19-206-0302 CHEMICAL PROCESS

PRINCIPLES(CPP)
• Module I
• Material balance
• Introduction to chemical engineering, basic chemical
calculations-mole concept, methods of expressing
composition-mole fraction, weight fraction, volume fraction,
concentration of liquid solutions- molarity, molality, normality,
ppm.
• Ideal gases and gas mixtures- ideal gas law, Amagat’s law,
Dalton’s law, Henry’s law, average molecular weight, density of
gases, partial
• pressure and partial volume calculations.
• Material balance involving chemical reactions and not involving
chemical reactions, simple calculations involving recycle, bypass
and purge streams.
 Introduction to chemical engineering
• Chemical engineering is the application of the
principles of physical sciences together with
• the principles of economics and human
relations to fields that pertain directly to
processes and process equipment
• in which matter is treated to effect a change
of state, energy content or
• composition.
 Introduction to chemical engineering
• The chemical process industry generally employs
“chemical changes” for the production of useful
materials.

• They include not only chemical reactions, but also

many physiochemical changes such as the
separation and purification of the components of
a mixture.
• Products of the chemical process industries are
used in all areas of everyday life.
• Some greatest contributions of chemical
engineering to improve the standard of living
of modern human beings are as follows:
• 1. The contribution of chemical engineering
towards isolation of isotopes by splitting
atoms
• revolutionized such varied areas as biology,
medicine, power generation, metallurgy and
archaeology.
• 2. The concept of unit operations was extended to
analyze the functioning of human body that have
helped improve clinical care, diagnostic and
therapeutic devices and development of artificial
organs.
• 3. Chemical engineers could improve the yield of
antibiotics through mutation and special brewing
• techniques. Low priced, high-volume drugs and
pharmaceuticals owe their existence to the work
of chemical engineers.
• 4. Introduction of synthetic fibres such as
nylon, polyester, etc. had a profound impact
on many areas of life and it also reduced the
strain on natural sources of cotton and wool.
• 5. The liquefaction and subsequent separation
of air into pure nitrogen and oxygen was
another major contribution of chemical
engineering. Nitrogen can be used to recover
petroleum, freeze food, etc.
• 6. Chemical engineers’ contribution in the
areas of waste treatment and pollution
abatement helps keep the environment clean.
Catalytic converters, reformulated gasoline
and smoke stack scrubbers and new recycling
technologies are notable achievements in this
area.
 UNIT OPERATIONS AND UNIT
PROCESSES
• The unit operations involve the addition or removal of
some form of energy in the contacting, transport, and
the conditioning of materials by physical means with
or without any chemical changes taking place.
• The unit processes on the other hand, result in
chemical changes—in composition, character, and
properties—of materials and are most often affected
or controlled by temperature and pressure changes,
catalysis, intimacy of mixing, and other physical
phenomena.
 Unit operations
• Distillation
• Absorption:
• Liquid–liquid extraction:
• Leaching:
• Adsorption:
• Humidification:
• Drying:
• Crystallization:
 Unit processes
• Nitration
• Sulphonation
• Ammoniation
• All chemical reactions
 STOICHIOMETRY AND PROCESS
CALCULATIONS
• There are certain fundamental principles
underlying all unit operations and unit
processes.
They are
• the material balances
• energy balances
• laws of equilibrium
• and the rate processes.
 STOICHIOMETRY
• The conventional meaning of the word limits
its application to calculations involving the
quantities of materials involved in chemical
reactions.
 THE MOLE CONCEPT
• A chemical element is made up of very minute,
discrete and indivisible particles called atoms.
• An atom is the smallest particle that can take part
in a chemical change
• The atomic weight of an element is the mass of an
atom based on a scale that assigns a mass of 12
for the carbon atom 12C.
• On this scale, the atomic weight of oxygen is 16
and that of hydrogen is 1.008.
• Atomic weight is a dimensionless number.
• A molecule of an element or a compound is
made up of a number of atoms of the
constituent elements. The molecular weight is
the sum of the atomic weights of the elements
constituting the molecule.
• A gram-atom of an element is the mass in grams
that is numerically equal to the relative atomic
• weight of the element.
• Thus the mass of one gram-atom of carbon is 12g
and the mass of one gramatom of oxygen is 16 g.
A gram-molecule of a compound is the mass in
grams of the compound numerically equal to its
molecular weight. Thus one gram-molecule of
water is 18.016 g of water.
• Since an atom of oxygen is 16/12 times heavier than
an atom of carbon, the number of carbon atoms
• present in one gram-atom (12 g) of carbon and the
number of oxygen atoms present in one gram-atom
• (16 g) of oxygen are the same.
• This is true for all elements, and in general, we can
say that a gram atom of any element contains the
same number of atoms. This number is equal to 6.023
x 1023, and is known as Avogadro’s number. Similarly,
a gram molecule of all compounds contains the same
number
• of molecules and this number is 6.023 x 1023.
• The term gram-molecule is generally abbreviated into gram mole
and is referred simply as mole (symbol mol in SI units). In process
calculations, for convenience, gram mole or mole is used for
• referring gram-atom of an element as well as gram-molecule of a
compound.
• Thus one mole of aluminium represents 26.9815 g of aluminium
and one mole of water means 18.016 g of water.
• A mole of O2 signifies 32 g of oxygen, while a mole of O would
mean 16 g of oxygen.
• In short we can designate a mole as the amount of the substance
that contains as many elementary entities as there are
• atoms in 12 g of carbon.
• .
• The number of moles of a substance can be
determined by the following formula:

• Mol=

Kilogram mole or kilomol or Kmol =

 Q.1
• How many molecules are present in 691 g K2CO3?
• Solution
• The atomic weights of the elements are:
• potassium = 39.1, carbon = 12.0, oxygen = 16.0
• The molecular weight of K2CO3 is
• 39.1 x 2 + 12.0 + 16 x 3 = 138.2
• 691 g K2CO3 =691/138.2 = 5 mol K2CO3
• One mole of a substance contains 6.023 x 1023 molecules.
Therefore, 5 mol K2CO3 contains 5 x 6.023x 1023 = 30.115 x 1023
molecules.
 Q.2
• a)How many moles of sodium sulphate will
contain 100 kg of sodium?
• (b) How many kilograms of sodium sulphate
will contain 100 kg of sodium?
• Solution
• The molecular formula of sodium sulphate is Na2SO4
• (a) Since the atomic weight of sodium is 23,
• 100 kg sodium =(100×103 )/23
• = 4.348 x 103 g-atoms of sodium.
• One mole Na2SO4 contains 2 g-atom sodium.
• Therefore, the number of moles of Na2SO4 that
contains 4.348 x 103 g-atom sodium is 4.348×103 x 2
• = 2.174 x 103 mol = 2.174 kmol
• (b) 2.174 kmol sodium sulphate contains 100
kg sodium. The molecular weight of sodium
sulphate is 23 x2 + 32.06 + 16 x 4 = 142.06
Therefore,mass of 2.174 kmol sodium
sulphate is(molx molecular weight)
• 2.174 x 142.06 = 308.84 kg sodium sulphate.
 Q3.
• Sulphur trioxide gas is obtained by the
combustion of iron pyrites (FeS2) according to
the following reaction:
• 4FeS2 + 15O2→ 2Fe2O3 + 8SO3
• How many kilograms of pyrites are burned to
obtain 100 kg of sulphur trioxide? How many
kilograms of oxygen are consumed in the
production of 50 kg of SO3?
• Molecular weight of FeS2 = 55.85 + 2 x 32.06 = 119.97
• Molecular weight of Fe2O3 = 2 x 55.85 + 3 x 16 = 159.7 Molecular
weight of SO3 = 32.06 + 3 x 16 =80.06
• Using molal quantities
• 100 kg of SO3 =8 mols SO3
• Since 4 kmol FeS2 gives 8 kmol SO3, pyrites needed to produce
100 kg of SO3 (i.e., 1.2491 kmol) is
• 1.2491x(4/8)=0.6246 kmol = 0.6246x 119.97 = 74.93 kg
• 50 kg of SO3 =0.6246 kmol
• Since 15/8 kmol oxygen is required for the production of 1 kmol
SO3, oxygen consumed in the production of 50 kg (0.6246 kmol)
SO3 is (15/8)x 0.6246 = 1.1711 kmol = 1.1711 x 32 = 37.48 kg
 HW
1. How many grams of NH4Cl are there in 5
mol?
2. Convert 750 g CuSO4.5H2O into moles.
3. How many kilogram of CS2 will contain 3.5
kg-atom carbon?
Molar Volume of Gaseous Substances
• The volume occupied by one mole of a gaseous
substance at a given temperature and pressure is
called the molar volume of the gas under those
conditions.
• The molar volume of an ideal gaseous
• substance is found to be a constant under
standard conditions of temperature and pressure
(STP).
• The standard temperature is 273.15 K and
standard pressure is 1 atm (101.325 kPa).
• one mole of an ideal gas under standard
conditions of temperature and pressure
occupies a volume of 22.414x10–3 m3.
• One Kilo mole of an ideal gas under standard
conditions of temperature and pressure
occupies a volume of 22.414 m3.
 Q
• Determine the volume of oxygen obtained under standard
conditions, by the decomposition of 100 kg of potassium
chlorate. 2KClO3→ 2KCl + 3O2
• The molecular weight of potassium chlorate is (39.10 +
35.45 + 3 x 16) = 122.55.
• Mols of potassium chlorate is= 100/122.55= 0.816 kmol.
When 2 mol of potassium chlorate is decomposed, 3 mol
oxygen is produced.
• So 0.816 kmol potassium chlorate will liberate (0.816x3/2)=
1.224 kmol oxygen.
• Since one kmol oxygen under STP occupies a volume of
22.4143 m3, the volume of oxygen produced at STP is
• 1.224 x22.4143 = 27.43 m3.
 Q
• Iron reacts with steam according to the
following reaction:
• 3Fe + 4H2O → Fe3O4 +4H2
• (a) How many kilograms of iron and steam are
required to produce 100 kg of hydrogen?
• (b) What volume will the hydrogen occupy at
standard conditions?
• (a) 100 kg of hydrogen
• 100 / 2.016= 49.60 kmol
• Since three moles of iron reacts giving 4 moles of
hydrogen, the moles of iron required to produce
• 49.6 kmol (i.e. 100 kg) hydrogen is
• 3/4 × 49.6 = 37.2 kmol
• 37.2 kmol iron is equivalent to 37.2 x 55.85 =
2077.62 kg.
 DENSITY AND SPECIFIC GRAVITY
• The mass per unit volume of a substance is
designated as the density of the substance. Since
the volume of a given mass of a substance varies
with temperature, density is a function of the
temperature.
• The term specific gravity refers to the relative
density. It is a dimensionless ratio. For liquids and
solids, it is defined as the ratio of the density of
the substance at 288.8 K to density of water at the
same temperature.
 API scale:
• The petroleum industries had been using the
API (American Petroleum Institute) scale for
representing specific gravity for oils.Sp.gr.
should be taken at 288.8 K
 A body weighs 1.0 kg in air, 0.90 kg in water and 0.82 kg in a liquid. What is
the specific gravity of the liquid?

• Solution: The loss in weight of a body in a liquid is equal to the weight of liquid displaced by
the body.
• Since the weight of liquid displaced is equal to the product of the volume of liquid displaced
and density of the liquid, the volume of liquid displaced is loss in weight/density of the liquid
• Loss in weight in water = 1.0 – 0.9 = 0.1 kg
• Loss in weight in the given liquid = 1.0 – 0.82 = 0.18 kg
• Since the volume displaced by the solid is the same in water as well as in the liquid, we have
0.1/ρw= 0.18/ ρ ( 1)
• Where ρw and ρl are density of water and density of the liquid respectively
• The specific gravity of the liquid is the ratio of its density to the density of water. Here this
ratio is from eqn.(1)
• Ρl / ρw = 0.18/0.1 =1.8
 COMPOSITION OF SOLIDS, LIQUIDS
AND GASES
• Mass Fraction (Weight Fraction)
• Compositions of solid and liquid mixtures are usually
expressed as mass fraction or weight fraction.
• The mass fraction of a component in a mixture is the ratio
of the mass of the component to the total
• mass of the mixture. Consider a binary mixture made up of
components A and B. Let the mass of A
• and the mass of B in the mixture be mA and mB,
respectively.
• Then,
• wA, mass fraction of A =mA/(mA+mB)
• wB , mass fraction of B =mB/(mA+mB)
• Mass Percent (Weight Percent)
• The weight (mass) percent of a component in
a mixture is the number of parts by weight
(mass) of the constituent in 100 parts by
weight (mass) of the mixture.
• weight percent of A=[mA/(mA+mB)]*100
• Mass Ratio In a mixture made up of
constituents A and B, the mass ratio of A is the
mass of A per unit mass of B.
 Dry Basis and Wet Basis
• In the conventional method of expressing the concentration—the
wet basis—the percentage of water in the solid is the mass of
moisture contained in 100 parts by weight of the wet material.
• The water content of a wet material can be expressed on a
moisture-free basis or dry basis also.
• Percent moisture on a dry basis is the mass ratio of moisture to
moisture-free solid expressed as percentage.
• Thus, when the moisture content of the solid is 25% on a dry basis,
there are 25 parts by weight of water associated with 100 parts by
weight of dry solid.
• Or, 125 parts by weight of the wet solid contains 25 parts by
weight of water.
• Therefore, the percent water on wet basis is 20.
• 250 kg wet ammonium sulphate containing 50 kg
moisture is sent to a dryer in order
to remove 90% of the moisture in the feed.
Calculate for the entrance and exit to the dryer,
the following:
• (a) The weight fraction of water
• (b) The weight ratio of water
• (c) The weight percentage of moisture on a wet
basis
• (d) The weight percentage of moisture on a dry
basis.
• Solution Basis: 250 kg wet charge.
• Entrance to the dryer
• Dry ammonium sulphate = 250 – 50 = 200 kg
• Water in the charge = 50 kg
• (a) The weight fraction of water is mass of
water/total mass=50/250=0.20
• b)Weight ratio of water = mass of water/mas of
dry solid=50/200=0.25
• c)Weight percent of moisture on dry basis
=(50/200)*100=25%
• Exit of the dryer
• Mass of dry ammonium sulphate = 200 kg.
• Since 90% of water in the charge is removed, the mass
of water present in the solid =
0. 1x50 = 5 kg.
• (a) The weight fraction of water is
• mass of water 5/205=0.0244
• (c) The weight percent of moisture on a wet basis is
mass of water=(5/205)*100= 2.44%
• (d) The weight percent of moisture on a dry basis
is(5/200)*100=2.5%
 H.W
• A wet stock of ammonium sulphate containing
20% water is sent to a drier. The material
leaving the dryer contains 2.44% moisture.
Determine how many kg of water is removed
per kg of wet material charged. Also find the
percent of original water in the feed that is
removed by drying.
 Mole Fraction and Mole Percent
• The mole fraction is the ratio of the moles of
the constituent to the total moles in the
mixture. Consider a solution containing nA
moles of A and nB moles of B. Then mole
fraction of A,
• xA =nA/(nA+nB) and
• xB = nB/(nA+nB)
Volume Fraction and Volume Percent
• The volume fraction of a component in a solution
is the ratio of its pure-component volume to the
total volume of solution both at the same
temperature and pressure. By pure-component
volume, we mean the volume occupied by the
component in its pure state. Thus if VA is the
pure-component volume of A and V is the volume
of the solution, then volume fraction = vA /V
• The volume fraction multiplied by 100 gives the
volume percent of the component in solution.
 Q
• The solubility of sodium chloride in water at 290 K is 35.8 kg/100
kg of water. Express the solubility as the following:
• (a) Mass fraction and mass percent of NaCl
• (b) Mole fraction and mole percent of NaCl
• (c) kmol NaCl per 1000 kg of water
• Solution:
• Basis: 100 kg of water and the salt dissolved in it in a saturated
solution at 290 K.
• (a) Mass of NaCl = 35.8 kg
• Mass of solution = mass of water + mass of NaCl = 100 + 35.8 =
135.8 kg
• Mass fraction of NaCl =35.8/135.8=0.2636
• Mass percent of NaCl = mass fractionx100 = 0.2636 x100 = 26.36%
• (b) kmol of NaCl = mass of NaCl in g/molecular weight
of NaCl =35.8/58.45= 0.6125 kmol
• kmol water= mass of water in kilograms/mol.weight of
water=100/18.02
• = 5.5494 kmol
• Mole fraction of NaCl= Mols of NaCl/Mols of solution=
0.6125/( 0.6125+ 5.5494)
• Mole percent = mole fraction x 100 = 9.94%
• (c) 100 kg of water dissolves 0.6125 kmol NaCl.
Therefore, kmol NaCl per 1000 kg of water is 6.125
kmol.
• OTHER EXPRESSIONS FOR CONCENTRATIONS
• The component present in larger proportions in a
solution is the solvent and that present in smaller
proportions is called the solute. In addition to the
different methods of expressing compositions as
discussed above, the concentration of solute in a
solution can be expressed as parts per million,
molarity, molality and normality.
• Parts per million (ppm): It is used to represent
extremely small amounts of solutes present in
solutions. It is the ratio of the number of parts by
weight of the solute to 10 6 parts by weight of
solution.
• Molarity: . It is defined as the number of moles of
the solute per litre of solution.
• Molality: It is the number of moles of the solute
present per 1 kg of solvent.
• Normality: It is the ratio of the number of gram
equivalents of the solute per litre of solution.
• The product of normality and equivalent weight is
equal to the weight in grams per litre of solution
 Q
• An aqueous solution of K2CO3 contains 50% salt
and the specific gravity of the solution is 1.53.
Determine the following:
• (a) The mole percent of the salt in the solution
• (b) The volume percent of water assuming
density of water is 1000 kg/m3 and there is no
volume change on mixing
• (c) The molality of the solution
• (d) The molarity of the solution
• (e) The normality of the solution
• Solution Basis: 100 g of solution
• Molecular weight of K2CO3 = 138.20
• (a) Mass of K2CO3 = 50 g
• Moles of K2CO3 =50/138.2= 0.3618 mol
• Mols of water =50/18.02= 2.7747 mols
• Mole percent of salt= 0.3618 *100/ (0.3618+2.7747)= 11.53%
• (b) Volume of the solution = mass /density = 100/1.53=65.36 mL
• Volume of water in the solution = mass/density = 50/1 = 50 mL
• Volume percent of water = (volume of water/solution volume)×100
• =(50/65.36) x 100 =76.50%
• (c) Molality=mol solute/ kg of solvent
• =0.3618/50x 10-3 == 7.236 mol/kg
• (d) 65.36 mL solution contains 0.3618 mol K2CO3 .
• Molarity = mol solute/litre solution
• = 0.3618/(65.36×10–3 )= 5.536 mol/L
• e) Equivalent weight of K2CO3 = molecular weight/2 =
138.20/2 = 69.10
• Normalityof K2CO3 =gram equivalents/litre of solution
• Number of gram equivalents of K2CO3 = weight/
equivalent weight =50/ 69.10 = 0.7236
• Normality = gram equivalents/ litre solution
• 0.7236/65.36×10 –3 = 11.07 gram equivalents/L
• or 11.07 N
 Ideal Gases and Gas Mixtures
• Boyle’s law: Boyle in 1662 proposed that for a fixed quantity of a gas the
volume is inversely proportional to pressure at constant temperature. PV
= constant (at fixed T and n)
• where P = pressure, V = volume, T = temperature and n is the number of
moles of the gas.
• Charles’ law: The dependence of the volume of a gas on temperature was
reported by Charles in 1787. A quantitative relationship between volume
and temperature was proposed by Gay–Lussac in 1802. The laws of
Gay–Lussac and Charles state that the volume of a fixed quantity of gas at
constant pressure varies directly with temperature.
• V =constant x T (at fixed P and n)

• Avogadro’s principle: According to Avogadro’s hypothesis equimolal

quantities of all gases at the same temperature and pressure occupy the
same volume.
 Ideal Gas Equation
• The ideal gas equation is obtained by combining Boyle’s law and Charle’s
law
• Assume that one mole of a gas is initially at temperature T0 , and pressure
P0 and let the volume occupied by the gas under these conditions be V0 .
• Now let the gas be brought to the final state where the pressure, volume
and temperature are, respectively, P, V and T.
• Let this change be accomplished in two steps.
• First, an isothermal process in which the temperature is kept constant at
T0 , and pressure is changed to P.
• In the second step, the gas pressure is kept constant at P and the
temperature is changed from T0 to T.
• In the first step the volume of the gas changes from V0 to V
• at constant temperature T0 and Boyle’s law is applicable.
• P0V0/T0 = PV/T=¢ = constant Rearranging this equation, we get
• Assigning standard values for the reference conditions
P0 and T0 , the volume occupied by any gas at the
reference state V0 would be constant according to
Avogadro’s principle, so that we can take the quantity
P0V0 /To on the right hand side of Eq. to be a universal
constant which is denoted by R. or PV = RT
• R is known as the gas constant and its magnitude
depends on the units of standard pressure P0 ,
standard volume V0 and standard temperature T0
• . In SI units the ideal gas constant is equal to 8.314
J/(mol K) or 8.314 kJ/ (kmol K).
 Calculations for Ideal Gas
• Q. Assuming air to behave as an ideal gas, calculate the
molar volume of air at 350 K and 1 bar.
• Solution:One mole of a gas at STP (standard conditions of
temperature and pressure) occupies 22.4143 x 10 –3 m3
(That is P0 = 1.01325 bar, T0 = 273.15 K, and V0 = 22.4143x10
–3 3
m ).
• P1V1=nRT1
• P2V2=nRT2
• So P1V1/T1 = P2V2 /T2
• At Standard conditions,P0V0/T0=P1V1/T1
• substituting,
• V1= 22.414x10-3(1.01325/1)x350/273=2.91x10-2m3
• Q. A 150 L oxygen cylinder contains gas at 300
K and 10 bar. What is the mass of oxygen in
the cylinder?
 MIXTURES OF IDEAL GASES
• Consider a mixture of different gases A, B, C, etc. at temperature T and
pressure P and let the total volume of the mixture be V.
• Let nA , nB , nC, etc. be the number of moles of the different components.
If all the component gases are ideal, then the behaviour of the individual
species is not influenced in the presence of other gases in the mixture.
• This is because of the absence of intermolecular forces in an ideal gas.
• The pressure exerted by nA moles of A in the mixture will be the same as
the pressure exerted when nA moles of A alone occupy a volume V at
temperature T.
• This is true for the other constituents B, C, etc. as well.
• The pressure exerted by a constituent in a mixture of gases when it alone
occupies the total volume at a given temperature is called the partial
pressure of that constituent in the mixture.
• The partial pressure of constituent i is denoted by pi . In the case of ideal
gases this is also equal to the pressure exerted by the constituent i in the
mixture.
• Pure-component volume is defined as the volume occupied by a component if it
alone were present at the total pressure and temperature of the mixture.
• The volume Vi occupied by the pure component i at T and P, the temperature and
pressure of the mixture, is the pure-component volume of i in the mixture.
• This is in fact a fictitious volume as the constituents cannot have individual volumes
in the mixture as they get distributed throughout the container.

• However, it can be viewed as the contribution of individual constituents to the total

volume of the mixture, in which case it is also known as the partial volume. Even this
is strictly true only for ideal gases.
• The partial volume of a component in the mixture is the increase in the volume of
the mixture resulting by the addition of a given number of moles of the constituent
at the temperature and pressure of the mixture.
• For ideal gases, this increase in volume will be the same as the pure-component
volume because the intermolecular forces are negligible.
• For real gases, however, there may be volume change on mixing and the partial
volume and pure-component volume will be different.
 Dalton’s Law
• Dalton proposed the law of additive pressures in 1805
which states that the total pressure of a mixture of
gases is equal to the sum of the partial pressures of
the individual components.
• Stated mathematically,
• P=pA+pB+pC+… =£pi
• Dalton’s law is strictly true only for ideal gases.
• Also, by the definition of partial pressures, pAV = nART,
pBV = nBRT ,pCV = nCRT
• Adding the terms on both sides of Eq.
• we get (pA + pB + pC + ...)V = (nA + nB + nC + ...)RT
• Another useful result that follows from
Dalton’s law is that the partial pressure of a
component gas in an ideal gas mixture is the
product of its mole fraction and the total
pressure.
Amagat’s Law of Additive Volumes
• Amagat’s law states that the total volume of a mixture of gases at a given
temperature and pressure is equal to the sum of the pure component
volumes of the constituents at the same temperature and pressure.
• This law is strictly true only for ideal gases.
• It can be stated mathematically as
• V = VA + VB + VC + ... = £ Vi
• Using the definition of pure component volume and assuming the gases
are ideal,
• we can write
• PVA = nART
• PVB = nBRT
• PVC = nCRT
• Adding the terms on both sides we get
• P(VA + VB + VC + ...) = (nA + nB + nC + ...)RT =nRT
• P(£ Vi ) = £( ni ) RT
• Since this is applicable for the mixture as a whole,
we see thatV = £ Vi which shows that Amagat’s
law is applicable for ideal gases.
• Also, Vi/V= ni/n=yi
• where yi is the mole fraction of gas i A,B,C,…)in
the mixture means that the volume fraction and
mole fraction in an ideal gas mixture are identical.
Combining Eqs.the following general result of
great applicability is deduced:
• mole fraction = volume fraction = pressure fraction
 Average Molecular Weight
• We can calculate the average molecular weight of a mixture of
gases knowing its molal composition.
• Assume a suitable basis, say 100 moles of the mixture, and
evaluate the number of moles of each constituent in the mixture.
• The mass of each constituent in the mixture is obtained by
multiplying the number of moles by the respective molecular
weight.
• If m is the mass of a mixture of gases and Mav its average
molecular weight, then the number of moles of the mixture n is
given by
• m = n Mav
• The mass of each constituent in the mixture is obtained by
multiplying the number of moles by the respective molecular
weight.
 Density and Specific Gravity
• The density of a mixture of gases is the mass
per unit volume of the mixture at the specified
conditions of temperature and pressure.
• The specific gravity of a gas is the ratio of the
density of the gas to the density of dry air at
the same temperature and pressure.
 Q
• An analysis of the vent gases from the
chlorinator in a plant for making chlorinated
rubber showed 70% by volume HCl, 20% by
volume Cl2 and the rest CCl4 . Determine the
following:
• (a) The percent composition by weight
• (b) The average molecular weight of the gas
(c) The density at standard conditions (in
kg/m3 )
• Solution :
• For gas mixtures, the volume percent and
mole percent are the same.
• Therefore, the gas contains 70% (mole) HCl,
20% (mole) Cl2 and 100 – 70 – 20 = 10% (mole)
CCl4 . Basis: 100 kmol gas mixture
• (a) The calculations are presented as follows:
Component No. of kmol Molecular Weight in kg weight percent
Mass
HCl 70 36.45 2551.50 46.33
Cl2 20 70.90 1418.00 25.75
CCl4 10 153.8 1538.00 27.92
Total 100.00 5507.50

Mass in kg is obtained by multiplying the number of kmol of each

constituent by its molecular weight. Weight percent is calculated
by dividing the mass in kg of each component by the total mass
and by multiplying by 100. For example, for chlorine, the mass is
1418.00 kg and the mass percent is (1418.00/ 5507.50)*100
=25.75%
• (b) Average molecular weight of the gas is
obtained by dividing the total mass by the number
of moles. Here, 100 kmol has a mass = 5507.5 kg.
• Therefore, average molecular weight = 5507.50 /
100=55.075
• (c) 100 kmol of an ideal gas occupies a volume of
100x22.414 m3 at STP. We have already found out
that the mass of 100 kmol is 5507.50 kg.
• Since density is mass/volume,
• 5507.50/(100 × 22.414) = 2.4572 kg/m3
 Material Balance with Chemical
Reaction
• In the absence of generation and consumption
of materials, the material balance equation
reduces to
• input – output = accumulation
• Under steady state, there is no accumulation and the terms
on the right-hand side of the above equation reduce to
zero. For processes with chemical conversion, Eq is not
universally valid. It is valid for the total material balance
written on a mass basis, but not valid on a mole basis.
• Consider, for example, a process in which 1 kmol (100.9 kg)
CaCO3 is subjected to calcination reaction in a kiln. The
following reaction takes place
• CaCO3→ CaO + CO2
• Assume that only 90% of the feed is converted. Then the
quantities of the reactants and products in mass and molar
units are given as follows:
• Material Input Output
• Mass (kg) Moles(kmol) Mass (kg) Moles(kmol)
• mols x mol .wt .
• CaCO3 100.9 1.00 10.09 0.1
•
• CaO 0 0 51.21 0.9

• CO2 0 0 39.60 0.9

• Total 100.9 1 100..9 1.9

• A producer gas contains 9.2% CO2 , 21.3% CO,
18% H2 , 2.5% CH4 , and the rest N2 . It is burned
with an excess supply of air. The flue gas analysed
9.05% CO2 , 1.34% CO, 9.98% O2 and 79.63% N2 .
Determine the following:
• (a) The volumetric ratio of air supplied to the fuel
burned
• (b) The percent excess air supplied
• (c) The percent of nitrogen in the flue gas that
came from the fuel.
• Excess and Limiting Reactant
• In industrial processes one would rarely come across the use
of exact stoichiometric quantities for chemical conversion.
Frequently, one of the reactants is supplied in excess to
ensure completion of the reaction. Excess reactants may be
necessary in certain cases to prevent the occurrence of
undesired side reactions or to ensure the complete use of
costly reactants.
• When the reactants are not in stoichiometric quantities, the
reactant present in excess of the stoichiometric quantities is
termed the excess reactant and the material that is not
present in excess of that required to react with any of the
other materials or the material that is present in least
stoichiometric proportions is termed the limiting reactant.
• The limiting reactant is present in the smallest
stoichiometric amount and if the reaction is
allowed to go to completion, it would
disappear first from the reaction mixture.
• Conversion
• The conversion is the fraction of the feed or
fraction of certain constituents of the feed
that is converted into products.
• Percent conversion = (moles of the feed reacted/moles of the feed charged)×100
• Yield
• The percent yield of any product is the percentage ratio of the amount of
the reactant that is required to give the desired product in such quantities
as is present in the reactor effluents to the amount of the reactant that
has undergone chemical conversion
• Percent yield = (moles of the reactant converted to the desired product /total moles of the
reactant converted)×100
• Extent of Reaction
• The extent of reaction, also called reaction coordinate measures the progress of a reaction
and is defined as the degree to which a reaction has advanced.
• EXAMPLE 3.21 In the vapour-phase hydration of
ethylene to ethanol, diethyl ether is obtained as a
by-product.
• C2H4 + H2O → C2H5OH
• 2C2H4 + H2O → (C2H5 )2O
• A feed mixture consisting of 60% ethylene, 3%
inerts and 37% water is sent to the reactor. The
products analyzed 53.89% ethylene, 14.37%
ethanol, 1.80% ether, 26.35% water, and 3.59%
inerts. Calculate the conversion of ethylene, yield
of ethanol and ether based on ethylene.
Module II
Energy balance
Energy balance- heat capacity, specific heat and enthalpy, heat capacity of gases at
constant pressure, heat capacity of gaseous mixtures, latent heats, enthalpy changes
accompanying chemical reactions- standard heat of formation and standard heat of
combustion, standard heat of reaction.
 Energy Balance

LAW OF CONSERVATION OF
ENERGY
The law of conservation of energy states that although
energy may be converted from one form to another, it
cannot be created or destroyed.
Internal Energy
A given system under a given set of conditions has a definite internal energy.
In a cyclic process the internal energy of the system after a series of changes
remains the same as it was before.
The heat and work involved in a non-cyclic process are not equal. Consequently,
during a non-cyclic process some energy gets stored in the system or some stored
energy gets removed from the system.
These changes in the stored energy are measured as the change in the internal
energy of the system.
The change in internal energy ∆U in a closed system is equal to the heat added to
the system (Q) minus the work done by the system (W).

∆U = Q – W

This Equation is the mathematical statement of the first law of thermodynamics for
a closed system.
 Enthalpy
For a system kept at constant volume in which no work of expansion or any
other kind of work is done, the entire heat supplied goes to change its
internal energy.
When the system is free to change its volume against a constant external
pressure, the change in internal energy is no longer equal to the energy
supplied as heat.
In effect, a part of the energy supplied is utilized by the system for
occupying a new volume; the energy thus utilized is equal to the work
required to ‘push’ the surroundings against a constant pressure.
Consequently, ∆U < Q. However, the heat supplied at constant pressure
can be measured as the change in another thermodynamic property of the
system which we call the enthalpy.
Enthalpy is denoted by H and is perhaps, the most widely used of all
thermodynamic functions. It is defined as
H = U + PV
Here U is the internal energy of the system, P the absolute pressure and V
the volume of the system.
H = U + PV
In differential form
dH=dU+d(PV)
Which on integration gives
∆H= ∆U+ ∆(PV)

This Equation is applicable for any finite change occurring in the system.
We can show that the change in enthalpy for a reversible, non-flow process
at constant pressure is equal to the heat supplied.
dH = dU + P dV + V dP
Substituting
we get dH = dQ – dW + P dV + V dP Since dW = P dV and V dP = 0 for constant
pressure process, the above equation simplifies to dH = dQ (for constant
pressure process)
That is, when a system is heated at constant pressure, and only expansion
work can occur, the change in enthalpy is equal to the heat supplied.
On the other hand, for a process occurring at constant volume, work of
expansion is zero, and Eq.
reveals that the change in internal energy is equal to the heat supplied.
dU = dQ (for constant volume process)
A spherical storage tank of 3 m in diameter is half-filled with 12 500
kg of an organic liquid at 7000 kPa. If the total internal energy in the
tank is 5.3 ¥ 10 6 kJ, what is the specific enthalpy of the fluid in the
tank?
 HEAT CAPACITIES

The heat capacity of a substance is the quantity of heat to be

supplied to cause a temperature rise of one degree.
Thus, dQ = C dT where C is known as heat capacity of the
substance.
The heat capacity of the unit mass of a substance is also
known as specific heat of the substance.
Heat capacity depends on the way in which the heat is
supplied.
When heat is supplied to a system at constant volume, the
system is unable to do any work and the quantity of heat
required is given by
dQ = CV dT (constant volume)
where CV is known as the heat capacity at constant volume
If heat is supplied to a substance at constant pressure, it is
free to expand doing work against the constant pressure.
A part of the heat supplied to the system is utilized for the
work of expansion and more heat will be required to rise the
temperature than that required in a constant volume process
for the same temperature change.
The amount of heat required is related to the temperature
rise as
dQ = CP dT (constant pressure) where CP is called the heat
capacity at constant pressure
Generally, the heat capacity of a substance is not constant; but varies with
temperature.
For convenience in engineering calculations, it is usually expressed by a
polynomial equation such as
CP = a + bT + cT 2
where a, b and c are constants.
The enthalpy change in a constant pressure process occurring between
temperature limits T1 and T2 can be evaluated by integrating the equation
dH= Cp dT

T2
∆H=∫ Cp dT
T1
 Mean Heat Capacity

For calculating the heat interaction and enthalpy changes in processes involving
gases, it is sometimes convenient to use a mean or average heat capacity in the
temperature range of interest.
The mean heat capacity at constant pressure may be denoted by CPm and can
be obtained as
CPm =
Heat Capacity of Mixtures of Gases

The heat capacity of an ideal gas mixture can be evaluated as the sum
of the heat capacities of the individual constituents each weighted
according to the mole fraction in the mixture.
Thus

where yi represents the mole fraction of component i in the mixture of

n components and CP,i is its specific heat in the pure state. If the heat
capacity can be expressed as a quadratic function of temperature, i.e.
CP = a+ bT + gT 2 the heat capacity of the mixture is
Kopp’s rule:
When experimental data are lacking, Kopp’s rule may be used for
making a rough estimation of the heat capacity of solids.
Kopp’s rule predicts that the heat capacity of a solid compound
at room temperature is approximately equal to the sum of the
heat capacities of the individual elements.

According to Kopp’s rule, the heat capacity of potassium permanganate may be

estimated as equal to the heat capacity of potassium + heat capacity of manganese +
4 times the heat capacity of oxygen. This is equal to 25.96 + 25.96 + 4 x 16.8 = 119.12
J/mol K. This compares well with the experimental value of 117.2 J/mol K. The
deviation is less than 2%.
 Latent Heats
• ENTHALPY CHANGE OF PHASE CHANGES
• Latent heat (also known as latent energy or heat of
transformation) is energy released or absorbed, by a body
or a thermodynamic system,during a constant-temperature
process — usually a phase transition.
• This change of state from the solid to the liquid occurs at
constant temperature and constant pressure. The enthalpy
change accompanying this process is known as heat of
fusion or latent heat of fusion.
• The heat required to change the state of unit mass of a
substance from the liquid to the vapour state is known as
the heat of vaporization or the latent heat of vaporization
 Example
• Enthalpy of steam at 75 kPa and 573 K is 3075 kJ/kg referred to
liquid water at 273 K. If the mean heat capacity of liquid water
and water vapour are 4.2 kJ/kg K and 1.97 kJ/kg K respectively,
calculate the heat of vaporization of water at 75 kPa. The
saturation temperature of water at 75 kPa is 365 K.

• Solution: Since the boiling point of water at 75 kPa is 365 K, the

vapour at 573 K and 75 kPa is superheated steam. The process of
converting liquid water at 75 kPa and 273 K to superheated steam
at 75 kPa and 573 K can be assumed to take place along the
following route (Figure 11.5): Step 1: Water is heated from 273 K
to 365 K at constant pressure. Enthalpy change, DH1 is equal to
the heat required to raise the temperature of water from 273 to
365 K = mCPDT = 1 x 4.2 x (365 – 273) = 386.4 kJ/kg
 HEAT EFFECTS ACCOMPANYING
CHEMICAL REACTIONS
• Energy changes are involved in the course of a
chemical reaction; heat is either absorbed or
evolved during the reaction. The reactions in
which heat is absorbed are called endothermic
reactions and those in which heat is evolved are
called exothermic reactions. Knowledge of the
heat effects accompanying chemical reactions and
the influence of the operating parameters on
these energy changes is essential for the proper
design and operation of reaction vessels.
 The Standard Heat of Reaction
• It is the difference between the enthalpy of products
and the enthalpy of reactants and is denoted by ΔH.
Thus, positive values of DH indicate increase in the
enthalpy and therefore represent endothermic
reactions and, negative values of Δ H mean decrease
in enthalpy and therefore refer to exothermic
reactions. ΔHr = £HP – £HR
• where ΔHr is the heat of reaction and £HP and £HR
• are the enthalpies of the products and reactants
respectively. To complete the definition of the heat of
reaction, it is necessary to specify the conditions of
every product and reactant involved in the reaction.
• To complete the definition of the heat of reaction, it is
necessary to specify the conditions of every product
and reactant involved in the reaction.
• The standard heat of reaction is the enthalpy change
accompanying a reaction when both the reactants and
products are at their standard states at constant
temperature T. It is represented by the symbol Δ H0 ,
the superscript ‘0’ indicating that the heat of reaction
refers to the standard T conditions. By convention, the
standard heats of reaction are reported at a
temperature of 298 K and are represented by ΔH0
 Class work
• Carbon dioxide has a molal heat capacity of CP
= 26.54 + 42.454 x 10 –3 T – 14.298 x 10 –6 T 2
where CP is in J/mol K and T in K.
• (a) Calculate the heat capacity at 400 K.
• (b) Calculate the mean heat capacity between
400 and 300 K.
• (c) Calculate the heat requirement for heating
88 kg of the gas from 300 K to 400 K.
• The vapour-phase hydration of ethylene to ethanol is represented by: C2H4 (g) + H2O
(g) → C2H5OH(g)
• Calculate the standard heat of reaction if the following data are available:
• 2CO2 (g) + 3H2O (l) → C2H5OH (l) + 3O2 (g) ΔH0 = 1366.91 kJ298
• The standard heat of combustion of ethylene at 298 K is – 1410.99 kJ/mol and heats
of vaporization of water and ethanol are, respectively,
• 44.04 kJ/mol and
• 42.37 kJ/mol.
• Solution The following equations may be formulated using the given data: 2CO2 (g) +
3H2O (l) → C2H5OH (l) + 3O2 (g ΔH0 = 1366.91 kJ (A)
• Δ H 298 = – 1410.99 kJ (B)

• H2O (l) → H2O(g) Δ Hv,298 = 44.04 kJ (C)

• C2H5OH (l) → C2H5OH (g) Δ Hv,298 = 42.37 kJ (D)
• Perform the following arithmetic operations on the above equations: Eq. (A) + Eq.
(B) + Eq. (D) – Eq. (C) The result is
• 45.75kJ
• Module III
• Chemical Engineering Thermodynamics
• Chemical thermodynamics, fundamental concepts and
definitions- types of thermodynamic systems and
properties- closed, open and isolated system- intensive and
extensive properties-path and state functions, first law of
thermodynamics, second law of thermodynamics, entropy,
• change in entropy, Maxwell relations, heat capacity in
terms of entropy, equation of state of gases, the principle of
corresponding states, compression and expansion of fluids
– Joule Thomson expansion. Gibbs free energy change,
equilibrium constant, effect of temperature on equilibrium
constant.
 DEFINITIONS AND FUNDAMENTAL
CONCEPTS
• Systems and Processes
• System. In thermodynamics, a substance or group of substances in which we have
special interest is called a system.
• It is that part of the universe which is set apart for our special consideration.
• It may be a reaction vessel, a distillation column, or a heat engine.
• Process. The changes taking place within the system is referred to as a process.
• Thus, hydrocarbon fuel and oxygen in a combustion chamber constitute the system
and the combustion of fuel to form water and carbon dioxide constitutes a process.
• Surroundings. The part of the universe outside the system and separated from the
system by boundaries is called surroundings. The boundaries may be either physical
or imaginary; they may be rigid or movable.
• For practical reasons, the surroundings are usually restricted to that portion of the
universe which is in the immediate vicinity of the system and are affected by
changes occurring in the system.
• For example, when the steam condensing in a shell-and-tube heat exchanger is
treated as the system, the cooling water to which the latent heat of vaporisation is
transferred may be treated as the surroundings.
 Homogeneous and Heterogeneous
Systems
• Homogeneous system. This system is also called a phase.
• Here the properties are the same throughout or the properties vary
smoothly without showing any surface of discontinuity.
• Liquid water in a beaker and a column of dust-free air above the earth’s
surface are examples of homogeneous system. Heterogeneous system.
• This is a system which consists of two or more distinct homogeneous
regions or phases. There is a sudden change in properties at the phase
boundaries.
• A liquid mixture of benzene and water forms a heterogeneous system
made up of two immiscible liquid phases. Water and water vapour taken
in a closed container is another example of a heterogeneous system.
Systems consisting of only gases and vapours are always homogeneous.
With liquids, two phases are common, and with solids any number of
different phases are possible.
 Closed and Open Systems
• Closed system and open system.
• Systems that can exchange energy with the surroundings but
which cannot transfer matter across the boundaries are known as
closed systems.
• Open systems, on the other hand, can exchange both energy and
matter with their environment. In a multiphase system, each
phase is open since material is free to enter and leave each phase,
although the system as a whole may be closed to the flow of
matter.
• A batch reactor is a closed system while a tubular flow reactor is
an open system. Cyclical processes, like power and refrigeration
cycles are closed systems when considered as a whole, whereas
each component of the cycle such as compressor, pump, and heat
exchanger is open.
• Isolated system.
• This is a system, which is totally unaffected by the changes
in its environment. Neither energy nor matter can cross the
boundaries of an isolated system.
• A closed system is thermally isolated, when the enclosing
walls are impervious to the flow of heat; it is mechanically
isolated, when enclosed by rigid walls, and is completely
isolated, when neither material nor energy in any form can
be added to it or removed from it.
• A perfectly isolated system is an ideal concept that cannot
be attained in practice. The system and surroundings
considered together constitute an isolated system. Thus,
the universe can be treated as an isolated system
• State and Properties
• Certain specifications such as pressure,
volume, and temperature are necessary to
define the conditions of a given system. The
condition defined by such specifications is
called the state of the system.
• The variables used to define the state are
called the state functions or the properties of
the system.
Intensive and Extensive Properties
• The extensive properties depend on the quantity (or extent) of matter
specified in the system. Mass and volume are extensive properties.
• The total value of any extensive property is the sum of the values of the
property of individual components into which the system can be
subdivided.
• An intensive property is independent of the size of the system. Pressure,
temperature, specific volume, density, etc., are intensive properties.
• Some intensive properties are derived from the extensive properties by
specifying the unit amount of the substance concerned. Examples are
specific volume, specific heat, and density.
• Heat capacity is an extensive property, while specific heat is an intensive
property.
• As the intensive properties are independent of the amount of the
substance, they describe specific characteristics of a substance in a given
state.
 State and Path Functions
• State functions. Properties of a substance describe its present
state and do not give a record of its previous history.
• They are state functions in the sense that they are fixed for a
particular state of the system and do not in any way depend upon
the past history or the path by which the state was arrived at.
• When a system is considered in two different states, the
difference in property between the two states depends solely
upon those states themselves and not upon the manner in which
the system changes from one state to the other.
• For example, ΔM, the change in some property M of the system as
it changes from state 1 to state 2, is always the same regardless of
the process by which the change is brought about. For a cyclic
process, the initial and final states are the same and the change in
the property Δ M will be zero.
• Path functions. The values of heat and work accompanying a
given change in state vary with the path from the initial to the
final state. For example, some mass of hydrocarbon may be
completely burnt in air at constant volume in a combustion
chamber
• All the energy lost by the system appears as heat, no work being
done. In contrast, a large part of the energy of the
hydrocarbon-air system is converted to mechanical work and only
the remainder into heat in an internal combustion engine.
• It means that the heat and work involved in a given change of
state are not to be determined solely by the initial and final states;
they also depend on the manner in which the change is carried
out.
• Heat and work are therefore not thermodynamic properties of the
system. They are properties of the process and are called path
functions.
 First Law of Thermodynamics
• GENERAL STATEMENTS OF FIRST LAW OF THERMODYNAMICS
• The fundamental implication of this law is that “although energy
may be converted from one form to another, it cannot be created
or destroyed”. Whenever a quantity of one form of energy is
produced, an exactly equivalent amount of another kind must be
used-up.
• Any loss or gain of energy by the system must be exactly
equivalent to the gain or loss of energy of the surroundings.
• For an isolated system—a combination of the system and the
surroundings—the total energy therefore, remains constant,
although it may be changed from one form to another. The
universe can be treated as an isolated system and therefore we
can say, “the energy of the universe is conserved”.
FIRST LAW OF THERMODYNAMICS FOR
CYCLIC PROCESS
• Consider a static system undergoing a cycle of changes.
• Work is done on the system by forces acting from the surroundings, or
vice versa, and heat is transferred between the system and the
surroundings during the process.
• Then, according to the first law of thermodynamics, the algebraic
summation of all work effects exactly equals the summation of all heat
effects.
• Let Q denote the heat added to the system and W the work done by the
system (Q is negative when heat is rejected by the system and W is
negative when work is done on the system) and if both are measured in
consistent units,
• SW=SQ
• If the units chosen for heat and work are different, the above equation
can be written as S W = J S Q
• J is the mechanical equivalent of heat if the work is mechanical, and
electrical equivalent of heat if the work is electrical.
FIRST LAW OF THERMODYNAMICS FOR
NON-FLOW PROCESS
• The first law of thermodynamics requires that the
change in the total energy of the system be
compensated by an equal but opposite change in
the total energy of the surroundings, so that,
there is no net change in the energy in any pThe
change in the total energy of the surroundings
occurs only through the exchange of heat or work
with the system.
• Then the change in the total energy of the
surroundings, (Δ E)sur , must be equal to the
energy transferred to or from it as heat and work.
• Since Q is the heat transferred to the system and W is the work extracted
from it during the process,
• (ΔE) sur = – Q + W………(2.1)
• For a closed system undergoing only changes in the kinetic, potential, and
internal energies, the total energy change of the system (Δ E)sys is given
by
• (Δ E)sys = Δ(KE) + Δ(PE) + Δ U………(2.2)
• Since (Δ E)sys = – (Δ E) sur , we can combine Eqs. (2.1) and (2.2) as follows.
Δ(KE) + Δ(PE) + Δ U = Q – W………(2.3)
• In the above equations Δ(KE) and Δ(PE) denote changes in kinetic energy
and potential energy respectively.
• Equation (2.3) means that the total energy change in a closed system is
equal to the heat added to the system minus the work done by the
system. For a steady-state non-flow process in which there are no changes
in the kinetic energy and potential energy, the above equation simplifies
to
 ENTHALPY
• For a system kept at constant volume in which no work of expansion or any other
kind of work is done, the change in internal energy is equal to the heat supplied to it.
• When the system is free to change its volume against a constant external pressure,
the change in internal energy is no longer equal to the energy supplied as heat.
• In effect, a part of the energy supplied is utilised by the system for occupying a new
volume; the energy thus utilised is equal to the work required to ‘push’ the
surroundings against a constant pressure. Consequently,
• ΔU < Q. However, the heat supplied at constant pressure can be measured as the
change in another thermodynamic property of the system which we call the
enthalpy.
• Enthalpy is denoted by H and is perhaps the most widely used of all thermodynamic
functions. It is defined as H = U + PV………(2.6)
• Here U is the internal energy of the system, P the absolute pressure and V the
volume of the system.
• Since U, P, and V are all state functions, any combination of them
also must be a state function.
• Enthalpy is, therefore, a state function. The product, PV, in Eq.
(2.6) represents the work that must have been done against an
environmental pressure P to create a volume V occupied by the
system, or rather, the energy that the system possesses because
of it occupying a space.
• Thus, enthalpy may be treated as ‘total energy’, because it
includes both the intrinsic energy it possesses (U) and the energy
due to the expansion possibilities of the system (PV).
• In differential form, Eq. (2.6) can be written as
• dH = dU + d(PV)………(2.7)
• Since all the terms in Eq. (2.7) are state functions, it can be readily
integrated to give Δ H = Δ U + Δ(PV)………(2.8)
• Equation (2.8) is applicable for any finite change occurring in the system.
• We can show that the change in enthalpy for a mechanically reversible,
non-flow process at constant pressure is equal to the heat supplied.
• Equation (2.7) can be expanded as dH = dU + P dV + V dP………(2.9)

• Substituting Eq. (2.5) into Eq. (2.9), we get dH = dQ – dW + P dV + V dP

• Noting that dW = P dV for a reversible non-flow process and V dP = 0 for
constant pressure process, the above equation simplifies to
• dH = dQ (for constant pressure process)………(2.10)
• That is, when a system is heated at constant pressure, and only expansion
work occurs, the change in enthalpy is equal to the heat supplied. On the
other hand, for a process occurring at constant volume, work of expansion
is zero and Eq. (2.5) reveals that the change in internal energy is equal to
the heat supplied.
• dU = dQ (for constant volume process)………(2.11)
 HEAT CAPACITY
• The heat capacity of a substance is the quantity of
heat to be supplied to effect a temperature rise of one
degree. Thus dQ = C dT where C is known as heat
capacity of the substance. Heat capacity of unit mass
of a substance is also known as specific heat of the
substance. The heat capacity depends on the way in
which heat is supplied. When heat is supplied to a
system at constant volume, the system is unable to do
any work and the quantity of heat required is given by
dQ = CV dT (constant volume)………(2.15) where CV is
known as the heat capacity at constant volume. Thus,
• Since for a given temperature change, the heat required is
more in a constant pressure process than that in a constant
volume process, CP > CV. However, the difference between
CP and CV for solids and liquids are very small compared to
that for gases, as the change in volume of solids and liquids
during heating is not very significant. Equations (2.17) and
(2.20) give dU = CV dT (constant volume)………(2.21)
• dH = CP dT (constant pressure)………(2.22)
• For a constant volume process, change in the internal
energy is given by Eq. (2.21). Since internal energy is a state
function, Eq. (2.21) should give the change in internal
energy in any process, provided the initial and final volume
are the same irrespective of the path along which this
change is broughy about.
• Show that CP – CV = R for an ideal gas.
• Solution: Enthalpy is defined as H = U + PV Therefore,
dH = dU + d(PV)
• For ideal gas, PV = RT, and hence,
• dH = dU + R dT
• But
• dH= CP dT and dU = CV dT
• Substituting into the above equation, we obtain
• CP dT = CV dT + R dT
• Rearranging this equation, we get
• CP – C V = R
 Second Law of Thermodynamics
• LIMITATIONS OF THE FIRST LAW OF THERMODYNAMICS
• The first law of thermodynamics deals with energy changes involved in a
process.

• But, it alone cannot answer many questions related to transformation of

energy.
• The first law specifies only this: if energy is produced during a process, it
must be compensated with a loss of an exactly equal quantity, so that the
total energy before and after the process are the same.
• It helps us to determine the energy changes involved in a process, but it
cannot tell us whether a proposed change would actually occur or not.
• If it occurs, what is the direction of the change and what are the
conditions of equilibrium under which the system undergoes no further
change?
• The major limitation of the first law of
thermodynamics is, therefore,
• its inability to deal with the direction of the
process and the extent of change. Also, according
to the first law, all forms of energy are
quantitatively equivalent and they are just
additive terms in an energy balance.
• It fails to recognise the qualitative differences
between various forms of energy. This difference
is apparent when we attempt to convert heat into
work by means of a heat engine.
• Direction of Change
• Qualitative Difference between Heat and
Work
 GENERAL STATEMENTS OF THE
SECOND LAW OF THERMODYNAMICS
• The second law of thermodynamics is just the
generalisation of our experiences with spontaneous
processes and can be stated in a number of ways:
• 1. All spontaneous processes are, to some extent,
irreversible and are accompanied by a degradation of
energy.
• 2. Heat cannot by itself pass from a cold to a hot body.
• 3. Every system, when left to itself, will on the
average, change toward a system of maximum
probability.
• 4. Kelvin–Planck statement., the statement implies that no heat
engine can have 100% efficiency because heat cannot be
completely converted to work.. Consider the isothermal expansion
of an ideal gas. The change in internal energy, ΔU, is zero in this
process. This means that the heat absorbed by the gas is
completely converted to work. Though it may appear to contradict
the second law, in fact, it is not so. What the second law requires
is that there should be no change in the system or in the
surroundings other than the complete conversion of heat into
work.
• Here, the pressure of the gas has decreased and the process
cannot be carried out continuously. The pressure of the gas would
soon become equal to that of the surroundings, and further
expansion would be impossible. The continuous conversion of
heat to work is possible only in a cyclic process. But, in the cyclic
process, energy from the surroundings is utilised in the form of
work, in order to compress the gas back to its original pressure.
• 5. Clausius statement. It is impossible to construct
a heat pump that, operating continuously, will
produce no effect other than the transfer of heat
from a lower temperature body to a higher
temperature one. In other words, any process,
which consists solely in the transfer of heat from
one temperature to a higher one, is impossible. It
means that energy in the form of work must be
supplied to the heat pump in order to transfer
heat from a cold body to a hot body. Therefore,
the coefficient of performance of a heat pump can
never be infinity.
 ENTROPY
• The second law of thermodynamics states that all
spontaneous processes are, to some extent,
irreversible and are accompanied by a
degradation of energy.
• It also means that it is impossible for any
self-acting machine to transfer energy from a
given state to a higher state of availability.
• To make these statements quantitative there is
required some function that always changes in a
certain way during a spontaneous process and
therefore, will characterise such a change
• The function that is fundamental in the
development of the second law is entropy,
which means transformability (change) .
• The second law of thermodynamics
necessitates that all spontaneous processes
result in an increase in the entropy and no
process is possible that results in a decrease in
entropy.
• Entropy is the thermodynamic property, which serves as a
measure of the unavailability or degradation of energy.
• An increase in unavailability of the total energy of a system is
quantitatively expressed by a corresponding increase in its
entropy. Entropy, being an intrinsic property of matter, is not
affected by the external position of the body or its motion relative
to other bodies. The entropy of unit mass of water at the top of
the mountain is equal to the entropy of the same amount of water
at the bottom of the falls, if the temperature and pressure are the
same.
• Similarly, the entropy of unit mass of water in the flowing stream
will be equal to the entropy of water in a stagnant pool, provided
that the conditions such as the temperature and pressure are the
same in both the cases. The entropy of a system is affected only
by the nature of matter under consideration and by the state in
which it exists.
• , the entropy of the system is increased by the
addition of heat through any mechanism or
from any source.
Entropy and the Nature of the Process
• the quantitative definition of entropy requires the following
specifications:
• 1. The amount of heat transferred.
• 2. The temperature level at which the transfer occurs
• 3. The nature of the process, whether reversible or
irreversible.
• To comply with these requirements, we define entropy

• change in a process as
• In Eq. (4.1), S denotes the entropy, Q the heat transferred, T
the absolute temperature, and the suffix R indicates the
reversibility of the process.
CALCULATION OF ENTROPY CHANGES
• The entropy change in phase transitions like
fusion, vaporisation, or transition from one
crystalline form to another can be evaluated from
the values of the latent heat of phase change and
the temperature at which the change is carried
out. The phase changes can be treated as changes
occurring reversibly at constant temperature. For
example, the entropy of vaporisation ΔSV is found
out
• as
• Processes involving Ideal Gases For a differential
change in the thermodynamic state of a closed
system, the first law of thermodynamics [Eq. (2.5)] can
be written as
• dQ = dU + dW
• When the process is reversible and the work involved
is only work of expansion (P dV), the above equation
can be modified as
• dQR = dU + P dV Since this infinitesimal change in the
state of the system can be assumed to occur at
constant temperature T, the entropy change by Eq.
(4.1) is
Because change in entropy depends only on
the end states and not on the history of the
system .
 Fundamental Property Relations
• The differentials of energy properties form the basis for the
derivation of a large number of equations relating
thermodynamic properties.
• These are developed below for systems of constant mass
and composition in which the only external force is the
pressure and the process occurring is reversible.
• The first law for non-flow process is provided by Eq. (2.5) as
• dU = dQ – dW.
• For the present case, the heat and work terms are related
to the properties of the system as
• dQ = T dS and
• dW = P dV, so that Eq. (2.5) becomes
 Maxwell’s Equations
• Maxwell’s equations are helpful in replacing
unmeasurable quantities appearing in
thermodynamic equations by measurable
quantities.
• Using these relations, the partial derivatives of
entropy with respect to pressure and volume are
expressed as derivatives possessing easily
identifiable physical meaning.
• Each of the four Maxwell’s equations is derived
from the exact differential equations of the four
energy properties.
Consider the exact differential of internal energy, i.e.
Eq. (6.14). At constant volume, it becomes
 EQUATIONS OF STATE FOR REAL
GASES
• van der Waals Equation
• van der Waals proposed the following
equation to explain the P-V-T behaviour of
real gases.

• where a and b are called van der Waals

constants.
 COMPRESSIBILITY CHARTS
• the compressibility factor measures the deviation of a
real gas from ideal
• behaviour. It is defined as Z = PV/RT. It is the ratio of
the volume of a real gas at a set of specified
• temperature and pressure to the volume occupied by
the gas at the same temperature and pressure if it
• were an ideal gas. The compressibility factor of a
perfect gas has a value of unity at all conditions.
• Since a real gas behaves ideally as pressure is reduced,
the compressibility factor of a real gas
• approaches unity as the pressure is reduced to zero.
Principle of Corresponding States
• This principle states that all gases when
compared at the same reduced temperature
and the reduced pressure, have approximately
the same compressibility factor and all deviate
from the ideal behaviour to the same extent.
• The critical properties are used as basis for
setting up a scale for comparing the
properties of substances.
• The reduced variables are obtained by dividing
the actual variables by the corresponding
• critical constants. Thus the reduced pressure
Pr = P/PC, the reduced temperature Tr = T/TC,
and the
• reduced volume Vr = V/VC.
 Throttling Process (Joule–Thomson
Expansion)
• Throttling process, also known as Joule–Thomson expansion, is a
steady-state steady-flow process
• across a restriction, which results in a reduction in pressure for the fluid.
The flow through a partially opened valve or a porous plug is a typical
example of throttling process. The throttling process may be treated as an
adiabatic operation, because the expansion takes place in a very short
time within a very small region, so that the heat exchange between the
system and the surroundings is negligible.
• As no mechanisms are present for extracting work, the process is a highly
irreversible one.
• Since the kinetic and potential energy changes are negligible, we can use
Eq. (5.10) to describe the throttling process. Since dQ = 0 and dWS = 0, this
equation reduces to dH = 0.
• That is, Joule– Thomson expansion is an isenthalpic process. The
temperature of the gas changes as a result of this expansion. The change
in temperature resulting from the throttling operation is known as the
Joule– Thomson coefficient m, which is defined as
During expansion DP is negative. Therefore, a positive
value of Joule–Thomson coefficient means
that DT is negative and the gas cools on throttling. On the
other hand, a negative Joule–Thomson
coefficient means that throttling results in an increase in
temperature

Only within these temperatures a gas cools on

throttling. For a perfect gas,
enthalpy being a function of temperature alone,
throttling, which is essentially a constant
enthalpy process
 Module IV

• Mechanical Operations
• Solids: Properties of solids, screening, screening equipment,
effectiveness of screens, sieve analysis, average diameter and
specific surface. Size reduction, types of equipment used in the
various stages of reductions. Laws of crushing power
requirements.
• Belt conveyer, bucket conveyer, pneumatic conveyers. Capacity
and power requirements of conveyers.
• Flow of solids through fluids, terminal settling velocity &amp;
hindered settling. Laboratory batch sedimentation, Kynch theory,
calculation of area and depth for continuous thickeners.
• Filtration: Filtration theory, equipment for filtration, constant
pressure and constant rate filtration,filter calculations, optimum
cycle time &amp; filter aids.
 SCREENING
• Screening is a method of separation according
to its size alone.
 Characterization of solid particles
• Particles are characetrized by their
• Size,
• Shape and
• Density
• Particle has the same density as that of bulk
material
Particle shape
• The equivalent diameter is defined as the
diameter of a sphere of equal volume.
 Particle size
• Particle size is often taken as the second
largest dimension as the particle diameter.
Arithmetic mean diameter
Screen analysis apparatus
• Calculate the mean size and specific surface
area of the cement sample from the size
distribution data given below. The particle
density of cement sample may be taken as
3260 kg/m3. (Take Øs=0.7)
Particle 75-53 53-37 37-25 25-20 29-15 15-10 10-5 5-0
size
mm:

Weight 0.05 0.12 0.18 0.23 0.14 0.12 0.1 0.06

fraction:
 Size reduction
• - Compression—nut cracker
• Impact ---- hammer
• Attrition/rubbing --filing
• Cutting----pair of shears
• (eg.scissors
 Size reduction equipment
• Crushers
• Grinders
• Ultrafine grinders
• Cutting machines
Jaw crusher
Jaw crusher
Roll crushers
Ball mill
Critical speed of ballmill

Ball mills run at 60-80 % of the critical speed

 Filtration
• Filtration is the removal of solid particles from a
fluid by passing through a filter medium or
septum on which the solids are deposited.
• Fluid flow through the filter medium by virtue of
the pressure differential across the medium.
• Therefore filters are classified that those working
with a pressure from upstream or those working
with a vacuum in the downstream side.
• Most industrial filters are either pressure
filters or vacuum filters or centrifugal filters
• Working either as continuous or batch.
• Filters are classified into three main groups;
• Cake filters
• Clarifying filters and
• Cross flow filters.
 Cake filters
• Cake filters separate large amounts of solids
as a cake or sludge
• They are provided with washing the cake and
discharge of filtrate
 Clarifying filters
• Clarifying filters remove small amounts of
solid to produce a clean gas or sparkling clear
liquid. The solid particles are trapped inside
the medium or on the surface.
 Cross flow filter
• In a cross flow filter the feed suspension flows
under pressure with a high velocity across the
filter medium.
• A thin layer of solids may form on the surface
of the medium but the high velocity keeps the
layer from building up.The filter medium is
ceramic ,metal ,or polymer
membrane.Eg.Ultra filters
 Filter media
• Should meet the following requirements:
1. It must retain the solids to be filtered ,giving a
clear filtrate,
2. It must not plug or blind the pores
3. It must be resistant chemically and and strong
enough physically to withstand the process
conditions
4. It must permit the cake formed to discharge
cleanly and completely
5. It must not be prohibitively expensive.
Plate and frame filter press
Plate and frame
Rotary drum Filter
Rotary drum Filter
• In filtration flow resistance increases with
time as the filter medium becomes clogged or
a filter cake builds up.
• The chief quantities to be referred are rate of
filtration and the pressure drop across the
medium.
• As time passes during filtration either the flow
rate diminishes or pressure drop rises.
• In constant pressure filtration the pressure
drop is held constant and the flow rate is
allowed to vary with time.
• When pressure drop is increased at constant
flow rate ,it is called constant rate filtration