Chemical Reaction Engineering I – Kinetics

Instructors: Dist. Prof. Dr. – Ing. Belay Wol

Ato Adane Bazezew (M.Sc.)
Lecture Hrs: Tuesday and Thursday : 8:30AM
Consultation Hours: Thursday : 10 - 11 AM

Course References

1. Belay Woldeyes, Chemical Reaction

Engineering - Kinetics,
2. H. Scott Fogler, Elements of Chemical
Reaction Engineering, 2016
3. Octave Levenspiel, Chemical Reaction
Engineering, 3rd edition,
Grade allocation for the course
Quiz 30 %
Assignment 10 %
Final Examination 60 %
Quiz
Students are expected “
to take Quiz’s following each
chapter.”
Assignments
Following each tutorial, students are
expected to complete an assignment
and submit it within one week.
Examination The examination is composed
of theoretical and calculation parts
Course Contents
1.Introduction to Chemical Reaction Engineering
(2- Weeks)
2. Chemical Kinetics (2- Weeks)

3. Development of the rate of reaction for

homogeneous single reactions (3- Weeks)
4. Development of the rate of reaction for
multiple reactions (2- Weeks)
5. Development of the rate of reaction for
heterogeneous reactions (2- Weeks)
6. Development of the rate of reaction in
heterogeneous porous reactions for
external and internal processes (2- Weeks)
Chapter
1. Introduction to chemical
reaction engineering
1.1Chemical Conversion
1.2 Steps of a chemical conversion
1.3 Subject of Chemical reaction
engineering
1.4 The General Mole Balance of a
chemical reactor
1.5 Stoichiometry relationship in
reaction 5
1.6 Performance of chemical reactors
1.1 Chemical Conversion

To sustain life, we require the

essentials:
water, air, and food

To sustain life in modern

society, additionally we need
chemical products
To sustain life in modern society,
additionally we need chemical products.

Medicines

ቁስ
ኮስመቲክሰ Gasoline

Fertilizer
Chemical products provides us, all
essential items for our lives
Food House fer.
Con. Materials
Energy
Chemicals
Pharmaceu
ticals Batteries
Textile Comp.
Accessories
Fertilizer Pesticide
 The chemical industry produces
Secondary raw materials, such as
Plastics and Polymers,
which provide.
Medical Household
instrument utilities
s
Automotive
Food
industry
industry Computers,
Building TVs, Pens
Materials
Chemical industry
Chemical products are made

by Chemical Conversion

in chemical industries

Question
What is chemical Engineering?
 Chemical industry products are
derived from raw materials conversion
Conversion
Raw Material Products
Example: Production of ammonia
Conversion
N2 + 3H2 2NH3
The process is
governed by the principles of

Chemical engineering
The subject chemical engineering
Deals the converting of raw
materials to products using
physical or chemical change
Conversion
Physical or chemical
(physical or chemical)
Raw materials conversion Products
Generally
 The chemical production
practitioners are called chemical
engineers.
The jobs of chemical engineer are to
 to make pure chemicals
products that can be sold
for high prices from
inexpensive raw materials.
This can be done, by
 finding cheap and abundant
raw materials,
 finding a good and reliable
market
Thus
The jobs of chemical engineer are to

1. Maintain and operate processes,

2. Fix some perceived problem, or

3. Increase capacity or selectivity at

minimum cost.
Specific Job Functions of Chemical
Engineers?
• Chemical engineers improve
 food processing techniques, and
 methods of producing fertilizers

• Chemical engineers construct

 the synthetic fibers that make
our clothes more comfortable
and water resistant
•Chemical engineers develop methods
 to mass-produce drugs, making
them more affordable
 • Chemical engineers create safer,
more efficient methods of
 refining petroleum products,
making energy and chemical
sources more productive and
cost effective.
• Chemical engineers develop
 solutions to environmental
problems, such as pollution
control and remediation.
•Chemical engineers process chemicals,
which are used to make or improve just
about everything you see around you
 •Chemical engineers need information

on prices,
markets, and
processes on which to base
calculations and estimations.
Summerizing
Performance of any Chemical Engineer
(production engineer) is measured through
 Quality
 Cost
 Time
Place work for Chemical engineers
o manufacturing,
o pharmaceuticals,
o healthcare,
o design and construction,
o pulp and paper,
o petrochemicals,
o food processing,
o specialty chemicals,
o microelectronics,
o electronic and advanced materials,
o polymers,
o biotechnology, environmental health
The UK chemical industries usage in
different industry sectors
Top 8 highest-paying engineering jobs in USA
1.Petroleum engineers. National average
salary: $94,271 per year. ...

2.Electrical engineer. National average

salary: $93,420 per year. ...
3.Computer engineer. National average
salary: $93,086 per year. ...
4. Aeronautical engineer: $92,804 per year
5.Chemical engineer: $92,790 per year..
6.Materials engineer. ...
7.Biomedical engineer. ...
8.Nuclear engineer.
 In Job markets,
where are Chemical
Engineers in
Ethiopia?
Conducting chemical conversion
Raw Materials

Chemical Conversion
Reactor

Products
 Reactor
Raw Material Products
1. Raw Material
are broadly classified into two
main categories:

 Organic and

Inorganic
Organic raw materials (H/C)
constitute approximately 80% of
the raw materials used in the
chemical industry.
These are  Coal

 Crude oil

 Natural gas
 Bio mass
Organic raw materials are used
to produce approximately 80%
of chemical products, including

 chemicals
 fertilizers,
 pharmaceuticals,
 plastics, and polymers
 energy
  Inorganic raw material
for the chemical industry include
 air,

 water,

 iron, and

 minerals.
Among in organic raw materials
Salt, sulfur, phosphate, potash, sodium, Nickel,
copper, lithium, platinium, limestone, asbestos,
fluorite, betonies, marble, talc, trona, kaoline
2. Reactor
Reactor
Raw materials Products
Raw Materials

Chemical process
Reactor

Products
2. Reactor
Reaction
Raw materials Products

This reactions
take place in
reactors (vessel)
Reactors are considered
the heart of a chemical plant.
Reactors
Batch

Mixed

Plug Flow

V
Def. of Chemical reactor:

The vessel in which change in

composition of matter (Chemical
reaction) occurs

A chemical reactor

is the “heart” of an overall chemical

or biochemical process
Also, we can call, a chemical reactor as a
device for involving:
• energy production, as in engines (internal-
combustion, jet, rocket, etc.) and
• in certain electrochemical cells (lead-acid,
fuel),
• in animate objects (e.g., Human Body as a
System of Reactors),etc.

The rational design of these are rather beyond our

capabilities
In addition to the production
(mainly @ laboratory)
• Chemical reactor is used as a tool
for determining something about
the reacting system:
 rate of reaction, and

 dependence of rate on
various factors, such as
concentration of species (cj)
and temperature (T)
1.2 Steps of a chemical conversio
Raw Materials /process/
raw materials
conversion to
Chemical process products could
Reactor pass through a
number of
steps.

Products
This steps of a chemical
conversion /process/
might be simple or complex
Example
The process involved in the
chemical conversion to produce
ammonia
N2 + 3H2 2NH3
1. Preparation of the raw material,
A. Nitrogen
Nitrogen is obtained mainly from Air
by cooling, isolate and separate
cool, isolate
Air N2 + O2 + CO2 + Ar + exs
Fractional Distillation
N2 + O2 + CO2 + Ar + exs N2
Separation
B. Hydrogen
Hydrogen from fossil fuel / Gasification
Gasification
Natural gas + H2O H2 + CO
CH4 + H2 O 3H2 + CO
Separation
H2 + CO H2
2. Conversion of the raw material,
Chem rxn
N2 + 3H2 2NH3 +by products

3. Products Separation / Purification

Fig: Process diagram of Manufacturing
of Ammonia

Fossil fuel
Gasification
H2
Air Distillation Chem rxn
N2

NH3 +by products

NH3
By products
Products Separation
Fig: Manufacturing of Ammonia using
Photo: Manufacturing of Ammonia
using natural gas
General schematic approach for a chemical
process I II
Physical Chemical Physical
Preparation conversion Un converted
Chem rxn Unit operation
Raw 1 2 3
materials IV
Products
III separation
Unit operation
Wanted
4
products
Unwanted
 Generally, the steps of chemical /conversion /
process can be stated as:
Step 1. Physical preparation of raw materials
(Refining Purification, Grinding, Disti, etc.

Step 2. Chemical process with partial conversion

Step 3. Separation of non-converted raw
material (obtained from step 2)

Step 4. Physical Separation of unwanted and

wanted products
In the above processes, the steps 1, 3 and 4
are physical treatments and are mainly carried
out in unit operations. Step 2 is the chemical
treatment process / which is carried out in the
reactors /
1.3 Subject of Chemical reaction
engineering
Raw Material

Reactor
(Chemical reaction engineering)

Product
Fig. Chemical conversion process
Def. of the subject of chemical reaction
engineering (CRE)
 is the rational design and/or
analysis of performance of
chemical reactors.
When we say rational design of a reactor
 means to determine something
about the reactor:.
 size,  thermal configuration,
 product distribution,
 cost,  operating conditions of
 flow the reactor etc
When we say Performance of chemical
reactors
Measured by
Fraction of unreacted material

Based on material
balance equation
Yield

Conversion

Selectivity

Throughput (capacity) Feed Rate

Load (Intensity)
 Some of main objective of the
chemical engineer is
 to design appropriate reactor
(rational design of a reactor)
Rational (1)
secure quality of the wanted
(2)
products with a minimum cost and
(3) time of production
1.Quality; 2. Cost; 3. Time
This can be Chemical reaction
achieved by engineering
learning
 Chemical reaction engineering (CRE)
is expressed using
material balance
stoichiometry ,
energy balance
rate of reaction (speed of the
rxn: kinetics)

These are also dependent on by

reactions type and operation
conditions
Classification of Reactions
CH4 + H2 O 3H2 + CO
• According to the number of phases
involved in the reactions (Hom, Hetero)

• According to the type of reaction

(Sin;Mul)

• According to the process nature of the

reaction (Irre; Rev)

• According to the conditions of the

process of reactions (T,P,V)
Single Multiple
 The subject Chemical Reaction Eng’g
 is the rational design and/or analysis
of performance of chemical reactors.
Under CRE Cover
1. Reactor design (Deign eq.) and around it
Rxn II
2. Kinetics specially rate of reaction
Rxn I
3. The rate of production using mole
balance and kinetics
4. Stoichiometry
5. Performance of reactor expressed by
 Selectivity , Conversion, Yield
 CRE does not provide all the
information required for the reactor
design, and other rate processes
are involved in designating a
reactor.
Among them are included :
 fluid mechanics and mixing,

 heat transfer, and diffusion

 mass transfer
 to ensure good designing of a
reactor in the chemical
conversion it needs to know:
1. The size of the reactor & surrounding
Rxn II parameters
 Reactor design
2. What changes can we expect to occur ?
- heat and other forms of energies

Thermodynamics
3. How quickly will they take place?
Rxn I
Rate of the process -Kinetics
4. Information, knowledge and experience
from the different sciences such as

 fluid mechanics,

 heat transfer,

 mass transfer,

 economics etc.

 Sustainable Manufacturing concept:

Sustainable
means to meet current needs without
compromising the ability of future
generation to satisfy their needs
Sustainability is achieved by:
• Minimizing materials and
energy usage;

• Ensuring acceptable quality of

life for people;
Information

Qual. & Env.

friendly
 Sustainability

Reactants

Raw materials Products

Energies
Requires
Needs
Profit & tim
Laws Customer
Economies Satisfaction

Renewability

Fig. Integrated approach for Chemical reaction Engineering

Conclusion to a reactor design
 Reactor design is not routine mater

 It needs almost all fields of Natural

and human sciences

 We have to scrutinize, which

subject directly involved to the
reactor design and

 Answer the three questions that is

related to the reactor design
The three questions that must be answered
for reactor design :
(1) - Is the reaction will happen and in
which direction?
- What changes are expected to
occur
Thermodynamics

(2) How fast will they occur?

Rate of individual reactions
(3) Mechanism,
why a certain reaction path are favored
 to ensure good designing of a
reactor in the chemical
conversion it needs to know:
1. The size of the reactor & surrounding
Kin IIparameters  Reactor design
2. What changes can we expect to occur ?
- heat and other forms of energies

Thermodynamics
3. How quickly will they take place?
Kin I Rate of the process -Kinetics
1.3.1 Thermodynamics in a Chemical Process
thermo refers to heat
Thermodynamics
dynamics refers to movement

We are aware that chemical

reactions have energy (heat)
associated with it
Hence, for chemical engineering
Thermodynamic is the study of
how energy changes during a
chemical reaction.
The energy changes during a chemical
reaction governed by laws of
thermodynamics
Laws of Thermodynamics

1)First Law of Thermodynamics, which

says that energy cannot be created
or destroyed; it can only be
converted from one form to an
other,
∆U = Q - W
that heat is a form of energy
Table : Simple thermodynamic Processes and the first law

First Law of
∆U = Q - W Thermodynamics
Process Constant The first Law ∆U=Q-W
Isothermal T ∆T=0 makes ∆U=0, so Q=W

Isobaric P Q = ∆U+W = ∆U +P∆V

Isohoric V ∆V=0 makes W=0 , so Q =∆U

Adibatic Q=0 ∆U= -W

2) Second Law of thermodynamics,
which deals with the direction of
chemical change. ΔG
ΔG=ΔH−TΔS

Thus, 2nd law of thermo. specially

using changes in Gibbs free energy
indicate
 the possibilities of reactions and

 achievable equilibrium
  thus, using changes in Gibbs free
energy ΔG
we, predict whether a reaction will be
spontaneous in the:
 forward direction ΔG<0

 reverse ΔG>0

 at equilibrium ΔG=0
When ΔG<0 the process will proceed
spontaneously in the forward direction to
form more products.
 When ΔG>0 the process is not
spontaneous in the forward
direction. Instead, it will proceed
spontaneously in the reverse
direction to make more starting
materials.
ΔG=ΔH−TΔS
 When ΔG=0 The system is in
equilibrium and the
concentrations of the products and
reactants will remain constant.
3. Third Law of thermodynamics, which
helps to evaluate the thermodynamic
parameter like entropy
ΔS
The reacting system is favorable by

 maximizing the entropy and

 minimizing the Gibbs free energy

From The second law of thermodynamic
ΔG=ΔH−TΔS
 It says that the entropy of the
universe always increases for a
spontaneous process:

ΔSuniverse=ΔSsystem+ΔSsurroundings>0
From the equation ΔG=ΔH−TΔS
1. A chemical reaction can not be
made conversion for
 negative entropy &

 positive Gibbs free energy

2. The sign of ∆G indicates the
direction in which a reaction moves
to reach its equilibrium position.
3. A reaction is thermodynamically
favorable when its enthalpy, ∆H,
decreases and its entropy, ∆S,
That means a reaction is
thermodynamically favorable , when

 ∆H < 0

 ∆S > 0

 ∆G is negative.

4. When ∆G is positive the reaction is

unfavorable as written (although the
reverse reaction is favorable).
Table : The sign of ∆G depends on the sign o
∆H, ∆S and T
ΔG=ΔH−TΔS
∆H ∆S ∆G
+ - ∆G< 0, @ all temperature

- - ∆G< 0, @ low temperature only

+ + ∆G< 0, @ high temperature only

+ - ∆G> 0, @ all temperature

Chemical equilibrium
kf
Consider the rxn A B
kr

Depending on initial conditions the

reaction may move to the left, it may
move to the right, or it may exist in a
state of equilibrium. Understanding
the factors that determine the
reaction’s final equilibrium position is
one of the goals of chemical
thermodynamics.
Chemical equilibrium
Thermodynamics allows us to calculate the
equilibrium constant, (Thermodynamics Equ.
Constants) K from the well known standard free
energies ∆G0R equation of the reacting material.

G0R  H 0R - T S0R  - RT ln K

With the equilibrium constant known:

 the expected maximum conversion of the
reactant and or
 the yield of the product of reaction can be
estimated
Thermodynamics
 to ensure good designing of a
reactor in the chemical
conversion it needs to know:
1. The size of the reactor & surrounding
Kin II parameters
 Reactor design
2. What changes can we expect to occur ?
- heat and other forms of energies

Thermodynamics
3. How quickly will they take place?
Kin I Rate of the process -Kinetics
1.3.2 Kinetics in the chemical
process
Def. Chemical kinetics
• is the study of the rate and
mechanism in the reactor

Chemical kinetics in terms of reaction rate

• gives us a quantitative description
of how fast chemical reactions
occur, or
• determines how and how fast you
get the products
Factors affecting the rate
• the rate of rxn depends on
variables such as C, T & P
Chemical kinetics
• enable us to predict beforehand

the rate at which given

chemical substances react, and

to control the rate in some

desirable fashion;
Chemical kinetics
• enable us to choice of an
appropriate catalyst

• Enable us to define the

spontaneous of reaction

 Irreversible reactions that proceed

to the right until completion
Chemical kinetics
 Reversible reaction is one in which
products react to form reactants

 Reversible reactions achieve an

equilibrium state after an infinite
period of time
The main core in chemical kinetics is
to find reaction rate experimentally
and interpret experimental data
for that, we need rate equation
Rate equation is expressed by
r  r Rate equation
j j r  r  k C C .....
j j j j A B
Rate of reaction
Rate of production (exp. out come)
using mole balance
Approach to Develop the rate
equation
1. Write the rate of production
from kinetics
2. Find rate of production from
mole balance
3. Combine equations
4. Assume the rate of rxn to
find the rate equation
Application Example to
formulate the rate equation
 Formulate the rate equation
Step#1:
- For single reaction
A  B  C  .....  Pr oducts

1. Write the rate of production from

kinetics
r  r
j j
2. Find the rate of production using
mole balance
 v dn j
F j ,0  F j   r j dV 
dt

dn Constant volume
1 j
Ex. BR r j  dC
j
V dt r 
f j dt
dC dC
dF j j
j r   
PFR r  j d dt
j dV F
F - F C - C C - C
j j ,0 j j ,0 j
PFR r  j,0 r
t


j V j
F
3. Combined equations
1 dn
j  r
V dt j
f
4. Assumed the rate of reaction

r  kC j C  C 

......


Substituting @ constant volume

dC j
dt
 
  j kC j C  C  ......
 the rate
equation
Develop the rate of rxn
Rxn –1: Kinetics
1. Develop the rate equation
2. Secure experimental data

3. Interpret experimental data

to find rate of rxn
characteristics of Kinetics:
rate constant, concentration
profile product distribution
Approach to Develop the rate of rxn
through formulating the rate
equation
1. Write the rate of production
from kinetics
2. Find rate of production from
mole balance
3. Combine equations
4. Assume the rate of rxn to
find the rate equation
4. find the rate of reaction from
experiment (kinetics data)
 Development of the (rate of rxn)
can be found using Rxn- 1 –
Kinetic
3. Development of rate of reaction for
homogeneous single reactions
4. Development of rate of reaction for
multiple reactions

5. Development of rate of reaction for

heterogeneous reactions
6. Development of rate of reaction for
heterogeneous porous reactions for
external and internal processes
Approach to Develop the rate of rxn
through formulating the rate
equation
1. Write the rate of production
from kinetics
2. Find rate of production from
mole balance
3. Combine equations
4. Assume the rate of rxn to
find the rate equation
4. find the rate of reaction from
experiment (kinetics data)
Approach to Develop the rate of rxn
through formulating the rate
equation
1. Write the rate of production
from kinetics
2. Find rate of production from
mole balance
3. Combine equations
4. Assume the rate of rxn to
find the rate equation
4. find the rate of reaction from
experiment (kinetics data)
The rate of production
The rate of production is expressed by
using
 Mole balance

 Kinetics
The rate of production in kinetics
is a measure of how much reactant is
consumed, or how much product is
produced, by the reaction in a given amount
of time. The rate of production is the change
in the amount of a reactant or product per
unit time
The rate of production using mole
balance
The rate of production
 is defined as the time rate of change
in the quantity of a particular
dn j species (say J) participating in a
reaction divided by a factor that
dt characterizes the reacting system's
geometry (batch) the time rate of
change
dn j
r  1
j (Re acting System Geometery) dt
rj = (1/ Unit * the time rate of change)
The rate of production is formulated using
mole balance equation

v General
dn j mole balance
F j,0  F j   r j dV  (1.3.1)
dt
Where
rj – rate of production
To find rate of production from mole balance
1.4 The General Mole Balance of a
chemical reactor
 A mole balance (also called a
mass or material balance) is
an accounting of material
entering and leaving a system
Principle
 is the conservation of mass
principle, i.e., that matter can
not disappear or be created
Belay Woldeyes(DProf.Dr.-Ing)
That is

 for the total mass crossing the

boundaries of a system, the mass
that enters a system must
(conservation of mass principle)
either leave the system or
accumulate within the system, i.e.

IN - OUT = ACC
Where:
IN- denotes what enters the
system,

OUT- denotes what leaves the

system and

ACC- denotes accumulation within

the system (which may be
negative or positive).
Hence  When mole balances for a
control volume with inflow of Fo
and outflow of species j,

Without
Fj,0 Reaction

Fj
IN - OUT = ACC (1.1)
Mathematically a mole balance of species j,
dn
j
F F  (1.1.1)
j,0 j dt
When mass balances are written for
reaction of specific compounds

With
Fj,0 Reaction

Fj

For the production term (PROD) a rate

of generation of component j by
chemical reactions is introduced
IN + PROD = OUT + ACC (1.2)
 PROD- describes the chemical reaction rates,
Hence rate of generation
Mole balance for chemical rxn of species j
becomes Rate at which component A
IN enters the volume +
PROD  Net rate at which component j is
formed by reaction
Gj = rjVf Gj =rate of generatio
rj – rate of production
= Vf – Volume of fluid
 Rate at which component j
Out leaves the volume +
 Rate at which component j
ACC accumulates within the volume
Mole balance for chemical reaction
becomes IN + PROD = OUT + ACC

Fj,0 + Gj = Fj + dnj /dt

(1.3)
Fj,0 + rjV = Fj + dnj /dt
Where F = total molar flow rate entering
o
control volume (moles/sec)
Fj= molar flow rate of species j
leaving control volume
Fj,0 = molar flow rate of species j
entering control volume
nj = Moles of species j
Looking to inside the system (reactor),
rate of generation representing rate of
reaction in volume system

during rxn T, V, P etc might change

i.e rate of Generation need to integrate
over reactor volume, as reaction
conditions( T,C) may vary
G j  ( Rate production of j) * V
v
  r j dV
If j is consumed, add a-ve sign
Substitution of rate of generation to the
mole balance equation becomes

v General
dn j mole balance
F j,0  F j   r j dV  (1.3.1)
dt
Where
rj – rate of production
From this general mole balance we develop
a rate and design equation of any type of
reactors
Basic model of reactors

Other Reactor types:

-Fixed bed reactor
-Fluidized bed reactor
Application Example of mole
balance
1. Batch Reactor

 No material is supplied to or withdrawn

from the reactor during the reaction.
 The amounts of individual components
may change due to reaction, but not
due to flow in or out
of the system.
General v dn
j
F  F   r dV 
mole balance j,0 j j dt
In a batch reactor, Fj,o = Fj = 0
dn V
j   r dV
dt j
we assume no variation of concentration or
temperature. i.e.; lumped parameter
system(well-mixed), we can take the rate of
formation out of the integral
V V
 r dV  r  dV  r V
j j j
and can rewrite the design equation of
the mole balance for a batch reactor in
the form of :

dn j
 r jV Mole balance
dt

dn Rate of
r  1 j (1.3.1a)
j V dt production
2.Continuous Flow Reactors
a. Continuous Stirred tank reactor (CSTR)

 In this type of reactors, the chemical

reactions occur while the reacting
stream is flowing through the
reactor.
  In CSTR reactor, we assume no
Dimenvariation of concentration or
sional temperature. i.e.; lumped
space parameter system(well-mixed)
V V
 r dV  r  dV  r V
j j j

For flow reactor operating at steady-

state (no time variation of flows,
concentrations, temperature)
dn j
Accumulation is zero 0
dt
The mole balance for the CSTR becomes
F  F  r V 0 CSTR
j,0 j j

F j ,0  F j  r jV
V

F F
r  j,0 j Rate
(1.3.1b)
of
j V production
b) Pipe reactor (Plug Flow Reactor)

Input
Output Rate
Rate

Assumption
 The material balance has to be
applied to a differential element
of volume
 F j ,in Fj F j  dF j F j ,out
V

Figure: Plug flow reactor

Mole balance for differential element of
volume of PFR
F j , 0  F j  r j V  0
The differential element of volume can be
expressed in equation form as under:
 
F   F  dF   r V  0
j  j j j
and taking the limit as ∆V  0, we obtain
V  dV
dF  r dV
j j
Design equation for pipe reactor

dF j Rate of
r  (1.3.1c)
production
j dV
 The subject Chemical Reaction Eng’g
 is the rational design and/or analysis
of performance of chemical reactors.
Under CRE Cover
1. Reactor design (Deign eq.) and around it
Rxn II
2. Kinetics specially rate of reaction

3. The rate of production using mole

balance and kinetics Rxn I
4. Stoichiometry
5. Performance of reactor expressed by
 Selectivity , Conversion, Yield
1.5 Stoichiometry relationship
in reaction
Generally
Chemical reaction /change of elements/
N2 + O2 2NO

A chemical species
(Reactant) is said to have
reacted /Chemical reaction
takes place/ when
it has lost its chemical identity
There are three ways a chemical
species loses (change of elements) its
identity
1. Decomposition

CH3CH3 CH2=CH2 + H2

2. Combination
N2 + O2 2NO
3. Isomerization
C2H5 = C(CH3)=CH2 CH3 - C(CH3)=CH-CH3
stoichiometry  This lost of identity of a
chemical species is
determined by the kind,
number, atoms, molecules etc

 Chemical reaction /change of

elements (chemical species loses)
/ inside reactor can occur in to two
ways: 1. Advective change
2.The internal change
change of elements
1. Advective change /transfer of a
property/ due to material
brought into the system or
removed from it

This is expressed in
the material balance
equation appropriate
to the reactor
 The internal change /composition
Change / due to chemical reactions
and are common to all types of reactor
and expressed in

Stoichiometry
Our interest is here to study the
composition change /internal
change/ which occurs during
reaction.
Stoichiometry
 is defined as the measurements of the
change of elements (composition change)
 is the study of quantitative relationships
between substances involved in chemical
change
 Provide the basis for the relationships
between the reactants and products in
chemical reaction
 Can be used to predict how much reactant
is needed to create a certain amount of
product.
The internal change / The
composition change /

which occurs during the reaction

obeys certain laws.

1. the law of Conservation of Mass,

2. Conservation equation
 Law of Conservation of Mass
Means that with the same problem domain,
the amount of mass remains constant:
Mass is neither created nor destroyed,
simply converted from one form to another
For any chemical process in a closed
system, the mass of reactant must equal
the mass of product 2H2 + O2 2H2O
Example 2H2 + O2 = 2H2O
11.2 g of hydrogen and 88.8 g of oxygen are
produce 100 g of water.
 Conservation equation
For each element in the closed reacting system,
there is a conservation equation stating that
the amounts of that element are fixed, no
matter how combined or recombined

To understand this phenomena, let us take

a well known reaction, 2H + O 2H2O
2 2

Reaction such as this can have two

meanings:
Kinetic description
Stoichiometric description
 2H2 + O2 2H2O
i) Kinetic description
Two molecules of hydrogen
combine directly with one of
oxygen to form two molecules of
water
ii) Stoichiometric description
The numbers of hydrogen and
oxygen molecules combining
to form water in the ratio 2:1

H
2H2 + O2 = 2H2O 2  2  Fixed

upsilon O
2
1
ThusIn a chemical balanced reaction,
the reactant & product ratio are fixed
where

αΑ → βB
A  Fixed
  Atom;
Molecule;
 Mol;
B
Kg ቆሎ
i.e. the amounts of that element are fixed
2H2 + O2 = 2H2O
The proportions 2:1 in the Stoichiometric
description are absolutely definite
an equation such as 3H2 + O2 ≠ 3H2O is
nonsence
Using the above Stoichiometric description
one can also express by

Conversion factor/chemical factor

a conversion factors i.e

 the ratio of the number of moles

of molecules (or formula units)
to the number of moles of atoms
Conversion factor/chemical factor for
N2 + 3H2 2NH3
chemical
3 molecules H 3 atoms H 3 moles H
factor or
2 or 2 or 1 mol N 2 conversion
1 molecule N 1 atom N 2
2 2 factor.
Find the mass of 3.987mol of Al
Steps
Calculate the molar mass for one mole
1 mol of Al = 26.98g
Conversion factor 26.98 g Al
1 mol of Al
26.98 g Al  X g Al
Hence 1 mol of Al 3. 957mol of Al
3.987×26.98g Al/1 mol of Al = 107.6g Al
Progress Test 1.1
a) What are all the conversion factors
that can be constructed from
the balanced chemical reaction
2H2 + O2 2H2O
b) For the sodium and water reaction
Na(s) + H2O(ℓ) → NaOH(aq) + H2(g)
How many molecules of H2 are
produced when 332 atoms of Na
react?
Solution a)
2 molecules H 2 molecules H 1 molecule H
2 2
1 molecule O or 2 molecules H O
2
or 1 molecule H O
2 2 2
b)
Balancing the reaction,
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
2 atoms Na chemical factor
2 molecules Na
1 molecule H or 1 atom H conversion
2 2 factors
2 molecules Na(s) → 1 molecule H2(g)
2 atoms Na(s) → 1 atom H2(g)
322 atoms Na(s) → 166 atoms H2(g)

166 molecules of H2 are produced

2 atoms Na  322 atoms Na
1 atom H y atom H
2 2
atom H  322 atoms
2 2
Stoichiometric law
tells us that the change of various
chemical species are formed or
consumed in fixed proportions.
Coming to the reaction
2H2 + O2 = 2H2O (a)
Using Stoichiometric law
The reaction (a) can be expressed in one
side and set equal zero as:
2H2O - 2H2 - O2 =0
If we identify A1 with H2O;
A2 with H2 and
A3 with O2,
then the above reaction (a) can be
expressed 2A1-2A2-A3 = 0
 The changes in a chemically
reacting system can frequently, be
characterized by a stoichiometric
equation
s
  jAj 0
Stoichiometric law
(1.4)
j 1
 j -Stoichiometric Coefficient
 2A1-2A2-A3 = 0
1 =2,  2 =-2, 3 = -1 is called the Stoichiometric
Coefficient of Aj in the reaction.

The species with positive stoichiometic

coefficients are the product of the reaction
and those with negative Stoichiometric
coefficients are the reactants.
The important thing to observe at this
point is that the meaning of the reaction
equation is unchanged if it is multiplied by
non-zero constant.
The reaction -2 H2O + 2 H2 + O2 =0 is
multiplied by (-1), the same reaction with the
decomposition of H2O, can be viewed from the
other side.
Conversion factor
Measurement of the quantity
of changes (Stoichiometry)
can be described based on:

 type of reactor

BR, CSTR, PFR

 Type of reaction
Single (simple) reaction
Multiple (complex) reactions
1.5.1 Measurement of the quantity of
changes (Stoichiometry) with single
reaction in a batch reactor
2H2 + O2 2H2O
nj,0
 A  C
j C

nj
nj,0 number of moles j originally present

nj number of moles j present at any time

A) Extent of reaction
Considering the following reaction
 A   B  C   D
A B C D
 A   B   C   D  0
A B C D
We know, from stoichiometry Law
that the change of various
chemical species are formed or
consumed in fixed proportions.
And written
n n n n
A  B  C  D  (1.5)
   
A B C D
Law of Definite Proportions
 A   B  C   D
A B C D
Change in the reactor (Change in the system

n n n nj,0 n
j j j,0
    (1.5.1) j
j j
Law of Definite Proportions
Where
 is called molar extent of reaction or
reaction coordinate or degree of
advancement of the reaction. and does
not depend on the species
 n n n
j
  j  
j,0
j j
where

nj Change in the system (Change in the

reactor)

nj number of moles j present at any time

nj,0 number of moles j originally present

Ex. Formulate, Law of Definite Proportions
aA + bB + cC→ lL + kK
The reaction can be written
A + b/aB + c/aC→ l/aL + k/aK
Extent of reaction 
, for single rxn
from Law of Definite Proportions
n n n
 
j 
j

j,0
fixed
j j
n n n n n n n n n n
  A A,0  B B,0  C C,0  L L,0  K K ,0
1 b / a c/ a l/a k /l
Using equation (1.5.1), Extent of reaction
n n n
   j  j  j,0
j j
or Mole Change in the system, becomes
n    (1.5.2)
j j
n  n  n
j j j,0
The mole in reactor @ any time
n  n   (1.6)
j j,0 j
where Stoichiometry
 j : (+) for products; (-) for reactants
The total mole in terms of extent of rxn is
expressed n  n  
j j,0 j
s s s
 n   n   
j j ,0 j
j 1 j 1 j 1

nT  nT ,0   (1.6.1)

where     
pr rea
 and  are the sum of
pr rea
Stoichiometry coefficient
of products and reactants
Progress Test 1.2
For the system in which the following
reaction occurs
3H 2  CO  CH 4  H 2O

On Rxn
Assume there are initially 2 moles of CH4, 1
mole of H20, 1 mole of CO and 4 moles of
H2 . Solution
Write mole of each species
as a function of extent of
reaction
Solu.
3H 2  CO  CH 4  H 2O
Taking eq. (1.6.1) n (t)  n    (t)
j j,0 j
n (t )  4  3 (t )
n n  3 H
2
H H n (t )  1   (t )
2 2,0 CO
n n  (t )  2  1 (t )
CO CO,0 CH
4
n n  n (t )  1  1 (t )
CH CH ,0 H O
4 4 2
n n
H O H O,0
 n  8  2
2 2 T
B) Concentration
Analog to mole, using stoichiometery
relation, concentration can be written
in terms of extent of reaction
C C C
Law of j j j,0
Definite
    (1.5.3)
Proportions j j

C (t)  C   (t) (1.6.2)

j j,0 j
C) Conversion
Measurement of the quantity of
changes /Stoichiometry/

Conversion
 In a chemical reaction, the
composition of the reaction
mixture can be expressed in
terms of one variable, the
conversion of the reaction.
Defining Conversion
For the reaction

 Taking species A as our basis of

calculation (limiting reactant) we
divide the reaction expression
through by the stoichiometric
coefficient of species A (to basis A)

nC
nA,0 nA
nB,0 nB
nD
Def. of conversion

The conversion of XA is the

number of moles of A that have
reacted per mole of A fed to the
system,
or in other word
Moles of A reacted n -n
   A.0n A (1.7)
A Moles of A fed A.0
For batch system
nA,0
n n n
  An,0 A A nA(t)
A n
A,0 A,0
(1.7.1)

nA,0 number of moles A present originally

nA number of moles A present at any time
Note, to take understanding that,
For Irreversible reactions
The maximum value of conversion, XA, is that for
complete conversion, i.e., XA = 1.0
For Reversible reactions
The maximum value of conversion, XA, is the
equilibrium conversion, i.e., XA = XA,eq.
Since conversion is unit less, it can be
used for many variables like moles,
concentrations, etc. As for example,
we can see:
For constant density, batch and
continuous process
C A, 0  C A
XA  (1.7.2)
C A, 0
Extent of reaction and conversion
 A   B  C   D
A B C D
Extent of reaction for reactant can be
rearranged


n n


 n n  n n
 
A A, 0 A A, 0 A, 0 A
   A
A A

also conversion can be rearranged n -n

  A.0 A
A n
A.0
n  n  n A  n A, 0  A
A, 0 A
Substituting this equation into the above
equation we get the relation b/n
substances involved with limiting reactant
in the rxn
n A, 0  A (1.8.1)

A

For j species
n n n X
j j,0  A,0 A
 (1.8.2)
j 
A
 Progress Test 1.3 Considering the following
reaction A+B=C
Using mole change, calculate the mole of C
as a function of conversion A
nC
nA,0 nA
nB,0 nB

Mole change in the system as a

function of the limiting reactant
n n n X
j j,0  A,0 A
 (1.8.2)
j 
A
 n n n X
C C,0  A,0 A

C 
A
Since rxn is 1:1 , then
n n n X
C C,0  A,0 A
1 1
nC
Assuming nC,0 =0 , then X An
A,0
Or nC  n A,0 X A
Progress Test 1. 4 Calculate the mole of C as
a function of conversion A:
nA,0 A + B = 2C nA
nC
nB,0 nB
(1.8.2)
n n n X
For limiting reactant A j j,0  A,0 A
n n n X 
C C,0  A,0 A j 
2 nC A
 X A
A 2n A,0

nC  2n A,0 X A
The limiting reactant
For more than one reactant, in
defining conversion, we choose one
of the reactants as the basis of
calculation and then late the other
species involved in the reaction to
this basis.
The limiting reactant (or limiting
reagent) is the reactant that gets
fully reacted first in a chemical
reaction and therefore limits how
much product can be formed.
To ensure that one reactant fully reacts
(the limiting reactant)
we use an excess of the other reactant.
Hence again the limiting reactant
is the reactant that is fully reacted
(completely used up ) in a
reaction, and thus determines
when the reaction stops.
Consider the reaction
H2 + Cl2 → 2HCL
We know H

Cl
2  1
1 Stoic. Ratio is fixed
2
If other amount than Stoic.
Ratio is provided , we call
 one reactant is limiting
(entirely consumed
reactant) &

 the other is excess (not

entirely consumed
reactant)
Finding the Limiting Reactant
 From the reaction stoichiometry, the exact
amount of reactant needed to react with
another element can be calculated.
Procedure
Determine the balanced chemical equation
 Calculate the fixed mole ratio from the
given information (Theoretical Stoic.
Ratio)
 Calculate the limiting and excess reactant
Remember:-
the limiting reactant is the one that is
completely used up in a rxn
Example Consider the reaction
H2 + Cl2 → 2HCL
To the rxn provided:- 3moles of
hydrogen & 2 moles of chlorine
Calculate the limiting reactant
i) the fixed mole ratio (Theoretical
H 1mol H
Stoic. Ratio) is Cl
2 
1mol Cl
2 1

ii) Actual data is H 2 3mol H 2

2 2
  1.51
Cl 2mol Cl
2 2
Actual data (Rate of H2 to Cl2) is
grater than Stoi. ratio
iii) Calculate the limiting and excess reactan
H2 + Cl2 → 2HCl
the limiting reactant is the lesser amount of
product
Solu.
Stoic. 1mol H2 + 1mol Cl2 → 2mol HCl

Given 3 mol H2 → 6mol HCl

2 mol Cl2 → 4mol HCl
From this we see
The chlorine offer lesser amount of product
& completely consumed to produce 4 mol
of HCl as per stoic. : Limiting reactant
1 mol of hydrogen is excess
Limiting and excess reactant
1.5.1.1 Mole change with conversion
(to calculate the mole of each
components when conversion of
limiting reactant is given )
Consider the reaction,

Which is carried out in batch reactor

nj,0 nj(t)
Eq. (1.8.1) gives extent of reaction and
conversion relation
n A, 0  A
 (1.8.1)
A
Or for any mole change in the system

n n n X
j j,0  A,0 A
 (1.8.2)
j 
A
Remaining mole in the system at
time as a function of conversion

nj,0 nj(t)


n j  n j ,0  j
n A, 0  A (1.9)

A
The total mole as a function of
conversion
S S 1 S
 n   n    jn 
j
j 1 j ,0
j 1 A,0 A
 j 1
A

1
n n   n 
T T ,0
A A, 0 A (1.10)

Where
s
      pr   re
j 1 j
Progress Test 1.5 In batch reactor in which
the following reaction occurs
A+B=C+D

For initial 1 mol of A and B, calculate the

mole of each species remaining in the
system at time t after conversion of A :-

a) 10 %
b) 50 %
c) 99 %
Solution A+B=C+D n A, 0  A

A
Given: initial 1 mol of A and B Conversion

a) 10 %
n n  j n 
j j,0  A,0 A b) 50 %
A c) 99 %
a) 10 % conversion b) 50 % conversion
c) 99 % conversion
n 11(0.20)  0.8
A n 11(0.99)  0.01
n 11(0.20)  0.8 A
B n 11(0.99)  0.01
B
n  1(0.20)  0.2 n  1(0.99)  0.99
C C
n  1(0.99)  0.99
n  1(0.20)  0.2 D
D
Describing individual mole changes
(Change in the system) in batch
reactor
Change in the
system
nj
nj,o nj
Remaining mole in the system at time t is
expressed by

n j  n j ,0  j
n A,0  A (1.9)

A
Mole initially Change in the system
present (reactor)


n j  n j ,0  j
n A, 0  A

A
Mole Change in the system in
n  n  n
terms of conversion j j j,0
n j  n j  n j,0
j
n j  n j,0  n A,0  A  n j,0
A
j
n j 
A
n A,0  A (1.11)
Mole in the system is expressed

n j  n j ,0  j
n A, 0  A

A
Mole Change in the system

j
n  n  n n  n  n  n
j j j,0 substituting j j,0  A,0 A j,0
A

Mole change in terms of conversion

j
n j  n A,0  A
A (1.11)
Calculating Mole change in the
system in terms of conversion
For the reaction aA  bB  cC  dD
Equation (1.11) Change of moles in terms of
conversion
j
n j  n A,0  A (1.11)
A
b
n A  n A,0  A n B  
a
n A,0  A

d
n C 
c
n A,0  A n D  n A,0  A
a a
Progress Test 1.6 Calculate individual mole
changes in terms of conversion for the
following reaction
n A, 0  A b c d
  A  B  C  D
A a a a
j
n j  n A,0  A
A
n  n  n
j j j,0
j
n  n  n X Solution
j j,0  A,0 A
A


j
n  n  n  n
j j,0  A,0 A j,0
A
Substituting to the individuals species,
mole change in the system in terms of
conversion
n  n - n n -an X - n  -n X
A A A,0 A,0 a A,0 A A,0 A,0 A

n  n  ab n  - n   bn  Mole change

B B,0 A,0 A B,0 a A,0 A in the system
j
n j  n A,0  A
n  n  ac n  - n  c n  A
C C,0 A,0 A C,0 a A,0 A

n  n  da n  - n  d n 
D D,0 A,0 A D,0 a A,0 A
Stoichiometry in single reaction
Stoichiometric table
Relationships between substances
involved in chemical reaction with
limiting reactant can be represented
using eq.
n A, 0  A
 (1.8.1)
A
For any mole change in the system
n n n X j
j j,0  A,0 A
 (1.8.2) or n j   n A,0  A
j  A
A (1.11)
Stoichiometric table is constructed
Column 1 The particular species

Column 2 The number of moles of each

species initially present. nj,o

Column 3 The change in the number of

moles brought through the
system. j
n j  n A,0  A (1.11)
 A
Column 4 The number of moles remaining
 in the system at time t.
n j  n j ,0 
j
n A, 0  A

A
Stoichiometry table
Change in the system
(change in the reactor)
j
n j 
A
n A,0  A (1.11)

nj,o Remaining mole

Mole in the reactor at
initially nj(t) time t nj(t)

present n j  n j ,0  j
n A, 0  A
A
Stoichiometry table
Species Initial Remaining mole
Change in the
system in the system
Write Stoichiometry (BoP20)
1.5.1.2 Concentration change with
conversion for a batch system
Concentration for Batch process

n
C  j  mol (1.12)
j V m3
Concentration for flow process
F
C   mol
j h  mol
j F 3 3 (1.12.1)
V, f m h m
To calculate the concentration of each
components when conversion of limiting
reactant is given )
nj
Cj  (1.12)
Vf
Mole @ time in the system

n j  n j ,0  j
n A, 0  A (1.10)

A

n  jn 
j,0  A,0 A (1.12.2)
C  A
j V
f
a) Concentration @ Constant Volume
Reaction System
V V
0 f
 occur when total mole is
independent function of
conversion and

 Specially for liquid reaction


j
A  B  0
n n  n 
j j ,0  A,0 A
A
n n n 
A A,0 A,0 A
n n n 
B B,0 A,0 A
n n
T T ,0
Hene, for constant Volume Reaction
System, the change of concentration at any
time V V
0 f
j
C j  C j ,0  C A,0  A (1.12.3)
A
the total concentration
1
C C   C 
T
A
T ,0 A, 0 A
(1.12.4)
   pr   re
Write Stoichiometry (BoP23)
Exercise 1.1 (Bo P2.1 p69)
The saponification for the formation of
soap from aqueous caustic soda and
glycerylstearate is

Letting XA represent the conversion of

sodium hydroxide (the moles of sodium
hydroxide reacted per mole of sodium
hydroxide initially present), set up a
stoichiometric table expressing the
concentration of each species in terms of
its initial concentration and the conversion
XA
b) Concentration @ Variable Volume V0 V f
Reaction System
 occur when total mole is a
function of conversion
A  2B   0 n
A A,0
n
A,0 A
n 
 n n  2n 
j
n n  n  B B ,0 A,0 A
j j ,0  A,0 A
A n n n 
T T ,0 A,0 A
 The volume change during
reaction can be determined using
equation of state (Ideal Gas Law)
At time t = 0 equation of state becomes
P0V 0  nT ,0 RT0 (1.14)
At any given time t, PV f  nT RT
Dividing the two equations, and
rearranging, we obtain
 P0  T  nT
V f  V0    (1.13)
 P  T0  nT ,0
We know n n  1  n  (1.10.1)
T T ,0  A,0 A
A
The ratio of total moles can be calculated for  A 1
n n
T 1  A,0  (1.13.1)
n A n
T ,0 T ,0 A
and the mole fraction is defined by
nj n j ,0
yj  ; y j ,0  (1.14)
nT nT , 0
Substituting to equation (1.9.1), we get
nT
 1   y A, 0  A (1.13.2)
nT , 0
and then equation (1.9) becomes,

 P0  T  ?
(1.13.3)
V f  V0   (1   y A,0  A )
 P  T0 
Let,
/expansion factor/(1) epsilon
 
Change in total number of moles when the reaction is completed
Total number of moles fed to the reaction

Expansion factor
1. using total mole change
n
 n T (1)
T ,0
V  V
2. using volume   0
change
A V
0 (2)
1. Total mole change n
T
For the reaction aA  bB  cC  dD
Equation (1.5) for the reaction
n n n X
j j,0  A,0 A

j 
Then, mole change becomes A
j
n j  n A,0  A (1.11)
A

n   n X
The total mole change
T  A,0 A
A
Then nT   n X
A,0 A

Substiuting,
 n X
n
 n T  A,0 A   y X
T ,0 n A,0 A
T ,0

For XA=1
  y (1.14)
A,0
Substituting equation,
 P0  T 
V f  V0   (1   y A,0  A ) (1.13.3)
 P  T0 
to (1.14) becomes

P  


V V 0  T (1  )



f 0 P T 


A A
 0 



@ constant T and P, becomes

V V (1  ) (1.13.4)
f 0 A A
2. Change volume in the systems
Change of volume in the system vs
conversion
V V
0
V V (1 ) or   f
f 0 A A V 
0
For complete conversion of reactant
A, define as
For XA=1 V  V
  0   y
A V A,0
0
Progress Test 1.7 Find the expansion factor
for the rxn using change in volume
systems (Bo p25)
2NH3 N2 + 3H2
a) For a feed of pure ammonia (A)

At conversion =1 VX  VX V  V
 A A 1 A 0  0
VX V0
A 0
2V0 V + 3V
V  V0 4  2
 A  1
V0 2
b) For 25% of ammonia (A) & 75 % inert
2NH3 + In N2 + 3H2 + In
25% = 2V
75% ? 6V

2V0 + 6V0 V + 3V + 6V

At conversion =1

V  V0 10  8
 A   0.25
V0 8
Progress Test 1.8
The adiabatic exothermic irreversible gas
phase reaction 2A + B→ 2c
is to be carried out in a flow reactor for an
equimolar feed of A and B.
What is the expansion factor of the volume
change for limiting reactant A
  y 
Stoic reaction 2A + B→ 2c A,0
Equimolar feed of A and B per stoic.
2A +B → 2C
1 mole of A 0.5 mole of B 1 mole of C
y   0.5   1 - 1 -0.5  - 0.5
A,0
  0.5 (-0.5)  - 0.25
 Then concentration as a function of
conversion in a variable volume batch
system becomes nj
 Cj 
n n 
j
n  Vf

V V (1  )
j j ,0 A,0 A
A
Substituting becomes f 0 A A
j
C j ,0  C A, 0  A
A
Cj  (1.12.5)
1  
A
Mole Fraction as a function of Conversion

nj
y j (1.15)
nT

n j  n j ,0  j
n A, 0  A
A
s
n   n
j 1
T j

 n A,0  A
1
nT  nT , 0 
 A
 

j
n  n 
j,0 A,0 A


n A
j
y  


j n 1
T n   n 
T ,0 A,0 A
A

j
y j ,0  y A, 0  A
A
yj  (1.15.1)
1
1  y A, 0  A
A
1.5.2 Measurement of the quantity of
changes with single reaction in a flow
system
Continuous Stirred-
Tank Reactor
Model (CSTR)

Plug flow reactor

FA,0
FA
  A A  B B  C C  D D

FB,0 FB

FA,0 FA

Input Output
FC,0 FC

FD,0 FD
FIn,0 FIn,0 = FIn
1.5.2.1 Molar flow rate change with
conversion
Consider the reaction
 A A  B B  C C  D D
Law of Definite Proportions for the rxn:
We use batch system

n n n n
A  B  C  D  (1.5)
   
A B C D
nj mole change in the system
for flow system, Law of Definite
Proportions for the rxn: is expressed:
F F F F F
A  B  C  D ..  j 
     (1.5.4)
A B C D j

F F
  j j,0

j (1.5.5)

Fj Change in molar flow rate

Fj number of molar flow rate j present at
any time, [mole / time]
Fj,0 number of molar flow rate j originally
present, [mole / time]

Hence, using Law of Definite

Proportions,

extent or reaction coordinate or

degree of advancement of the reaction
and the change in molar flow rate
becomes
F  F   (1.5.6)
j j,0 j
Conversion for the flow system, we have
Fj ,0  Fj
Xj  (1.7.3)
Fj ,0
Similarly to the batch system,
for flow system, conversion of a limiting
reactant A and extent of reaction have a
relation F X
A
  A,0

F F F X A
j j,0  A,0 A

j 
A
Thus, the change in molar flow rate as a function
of conversion can also be obtained

j (1.16)
F j  F j ,0  FA,0  A Notice similarity
A to that of a batch
system
The total molar flow rate can be expressed as
S S 1 S
 F   F   F 
j 1 j j 1 j ,0 A j 1 j A,0 A

F  F  F X (1.16.1)
T T ,0 A, 0 A
Progress Test 1.9
Reactor with reactants A and B constantly flowing
in and product C and unused reactants A and B
flowing out. Find molar flow rate of individual
species for limiting reactant A

A + B = 2C
Solution

Calculate : FB and FC in terms of XA

Solution: Next slide
Solution F X
A
Using equations   A,0

F F F X
j j,0  A,0 A 
A

 j
j  F - F  F X
j j,0 A,0 A
A 
A + B = 2C A

F
FC  2F A,0 X A X  C Write
A 2F
A,0 Stoichiometry
FB  FB,0 - F A,0 X A table (Bo p35)
 F
Mole fraction y  j
j F
T
j
F j  F j ,0  F A, 0  A
A
F F  F A,0 X A
T T ,0
j
y j ,0  y A, 0  A
A
yj 
1 (1.15.2)
1  y A, 0  A
A
Progress Test 1.10
The reaction is carried out in continuous
reactor at constant density. Considering
C2H4 as a limiting reactant, write the mole
fraction as a function of conversion for the
following reaction taking stoichiometry
coefficient as an initial molar flow rate
2C2 H4 + O2 2C2H4O
C2 H4 + 1/2O2 → C2 H4O j
y j ,0  y A, 0  A
A
yj 
1
1  y A, 0  A
A
1.5.2.2 Concentration as a function of
conversion for flow process
Concentration for flow
(continuous process)
F
C  j  molar flow rate  mol
j F volumetric flow rate m3
V,f
(1.12.1)
Where:-
Fj = molar flow rate, mol/s;

FV,f=volumetric flow rate, m3/s

i) Constant Volume Reaction System

Constant Volumetric flow rate (const density

F  F
V, f V ,0 (1.14)

CA,0 C
FV,0 j FV,f
CA
 j
F j ,0  F A, 0  A
Fj A
Cj  
FV , 0 FV , 0

C C j
 C 
j j,0  A,0 A (1.17.1)

A
(Bo p36)
ii) Variable Volume Reaction System
FV,0≠FV,f
CA,0 C
FV,0 j FV,f
CA

Fj
Cj  j
FV , f F  F 
j ,0  A,0 A
A (1.17.2)
C 
j F
V, f
At time t = 0 equation of state becomes
P0V 0  nT ,0 RT0
n P
T ,0  0
V RT
0 0

n P
T ,0
C   0
T ,0 V RT
0 0
Defining F
Fj 
T ,0
Cj  or
C
T ,0 F
V ,0
FV , f
Hence F
T ,0 P
C   0
T ,0 F RT
V ,0 0

or
RT
F F 0
V ,0 T ,0 P
0

Similarly RT
F F
V, f T P
 F F  P0  T 
 T   
Hence V, f
F F P  T 
V ,0 T ,0   0 
or
F  P0  T 
F F T   
V, f V ,0 F  P  T 
T ,0   0 

The ratio of total moles can be calculated for

 A 1

F  F  F X
T T ,0 A, 0 A
 F F
T  1   A,0 
F F A
T ,0 T ,0
F
T  1  y   1  
F A,0 A A
T ,0 ?
Recalling equation F  P0  T 
F F T   
V, f V ,0 F  P  T 
T ,0   0 
Substitution becomes

 P0  T 
FV , f  FV ,0 (1    A )   
 P  T0 
For constant C &P the equation becomes
F F (1  ) (1.18)
V, f V ,0 A
Substitution becomes j
F j ,0  F 
Fj A A, 0 A
Cj  
FV , f F (1 )
V ,0 A
Then Concentration for variable volume reaction system

C  jC 
j,0  A,0 A
C  A (1.17.3)
j 1
A
Progress Test 1.11
Copy and exercise how to derive

Bo. P41 Fig. 2.2 Express Concentration

Exercise 1.2 (Bo P2.2 p69)
A mixture of 28% SO2 and 72% air is
charged to a flow reactor in which SO 2 is
oxidized.
a) Set up a stoichiometric table using only
symbols the concentration of each
species in terms of its initial
concentration and the conversion S02
b) Taking SO2 as the basis of calculation,
evaluate the concentrations of each
species at various conversions (0; 0.25;
0.50; 0.75; and 1.00) when the total
pressure is 1485 kPa (14.7 atm) and the
temperature is constant at 2270C.
Exercise 1.3 Sulphur dioxide is burned with air at
250C and 1 atm in the following reaction
1
SO2  O2  SO3
2
The initial mixture contains 7 % SO2, 10 % O2
and 83 % N2 as inert. Determine for = 85 %.
Conversion of SO2
a) the composition of the product in terms
of mole fraction

b) the change of concentration of each

species at constant volume
1.5.3 Measurement of the quantity of
changes /Stoichiometry/ with
Multiple reactions in batch reactor
Example of Multiple reactions
2NH3  2.5O2  2NO  3H2O X NH  97 %
3
2NH3  1.5O2  N2  3H2O X NH  3 %
3
1.4.3.1 The mole changes with conversion
in batch system for multiple rxns
Consider multiple reactions:
aA  bB  cC  dD ( 1 ) X1, A 
1
 1

fC 
  2
gA  eE ( 2 ) X 2, A 2
Where:
X1,A : Conversion for the first reaction,

X2,A : Conversion for the second reaction,

 : Extent of reaction for the first rxn

1

2 : Extent of reaction for the second rxn
1 : Sto. coefficient for the first rxn
 2 : Sto. coefficient for the second rxn
We defined X1,A as the conversion of A to form C
and D in reaction 1 aA  bB  cC  dD

moles of A consumed by reaction 1

X 
1, A moles of A initially
and we define X2,A as the conversion of A to
form E in reaction 2
gA  fC  eE
moles of A consumed by reaction 2
X 
2, A moles of A initially
A) Mole change with extent of reaction
we know for single reaction,
n (t)  n    (t)
j j,0 j
for multiple reactions,
R
n  n   
j j,0 i, j i
i1 (1.18)

Changes in moles
R
n     (1.18.1)
j i1 i, j i
B) Concentration change with extent
of reaction
we know for single reaction,
C (t)  C   (t)
j j,0 j
for multiple reactions,
R
C  C   
j j,0 i1 i, j i (1.19)

Changes in concentration
R
C     (1.19.1)
j i1 i, j i
Progress Test 1.12 : Using stoichiometry relation
find the concentration of each species for the
following rxns C C C
j C C C C   j  j,0
3A → 2B A A,0

B B ,0
j

j
3 2
C C C
B + 2C→ D
C C C
B B ,0 C C ,0 D D ,0
 
2 1 2 1
C C  C C
B B ,0 3 A,0 A

C C
C ,0 C
C C 
B B ,0 2
C C C C
B B ,0 D D ,0
   2  
C C 
2 C C  C  2  C C 
C C ,0  B  C ,0  3  
 B , 0   A, 0 A 
 
C 2 C - C 
C  
 B , 0 B 
 C C C C
D D ,0 B ,0 B

C - C
C C  C ,0 C
D D,0 2

1  4  
C C    
C - C 
D D,0 2  3  A,0 A 

1  4  
C C    C - C 
D D ,0 2  3  A,0 A

 2  
C C    C - C 
D D ,0  3  A,0 A

 2  3  
C C     C - C 
D D ,0  3  2  B,0 B
C) Mole change with – conversion for
multiple reaction
For single reaction, we have

n j  n j ,0  j
n A, 0  A

Mole change, is expressed A

R
 i, j (1.20)
n n n i 1 
j j ,0 A,0 i, A
 i, A
Total mole (1.20.1)
R
  i
n n n i 1 
T T ,0 A,0 i, A
 i, A

i  i, pr  i, re



Progress Test 1.13

Consider the following reactions
aA  bB  cC  dD X1,A
gA  fC  eE X2,A
a) Write mole relationship vs conversion of
each species using A as a base for
calculating directly from the equation
b) Write Stoichiometry table
Solution
Mole relationship Vs conversion is given
R
 i, j
n n n i 1 
j j ,0 A,0 i, A
 i, A

Stoichiometry table Bo. p44

Mole fraction can be computed using the
relation

R
  i, j
n n i 1 
n
j
j ,0 A,0
 i, A i, A
y  
j n R (1.20.2)
T  i
n n i 1 
T ,0 A,0
 i, A i, A
Exercise1.4 Ammonia is oxidised with air on the
metal supported platinium catalyst. The following
gas phase reactions take place:
2NH3  2.5O2  2NO  3H2O X NH  97 %
3
2NH3  1.5O2  N2  3H2O X NH  3 %
3

The initial mixture of gases participating in the

;

reactions contains

11 % NH3 23.1 % O2 63 % N2 2.5 % H2O

Calculate the mole fraction of each species which

have left after.
Bo. P2.6
1.5.3.2 Measurement of the quantity of changes
with multiple reactions in a flow system
A) Molar flow rate vs Conversion in multiple
reactions
In a similar way for flow system we have
R
 i, j
n n n i 1 
j j ,0 A,0 i, A
 i, A

R
 i, j
F F F i1  (1.21)
j j,0 A,0  i, A
i, A
Progress Test 1.14
Consider the following reactions
aA  bB  cC  dD X1,A
gA  fC  eE X2,A
a) Write molar flow rate relationship Vs
conversion of each species using A as a
base for calculating directly from the
equation
b) Write Stoichiometry table
Molar relationship Vs conversion is given
R

 i, j
F F F i1 
j j,0 A,0  i, A
Bo. p46 i, A
1.5.3.3 Concentration change with
conversion for multiple reactions
a)Batch process R
 i, j
n n i 1 
j ,0 A,0 i, A
n
j  i, A (1.22)
C  
j V V
f f
i) Constant volume Vf = Vo

i, j
R
n n 
C 
j

j
C C i 1  (1.22.1
j j ,0 A,0 i, A
V
f
V
0  i, A
 R
C C  1 C   
T T ,0  A,0i1 i i,A
(1.22.2)
i,A

ii) Variable volume

The volume change for multiple reactions in a
batch process can be defined

 P0  T  n
V V    T
f 0 P  T n
  0  T ,0
  P0  T  n
V V    T
f 0 P  T n
  0  T ,0
Recalling

R
  i
n n n i 1 
T T ,0 A,0 i, A
 i, A

R
n n  
T 1 A,0 i1 i 
n n i, A
T ,0 T ,0 
i, A
 R
n  
T 1 y i1 i 
n A,0  i, A
T ,0
i, A

 R
 

   P  T 
V f  V0 1  y A,0 i 1 i  i , A  0  (1.23)

  P  T 
 i, A   0
 
We know fractional change / expansion
factor/ for multiple reaction as
 R R
 i  i
y i1   i1 
A,0  i, A  i, A
i, A i, A
 
R

 

  i

 
  P 



Then substituting

V V 1
 i 1    
 0   T 

f 0   i, A  P T 
  0 

 i, A 
 
 
For constant Temperature and pressure eq.
(h) becomes
 
R

 
 
 

V V 1 i1 i 
 

(1.23.1)
 
 
f 0  
 i, A 

 



i,A 


 Concentration for multiple
reactions as a function of
conversion in a variable volume
batch system under constant
temperature and pressure
R
 i, j
C C i 1 
j,0 A,0  i, A
C  i, A
j R
 i
(1.23.2)
1 i1 
 i, A
i, A
b) Flow process
Concentration vs Conversion in
multiple reactions for

Concentration in continuous reactor

F
C  j
j F
V, f

i) Constant volumetric flow rate

FV ,0  FV , f
 R
 i
C  C C i1 
j j,0 A,0  i,A
i,A

ii) Variable volumetric flow rate

The volumetric flow rate change for multiple
reactions in a continuous process can be defined
similarly
 R  T  P 
i 
1
F F 1  y    0 
V, f V ,0 
  A A,0 i 1 i, A  T  P
 0  
For constant temperature and pressure
 
 
 
R
F 1  1  
 
F  



V, f V ,0  i1 i i, A




i, A 




R
 i, j
F F i 1 
F j,0 A,0  i, A
C  j  i, A
j F 
R 

 i
 
V, f 




1 i1 
 
F 



V ,0 
  i, A 


 i, A 

 
 
Concentration for variable density /
volumetric flow rate/ for flow reactors
become

R
 i, j
C C i 1 
j,0 A,0  i, A
C  i, A (1.23.2)
j R
 i
1 i1 
 i, A
i, A
Stoichiometry in multiple reactions
Progress Test 1.15
Consider the following reactions
aA  bB  cC  dD X1,A ε1
gA  fC  eE X2,A ε2
Write concentration relationship of each
species at variable volume for batch
process using A as a base of calculation
R
 i, j
C C i 1 
j,0 A,0  i, A
C  i, A
j R
 i
Bo. p49 1 i 1 
 i, A
i, A
 1.6 Performance of chemical reactors
We have said
Chemical reaction engineering
 is the rational design and/or
analysis of performance of a
chemical reactors.
Reactors performance is measured by
Selectivity
Yield Load (Intensity)
Fraction of unreacted
Conversion
Throughput (capacity) Feed Rate
Consider multiple reactions
 A B B U
A nB
nA,0
nU
nA Unconverted
reactants
1.5.1 Selectivity
is defined in many ways:

1-Selectivity based on the key reactant

is the ratio between the amounts of a
desired product, B obtained with
respect of the key reactant converted
For a batch system

nA,0 - nA A n
Converted S  B
reactant in
B  B n A, 0  n A
side reactor (1.24.1)
For a flow system

A F
S  B
B  B F A, 0  F A
(1.24.2)
This definition refers to the performance of
the entire reactor as a whole, i.e. the
overall / integral/
If the system is also at constant density, this can
also be written C
S  B
(1.24.3)
B C A,0 - C A
2-Selectivity
is defined as the ratio formation of
the desired product, B divided by
the formation of all products
amount of desired product B formed
SB 
amount of all products formed
C
S  B (1.24.4)
B C  C
B U
For pure reactant, the following relations
exist C  C  C  CA
3-Selectivity selectivity is also defined on the
basis of reaction rate. This is the ratio of the rate
of production (reaction rate) of the desired
product to the unwanted product r
S
B
 B
r (1.24.5)
U

Differential selectivity/ local/ instantaneous

selectivity
For computational purposes it is often used the
differential selectivity. If there is a single
reactant A on which we can base the conversion
and selectivity, then the differential selectivity
(based on the product ratio) can be written as
dC
s  B (1.25)
B dC  dC
B U
For pure reactant, C C  C  CA
A,0 B U
C - CA  C  C
A,0 B U
- dC A  dC  dC
B U
Substituting we get
dC dC
s  B
- B
(1.25.1)
B dC  dC dC
B U A
Which is the rate of forming B divided by
the rate of loss of A or which determines to
what extent reactant A being is converted
into B at some place or at some moment.
This is a useful tool for choosing local
reaction conditions in any reactor.
  Differential/ instantaneous/
dC selectivity, for a single reactant
s  - B
B dC A, is the rate of forming B
A
divided by the rate of loss of A

 or which determines to what

dC extent reactant A being is
s  - B
B dC converted into B at some place
A
or at some moment.
 Or Differential selectivity quantity
dC indicates the direction of the desired
s  - B
B dC product of species B at a certain
A
reactant concentration of A.
Differential selectivity is sometimes
known as local selectivity, while it
serve as tools for choosing local
condition of the reaction.

 This is a useful tool for choosing

local reaction conditions in any
reactor
 The concentration of the desired
product is computed dC
s  - B
B dC
A
C C
B A
 dCB  -  sBdC A (1.25.2)
0 C dC
A,0 s  B
B dC  dC
B U

CA
C  -  s dC (1.26)
B B A
C A,0
  The total selectivity is also obtained
by integration of differential
selectivity
(1.27)
by calling the definition of Selectivity as
C - 1 CA
S  B
  s dC
B CA,0 - CA CA,0 - CA C B A
A,0

1.5.2 Conversion
n n C A, 0  C A
  An,0 A XA 
A A,0 C A, 0
1.5.3 Yield
It refers to the amount of a
specific product formed in
a given reaction process
per mole of entering
reactant and is defined as
desired product j formed
  (1.28)
j reac tan t fed
 n
 n B
B A,0 (1.28)

Yield is frequently used to describe

the behavior of the system in
which more than one reaction
takes place.
1.5.4Fraction n
of unreacted A,0

is the simplest and is usually found nA

directly when solving the component
balance equations
C A (t)
n (t) U
U  nA (1.29) C A,0 (1.29.1)
A,0

XA 1 - U (1.30)
e)Throughput (capacity) Feed Rate
This is the volumetric or mass flow rate through
the reactor system. 
mj
C
t
Where 
mj is the mass flow rate of species j
f) Load (Intensity)
This is the volumetric or mass flow rate per unit
reactor volume or catalyst mass.
 
C mj 1 mj 1
I  
V t V t W
Exercise 1.5
Suppose it is desired to make 1,4-dimethyl-
2,3-dichlorobenzene by the direct
chlorination of para-xylene.

The desired reaction is

p-Xylene + Cl2 → desired product + 2 HCl

A feed stream containing 40 mol % p-
xylene and 60 mol % chlorine was fed to
the reactor. The results of one experiment
in a batch reactor gave the following
results on a molar basis:
Compute various measures of reactor
performance.