CHEMICAL ENGINEERING [GATE-2021] CRE

CHEMICAL ENGINEERING
REVISED AS PER GATE-2021

STUDY MATERIAL

CHEMICAL REACTION ENGINEERING-CRE

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CHEMICAL ENGINEERING [GATE-2021] CRE
GATE 2021 Syllabus: Chemical Engineering - CH.
Chemical Reaction Engineering: Theories of reaction rates; kinetics of homogeneous reactions,
interpretation of kinetic data, single and multiple reactions in ideal reactors, non-ideal reactors;
residence time distribution, single parameter model; non-isothermal reactors; kinetics of
heterogeneous catalytic reactions; diffusion effects in catalysis.
CONTENT
1. INTRODUCTION AND BASIC CONCEPT ……………………………………. 03-09

2. KINETICS OF REACTION ………………………………………………………. 10-19

3. INTERPRETATION OF BATCH REACTOR DATA ………………………… 20-34

4. DESIGN EQUATION FOR IDEAL REACTORS …………………………….. 35-46

5. DESIGN FOR SINGLE REACTION……………………………………………… 47-69

6. DESIGN FOR MULTIPLE REACTIONS ……………………………………… 70-84

7. TEMPERATURE AND PRESSURE EFFECTS …………………………….. 85-94

8. BASIC ASPECTS OF NON IDEAL FLOW ………………………………….. 95-107

9. HETEROGENEOUS REACTION ………………………………………………. 108-118

10. QUESTION BASED ON GATE PAPER …………………………………….. 119-128

11. MODEL TEST PAPER-I WITH SOLUTION …………………………………. 129-141

12. PRACTICE SET-1 ………………………………………………………………… 142-146

13. PRACTICE SET-2 ………………………………………………………………… 147-167

14. PRACTICE SET-3 Subjective Question ………………………………… 168-180

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CHEMICAL ENGINEERING [GATE-2021] CRE

CHAPTER-1
INTRODUCTION AND BASIC CONCEPT
Every industrial chemical process is designed to produce economically a desired product from a variety of
starting material through a succession of treatment steps.

Figure: Typical chemical process.

Raw material undergoes a number of physical steps to put them in the form in which they can be reacted
chemically. Then material passes through the reactor. The products of reaction must then undergo for further
treatment. In chemical reaction engineering subject we are concerned with chemical treatment step of a process.
CRE combines the study of chemical kinetics (reaction rates and reaction mechanisms) with the reactors in
which the reaction occurs.

Chemical Reaction: When any chemical starts to losing their identity, then we can say it reacts. Chemical
reaction takes place by decomposition, combination or change in configuration of molecules. Chemical reaction
may be classified depending upon so many factors, given below:
 Based upon number of phase involved: Homogeneous and Heterogeneous reaction.
 Based upon catalyst used or not: Catalytic and non-catalytic reaction.
 Based upon the molecularity i.e. number of molecules that takes part in the reaction: Unimolecular,
bimolecular and tri-molecular reaction.
 Based upon heat evolved or absorbed: Exothermic and endothermic reaction
 Based upon reaction takes place in one or both directions: Reversible or irreversible reaction.
 Based upon order of reaction: First order, second order and third order reaction.
 Based upon single or multiple reaction takes place: Single and multiple reaction.
 Based upon number of steps present in a reaction: Elementary and non-elementary reaction

Rate of Reaction: We define rate of reaction in terms of component. If the rate of change in number of moles
dNi
of this component due to reaction is then,
dt
1 dNi Moles of i formed
ri  
V dt (Volume of fluid) (Time)
i.e., the number of moles of component i formed per unit time per unit volume (mol/dm3s). If species i is a
reactant, the numerical value of ri is a negative number (e.g. ri = –3mol/dm3.s or –ri = 3mol/dm3.s)
If species i is a product, then ri = will be a positive number.
The rate of reaction can be a large value to essentially zero.
For constant volume system :

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CHEMICAL ENGINEERING [GATE-2021] CRE
d  Ni  d dC
ri     (Ci )  i
dt  V  dt dt
where, Ci is the concentration of species i in reaction mixture.

Relative rates of reaction:

For the reaction:
aA  bB  cC  dD
The relation between the rate of participants A, B, C, D in chemical reaction with their stoichiometric coefficient
 rA  rB rC rD
is:   
a b c d
 rA rC
Also, if we compare 
a c
a
 rA  rc
c
a
Rate of disappearance of A = (Rate of formation of C)
c
Factors affecting rate of reaction: Many variable may affect the rate of a chemical reaction. In
homogeneous system the temperature, pressure and composition affect the rate of reaction.
In heterogeneous system factors that affect the rate of reaction are rate of mass transfer i.e., heat transfer nature
of catalyst if present.
Note (1) Rate of reaction can also be given as:
i) Based on unit mass of solid in fluid-solid system,
1 dNi moles of i formed
ri '  
W dt (mass of solid)(time)
ii) Based on unit interfacial surface in two-fold systems or based on unit surface of solid in gas-solid system,
1 dNi moles of i formed
ri "  
S dt (surface) (time)
iii) Based on unit volume of solid in gas-solid systems,
1 dNi moles of i formed
ri "'  
Vs dt (volume of solid) (time)
iv) Based on unit volume of reactor, if different from the rate based on unit volume of fluid,
1 dN i moles of i formed
ri ''''  
Vr dt (volume of reactor)(time)
(2) Relation between different rate of reactions:
(ri )V  (ri ')W  (ri ") S  (ri "')Vs  (ri "")Vr

Rate law:
An algebraic equation that relates the reaction rate and concentration is known as rate law.
A  B  PRODUCTS
–rA  k A (T )  f n (C A , CB ) 
or
 rA  k A C A CB

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kA  Rate constant/ specific reaction rate
Order of reaction (n) =  + 
For the reaction where all the stoichiometric coefficients are 1, e.g.
A+BC+D
k A  k B  kC  k D  k
Important. Rate Laws Are determined by experimental observation.
1. A homogeneous reaction is one which takes place in only one phase; i.e., all the reacting material and
products and catalyst (if any) will be present in a similar phases.
1
Example: NO( g )  O 2 ( g )  NO 2 ( g )
2
A hetrogeneous reaction is one which involves the presence of more than one phase.
1
Example: SO 2 ( g )  O 2 ( g ) 
V2 O 5 ( s )
 SO 3 ( g )
2
2. Catalytic reaction are those reaction which involves use of catalyst to enhance the rate of reaction.

Example: C 2 H 4  H 2 
Ni
Heat
 C2H6
Ethylene Ethane

Non catalytic reactions are those reaction which does not involve use of catalyst.
1
Example: NO  O 2  NO 2
2
3. (a) Unimolecular Reaction: Reaction of single molecule.
H 2 C — CH 2
Example: | | 
Decomposition
 2C2 H 4
H 2 C — CH 2
(b) Bimolecular Reaction: Reaction between two molecules.
2 HI( g ) 
Decomposition
 I2 ( g )  H 2 ( g )
(c) Trimolecular Reaction:
2 NO  O 2  
Oxidation
 2 NO 2
4. The reaction may be classified as exothermic and endothermic reaction.
Exothermic reaction is one in which heat is evolved.
CO  2H2  CH3 OH  Heat
Cu
Example:
Endothermic reaction is one in which heat is absorbed
C 2 H 5 OH 
Al2 O3
Dehydration
 C 2 H 4  H 2 O  Heat
ethyl alcohol

5. The reaction may be classified as reversible and irreversible reaction. Reversible reaction are those in
which forward and reverse reaction takes place simultaneously.


H
C2 H 5 OH  CH 3COOH  CH 3 COOC 2 H 5  H 2 O
Irreversible reaction are those which can proceed only in one direction.
C6 H 6  HNO3  C6 H 5 NO 2  H 2 O

6. The reaction may be classified as first order, second order and third order reaction.
First order reaction:
1
Example: N 2 O 5 
Decomposition
 NO 2 + O 2
2

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Second order reaction: (Saponification of ester)
Example: CH 3COOC 2 H 5  NaOH  CH 3COONa  C2 H 5 OH

Third order reaction:

Example: 2 NO  H 2  N 2 O  H 2 O

7. Single and Multiple Reaction:

(a) When a single stoichiometric equation and single rate equation are chosen to represent the progress of
the reaction, we have a single reaction.
(b) When more than one rate equations are chosen to represent the progress of the reaction, we have a
multiple reaction.
Multiple reaction may be classified as.
Series Reaction: A  B  S
Parallel Reaction:
B A  B
A
and C  S
S Side by side
Competitive
Type

Complicated Reaction:
A  B  C
C  B  D
Here reaction proceeds in parallel with respect to B but in series with respect to A, C and D.
8. Elementary and Non Elementary Reaction:
Consider a single reaction with stoichiometric equation A  B  C
According to rate law, rate of disappearance of A is given by
 rA  K C A C B
Such reaction in which the rate equation corresponds to a stoichiometric of equation are called elementary
reaction.
When there is no direct corresponding rate and stoichiometric, then the reaction is called non-elementary
reaction. In other words, elementary reaction is a single step reaction whereas non-elementary reaction is
multistep reaction. The best example of a non-elementary reaction is that between hydrogen and bromine.
H 2  Br2  2 HBr
1
K [H ][Br2 ] 2
Which has rate expression: rHBr  1 2
[HBr]
K2 +
[Br2 ]
Molecularity and Order of Reaction:
The molecularity of an elementary reaction is the number of molecules involved in the reaction and this has been
found to have the values of one, two or occasionally three.
Molecularity refers only to an elementary reaction.
Consider a reaction aA  bB  cC  d D  P

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then rate expression  rA  K C Aa C bB C Cc C Dd  a+b+c+d=n
where a, b, …….. d are not necessarily related to the stoichiometric coefficient.
We call the power to which the concentration are raised the order of reaction. Hence the reaction is
- ath order with respect to A
- bth order with respect to B
- nth order overall
 Since the order refers to the empirically found rate expression, it may not to be an integer and can have a
fractional value.
 But, the molecularity of a reaction must be an integer because it refers to mechanism of reaction and applies
only to elementary reaction.

Rate constant (K):

The rate constant of a chemical reaction is a measure of the rate of reaction when all the reactants are at unit
concentration.
So, for any reaction say A  B
 rA  k C A
If we assume that the concentration are equal to unity then  rA  K
Where K is rate constant. The rate constant K depends on the temperature. It increasees with temperature. K is
also called specific rate constant.
The units of K depends upon the units of time and concentration.
Suppose :  rA  K C An
Then we know units of ( rA )  mol/l. sec
 mol 
and CA   
 lit. 
mol
sec. 1 n
 mol 
k  lit . n  (sec) 1 
 mol   lit . 
 
lit .
k  (time) 1 (concentration)1  n where, n is the order of reaction.

9. 
For reversible reactions: A 
FORWARD
BC
BACKWARD

kA
Equilibrium constant (kC) =
k A
kA  Rate constant of forward reaction
k-A  Rate constant of backward reaction

During the course of a chemical reaction, the rate of a reaction decreases as the reaction proceeds

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Solved Example
Q.1. For a homogeneous reaction system, where Ci is the concentration of i at time t, Ni is the no. of moles of i
at time t, V is the reaction volume at time t and t is the reaction time. The rate of reaction for species i is
defined as
dCi  dC  1 dN i  1 dNi 
(a.) (b.)   i  (c.) (d.)   
dt  dt  V dt  V dt 
Ans. c
Q.2. For an elementary reaction A  2 B  k
 3C
(a.) Rate of appearance of C is equal to rate of disappearance of A
(b.) Rate of disappearance of A is equal to rate of disappearance of B.
(c.) Rate of appearance of C is equal to rate of disappearance of B.
(d.) Rate of appearance of C is 3 times rate of disappearance of A.
ANS: c
rA  rB rC  Relative Rates 
   
1 2 3 of reaction 
 rA = rate of disappearance of A
 rB = rate of disappearance of B
rC = rate of appearance of C
 rC  3( rA )

Q.3. Rate expression of reaction

 rA  0.02 C A2 mol/cm 3 min
If concentration is to be expressed in mol/l and time in hours, the value of rate constant would be
(a.) 0.12hr-1 (mol/l)-1 (b.) 0.012hr-1(mol/ l)-1
-1 -1
(c.) 12hr (mol/ l) (d.) 1.2hr-1(mol/ l)-1
ANS: (c)
1L = 10cm3
1hr = 60min
mol
 rA  0.02C A2 2
 1  1
    hr
10 60
mol
 rA  0.02C A2  600
l hr
 rA  12C A2 mol l 1hr 1
Clearly k  12
rA molL1hr 1
unit of k    unit of k  mol 1l hr 1
C A2 mol 2l 2
k  12hr 1 (mol / l ) 1

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