Chemical Reaction Engineering

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CHEMICAL REACTION ENGINEERING

CONTENTS
1 INTRODUCTION 5
1.1 INTRODUCTION
1.2 TYPES OF CHEMICAL REACTIONS
1.3 RATE OF CHEMICAL REACTION
1.4 RELATIVE RATE OF REACTION
1.5 FACTORS AFFECTING THE RATE EQUATION
1.6 REACTION MECHANISM
1.7MOLECULARITY
1.8 ORDER OF REACTION
1.9 RATE CONSTANT
1.9.1 ARRHENIUS THEORY
1.9.2 COLLISION THEORY
1.9.3 TRANSITION STATE THEORY

2 HOMOGENEOUS SYSTEM 21
2.1 CONSTANT VOLUME SYSTEM
2.2 RATE EQUATION FOR DIFFERENT ORDER OF REACTIONS
2.2.1 ZERO ORDER REACTION
2.2.2 FIRST ORDER REACTION
2.2.3 SECOND ORDER REACTION
2.2.4 THIRD ORDER REACTION
2.3 HALF LIFE METHOD
2.4 RATE EQUATION FOR MULTIPLE REACTIONS
2.4.1 PARALLEL REACTIONS
2.4.2 SERIES REACTIONS
2.5 REVERSIBLE REACTION
2.6 AUTO CATALYTIC REACTION
2.7 VARIABLE VOLUME SYSTEM
2.7.1 RATE EQUATION FOR DIFFERENT ORDER OF REACTIONS
2.7.1.1 ZERO ORDER REACTION
2.7.1.2 FIRST ORDER REACTION
2.7.1.3 SECOND ORDER REACTION

3 DESIGN EQUATION 42
3.1 IDEAL BATCH REACTOR
3.2 FLOW PARAMETERS
3.3 IDEAL CSTR
3.4 IDEAL PFR

4 MULTIPLE REACTOR SYSTEM 51

4.1 CSTR IN SERIES
4.2 CSTR IN PARALLEL
4.3 PFR IN SERIES
4.4 PFR IN PARALLEL
4.5 TWO DIFFERENT TYPE OF REACTORS IN SERIES

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5 DESIGN OF MULTIPLE REACTION SYSTEM 60

5.1 PARALLEL REACTIONS
5.2 QUANTITATIVE TREATMENT OF PRODUCT DISTRIBUTION
5.3 SERIES REACTIONS

6 NON IDEAL FLOW REACTORS 89

6.1 RTD MEASUREMENT
6.1.1 PULSE INPUT EXPERIMENT
6.1.2 STEP INPUT EXPERIMENT
6.2 MEAN RESIDENCE TIME
6.3 RTD IN REACTORS
6.3.1 IN CSTR
6.3.2 IN PFR
6.4 REACTOR MODELING

7 EFFECT OF TEMPERATURE AND PRESSURE 109

7.1 HEAT OF REACTION
7.2 EQUILIBRIUM CONSTANT
7.3 EQUILIBRIUM CONVERSION
7.4 VAN HOFF EQUATION
7.5 RELATION BETWEEN TEMPERATURE AND CONVERSION
7.5.1 FOR ADIABATIC PROCESS
7.5.2 FOR NON-ADIABATIC PROCESS

8 HETEROGENEOUS SYSTEM 118

8.1 NON CATALYTIC REACTION SYSTEM
8.1.1 RATE EQUATION
8.1.2 RATE CONTROLLING CONCEPT
8.1.3 RATE EQUATION FOR PHYSICAL ABSORPTION
8.1.4 RATE EQUATION FOR ABSORPTION WITH CHEMICAL REACTION
8.1.5 HATTA NUMBER
8.2 CATALYTIC REACTION SYSTEM
8.2.1 STEPS OF CATALYTIC REACTION
8.2.2 RATE EQUATION FOR PORE DIFFUSION AND SURFACE REACTION
8.2.3 EFFECTIVENESS FACTOR
8.2.4 CHARACTERISTIC LENGTH
8.2.5 THIELE MODULUS
8.2.6 FOR STRONG PORE DIFFUSION RESISTANCE
8.3 EFFECTIVE DIFFUSIVITY
8.4 DESIGN EQUATION FOR REACTORS CONTAINING POROUS CATALYST
8.5 ACTIVITY OF CATALYST
8.6 DEACTIVATION OF CATALYST

9 MULTIPLE CHOICE QUESTIONS - LEVEL 1 137

10 MULTIPLE CHOICE QUESTIONS - LEVEL 2 157

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CHAPTER 1

INTRODUCTION
1.1 INTRODUCTION

Chemical Reaction Engineering is primarily knowledge of chemical kinetics and reactor

design that distinguishes the chemical engineer from other engineers. The successful and
economic design of chemical reactor is the aim of Chemical Reaction Engineering.

Design of the reactor is no routine matter, and many alternatives can be proposed for a
process. In searching for the optimum it is not just the cost of the reactor that must be
minimized. One design may have low reactor cost, but the materials leaving the unit may
be such that their treatment requires a much higher cost than alternative designs. Hence, the
economics of the overall process must be considered.

Reactor design uses information, knowledge, and experience from a variety of areas-
thermodynamics, chemical kinetics, fluid mechanics, heat transfer, mass transfer, and
economics. Chemical reaction engineering is the synthesis of all these factors with the aim
of properly designing a chemical reactor. To find what a reactor is able to do we need to
know the kinetics, the contacting pattern and the performance equation.A general chemical
process is shown below:

The Thermodynamics gives information about the

Feasibility of a reaction
Heat of reaction
Maximum possible extent of reaction

Chemical Reaction Engineering gives information about the chemical kinetics; Chemical
Kinetics is the study of chemical reaction rates (speed) and reaction mechanism (steps
reaction occurs)

Rate at which chemical reaction occurs

Effect of parameters (Temperature, Pressure &Composition) on the reaction rates.
Order of reaction / Type of reaction

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Since CRE focus on reactor design, the information required to predict what a reactor can do are
contacting pattern, kinetics and performance equation. CRE further deals with finding the
expression to relate input to output for various kinetics and various contacting patterns, or

output = f [input, kinetics, contacting]

This is called the performance equation. Why is this important? Because with this expression we
can compare different designs and conditions, find which is best, and then scale up to larger
units.

Contacting pattern means how material flow through and contact with in reactor or how early or
late they mix, their state of aggregation.

Kinetics means how fast things happen. If very fast then equilibrium tells what will leave the
reactor and if not so fast, than rate of chemical reaction will determine what will happen.

1.2 TYPES OF CHEMICAL REACTIONS

Chemical reactions can be classified on the basis of various parameters as follows:

i. On the basis of phase of reacting solution

Homogeneous / Heterogeneous Reactions

A reaction is homogeneous if it takes place in one phase alone. A reaction is heterogeneous if it

requires the presence of at least two phases to proceed at the rate that it does. It is immaterial
whether the reaction takes place in one, two, or more phases; at an interface; or whether the
reactants and products are distributed among the phases or are all contained within a single
phase. All that counts is that at least two phases are necessary for the reaction to proceed as it
does. Sometimes this classification is not clear-cut as with the large class of biological reactions,
the enzyme-substrate reactions. Here the enzyme acts as a catalyst in the manufacture of proteins
and other products. Since enzymes themselves are highly complicated large-molecular-weight
proteins of colloidal size, 10-100 nm, enzyme-containing solutions represent a gray region
between homogeneous and heterogeneous systems. Other examples for which the distinction
between homogeneous and heterogeneous systems is not sharp are the very rapid chemical
reactions, such as the burning gas flame. Here large non-homogeneity in composition and
temperature exist. Strictly speaking, then, we do not have a single phase, for a phase implies
uniform temperature, pressure, and composition throughout. The answer to the question of how
to classify these borderline cases is simple. It depends on how we choose to treat them.

ii. On the basis of catalyst presence

Catalytic / Non-catalytic Reactions
iii. On the basis of number of molecules participating in reaction
Uni-molecular / Poly molecular Reactions
iv. On the basis of heat of reaction
Endothermic / Exothermic Reactions

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v. On the basis of order of reaction

Zero / First / Second / Nth Order Reactions
vi. On the basis of steps involving in reaction completion
Elementary / Non elementary Reactions
vii. On the basis of reaction direction
Irreversible / Reversible Reactions

1.3 RATE OF CHEMICAL REACTION

The rate of reaction tells us how fast a number of moles of one component species are
being consumed to form another chemical species. The term chemical species refers to any
chemical component or element with a given identity.

dNA
We express the rate as the rate of disappearance of component A as The rate of
dt
change of A (in no. of moles of A). The negative sign indicates that disappearance of
reactant A during reaction.

The rate of reaction can be expressed in various forms as follows:

i. Based on unit volume of reacting fluid

1
=

ii. Based on unit mass of solid in fluid solid system
1
=

iii. Based on unit surface of solid in gas-solid system
1
" =

The reaction rate is an intensive quantity & depends on concentration& temperature. From
above rate equations, weve

= ( ) = "

GATE Tip

The reaction rate is an intensive quantity.

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1.4 RELATIVE RATE OF REACTION

The relative rate of reaction of various species involved in a reaction can be obtained from
the ratio of stoichiometric coefficients. For reaction given below

aA +bB cC + dD . (1.1)

We see that for every a mole of A reacted with b mole of B produces c mole of C and d
mole of D. In other words

Rate of Formation of C = (Rate of disappearance of A)

= ( )

= ( )

The relationship can be expressed directly from stoichiometry of reaction,

= = =

1.5 FACTORS AFFECTING THE RATE OF REACTION

i. Nature of reactant & product

ii. Concentration of reactants

iii. Temperature

iv. Pressure

v. Nature of catalyst

vi. Surface area of reactant

vii. Rates of heat & mass transfer

1.6 REACTION MECHANISM

It refers to a step or series of steps by which the initial reactants interact in the process of
forming products. A reaction usually does not take place in the single step rather takes
place in a series of steps which when added gives the overall stoichiometric equation, these
steps are the mechanism of reaction

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e.g.

2A+BR+S

Might take place as

A + B AB

A + AB A2B

A2B AB + R

AB S

2A + B R + S

The slowest step controls the rate of the chemical reaction & determines the form of overall
rate equation.

1.7 MOLECULARITY

The Molecularity of a reaction is the number of atoms, ions or molecules involved

(colliding) in a reaction step. It is the number of molecules, ions or atoms interacting or
colliding in any one reaction step.

GATE Tip

Molecularity of a reaction must be a whole number and never be zero or a fraction.

1.8 ORDER OF REACTION

The order of a reaction refers to the powers to which the concentrations are raised in the
kinetics rate law. This is experimental quantity. The algebraic equation that relates to
the species concentrations is called the kinetic expression or rate law.

For above reaction 1.1, the rate law can be expressed as

= [kA(T)][f(CA,CB,.)]

The dependence of the reaction rate, , on the concentration of the species present, f(Cj),
is almost without exception determined by experimental observations. One of the most

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acceptable and general form to relate this theory is power law model. Here the rate law is
the product of concentrations of the individual reacting species, each of which is raised to a
power, e.g.

= kACACB

The exponents of the concentration n above equation lead to the concept of reaction order.

The reaction order with respect to reactant A is and with respect to reactant B is . Here,
the overall order of reaction, n, is

n=+

GATE Tip

The dimensions of the rate constant k for the nth-order reaction are (time)-1
(concentration)1-n where n is the overall order of the reaction.

dC A
Example 1.1 For the gaseous reaction, the rate expression is kC An . Find the rate
dt
equation in terms of partial pressure (pA)
Solution: For gases
PV nRT
n
P RT
V
P CRT
n
where C = , write this equation for component A as
V
dpA
pA CART and dCA and put in given rate equation
RT
hence
n
dp A p
k A
RT .dt RT
dp A
k p A .( RT )1 n
n

dt

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Example 1.2 For a reaction A 3B 5C 7 D .Which is correct:

1 1 1
(a ) rA rB rC rD (Direct solution from article 1.4)
3 5 7
(b) rA 3rB 5rC 7 rD
1
(c) rA rB 5rC 7rD
3
1 1 1
(d ) rA rB rC rD
3 5 7
Example 1.3 For a rate expression, rA kCA CB , overall order of reaction is:
0.7 0.3

(a) 0.7 (b) 0.3 (c) 0.4 (d) 1

(Direct solution from article 1.8)

1.9 RATE CONSTANT (k)

The term k referred to as either specific reaction rate or the rate constant. It is almost
strongly dependent on temperature. In gas phase reactions, it may be a function of total
pressure. In liquid systems it can also be a function of other parameters, such as ionic
strength and choice of solvent. There are various theories giving the relation for
dependency of kA on Temperature. These theories are as follows:

1.9.1ARRHENIUS THEORY

For a reaction to occur it is first necessary to break or weaken the bonds between atoms &
molecules of the reactant which require a definite amount of energy. If colliding molecules
do not passes this energy a collision between then does not result in the formation of new
molecules. The minimum amount of energy which the colliding molecules must have in
order to bring about the reaction is knows as activation energy.

k k0e E / RT

Where,k0= Pre Frequency Factor and it has dimension as rate constant k but it is
independent of temperature

E = Activation Energy

Let log on both side of equation, we get

E 1
ln k ln ko
R T
E 1
ln k ln ko
R T

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If the rate is known at two different Temperature T1&T2, we can evaluate E.

r2 E 1 1
ln
r1 R T1 T2

E1 1
ln k2 / k1 =
R T1 T2

1.9.1 COLLISION THEORY

For bimolecular reactions,

k T 1/2e E / RT It fails with uni-molecular reactions.

1.9.2 TRANSITION STATE THEORY

It is based on statistical mechanics collision based on kinetic theory of gases.

Transition state theory views that formation of activated complier is very rapid where as
collision theory view that decomposition of activated compiler is very rapid.

k T .e E / RT

because the exponential term is so much more temperature-sensitive than the pre-exponential
term, the variation of the latter with temperature is effectively masked, and we have in effect

k k0e E / RT

Activation Energy and Temperature Dependency

The temperature dependency of reactions is determined by the activation energyand temperature

level of the reaction.

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1.From Arrhenius' law a plot of In k vs 1/T gives a straight line, with large slope for large E and
small slope for small E.

2. Reactions with high activation energies are very temperature-sensitive while reactions with
low activation energies are relatively temperature-insensitive.

3. Any given reaction is much more temperature-sensitive at a low temperature than at a high
temperature.

4. From the Arrhenius law, the value of the frequency factor k, does not affect the temperature
sensitivity.

1 1
Example 1.4 For a reaction A + B R + S has the rate equation rA 2CA0.5CB , what is
2 2
rate equation for given reaction A + 2 B 2R+S

Solution: Since, order of reaction does not depend on stoichiometric coefficient for non-
elementary reaction. Hence, Reaction rate will be same as rA 2CA0.5CB .

Example 1.5 On doubling the concentration of reactant the rate of reaction triples find the
reaction order:
(a) 1 (b) 2 (c) 1.6 (d) 0.6

Solution:
rA 2 kC An 2

rA1 k CnA1
3(rA1 ) k (2CA1) n

rA1 k CnA1
3 2n
ln 3 n ln 2
n 1.589
n 1.6

Example 1.6 The activation energy of a bimolecular reaction is about 9150 cal / mol, how
much faster this reaction will take place at 500 K then at 400 K.
(a) 9 times (b) 16 times (c) 10 times (d) 6 times

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Solution: from Arrhenius law, k k 0e E / RT

r E 1 1
Or ln 2
r1 R T1 T2
r 9150 1 1
ln 2
r1 1.98624 400 500
r r2
l n 2 2.303 e 2.303 10
r1 r1
r2 10(r1 )

Example 1.7 At 500 K, reaction is 10 times faster than that of at 400 K, find the
activation energy (E), by Collision theory,
(a) 9150 cal / mol (b) 10,150 cal / mol
(c) 8707 cal / mol (d) 7808 cal / mol

Solution: from Collision theory, k T 1/2 .e E / RT

Or
k T E 1 1
ln 2 ln 2
k1 T1 R T1 T2
k 500 E 1 1
ln 2 ln
k1 400 1.98624 400 500

cal
E 8707
mol

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Past GATE Questions on Concept of Rate Equation

1. Molecularity of an elementary reaction P + QR + S is

A) 1 B) 2 C) 3 D) 4

2. For the reaction A + B 2B + C

A) rA = rB B) rA = -rB C) rA = 2rB D) rA = rB/2

3. The experimentally determined overall order for the reaction A + B C + D is

two. Then the
A) reaction is elementary with a molecularity of 2.
B) molecularity of the reaction is 2, but the reaction may not be elementary,
C) reaction may be elementary with a molelcularity of 2,
D) reaction is elementary but the molecularity may not be 2,

4. The extent of a reaction is

A) different for reactants and products
B) dimensionless
C) dependent on the stoichiometric coefficients
D) all of the above

5. For the reaction 2R + S T, the rates of formation, rR, rS and rT of the substances R, S
and T respectively, are related by
A) 2 rR = rS = rT B) 2 rR = rS = rT
C) rR = 2 rS = 2 rT D) rR = 2 rS = 2 rT

6. Which is the correct statement from the following statements on the Arrhenius model of
the rate constant k = Ae -E/RT?
A) A is always dimensionless
B) For two reactions 1 and 2, if A1 = A2 and E1> E2, then k1 (T) >k2 (T)
C) For a given reaction, the % change of k with respect to temperature is higher at lower
temperatures.
D) The % change of k with respect to temperature is higher for higher A.

7. The rate expression for the reaction of A is given by

The units of k1 and k2 are, respectively,

A) (mol-1 m3 s-1), (mol-1/2 m3/2) B) (mol-1 m3 s-1), (mol-1/2 m3/2)

C) (mol m3 s-1), (mol-1/2 m3/2 s-1) D) (mol-1 m3 s-1), (mol-1/2 m3/2 s-1/2)

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Solutions
Q. No. Ans.

1. C

2. B

3. A

4. D

5. D

6. C

7. A

Explanatory Answer:

3. Ans: (A)

Explanation: A + B C + D
Given, order of the reaction is 2.
This equation is elementary with a molecularity of 2.
5. Ans: (D)
Explanation: 2R + S T
The rates can be written for different substances as
rR = 2rs = 2rT
6. Ans: (C)
Explanation: The rate constant from Arrhenius model
k = AeE/RT
Option (a)
eE/RT is dimensionless
Units of k and A are same.
A is not dimensionless.
Option (b) if A1 = A2
1
k1 E1 E2
= e RT
k2
If E1 > E2
k 1 > k2
Option (c) k = AeE/RT

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E
ln k = ln A
RT
Differentiate w.r.t. T,
d ln k E
=
dT RT 2
d ln k
For lower temperature, will be higher.
dT
correct statement.
Option (d)The percentage change of k w.r.t temperature is not related to A as can
be seen in option (c).

7. Ans: (A)
k1C2A
Explanation: Given, rA =
1 k 2C1/2
A

Or ( rA) + ( rA) k 2C1/2 1/2

A = k 2 CA

Each term in this equation will have same unit, i.e. ( rA).
The unit of ( rA) = mol
3
m s
mol
unit of 2
k1C = 3
A
m s
2
mol m
3
Or k1 = 3 mol
m s
Or k1 = mol1 m3 s 1
Now, unit of ( rA) k 2C1/2
A = unit of ( rA)
1/2

Or k2 mol3 = 1
m
Or k2 = mol1/2 m3/2

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Past GATE Questions on Concept of Arrhenius Equation

1. The units of frequency factor in Arrhenius equation,

A) Are the same as those of the rate constant.
B) Depend on the order of the reaction.
C) Depend on temperature, pressure etc. of the reaction.
D) Are cycles per unit times.

2. The dimensions of rate constant for reaction 3AB are (1 /g mole)/min. Therefore the
reaction order is
A) 0 B) 1 C) 2 D) 3

3. From Collision Theory, the Reaction Rate Constant Is Proportional To

4. For reaction P + 2Q 3R, molar rate of consumption of P is

A) double of that of Q B) same as that of Q,
C) half of that of Q D) 2/3 of that of Q

5. Overall order of reaction for which rate constant has units of (mol/L) -(3/2) sec-1 is
A) 3/2 B) C) 3/2 D) 5/2

6. The rate expression for the gaseous phase reaction CO + 2H2 CH3OH is given by
r = k1 co H k 2 CH
2 3

OH Which of the following is NOT possible?

A) = 1, = 1, = 1 B) = 1, = 2, = 1
C) = 1/3, = 2/3, = 1/3 D) = 1/2, = 1, = 1/2

7. For a homogeneous reaction system, where

Cj is the concentration of j at time t
Nj is the number of moles of j at time t
V is the reaction volume at time t
t is the reaction time.
The rate of reaction for species j is defined as

dC j dC j 1 dN j 1 dN j
A) B) C) D)
dt dt V dt V dt

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8. The rate constant of a chemical reaction increases by 100 times when the temperature is
increased from 400 K to 500 K. Assuming transition state theory is valid, the value of
E/R is
A) 8987 K B) 9210 K, C) 8784 K D) 8621 K,

9. At a given value of E/R (ratio of activation energy and gas constant), the ratio of the rate
constants at 500 K and 400 K is 2 if Arrhenius law is used. What will be this ratio if
transition-state theory is used with the same value of E/R?
A) 1.6 B) 2 C) 2.24 D) 2.5

10. The following rate-concentration data are calculated from experiment. Find the
activation energy temperature (E/R) of the first order reaction.
dp CA rA T

1 20 1 480

2 40 2 480

2 40 3 500

A) 2432.8 B) 4865.6 C) 9731.2 D) 13183.3

Solutions
Q. No. Ans.
1. A
2. C
3. D
4. A
5. D
6. A
7. C
8. C
9. D
10. B

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Explanatory Answer:

6. Ans: (A)

Explanation: CO + 2H2 CH3 OH

The rate of reaction
y
r = k1 pCO pH k2 pCH3OH
2

For this gas phase reaction , and should be in proportion to their respective
stoichiometric coefficients
Thus : : = 1 : 2 : 1
Option (a) is correct as : : 1 : 1 : 1.

7. Ans: (C)

1 dN i
Explanation: Rate of reaction =
V dt
10. Ans: (B)

Explanation: For first order reaction,

rA = kCA
or rA = A0CA eE/RT
or In
rA = In A E
0
CA RT

Draw the graph between, In

rA and 1
by using given data. The slope of this graph
CA T

will be E .
R
E
= 4865.6
R

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