate the you know input and
output streams of that, you know industrial scale any process like this here, whatever described
based on the material balance equation.

You can try yourself if suppose there is a target of you know 200 you know tons per day of
cumene productions or 1000s ton per day cumene production remaining all other you know
conditions are same there. Only thing is that your target will be changed then accordingly what
will be the you know input and output for you know several equipments which are being used for
this process that you have to calculate.

So I think you can you know practice it with a different you know target of that you know
process output for the cumene production.
(Refer Slide Time: 44:45)

957
So in the next lecture will try to you know discuss more about this process for energy balance .
Here you will see that there are several units also are being used however you are changing the
temperature of the processes streams with it is temperature. So accordingly how enthalpy would
be changing for that inlet and outlet streams and based on that energy balance equation, you can
calculate that in therapy for that inlet outlet streams for the several units there. So it will be
discussed in the next lecture, so thank you for giving attention for this lecture.

958
 Basic Principles and Calculation in Chemical engineering
Prof. S. K. Majumder
Department of Chemical engineering
Indian Institute of Technology-Guwahati

Module-12
Lecture-35
Case study (continuation)

Welcome to massive open online course on basic principles and calculations in chemical
engineering. Here we are actually discussing about case study for a process and in the previous
lecture we have described the material balance of a chemical engineering process like Cumene
production from benzene and propylene. And there we have described the material balance how.
(Refer Slide Time: 00:59)

And what amount of different raw materials are required for individual equipments and for the
whole process that we have described.
(Refer Slide Time: 01:15)

959
Still you know go through again that process for you know describing the energy balance
equation here in this lecture. So basically that Cumene is produced from the benzene and
propylene at a certain you know temperature and pressure in a particular reactor. And then the
product is being separated by you know different separator units like flash drum distillation
column.

And before going to process those benzene and propylene for a reaction that benzene and
propylene are heated up to a certain temperature of for its reaction. So here in this slides that
description of the process with layout is you know shown when we have described it in previous
lecture also. Now in this case basically these you know benzene and you know propylene those
raw materials are coming from the storage tank.

And these you know benzene and propylene after heating up by vaporizer those are mixed and
then it is again you know heat it up in a furnace to raise it is temperature around 350 degree
Celsius. For it is reaction in the tubular reactor and in the tubular reactor generally the catalyst
are being used as phosphoric acid that we have considered.

And then the output of that reactor is actually send to the separator through some vaporizer.
However this outlet streams of reactor is utilize to heat up that you know benzene and propylene
before entering to this reactor. And then outlet of those reactor and the furnace and whatever it

960
is) there. So after that it will be send to separator so that in the separator the you know reactor
products will be you know separated.

And that separation to be for just you know separating the unreacted you know materials that is
taking parts in the reactions. Now unreacted you know materials are here propane and propylene
also some amount of benzene will be there. So from the reactor these unreacted through
propylene propane and you know benzenes along with that products like Cumene and the small
amount of byproducts that is DIPV.

Those will be separated in a separator and there will not be only single separator because in a
particular separator you cannot separate all the products at a time. So for that to separate the
propane and propylene 1 you know flash drum is used as a separator where this propane and
propylene will be you know separated and it will be you know utilized for heating purpose in the
furnace.

And remaining that benzene DIPV and that is main Cumene will be reheated and then it will be
send to one distillation column it is called benzene distillation column. However benzene streams
would be you know separated from the mixture of that benzene, Cumene and I you know PV.
And in this you know benzene distillation column from the distillate that you know benzene
along with small amount of you know Cumene will be you know separated as a distillate
product.

And those benzenes will be you know recycle to that feed basal of that you know fresh feed of
benzene. And then it will be send to again to the reactor after vaporizing. Now from that benzene
distillation column that Cumene and byproduct DIPV again it will be you know send to another
distillation column which will be called as Cumene distillation column.

Now in that distillation column you will see that Cumene and DIPV will be separated from it is
distillate and bottom parts. So, as a distillate to that Cumene has a liquid it will be coming after
you know condensing and it will be around you know 99.9% as per that requirement of

961
production of this purity of this Cumene. And from the bottom part of this Cumene distillation
column that 100% of DIPV will be you know taken out.

And it will be you know used for preheating or that you know mixer benzene DIPV and Cumene
which is coming out from the separator of flash drum. And then DIPV you know used for other
purposes. So, in this your whole process is actually going on for the production of Cumene.
(Refer Slide Time: 06:40)

Now, in the previous lecture we have described that you know what is the background of that
reaction main reaction is basically propylene, benzene. And which will give you Cumene and
byproduct with that propylene and Cumene will give you that di-isopropyl benzene.
(Refer Slide Time: 06:56)

962
And different sections are here storage section, preheating section, vaporization section, pumping
section and also reactor section there. And in the reactor section, the pressure up to 25
atmospheric pressure will be considered and the reaction will be done at 350 degree Celsius.
(Refer Slide Time: 07:23)

And from that after purification, we are getting that 99.9% of Cumene.
(Refer Slide Time: 07:27)

963
Now, separation and purification section that involves that you know flash drum benzene
distillation column and Cumene distillation column.
(Refer Slide Time: 07:37)

And we have described that process here.

(Refer Slide Time: 07:42)

964
(Refer Slide Time: 07:43)

And then the details of that process description we have given in the previous lecture even also
here, we have mentioned in the slides there.
(Refer Slide Time: 07:52)

965
And in this case, you will see that.
(Refer Slide Time: 07:56)

The overall material balance whatever we have done based on that you know mass conservation
equation, that is described in our earlier lecture, what is the principles of material balance. And
what is the governing you know material balance equations that we have described to us for
those principles of that material balance we have done overall material balance.

And these overall material balance can be done for whole processes, if you are considering one
single unit and what is that other unit separately there. So, for those cases you have to you know
do the material balance, you can do overall material balance and also you can do the material

966
available balance for single unit or individual unit is separately. Now, in this case data
assumptions are given.
(Refer Slide Time: 08:47)

Here target is 500 tons per day of Cumene production, their conversion of propylene is 99%,
product molar selectivity is 31 : 1. And propylene whatever it is being used that is 95% of purity
remaining is along with that propylene is propane. And molar feed ratio of benzene to propylene
to be maintained at 2 : 1. And top product of Cumene separation will be 99.9 mole percent
Cumene and remaining 0.1% will be byproduct.
(Refer Slide Time: 09:25)

967
So, in this case based on this data assumptions we have done, that material balance by
considering that reaction stoichiometry.
(Refer Slide Time: 09:31)

And also the selectivity of that reactions are based on which we have calculated the you know
what will be the amount of byproduct will be produced that is given here. It is around 5.59
kilomole per hour. As per you know assume data for production of Cumene.
(Refer Slide Time: 09:52)

Now if we consider that individual unit for this whole process is here and if we do the material
balance we can get different you know composition of that inlet and outlet streams. Now if we
consider that feed vessel or that benzene fresh benzene and you know, recycle benzene from the

968
benzene distillation column is mixed here. And then as a outlet it will be coming to the you
know, that mixer where propylene will be mixed to this you know, mixture of these Benzene
from these feed vessel.

So, according to that what are the different components first of all we have to know that they are
we you know fresh benzene, recycle benzene you know that propylene, propane, Cumene you
know para di isopropyl benzene. And what is the pressure and temperature. Now all those you
know components to be considered for all the equipments individually.

So, in that case if we consider feed vessel what are the, you know fresh benzene is coming that is
178.75. whereas the recycle benzene that is coming from distillation column it is 189.92 as per
you know balance equation. The details of that balance equation and the calculation is given in
our previous lecture. So, we are not actually considering that details here again So, we are just
summarizing for this here feed vessel you know inlet and outlet what will be the composition of
different you know compounds there, so it is given.
(Refer Slide Time: 11:31)

Similarly, for benzene vaporizer propylene vaporizer, what are the different inlet and outlet
compositions are given. So according to that calculation, you will see that at the same has
already been discussed in details of that calculation given in the previous lecture. So, here just
summarized that calculation, these are the things for mixer and furnace also it is given.

969
(Refer Slide Time: 11:57)

Similarly, for reactor what are the you know fresh benzene is coming what would be the amount
of recycle benzene is coming. And also, you know profile in what would be the requirement for
that propane along with that propylene what amount of that propane is coming. Cumene also a
small amount it will come because the recycle benzene will contains that small amount of
Cumene after separation in the benzene distillation column.

And then byproduct of course, will not be there in the you know reactor because 100% you know
byproduct it would be you know separating out from the benzene distillation column and it is
used for some other purposes. So, it is not being recycled there, and in the reactor the pressure
will be you know 25 atmosphere and temperature will be 350 degrees Celsius.

Whereas from the outlet of this reactor the fresh benzene will not be there, because this benzene
will be reacting and to be consumed. And you will see that as per that reaction stoichiometry and
the conversion you can say that the unreacted benzene will be there that is will be coming out
from the reactor, that will be 189.92 moles this is kilo moles.

And propylene also that will be unreacted that will be 1.86 and propane this is 9.80 which is
coming along with that propylene. And Cumene after production this is the major amount here

970
this is 180.52 kilo mole. And a small amount of byproducts which will be coming out from the
reactor and that pressure and temperature of 305 degree Celsius.
(Refer Slide Time: 13:39)

And then it will be going to the separator from where you can say that top product of that you
know separator will be coming. So you know that propylene and propane will be separated.
Whereas in the bottom product that you know recycle benzene and Cumene and also you know
byproducts will be coming out.
(Refer Slide Time: 14:00)

And these are you know bottom product of the separator will go to the you know feed preheater
the same amount and to be coming out also the same amount. But from the top you can say that

971
PIDP will be coming out because this PDIP will be used for you know heating purpose of this
you know outlet of that you know separator. And then same amount of inlet of that feed
preheater from the separated will be coming out from that feed preheater after preheating it.
(Refer Slide Time: 14:38)

And then it will be going to that benzene distillation column where you will see that only recycle
benzene and Cumene and a small amount of p-DIPB will be separated. Whereas in the top
product of this benzene and benzene distillation column it will be only recycle the benzene and
small amount of Cumene. And the bottom product the main product that is Cumene will be
coming out along with that you know byproduct there.

And then this bottom product of this benzene distillation column again to be separated in a
Cumene distillation column.
(Refer Slide Time: 15:11)

972
Where input of the Cumene distillation column will be the same that is Cumene and you know
byproduct. And it is being separated and as a distillate on the you know that Cumene productive
becoming. And at the bottom on that only you know p-DIPB will be coming. So, this final
Cumene distillation column we are getting separation of this you know Cumene and byproduct.

So, we are getting here that you know desired you know purity of that Cumene and here that
byproduct will be separated at a bottom product which will be used for preheating purpose. So,
in this you have to tell procedure and the material balance and what will be the inlet and outlet
proportions of that compositions are given here. Now, in this lecture main objective was to
discuss that energy balance also.
(Refer Slide Time: 16:11)

973
In that case if we do the energy balance equipment wise for this process, we can say that for
benzene feed vaporizer, if we consider first that because benzene will be send to the reactor after
mixing with the you know propylene. And before that, those propylene and benzene will be you
know vaporized to a certain temperature. Now these are to be vaporize to you know at 40
degrees Celsius.

Now the stream of mixed feed of benzene and Cumene is fed to the human vaporizer with a 40
degree Celsius at 25 atmospheric pressure. So there if we do the you know material balance
there. We are having these benzene is 368.67 kilo mole, Cumene is 3.68 you know kilo mole,
total this amount. Whereas more fraction of those components would be here 0.99, 0.01 and 1 as
a total, and similarly for to the mass fractions.
(Refer Slide Time: 17:20)

974
Now, based on these you have to calculate in this you know vaporizer, what would be the vapor
pressure of those you know components in this you know feed vessel of benzene. Now, the
bubble point and the dew point of the mixer are found by using Antoine's equation. That means,
how to you know get that you know bubble point from that Antoine's equation.

From those you have to first calculate to the you know that vapor pressure and from those vapor
pressure what the respective temperature. That by that calculation you can easily get what should
be the bubble point and dew point of that mixer by that Antoine equation. That Antoine's
equation how to calculate already we have described in our earlier you know lecture. And then
the vapor pressure is calculated at various temperatures to find the saturated temperature there.

And in that case the vapor pressure for the benzene for this more fractions it is coming 2587.64.
And then Cumene is 660.50 as for data here, and then what will be the you know that partial
pressure of that benzene here that can be calculated based on this air. And what will be the total
pressure for that and what will be the more fraction of that, you know benzene accordingly is that
can be calculated.

And partial pressure would be up for benzene is 2560.07 and partial pressure of Cumene will be
6.52. And here we can say that this p is basically a total pressure here this total pressure in this
you know feed vessel. And p v it is vapor pressure at 243 degrees Celsius. So, at 243 degrees

975
Celsius or 516 Kelvin the mixed feed will be vaporized there. So, it is called bubble point of this
feed mixer.
(Refer Slide Time: 19:31)

Now heat required for vaporized this basically one should be that due to the raise in temperature
and also due to the feed change of that you know feed mixer. Now for that for feed change of
course you have to consider that latent heat and for temperature difference that heat to be
calculated based on that sensible heat like this is C p into D t. So, heat required for the vaporize
you know that it will be summation of that sensible heat and latent heat.

Latent heat of benzene here it is given that 23,773.60 kilo joule per kilo mole and latent heat of
Cumene it is given here 30919.2 kilo joule by kilo mole. And average heat capacity of the
benzene is given here 161.46 kilo joule per kilo mole k, k is the Kelvin here, it is here Kelvin.
And average heat capacity of Cumene is given to 46.92 kilo joule per kilo mole k.

Now, what should be the then enthalpy that means heat required for the vaporization of the
benzene, it will be simply sensible heat with you know latent heat that will be summation. So it
will be coming as here sensible heat will be simply C p is 161.46 it is given to you into no
temperature difference is what is that earlier temperature is 40 degrees Celsius and bubble
temperature is 40 to 43 degrees Celsius.

976
So, you have to subtract is this and before that you have to convert it to Kelvin, so it will be 243
+ 273 - 40 + 273 + latent heat it is given here 23773.63 kilo joule per kilo mole. So finally the
total amount is coming 56,550.01 you know kilo joule. Similarly, enthalpy of cumene can be
calculated based on that summation of sensible heat and latent heat as per this you know that
sensible heat is like this and latent heat is this.

So, total amount of enthalpy for kilo mole of that Cumene is 81043.96 kilo joule per kilo mole.
Now heat required for the mixed feed then it will be you know that what will be the fraction of
those mixer of benzene and Cumene accordingly, that heat required for the mixed feed will be
here, this is the percentage of that you know benzene into it is you know enthalpy of benzene it is
given it is calculated as for this you know equation.

And also remaining is basically Cumene, so as per that we can get, you know that total amount
of you know heat required for the mixed feed is like this 23863498.19 kilo joule.
(Refer Slide Time: 23:05)

For propylene feed vaporizer similarly you can calculate what should be the you know heat
required for those. Now in this case propylene and you know propane fed from the tank is at 25
degrees Celsius at 25 you know atmospheric pressure. The stream is vaporized and heat to the
temperature and mixed with benzene feed is at you know 243 degrees Celsius.

977
Now bubbling point and dew point of the mixer is about 62.5 degrees Celsius. Now latent heat of
propylene is given here 17,229.4 kilo joule per hour. And latent heat of propane is given here
17,611.41 kilo joule per hour. And then average heat capacity of the liquid you know propylene
is given is 123.51, average heat capacity of liquid propane is 125.48. The average capacity of
gaseous propylene is 82.86, the average heat capacity of gaseous propane is 97.48.
(Refer Slide Time: 24:19)

And for liquid state, the C p value for propylene is given 123.51 whereas it is for propane is
125.48. So, delta T is basically that bubble point temperature and tank temperature of this
propylene propane mixer and it is basically 62.5 – 25, then it is coming 37.5. And then what will
be the heat required for that liquid state to raise this the temperature from 25 degrees Celsius to
you know bubble point temperature of 62.5 degree Celsius.

So finally for propylene it is coming 463.625 kilo joule and you know that for propane it is
coming 4,705.5 kilo joule. And for gaseous state for that you know propylene and propane you
know after heating it you will see that it will be converting to you know gaseous state. Since it is
mixed to that 243 degrees Celsius of course it is you know more than that bubble point
temperature of that outlet stream of that benzene.

So there it is mixed of course immediately that propylene and propane will be converted into
gaseous states. So, for that what would be heat they are to converting these you know liquid state

978
to gaseous state of that propylene and propane. So for that at that gaseous state that specific heat
capacity of the propylene is 82.86 whereas it is for propane is 97.483.

And their temperature difference of course will be from that bubble point to that you know
benzene feed temperature up to 243 degrees Celsius. Accordingly, it will be coming as 180.5
degrees Celsius. So heat required for that it will be you know respectively for propylene and
propane are 14956.23 and 17595.681 this is kilo joule per hour.
(Refer Slide Time: 26:26)

Now a specific heat required for component of you know that propylene, propane then we can
say that heat required for the propylene how to calculate that total amount of heat. One is for you
know when it will be you know temperature change from certain you know degree to certain
degree Celsius at it is liquid state. And then converting that liquid state to the you know gaseous
phase.

So their transition at that transition point of that you know liquid gas what will be the heat
required that is latent heat. And again at that to gaseous state what will be the enthalpy change
for that temperature change of the gaseous state. So, for that heat required for that propylene then
finally we can say that after summing up all those whatever calculated here.

979
Based on which we can say that it will be total amount of you know 21861.08 kilo joule per kilo
mole per hour. Similarly, heat required for propane similarly summation of that liquid state,
sensible heat, latent heat and then gaseous state, sensible heat and summation of all those
components that will be coming out as final amount as 39912.5 kilo joule per hour. And also
heat required for the feed then accordingly what will be the total amount of moles for that
propylene and propane.

Accordingly you can calculate here what will be the total amount of heat required for the feed,
then it will be coming as like your 4461676.28 kilo joule. So, in this way we can calculate, you
know that what should be the you know heat required for individual components for vaporizing
it from a certain temperature to a certain temperature from liquid state to the gaseous state.

Similarly you have to do the energy balance for the fired heater also where these feed mixer of
propylene and benzene to be heated up to a temperature of 350 degrees Celsius.
(Refer Slide Time: 28:42)

So, for that what would be the amount of heat required for raising this temperature of this
reactant mixture of propylene and benzene to 350 degree Celsius. Now for that we have to
calculate what from the enthalpy for that individual components of that mixture. So compound
basically before going to that fire heater is you know that propylene, propane, benzene, Cumene
all those things.

980
And they are respective flow rate that fire heater is already calculated based on that material
balance. So, those amount are like this you know 186.20, 9.80, 368.67 and 3.68 respectively for
you know propylene, propane, benzene and Cumene. And then you have to calculate what
should be the specific heat capacity for individual you know components when that you know
temperature will be changing from 243 degrees Celsius to 350 degrees Celsius.

Here, it is very interesting that this you know specific heat capacity will be a function of this
temperature. Now how to be related this is basically related by this equation here given. That CP
will be equal to a  bT  cT 2  dT 3  eT 4 . So this is your you know specific heat capacity
equation as a function of temperature. Now, based on these you know function you have to
calculate what should be the specific heat capacity within a range of this temperature difference
up to 243 to 350 degree Celsius.

Now, for that to what you have to do, you have to calculate in this way that a specific heat for
this benzene it will be is equal to integration of this limit of this 243 to 350 degree Celsius of this
you know for this here CpdT. Now this will be coming as 243 to 350 CpdT to be simply that Cp is
equal to a  bT  cT 2  dT 3  eT 4 into dT.
(Refer Slide Time: 31:15)

981
And then you have to you know that integrate it within this you know limit of this integration
and then you can get what will be the specific heat capacity. And for this a, b, c, d you know E
all those are actually coefficients and these coefficients are you know varying according to the
you know compound or nature of the compound. Now, for the propylene that coefficients are
given here a, b, c, d, e respectively in this column here.

And similarly for propane these constants are given, for benzene also those constants are given,
for Cumene also those constants are given. So, once you know these or substitute this you know
this constants here in this integrant. And then do the integration you will see that after integration
you will it will be coming as 80  bT 2 / 2  cT 3 / 3  dT 4 / 4  eT 5 / 5
And then you have to calculate the limit of this you know integrant to in this limit what will be
the amount there. So, according to that for propylene it is the coming that here 1.04 into 10 to the
power you know 6 this amount of specific heat capacity for propylene. Similarly for propane
after integration it is coming 1.66 into 10 to the power 6 that means for propane.

Similarly for benzene it is coming 6.77 into 10 to the power 6, for Cumene it is come in you
know 7.29 into 10 to the power 6. So, once you know this specific heat capacity within this range
of temperature then based on this temperature difference of this 243 and 350 degree Celsius what
should be the enthalpy. These enthalpy is basically, what is that for that gaseous mixer, so it is
within that range of you know temperature change.

So, accordingly that enthalpy can be calculated simply what is that M that means here H will be
or H to be calculated N into you know that Cp here into delta t, so in this way you have to
calculate. So accordingly this amount respectively for propylene, propane, benzene and Cumene
can be obtained. And then total enthalpy after summation you can get it 2.73 into 10 to the power
9 ok.

So, in this way you can calculate what should be the heat required for that particular you need to
raise the feed mixer to it certain temperature for further processing. So we have described the
material balance and energy balance for the production of Cumene from the benzene and

982
propylene based on their reactions. And also we have obtained that different you know, input and
output streams compositions are based on that.

And also what should be the you know enthalpy change for that different components in the
particular units that we can calculate and also we have given some you know calculations here.
So, you can do the same way for other you know chemical processes for production of other you
know compound there in a particular industrial scale operation. Let us do another case study here
like production of phenol by sulphonation of benzene and subsequent fusion with caustic soda.

So, you can produce that phenol from the you know benzene by you know sulphonation process
and also subsequent fusion with the caustic soda. This process is basically large scale base cycle
operation due to slow reactions state for you know fascination of this you know benzene
sulphonic acid with caustic soda.
(Refer Slide Time: 35:43)

So, based on these principle we can you know have this you know process layout for this you
know production of phenol. Now, let us discuss this process flow chart for this for this
production of phenol from this. Like in this case you will see that benzene shulphonic acid is a
first you know method to prepared by passing vapor of benzene into you know, concentrated
sulfuric acid.

983
In that case the water form during the self sulphonation process is actually distilled out because a
sulphonic acid gets diluted and conditions accelerate you know backward reactions to the
process. So mainly here benzene is reacting with the sulfuric acid and giving your you know
benzene sulphonic acid and after that it will be you know neutralized and then you will see that it
will be you know fusioned at you know a fascinator with the you know that is caustic soda.

And after that you will see that some you know oily layer of crude phenol will be produced and
then that oily you know crude phenol will be distilled under vacuum to get pure phenol and in
this case the yield is about 80 to 90% of the benzene. So, what are the you know equipments are
being used here for this process one is melter and one is dissolver and then evaporator,
sulfonater, neutralizer, fusion parts or you can say that fusionator, settler.

And what is that you can say filter, acidifier and then you know that vacuum steel for distillation
process. So in this case first of all you will see that some sodium oxide will be melted from it is
solid to you know send to that fusion pots for the reaction with that you know benzene suphonic
acid. And before doing sending these you know sodium oxide there, sodium salt there what you
have to do, you have to you know mixed with some sodium carbonate with water to make a
solution.

And that solution to be send to the neutralizer for it is neutralization, and in that neutralizer you
have to send that you know sodium carbonate and sodium carbonate solution of you know along
with that you know benzene. And you can say that you know that sulfuric acid there. And after
neutralization you will see that those mixer will be sent to that fusion pots and however that
sodium oxide will be reacted.

And then you will see that unreacted benzene and you know that sodium sulphate that will be
formed during that fusion reaction. And also you will see that some you know water will be there
extra water to be there. And to get that particular concentrated solution that water to be vaporized
or distilled there. And also there is settler where that sodium salt will be you know that settle
down and where the benzene will be you know, again recycled to it is fresh benzene feed.

984
And from that settler after getting that you know mixer of you know oily you know phenol, good
phenol along with that sodium sulphate salt, it will be filtered out to separate that salt. And then
remaining portion of crude phenol it will be send to you know vacuum distillation column. And
they are it will be you know that distilled to get that you know some percentage of you know or
purified you can say that phenol there.

So, this is the whole process here, so for this process also you have to do the material balance
and also energy balance. And what should be the respective temperature of different units what
will be different pressure at different units. And also what will be the inlet and outlet streams and
what would be their composition and the amount that you have to find out by this material
balance and energy balance equation.
(Refer Slide Time: 40:44)

Now, process description that we have already described that this is the you know largest scale
batch cycle operation due to slow reaction step at fusionator. Sodium Benzene sulphonate is fed
to cast iron make fusion pots or who is already contains molten caustic soda there. Due to slow
reaction with take about you know that 5 to 6 hours of residence time, the pot is fed at regular
intervals where continuous loading and unloading of the pot occurs for continuation of the
process.

985
The sodium phenoxide fraction which is obtained is fed to acidifier to you know produce crude
phenol by reacting with sulfuric acid and sulfur dioxide there. Vacuum distillation column is
used to get phenol from crude phenol and remain salts are strip in a you know stream stripper to
remove himself from them and aqueous salts. Crystallizers are actually used to increase the
purity of the sodium sulphite which is coming out from that you know crystals.

And these crystals are separated from mother slurry by a continuous centrifugal separator you
can say which is recycled to you know neutralizer again. So, based on this process we are getting
this phenol.
(Refer Slide Time: 42:07)

Now in this case the process involves 4 major chemical reactions, whose as sulphonation where
benzene is reacted with sulfuric acid to form benzene sulphonic acid. Neutralization where
benzene sulphonic acid is reacted to sodium sulfite to form sodium benzene sulphonate. And in
the fusion reaction the sodium benzene sulphonate is fused with sodium hydroxide to form
sodium phenoxide.

And in the acidification reaction sulfuric acid and sodium phenoxide are reacted to produce
crude phenol and sodium sulphite and there it is you know separated.
(Refer Slide Time: 42:43)

986
That reaction step explains the requirement of the unit operation equipment in the process are
here filtration and distillation and crystallization.
(Refer Slide Time: 42:49)

And sulphonation of benzene basically is reacted based on this, this is reversible reaction. That
produces benzene sulphonic acid by adding sulfur trioxide and fuming sulfuric acid. The reaction
is reversed by adding hot aqueous acids to benzene sulphonic acid to produce benzene. Now to
produce a benzene sulphonic acid from benzene fuming sulfuric acid and sulfur trioxide are
added, fuming sulfuric acid is a concentrated solution of dissolved sulfur dioxide in sulfuric acid.

987
The sulfur in sulfur trioxide is electrophilic because the oxygen pull electrons away from it
because oxygen is very electronegative. That is why it will be regarded as electrophilic reaction.
And the benzene you know attacks the sulfur and subsequent photon transfers occur to produce
that benzene sulfonic acid. So this is the mechanism how the reaction is taking place.
(Refer Slide Time: 44:02)

Now sulfonation of benzene is a reversible reaction that we know that sulfur trioxide readily
reacts with water to produce sulfuric acid and heat. Therefore by adding heat to benzene
sulphonic acid in diluted aqua sulfuric acid the reaction will be you know reversed, so this is
your reverse reaction.
(Refer Slide Time: 44:21)

988
Now here in this slides whole material balance and energy balance is shown here, see for
equipment wise the material balance is being done. If we consider that melter here the what will
be the you know chemicals are actually coming into this melter. It is basically sodium oxide and
it is amount is 471.74. And as a outlet what would be the amount is coming into the fusion pots
higher it is given the same amount it will be becoming after melting.

And then in this you know dissolver you see that sodium carbonate, the amount is given in kg
here. And then here you know that water will be coming as you know there in the dissolver. And
then you will see that after coming out from the dissolver you know that it will be going to that
neutralizer there also what will be the amount of you know chemicals will be coming in basically
this amount is coming here.

But before neutralizer there will be sulfonator there also you have to do the material balance here
sulfuric acid coming this amount and benzene is coming here after evaporator. In this evaporator
this amount of benzene is like this is kg. And then accordingly also other unit like what will be
the inlet there and what will be the outlet there it is given there. So in the left side and the right
side it is given inlet and outlet you know amount there.

So, we can say that at different you know unit we can do that material balance at accordingly
what will be the inlet amount to be required for that you know particular you know basis of
production of 1 ton of phenol there. So, here in this case you know fusion pots what will be the
inlet what will be the outlet it is given, in the settler also what will be the inlet, what will be the
outlet it is given.

Even in filter what will be the inlet and what will be the outlet is given there and acidifier also as
per material balance what will be the sulfuric acid required also it is given. And what will be the
outlet potion of that is given as per this from this acidifier. And also after that what will be the
you know amount of inlet and outlet of this you know vacuum steel also it is given you know
schematically.

989
And you will see that we have done also that you know that energy balance and accordingly
what will be the heat required for that individual unit. It is given here as heat column you will see
that different amount for different you know compound even different for unit. And also outlet
also what will be the enthalpy that is at the outlet composition are also given.

And also inlet temperature of that is component what will be that and also outlet temperature
what will be that it is given according to that calculation. And also what would be the outlet
amount of individual compounds also given which is coming out from that individual unit all are
calculated. And in this way also you can calculate for a specific chemical engineering process
there and identifying that different units and reactions based on that reaction stoichiometry, what
will be the input what will be the output.

And also you have to calculate that enthalpy based on that you know temperature change that is
changeable heat and also latentity if there any you know compound is changing from it is liquid
state to the gaseous state. So please go through this you know slide here again for understanding
that material balance and energy balance. And respective amount of you know heat and you
know amount of stream at the inlet and outlet conditions and outlet streams there you can get it.

So, I think it will be very helpful for your further understanding of material balance for the
particular process in industry.
(Refer Slide Time: 48:43)

990
So, I suggest you to read further that this text book for your you know better understanding of
different you know chemical engineering processes. And also their respective you know
calculation based on material and energy balance.
(Refer Slide Time: 49:03)

I would thank you for choosing this course and also I wish you healthy and prosperous life
ahead. And of course all the best if is there any query please contact in this address email is
given to this slides also website you can follow there accordingly you can mail me for further
you know queries and also understanding. So I want to you know stop the lecture here, I
welcome you to you know learn this course and also wish you healthy and prosperous life ahead
and all the best, thank you.

991
 THIS BOOK IS
NOT FOR SALE
NOR COMMERCIAL USE

(044) 2257 5905/08 nptel.ac.in swayam.gov.in