CHE 2001 – Chemical Reaction Engineering

Dr. K. Sivagami
Associate Professor,
Department of Chemical Engineering – VIT, Vellore
Mail: sivagami.k@vit.ac.in
Chemical Reaction Engineering
 Books

O. Levenspiel, Chemical Reaction Engineering, 3rd Ed., Wiley

Publications, 1999.
Reference Books
H.S. Fogler, Elements of Chemical Reaction Engineering, 3rd
Ed., Prentice Hall India Pvt. Ltd.
Gilbert F Froment, Kenneth B Bischoff and Juray D Wilde
"Chemical Reactor Analysis and Design", John Wiley& Sons
J.M. Smith, Chemical Engineering Kinetics, 2nd Ed., McGraw-
Hill, 1981.
An Introduction to Chemical Engineering Kinetics and Reactor
Design – Charles G. Hill, Jr.
Books
 History
• 1944: Denbigh (UK) publishes his paper on "Velocity and Yield in Continuous Reaction
Systems“ (1944).
• 1947: Hougen and Watson (USA) publish Part 3 of "Chemical Process Principles: Kinetics
and Catalysis. (See p. 1012 for a plot of reciprocal rate vs. conversion.)
• 1953: Danckwerts (UK) publishes his paper on "Continuous Flow Systems -- Distribution of
Residence Times" (Chem. Eng. Sci. 2, 1-13, 1953).
• 1956: J. M. Smith (USA) publishes his "Chemical Engineering Kinetics."
• 1957: First symposium on CRE, at the 12th Meeting of the European Federation of
Chemical Engineering.
• 1958: W. Brötz (Germany) publishes "Fundamentals of Chemical
Reaction Engineering" (English translation of "Grundriss der chemischen
Reaktionstechnik," published in 1965).
• 1959: S. M. Walas (USA) publishes "Reaction Kinetics for Chemical
Engineers."
• 1962: O. Levenspiel (USA) publishes "Chemical Reaction Engineering."
 CHE2001 CHEMICAL REACTION ENGINEERING

1. CONCEPTS
2. KINETICS OF HOMOGENEOUS REACTIONS
3. CONVERSION AND REACTOR SIZING
4. ANALYSIS OF RATE DATA
5. ISOTHERMAL REACTOR DESIGN
6. MULTIPLE REACTOR
7. NON ISOTHERMAL REACTORS
8. NON-IDEAL REACTORS
9. CATALYSIS AND CATALYTIC REACTORS
10. ADIABATIC TUBULAR REACTOR DESIGN

7
Chemical Reaction Engineering (CRE) is the field that
studies the rates and mechanisms of chemical reactions
and the design of the reactors in which they take place.

10
 REACTORS occupy a
central role in every
chemical process

inside reactors a bulk of chemical

transformations take place

Chemical engineer has the ability to analyze systems in which chemical

reactions occur and to apply the results of the analysis in a manner
that benefits society. Scaleup & Commercial plant

11
The Most Common Chemical Reactor in the World

12
Automotive catalytic converter
Automotive catalytic converter (ACC)
There are >50 million automotive catalytic
converters operating throughout the world.
The catalytic converter is a tube wall
reactor in which a noble-metal impregnated
on an monolith mesh surface on which
reactions occur.

13
 FCC Reactor

The FCC reactor is

without question the
most complex and
important equipment in
chemical engineering.

It is only second to ACC

in amount of reactants
processed.

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Polymers, Plastics

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 The human reactor

HCl and enzymes (E)

catalyze most reactions.

The food mixes in the stomach (volume 0.5 liter), but its feed is
semibatch: - a transient CSTR.

Next the acidified food passes into the small intestine (a reactor 3/4
in. in diameter and 20 ft long), where it is neutralized and mixed with
more enzymes from the pancreas. This is the primary chemical reactor
of the body, operating with secreted enzymes and with E. coli bacteria
catalysts.
 Chemical Reaction
A chemical reaction is a process that leads to the
chemical transformation of one set of chemical substances
to another.

What happens to reactants during a chemical reaction?

The molecules of one reactant are combined with those of another

reactant to form a new substance during a chemical reaction. As the
chemical bonds are broken, the positions of electrons change,
resulting in a product with properties that are different from the
properties of the reactants.

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 How Reaction occur
Always system wants to be in more stable state.

System prefers lower Gibbs energy state instead of Higher energy

state.

Initially the system needs some energy to initiates the reaction

process(that is called Activation energy). It is part of energy change
not exactly heat of reaction.

Various temperatures, pressure and catalysts are needed for different

chemical reactions to occur.

Reactions occur when two or more molecules interact and the

molecules change. The bonds between atoms are broken and created
to form new molecules.

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How will you quantify the reaction.

By measuring the concentration of a reactant or a

product changes over time.

Concentration, Temp, Total Pressure, pH,

conductivity, refractive index, viscosity, …
FTIR, HPLC, etc…
A chemical engineer wishes to know

(i)can the reaction occur? ( Thermodynamics) and

(i)how long will it take? ( Chemical Kinetics)

i.e., whether a given reaction is feasible or not and if

feasible,

what is the maximum possible extent of reaction and time

required for a specific extent of reaction.
Chemical kinetics is a study of the rates at which chemical
reactions occur and the effect of parameters such as
temperature, pressure, and reactant concentration/composition
on the reaction rates.

The chemical kinetics provides us information about the reaction

mechanism,

speed of a chemical reaction and type of rate equation

(that represents satisfactorily a given chemical reaction) which

is to be used in the design of reactors.
 REACTION RATES?

Unfortunately, there are no tables of chemical reaction

rates listed in literature.

Useful data tables and correlations can be found in areas

like: thermodynamics, heat and mass transfer, or
separations.

Reaction-rate data do not exist for most technologically

interesting processes.

If someone claims to have a general correlation of reaction

rates, then he is been questioned.

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 CHALLENGES for Chemical Engineers ?

Chemical engineer never encounters a single reaction in an

ideal single phase isothermal reactor.

Real reactors are extremely complex with multiple

reactions, multiple phases, and unpredicted flow patterns.

An engineer needs enough information to understand the

basic concepts of reactions, flow, and heat management and
how these interact.

The chemical engineer never have kinetics for the process

she or he is working on. The problem of solving the batch or
continuous reactor mass-balance equations with known
kinetics is much simpler than the problems encountered in
practice.
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Many industrial processes are mass-transfer limited so
that reaction kinetics are irrelevant or at least
thoroughly disguised by the effects of mass and heat
transfer.

Questions of catalyst poisons and promoters, activation

and deactivation, and heat management dominate most
industrial processes.

We usually encounter an existing reactor that may have

been built decades ago, has been modified repeatedly, and
operates far from the conditions of initial design.

Very rarely we have the opportunity to design a reactor

from scratch.
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Components of CRE

21
 Module I

 Classification of reactions- Rate and stoichiometry-rate

law- rate equation-rate constant-variables affecting the

rate of reaction-activation energy-reactions at equilibrium

Chemical Process Industry
 Classification of reactions

1. Homogeneous and Heterogeneous reactions – based on

number of phases involved.
2. Catalytic and Non-catalytic reactions – based on catalyst
usage.
3. Unimolecular, bimolecular and termolecular reactions –
based on molecularity of the reaction
4. Exothermic and endothermic reactions – based on heat
effect
5. First , second, third order, etc., nth order of reaction –
based on order of the reaction
6. Reversible and irreversible reactions – based on reaction
proceed in one or both directions
Homogeneous and heterogeneous reactions.
A homogeneous reaction is one which takes place in only one phase, i.e., all the
reacting materials, products and catalyst (if any) will all be present within a single
phase (one phase).

Examples: (i) Oxidation of nitrogen oxide to nitrogen dioxide with air, is a gas phase
reaction.

(ii) Formation of esters from organic acids and alcohols in the presence of sulphuric
acid is a liquid phase reaction.

A heterogeneous reaction is one which involves presence of more than one phase
i.e. reactants, catalyst or products in different phases.

Examples: Oxidation of sulfur dioxide to sulfur trioxide using vanadium pentaoxide

catalyst is a heterogeneous reaction as SO2, O2 and SO3 are gaseous while V2O5
is a solid material.

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 Catalytic and non-catalytic reactions.

Catalytic reactions which involve the use of catalyst to enhance the rate of a
reaction/speed of a reaction.
Hydrogenation of ethylene

Non-catalytic reactions are those reactions which does not involve use of catalyst.

Oxidation of NO to NO2 is a non-catalytic reaction.

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Chemical Reaction based upon the molecularity of a reaction
i.e., based upon the number of molecules that take part in the reaction (in the rate
determining step) as unimolecular, bimolecular and trimolecular reactions.

Decomposition of cyclobutane is a unimolecular reaction

Decomposition of hydrogen iodide is a bimolecular reaction which

involves collision of two molecules

Oxidation of NO to NO2 is a trimolecular reaction which involves collision of three

molecules

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 Chemical Reaction
An exothermic reaction is the one in which heat is evolved.

The reaction between CO and H2 to produce methanol is an exothermic

reaction.

An endothermic reaction is the one in which heat is absorbed (heat will be

supplied to the reacting system from the surroundings for reaction to take
place).

Dehydration of ethyl alcohol to produce ethylene is an endothermic reaction.

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 Chemical Reaction based upon the order of a reaction
as first order reaction, second order reaction, third order reaction,

A reaction of which overall order of reaction is one (i.e., sum of orders with respect
to participants in the reaction is unity) is called first order reaction.

A reaction of which the sum of orders with respect to reactants participated in the
reaction is two, is called second order reaction.

Saponification of ester is a second order reaction. .

third order reaction

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 Chemical Reaction
Reversible reactions are those in which the forward and reverse reactions take
place simultaneously.
dynamic equilibrium since forward and backward rxn occurs simultaneously

45
 Chemical Reaction
Irreversible chemical reaction, reactants combine to form products, but these
products cannot produce the reactants under similar conditions.
All the reactants react completely to form the products.
Irreversible reactions are those which proceed only in one direction (till the
reactants practically disappear).
 Law of mass action
The law of mass action is a mathematical model that
explains and predicts behaviors of solutions in dynamic
equilibrium.

It can be described with two aspects:

1) The equilibrium aspect, concerning the composition of a

reaction mixture at equilibrium and
2) The kinetic aspect, concerning the rate equations for
elementary reactions
 Rate of a chemical reaction
1. Based on unit volume of reacting fluid

1 dN A moles of A disappeare d
 rA   
V dt ( volume of fluid ) (time )

2. Based on unit mass of solid in fluid-solid systems

1 dN A moles of A disappeare d
 rA'  
W dt (mass of solid ) (time )
3. Based on unit interfacial area in a fluid-fluid systems or based on
unit surface area of solid in gas-solid systems

1 dN A moles of A disappeare d
 rA"   
S dt (surface ) (time )
4. Based on unit volume of solid in gas-solid systems
1 dN A moles of A disappeare d
 rA'"   
VS dt ( volume of solid ) (time )

Vs = Vp (volume of catalyst pellet)

5. Based on unit volume of reactor

1 dN A moles of A disappeare d
 rA""   
Vr dt ( volume of reactor ) (time )

(-rA)V = (-rA’)W = (-rA”)S = (-rA”’)Vs = (-rA””)Vr

Consider an irreversible reaction

aA + bB → rR
1 dN A moles of A disappeare d
 rA   
V dt ( volume of fluid ) (time )

For the constant volume systems,

d( N A / V ) dC
 rA    A
dt dt
Similarly,
d( N B / V ) dC
 rB    B
dt dt

d(N R / V ) dC R
rR  
dt dt
The relation b/w the rates of chemical reaction from the
stoichiometry of a reaction is

 rA  rB rR
 
a b r
For example:
2A + B → 3R

 rA  rB rR
 
2 1 3
 Check your understanding

1. What do you meant by homogeneous reactions?

2. What do you meant by heterogeneous reactions?
3. Differentiate order and molecularity of the reaction.
4. Define reversible and irreversible reactions.
5. Define exothermic and endothermic reactions.
6. Discuss the importance of catalyst.
7. Define law of mass action.
Factors affecting the rate of reaction ???
 Factors affecting the rate of reaction
For Homogeneous reaction
Nature of reactants and products
Concentration of reactants
Temperature of a system
Pressure of a system

For Heterogeneous reaction

Nature of catalyst
Surface area of reactants
Rates of heat and mass transfer
For homogeneous systems

Temperatur e Concentrat ion 

 rA  f  
dependent term , dependent term 
Consider reaction type, A → R
 rA  k C A

 rA  k o exp(Ea / RT) CA

Where, ko exp (-Ea/RT) = Temperature dependent term
CAα = Concentration dependent term
Ea = activation energy
α = order of reaction w.r.to A
Concentration dependent term of a rate equation

Temperature of the system should be maintained as constant

Different types of reactions

1. Single and multiple reactions

2. Elementary and non-elementary reactions

3. Molecularity and order of the reactions

 Single and Multiple reactions

Single reactions
A → Products
Multiple reactions
1.Series reactions A→R→S
2.Parallel reactions

3.More complicated form

(parallel w.r.to B and series
with A, R and S)
 Elementary and Non-elementary reactions
Elementary reactions
Consider a single reaction with stoichiometric equation
A + B→ R
- rA = k C A C B
Non-Elementary reactions
 Molecularity and order of the reaction

Consider the reaction type,

aA + bB → rR

Molecularity of the reaction = a+b

If the reaction is an elementary reaction

- rA = k CAa CBb

Over all order of the reaction, n = a+b

 Rate constant

For a homogeneous chemical reaction the dimensions of

the rate constant k for the nth-order reaction are

(time)-1(concentration)1-n

For 1st order reaction i.e., n =1,

(time)-1

For 2nd order reaction i.e., n =2

(time)-1(concentration)-1
 Kinetic models for non-elementary reactions
Kinetics of the reaction (non-elementary) A2 +B2 → 2 AB

Where * indicates unobserved intermediates

The type intermediates formed
1.Free radicals
2.Ions and polar substances
3.Molecules
4.Transition complexes
5.Non-chain reactions
6.Chain reactions
Free radicals
Free atoms or larger fragments of stable molecules that contain
one or more unpaired electrons are called free radicals.
Example: triphenylmethyl (stable)

Unstable and highly reactive free radicals

Ions and polar substance
Electrically charged atoms, molecules, or fragments of molecules

Molecules
Consider the consecutive reactions A → R → S
R is highly reactive its mean lifetime will be very small and its
Concentration in the reacting mixture can become too small to measure

Transition Complexes
The numerous collisions between reactant molecules result in a
wide distribution of energies among the individual molecules. This can
result in strained bonds, unstable forms of molecules, or unstable
association of molecules which can then either decompose to give
products, or by further collisions return to molecules in the normal state.
Such unstable forms are called transition complexes.
Non-chain reactions

Chain reactions

In the propagation step intermediate is acting as a catalyst

Examples of reaction mechanisms
 Check your understanding

1. List out the factors affecting the rate of the chemical

reactions?
2. Differentiate single and multiple reactions.
3. What is rate constant?
4. List out the different types of intermediates formed during the
reactions.
5. Differentiate chain and non-chain reactions.
 Temperature dependent term of a rate equation

The rate of reaction for an elementary reactions

According to Arrhenius law, (or) ln k = ln ko – (E/R)(1/T)

At the same concentration, but at two different temperatures, Arrhenius‘
law indicates that

Where, ko is the frequency or pre-exponential factor

E is the activation energy
R is the gas constant = 8.314 J/(mol.K)
Temperature dependency of the reaction rate
 Arrhenius equation from thermodynamics
k1
AB
Variation of equilibrium constant with
k2
temperature is given by Van’t Hoff
equation
d ln K H R

dT RT 2
Where K = (k1/k2)
d ln(k 1 / k 2 ) H R

dT RT 2

d ln k 1 d ln k 2 H1 H 2
  2

dT dT RT RT 2
Integrate the above equation, it will gives the Arrhenius equation

d ln k 1 H1 d ln k 2 H 2
 2
; 
dT RT dT RT 2
 Temperature dependency from collision theory

Collision theory
“Before molecules react, there must be collision between the
reactant molecules and only these collisions in which the colliding
molecules possess a certain minimum amount of energy are effective.”
Consider the Bimolecular collisions of unlike molecules
A + B → Products
According to collision theory the rate of the reaction is given by
-rA = (collision rate in mol/l.s) x (fraction of effective collisions)
Fraction of effective collisions = fraction of collisions releasing energy
equal to or greater than E = e (-E/RT)
For bimolecular collisions of unlike molecules in a mixture of A and B
from kinetic theory of gases,
1/ 2
  A  B 
2
  1 1 
Z AB  
 n A n B 8  k B T   
 2    M A M B 
1/ 2
   B 
2
 N2  1 1 
Z AB   A  8  k T
B    C A CB
 2  10 
6
 M A M B 

Where
σA, σB = molecular diameters of molecules A and B respectively in cm

 A  B 
 AB     average molecular diameter collision diamter , cm
 2 
M = mass of a molecule (molecular weight/N), g
MA = mass of a molecule A (molecular weight of A/N), g
MB = mass of a molecule B (molecular weight of B/N), g
CA = concentration of A, mol/l
CB = concentration of B, mol/l
N = Avogadro’s Number (6.023 x 1023 molecules/mol)
nA = number of molecules of A/cm3 (NCA/103)
nB = number of molecules of B/cm3 (NCB/103)
kB = Boltzmann constant (R/N = 1.30 x 10 -16 erg/K)

number of collisions of A with B

Z AB 
(s) (cm 3 )

Z AB 103
Collision rate in mol /( l.s) 
N

Z AB 103 E / RT
Rate of reaction  .e
N
 1/ 2
  A   B  N2   1 1  103 E / RT
2
Rate of reaction     
8 kB T   C A CB  e
 2  106   M A M B  N
1/ 2
   B  N   1 1 
2
 E / RT
 A  8  k T
B    .e .C A CB
 2  10 
3
 M A M B 

Rate of bimolecular type reaction is given by –rA = k CA CB

Compare the above two equations
1/ 2
  A  B  N   1 1 
2
 E / RT
k   8  k B T    .e
 2  10 
3
 M A M B 

where k  k 'o T1/ 2 .e E/RT (Collision s theory )

1/ 2
B N   1 1 
2
   
k o'   A  8kB   
 2  10 
3
 M A M B 
Taking the logarithm
E
ln k  ln k 'o  12 ln T 
RT
Differentiating the above equation

d(ln k ) 1 E
 
dT 2 T RT 2

In most cases, the term (1/2T) is small compared to (E/RT2), so

neglecting (1/2T), we get
d(ln k ) E

dT RT 2

The above equation is an equation originally proposed by Arrhenius.

For bimolecular collisions of like molecules/identical molecules
A + A → Products -rA = kCA2
1/ 2
8  k B T 
Z AA   2A n 2A  
 MA 

-rA = (collision rate in mol/l.s) x (fraction of effective collisions)

1/ 2
2 N 8  k B T 
2
Z AA  A 6   C 2A
10  M A 
Z AA 103 E / RT
Rate of reaction  .e where,
N
1/ 2
2 N 8  k B T 
 rA   A 3   e E / RT .C 2A
10  M A 
1/ 2 1/ 2
2 N 8  k B T  2 N 8  k B 
k  A 3   e E / RT ko  A 3 
"

10  M A  10  M A 

k  k "o T1/ 2 e E / RT
The temperature dependency of the reaction rate constant is given by

k  T1/ 2 e E / RT

Significance of Collision theory

1.This theory is satisfactory for number of bimolecular gas phase
reactions as well as for many reactions in solution involving simple ions.
2.Not suitable for unimolecular reactions.

Probability Factor (Steric factor, P):

Actual rate of reactions ≠ Rate calculated from the theory
k observed
P
k theory
 Temperature dependency from Transition state theory

The fundamental postulate of the theory

1. The reacting molecules must form unstable intermediate called
activated complex before being converted to products.
2. There exists an equilibrium b/w the activated complex and reactants
at all times and that the rate of decomposition of complex is the
same for all reactions and is given by

kBT/h
Where
kB is the Boltzmann constant (1.380 x 10-16 erg/K)
h is the Planck constant (6.024 x 10-27 erg.s)
The bimolecular reaction b/w a molecules of A and B

A+B AB* → Products

Rate = Concentration of activated X Frequency of decomposition of

complex activated complex
k T
 C AB*  B (1)
h
The equilibrium constant K*C for formation of the activated complex may
be written as
C AB*
K *c  (2)
C A CB

C AB*  K *c .C A .CB
Then the rate becomes

k BT *
Rate  K c .C A .C B (3)
h
The equilibrium constant can be expressed from thermodynamic terms

G*  RT ln K *c  H * TS *

TS * H *
ln K *c 
RT
 TS* H* 
 
K *c  e  RT 

Equation (3) becomes  S*    H* 

   
Kc  e
*  R   RT 
.e (4)

 S*    H* 
k B T  R   RT 
Rate  e .e .C A .C B (5)
h

Experimentally obtained rate equation, Rate = k CA CB (6)

Comparing equations (5) and (6)
 S*    H* 
k B T  R   RT 
k e .e (7 )
h
Equation (7) is the fundamental relation of the transition state theory

In the above equation, the term e(∆S*/R) is so much less temperature

sensitive that we may take it to be constant. The relationship b/w ∆H*
and the Arrhenius activation energy E for liquids and solids is

The relationship b/w ∆H* and the E for gases is

E  H * RT (8)
The difference b/w ∆H* and the E is small and of the order of RT; hence
transition state theory predicts approximately that
E  H * (molecularity  1) RT (9)

k  T e E RT (10)
 Comparison of theories
Collision theory Transition state theory
Predicted reaction rate Does not agree Agree
with experimental rate

Theory is based on Kinetic theory of gases Statistical mechanics

Activated complex (AC) The decomposition of AC Formation of AC is very rapid

is very rapid
Activated complex (AC) Formation of AC is slow The decomposition of AC is slow
and rate controlling and rate controlling

Temperature
dependency reaction k  T1/ 2 e E / RT k  T e E RT
rate
 Check your understanding

1. Define Arrhenius law.

2. Define activation energy.
3. Write the temperature dependency of a rate equation at two
different temperatures.
4. Derive the Arrhenius equation from Van't hoff equation.
5. List out the assumptions made in the Collision theory.
6. What is the relationship between rate constant and
Temperature from Collision theory?
7. What are the assumptions made in the Transition state
theory?
8. Give the relationship between rate constant and temperature
fromTransition state theory.
 Problems
1. A rocket engine, burns a stoichiometric mixture of fuel (liquid
hydrogen) in oxidant (liquid oxygen). The combustion chamber
is cylindrical, 75 cm long and 60 cm in diameter, and the
combustion process produces 108 kg/s of exhaust gases. If
combustion is complete, find the rate of reaction of hydrogen
and of oxygen.
2. A reaction has the stoichiometric equation 2A + B → 3R. What
is the order of the reaction.
3. An elementary reaction has the stoichiometric equation
2A + B → 3R . What is the order of the reaction.

4. What is the relationship b/w the rate of disappearance and rate

formation for the following reaction.
2 NO 2  12 O 2  N 2O 5

5. A certain reaction has a rate given by

 rA  0.5 C 2A , mol /(cm 3 . min)
if the concentration is expressed in mol/l and time in hours,
what would be the value and units of rate constant.

6. On doubling the concentration of reactant, the rate of reaction

triples. Find the order of the reaction.
7. Milk is pasteurized if it is heated to 63°C for 30 min, but if it is
heated to 74°C it only needs 15 s for the same result. Find the
activation energy of this sterilization process.
8. The pyrolysis of ethane proceeds with an activation energy of
about 75000 cal/mol. How much faster is the decomposition at
650 oC than at 500 oC.
9. At 500 K the rate of a bimolecular reaction is ten times the rate
at 400 K. Find the activation energy for this reaction
(i). From Arrhenius law
(ii). From Collision theory
(iii). What is the % difference in rate of reaction at 600 K
predicted by these two methods?
10. Show that the following scheme:
Is consistent with, and can explain, the observed first-order
decomposition of N2O5

k1
N 2 O 5  NO 2  NO *3
k2

NO 2  NO *3  NO 2  O 2  NO *
k
3

NO *  NO *3 k
4 2 NO 2
11. A reaction 2 HI(g) → H2 (g) + I2 (g) is studied over a range of
temperatures. The results obtained are tabulated below

Temperature K 633 666 697 715 781

Rate constant k, l/ 1.7 x 10-5 1.07 x 5.01 x 1.05 x 10-3 1.5 x 10-3
(mol. s) 10-4 10-4
(i). Find out the value of activation energy

(ii). Determine by what factor the rate increases when temperature

rises from 600 K to 700 K.

12. A common rule of temperature is that the rate of a reaction doubles

for each 10 oC rise in temperature. What activation energy would
this suggest at a temperature of 35 oC.
 Batch reactor
Symbolic representation of batch reactor system
For batch reactor
At constant volume (change in pressure)
At constant pressure (change in volume)
 Batch Reactor

Batch reactor (BR) – liquid phase reactions

Batch reactor

Advantages
1. Simple in construction
2. Simple to operate
3. It has flexibility of operation
4. Cost is relatively low
5. Requires small instrumentation and less supporting equipment
6. Give high conversion for long periods of time in the reactor

Disadvantages
1. High labor cost per unit volume of production
2. Requires considerable time to empty, clean out and refill
3. Quality control of product is poor
4. Large scale production is difficult.
 Design of Ideal Batch Reactor

Material balance of A on mole basis at any time, t

Input of A= Output of A+ Disappearance of A + Accumulation of A
by chemical reaction
within the reactor

Input = 0
Output = 0
Disappearance = - Accumulation
Where
Disappearance by
chemical reaction = (-rA)V

Accumulation = dNA /dt

 dN Ao (1  X A )

dt
dX A
 N Ao
dt
substitute the terms
 dX A 
(rA )V     N Ao 
 dt 
Re arranging
dX A
dt  N Ao
(rA )V
Integratin g with the lim its
X A  0 at t  0
X A  X A at t  t
t XA
dX A
 dt  N Ao  (rA )V
0 0
continue ...
XA
dX A
t  N Ao 
0 (rA )V
This is the general design equation for batch reactor

For a cons tan t volume system

 A  0 and V  Vo
N Ao X A dX A
t 
Vo 0 (rA )
XA
dX A
t  C Ao 
0 (rA )
CA
dC A
t 
C Ao ( rA )

This is the performanc e / design eqn for a batch reactor

for a cons tan t volume reactor system
For a change in volume / density system
XA
dX A
t  N Ao 
0 (rA )V
XA
dX A
t  N Ao 
0 (rA )Vo (1   A X A )
XA
dX A
t  C Ao 
0 (rA )(1   A X A )
This is the performanc e / design eqn for a batch reactor
for a var ibale density / volume system

 The above equations are applicable to both isothermal

and non  isothermal operations .
 Problems
1. The saponification reaction
NaOH + CH3COOC2H5 → CH3COONa + C2H5OH
follows second order kinetics. A laboratory well-stirred tank
reactor is charged with an aqueous solution containing NaOH
and ethyl acetate, both of 0.1 molar (mol/l). After 15 min, the
conversion of ethyl acetate is 18%.
For the initial charge containing NaOH and ethyl acetate in
equal concentration of 0.2 molar, what time is required to
obtain a conversion of 30 % in a commercial batch reactor?
 Analysis of
experimental
kinetic data
Batch reactor (homogeneous reactions)
Methods of analysis of kinetic data
1. Integral method of analysis
2. Differential method of analysis
3. Initial rate method
4. Half-life method
5. Ostwald’s method
Difference b/w integral and differential methods of analysis

Integral method Differential method

This method is easy to use and is This method is useful in more
recommended when testing specific complicated situations but requires
mechanisms, or relatively simple rate more accurate or larger amounts of
expressions data
This method is used to test the This method is used to develop or build
particular mechanism only up a rate equation to fit the data
 Constant-
Volume batch
reactor
Its also called as constant density reaction system
In constant volume system the measure of the reaction rate of
component ‘i’ becomes

1 dN i d(N i / V ) dC i
ri   
For ideal gases V dt dt dt
p N
C 
RT V
d(p i / RT)
ri 
dt
1 dp i
ri 
RT dt
 Relation b/w concentration and conversion for constant-
volume batch system

Material balance of A:
A initially = A reacted + A unreacted
A unreacted = A initially - A reacted
where
N A  N Ao  N Ao X A N Ao  initial moles A
N A  N Ao (1  X A ) N Ao X A  moles of A reacted
In constant-volume system, V = Vo
N N (1  X A ) moles of A reacted
C A  A  Ao XA 
V V initial moles A

N Ao (1  X A )
CA 
Vo
C A  C Ao (1  X A )
 Integral
methods of
analysis of rate
General procedure
data dC A
1. Assume a rate expression (i.e., order of the reaction)  rA    k. f (C)
2. Rearrange the rate expression to get in the following form dt

dC A
  k. dt
f (C)
C A dC
3. Plot the integral oft equation against time.
  A
 k  dt
The Cplot should yield a straight line with
Ao f (C) 0
slope equal to k.
4. If the above plot yields a straight line passing
through the origin – then the assumed rate equation is correct . If not then
the assumed rate equation is incorrect and another rate equation is tried.
 Integrated approach to different order reactions

1. Irreversible unimolecular-type first-order reactions

Consider the reaction A → Products
The rate equation is given by

dC A
 rA    k. C A
dt
dC A
  k. dt
CA
int egrating the above equation within the lim its
C A  C Ao at t  0; C A  C A at t  t
CA dC A t
  k  dt
C Ao C A 0

C  1 C 
 ln  A   k.t; k  ln  Ao 
 C Ao  t  CA 
In terms of conversion
dC A
  k. C A
dt
d(C Ao (1  X A ))
  k. dt
C Ao (1  X A )
dX A
 k. dt
(1  X A )
int egrating the above equation
X A  0 at t  0; X A  X A at t  t
XA dX A t
  k  dt
0 (1  X A ) 0

 ln(1  X A )  k.t
Characteristics of first order kinetics
Half life
“The time required to reduce the concentration of the reactant to
half of its original value.”

1 C 
k  ln  Ao 
t  CA 
2.303  C Ao 
t log  
k  A
C
apply the condition is C A  C Ao / 2 at t  t1/ 2
2.303  C Ao 
t1/ 2  log  
k  C Ao / 2 
0.693
t1/ 2 
k
2. Irreversible Bimolecular-type second-order reactions
Consider the reaction type 2 A → Products (or)
A +B → Products
For the equal concentrations of A and B, the rate expression is,

dC A
 rA    k. C 2A
dt
dC
 2A  k. dt
CA
int egrating the above equation within the lim its
C A  C Ao at t  0; C A  C A at t  t
CA dC A t
 2
 k  dt
C Ao C A 0
CA
 1   1 1  1 1 1 
  k.t; C    k.t; k  

 C A  C Ao  A C Ao  t  C A C Ao 
In terms of conversion
dC A
  k. C 2A continue ...........
dt
1 X A
dY
d(C Ao (1  X A ))    kC Ao t
  k. dt 2
1 Y
C 2Ao (1  X A ) 2
dX A [1 / Y]11 X A  kC Ao t
 kC Ao . dt
(1  X A ) 2 1
 1  kC Ao t
int egrating the above equation 1 XA
X A  0 at t  0; X A  X A at t  t XA
 kC Ao t
XA t
1 XA
dX A
  kC Ao  dt 1  XA 
0 (1  X A )
2
0 kt  1  X 
take 1 XA  Y
C Ao  A

 dX A  dY
At X A  0, Y  1
XA  XA , Y  1 XA
Test for bimolecular reactions
Characteristics of second order kinetics
Half life
Consider the reaction type 2 A → Products

1 1 1 
k  
t  C A C Ao 
 1 1 
kt 1/ 2    
 Ao
(C / 2) C Ao 
1
t1 / 2 
k C Ao
Significance
The
1 half life method cannot be used with reactions where the
t1 / 2 
concentrations of A and B are different, since A and B will have different times for
C Ao
half reaction.
Empirical rate equation for nth order
For the reaction A → Products
The rate is given by

dC A
 rA    k. CnA
dt
dC A
 n  k. dt
CA
int egrating the above equation
C A  C Ao at t  0; C A  C A at t  t
CA dC A t The dim ensions of rate cons tan t (k )
 n
 k  dt
C Ao C A 0 for n th order reaction are
C
 C An 1  A (time ) 1 (concentrat ion )1n
   k.t
  n  1 C Ao
1  1 1   1 1 
 n 1 n 1   k.t;  n 1 n 1   (n  1)k.t , n  1
n  1  C A C Ao   C A C Ao 
 Assignments

1. Derive the integrated rate equation for bimolecular-second order

reactions
reaction type is A +B → Products (i.e., A and B are not in equal
concentrations)
2. Derive the integrated rate equation for termolecular-third order
reactions
reaction type is A +B+C → Products (i.e., A, B and C are
equal concentrations)
3. Derive the integrated rate equation for termolecular-third order
reactions
reaction type is 2A +B → Products (i.e., A and B are not in equal
concentrations)
Half-life method
For the irreversible reactions aA + bB + … → Products
The rate equation is

dC A
 rA    k. C A CB ...
dt
For reac tan ts A and B at any time ,
CB b

CA a

dC b 
 rA   A  k. C A  C A  ...
dt a 
 k.(b / a) ....C A ...
 rA  k ' CnA
int egrating with initial condition
C A  C Ao at t  0
C1An  C1Ao
n
 k ' (n  1)t, for n  1
According to half  life concept
t  t1/ 2 when C A  C Ao / 2
12 C Ao 1n  C1Aon  k ' (n  1)t1/ 2
n
C1Ao n
 C1Ao  k ' (n  1)t1/ 2
21n
n  1 
C1Ao  21n   k ' (n  1)t1/ 2
 1
n n 1
C1Ao  
2  1  k ' (n  1)t1/ 2

t1 / 2 
2 n 1
 1 1n
C Ao

k ' (n  1)
taking natural log on both sides of equation
 2 n 1  1 
ln(t1/ 2 )  ln    (1  n) ln C Ao
 k ' (n  1) 
 Irreversible
reactions in
parallel
Consider the following elementary reactions in parallel
A 
k1
R
A
The rate of disappearance of 
k2
A is S by
given

dC A
 rA    k1 C A  k 2 C A
dt
int egrate this eqn and apply the lim its
 CA 
 ln   (k 1  k 2 ) t
 C Ao 
rates of formation of R and S
dC R dC S
rR   k 1C A ; rS   k 2C A
dt dt
rR (dC R / dt ) k 1
 
rS (dC S / dt ) k 2
dC R k 1

dC S k 2
int egrate the above equation
C R  C Ro k 1

CS  CSo k 2
 Irreversible
reactions in
series
Consider a unimolecular-type first –order series reaction of the type
A 
Rate equations for A, R and S 
k1
R  S
k2

dC A
 rA    k1 C A (1)
dt
dC R
rR   k 1 C A  k 2 C R (net rate of formation of R ) (2)
dt
dC S
rS   k 2 CR (3)
dt
Assume initially no R and S present and
let C Ao be the initial concentrat ion of A
dC A
  k1 CA (4)
dt
rearrangin g and int egrating ,
C 
 ln  A   k 1 t
 C Ao 
C A  C Ao e ( k1 t ) (5)
In order to find the var iation in concentrat ion of R, put the value of C A to rR
dC R
 k 2 C R  k 1 C Ao e ( k1 t ) (6)
dt
The above eqn is a first order linear differenti al eqn of the form
dy
 Py  Q (7 )
dx
comparing the eqns (6) and (7)
y  C R ; x  t; P  k 2 ; Q  k 1 C Ao e ( k1 t )
The solution of the linear differenti al eqn
y e  pdx   Q. e  pdx . dx  C
y  C R ; x  t; P  k 2 ; Q  k 1 C Ao e ( k1 t )
The solution of the linear differenti al eqn
y e  pdx   Q. e  pdx . dx  C
C R e  k 2dt   k 1 C Ao e ( k1 t ) e  k 2dt . dt  C
C R e k 2t  k 1 C Ao  e (k 2 k1 ) t dt  C
e ( k 2  k1 ) t
CRe k 2t
 k 1 C Ao C (8)
(k 2  k 1 )
Initial condition , C Ro  0 at t  0
k 1 C Ao
0 C
(k 2  k 1 )
k 1 C Ao
C (9)
(k 2  k 1 )
substituti ng C in eqn (8)
e ( k 2  k1 ) t k C
CRe k 2t
 k 1 C Ao  1 Ao
(k 2  k 1 ) (k 2  k 1 )
  e k1t e k 2t 
C R  k 1 C Ao    (10)
 (k 2  k 1 ) (k 2  k 1 ) 
 e k1t e k 2t 
C R  k 1 C Ao    (11)
 (k 2  k 1 ) (k 1  k 2 ) 
No change in total number of moles (cons tan t density system )
C Ao  C A  C R  CS
CS  C Ao  C A  C R
putting the C A value from eqn (5) and C R from eqn (10) in the above eqn
(  k1 t )  e k1t e k 2t 
CS  C Ao  C Ao e  k 1 C Ao   
 2
(k  k 1 ) (k 2  k 1 
)
 (  k1 t )  k 1  k 1e k 2t 
CS  C Ao 1  e 1    
  k 2  k 1 k 2  k 1

 (  k1 t )  k 2  k 1e k 2t 
CS  C Ao 1  e     (12)
  k 2  k1  k 2  k1 
 If k 2 is much l arg er than k 1 , the eqn (12) reduced to

CS  C Ao 1  e ( k1 t )  (13)
Maximum concentration
If k 1 is much l arg er than kof2 ,Rthe eqn (12) reduced to

CS  C Ao 1  e ( k 2 t ) 
 e k1t e k 2t 
C R  k 1 C Ao   
 2
( k  k 1 ) (k 2  k 1 
)
k C

C R  1 Ao e k1t  e k 2t
(k 2  k 1 )

dC R
dt
k C

 1 Ao  k 1e k1t  k 2 e k 2t
(k 2  k 1 )

dC R
At max imum R formation condition 0
dt
k 1 C Ao

(k 2  k 1 )

 k 1e k1t  k 2e k 2t  0
 k 1 C Ao
can not be zero
(k 2  k 1 )
  k 1e k1t  k 2 e k 2t  0
Taking log arithm , we get
ln k 2  k 2 t  ln k 1  k 1t  0
ln(k 2 / k 1 )  k 2 t  k 1t
t (k 2  k 1 )  ln(k 2 / k 1 )
ln(k 2 / k 1 ) 1
t  (14)
(k 2  k 1 ) k log mean
By combining eqns (10) and (14) the max imum concentrat ion of R is given by
k 2 /( k 2 k1 )
C R max  k 1 
  
C Ao k2 
 Autocatalytic reactions
“A reaction in which one of the products of reaction acts as a
catalyst is called as an autocatalytic reactions.”
Consider the following autocatalytic reaction A+R→R+R
The rate of the reaction is

dC A
rA    k CA CR
dt
at any time t
Co  C A  C R  C Ao  C Ro  cons tan t
dC A
rA    k C A (Co  C A )
dt
dC A
  k dt
C A (Co  C A )
Braking int o partial fractions , we get
1  dC A dC A 
    k dt
Co  C A (Co  C A ) 
 CA
dC A C A dC A
     kC o t
C Ao C A C Ao (C o  C A )

C   C  CA 
ln Ao   ln o   kC o t
 CA   Co  C Ao 
C (C  C A )
ln Ao o  kC o t
C A (Co  C Ao )
Co  C Ao  C Ro  C A  C R
C A  Co  C R
C Ao  Co  C Ro
C Ao (Co  Co  C R )
ln  kC o t
C A (Co  Co  C Ro )
 C .C  C /C 
ln Ao R   ln R Ro   kC o t  (C Ao  C Ro ) kt (1)
 C A .C Ro   C A / C Ao 
If M  C Ro / C Ao and X A is the fractional conversion A
C Ao (Co  C A )  C Ao C Ao  C Ro  C Ao (1  X A )
 C Ao C Ao  C Ro  C Ao  C Ao X A 
C 
 C Ao .C Ao  Ro  X A 
 C Ao 
C Ao (Co  C A )  C 2Ao M  X A 

C A (Co  C Ao )  C Ao (1  X A )[C Ao  C Ro  C Ao ]
 C Ao (1  X A ) C Ro
C Ro
 C 2Ao (1  X A )
C Ao
C A (Co  C Ao )  C 2Ao (1  X A ) M

Co kt  (C Ao  C Ro ) kt
 C Ao (1  C Ro / C Ao ) kt
Co kt  C Ao (1  M ) kt
Interms of M and X A , the eqn (1) becomes
 C 2 (M  X A ) 
ln 2Ao   C (M  1) kt
 C (1  X A )M  Ao
 Ao 
 (M  X A ) 
ln   C Ao (M  1) kt
 (1  X A )M 
 Reversible reactions
Reversible unimolecular type first order reaction

k1
Consider the reaction AR
k2

Where, k 1  forward reaction rate cons tan t

k 2  backward reaction rate cons tan t

The net rate of disappearance of A  rA  k 1C A  k 2C R

dC A dC R
   k 1C A  k 2C R
dt dt
C
Initial molar ratio, M  Ro
C Ao
Concentration of A at time t , C A  C Ao (1  X A )
 dC A  C AodX A
Concentration of R at time t , C R  C Ro  C Ao X A
 dC A dX A
  C Ao  k 1C Ao (1  X A )  k 2 (C Ro  C Ao X A ) (1)
dt dt

At equilibriu m, net rate is zero

(i.e., the rate of forward reaction  the rate of backward reaction )

dC A
0 and X A  X Ae (equilibriu m conversion )
dt

0  C Ao k 1 (1  X Ae )  k 2 (M  X Ae )
k 1 (1  X Ae )  k 2 (M  X Ae )
k 1 (M  X Ae ) C Re
  KC 
k2 (1  X Ae ) C Ae
k 1 (1  X Ae )
k2 
(M  X Ae )
from equation (1)
dX A
 k 1 (1  X A )  k 2 (M  X A )
dt
Substitue the k 2 value to the above equation
dX A k (1  X Ae )
 k 1 (1  X A )  1 (M  X A )
dt (M  X Ae )
dX A  (1  X A )(M  X Ae )  (1  X Ae )(M  X A ) 
 k1  
dt  ( M  X Ae ) 
dX A  X Ae (M  1)  X A (M  1) 
 k1  
dt  ( M  X Ae ) 
dX A k 1 (M  1)
 ( X Ae  X A )
dt (M  X Ae )
XA dX A k 1 (M  1) t
   dt
0 ( X Ae  X A ) (M  X Ae ) 0
  X  XA  (M  1)
 ln Ae   k 1t
 X Ae  (M  X Ae )
 X  XA   C  C Ae  (M  1)
 ln Ae    ln A   k 1t (2)
 X Ae   C Ao  C Ae  (M  X Ae )
The above eqn (2) is the desired int egrated rate eqn for
reversible first order reaction

 X Ae  X A 
plot  ln  Vs t
 X Ae 
Comparison of reversible 1st order and irreversib le 1st order

For a irreversib le 1st order

 ln (1  X A )   ln (C A / C Ao )  kt (1)
For a reversible 1st order with C Ro  0
 X  XA   C  C Ae  1
 ln Ae    ln A   k 1t
 X Ae   C Ao  C Ae  X Ae
If X Ae  1 (or ) C Ae  0 then the above eqn reduced to
 ln (1  X A )   ln (C A / C Ao )  kt (2)

The irreversib le 1st order reaction is simply a special case of

the reversible 1st order reaction
in which X Ae  1 (or ) C Ae  0 (or ) K C  
 Reversible bimolecular second order reaction
k1
(i ) 2A  R  S
k2
k1
(ii ) A BR S
k2
k1
(iii ) 2 A  2R
k2
k1
(iv ) A  B  2R
k2

with C Ao  C Bo and C Ro  CSo  0, the int egrated rate eqn

applicable to all the forms

 X  (2 X Ae  1) X A   1 
 ln Ae   2k 1   1C Ao t
 X Ae  X A   X Ae 
 Differential method of analysis of data

Procedure
1. Assume a rate equation -rA = - (dCA/dt) = k f (C)
2. Plot a graph of concentration v/s time (experimental studies)
3. Draw a smooth curve through these data.
4. Determine the slope of this curve by drawing tangents to the curve at
the suitably selected concentration values. dCA/dt are the rates of
reaction at the selected concentration.
5. Evaluate f (C) for each of the selected concentrations.
6. Plot a graph of - (dCA/dt) v/s f (C). If we get a straight line passing
through the origin then the rate eqn is consistent with the data (i.e.,
assumed rate eqn is correct). If we do not get a straight line then
another eqn should be tested.
Differential method of analysis of data
 Ostwald’s isolation method

This method is used to determine the order of the reaction by

taking a number of reactants in large excess except one. The rate of the
reaction depends upon this isolated reactant which is present in the least
amount.
The rate is given by
dC A
  k C A CB CC
dt
If B and C are taken in a l arg e excess
dC A
  k C A C 0B CC0
dt
dC A
  k C A (use int egral / differenti al method )
dt
Similarly ,  and  were det er min ed by assu min g the
rate of the reaxn is depends on one of the reac tan t
 Variable volume
batch reactor
(or)
constant
Example: Gas-phase reactions
pressure batch
N 2 O  N 2  12 O 2 reactor
The rate of change of component ' i '
1 dN i
ri 
V dt
1 d(C i V )
ri 
V dt
1  dC i dV 
 V  Ci
V  dt dt 
dC i C i dV
 
dt V dt
dC i d ln V
  Ci
dt dt
 For the volume of reaction system var ying linearly with conversion
V  Vo (1   A X A )
εA is the fractional change in the volume of the reaction system
b/w no conversion and complete conversion of reactant A

VX A 1  VX A 0
A 
VX A 0
Change in total number of moles for complete conversion
A 
Total number of moles fed to the reactor

Example
A  4R
4 1
A  3
1
Example :

50 mole % A  50 mole % inerts

A  4R
no conversion complete conversion

50 mole of A 4  50  200 mole of R
50 mole of I 50 mole of I

100 mole 250 mole

250  100
A   1.5
100
Exercise :

1). 75 mole % A  25 mole % inerts

A  3R

2). 40 mole % A  60 mole % inerts

A  4R

3). 90 mole % A  10 mole % inerts

A  2R

4). 55 mole % A  45 mole % inerts

A  4R
 Zero-order
reactions

1 dN A 1 dN Ao (1  X A )
 rA    k
V dt Vo (1   A X A ) dt
N Ao 1 d(1  X A )
 k
Vo (1   A X A ) dt
C Ao   dX A 
   k
(1   A X A )  dt 
C Ao  dX A 
  k
(1   A X A )  dt 
C Ao dX A
 k dt
(1   A X A )
int egrate the above eqn
t  0; X A  0
t  t; X A  X A
 XA dX A t
C Ao   k  dt
0 (1   A X A ) 0
use substituti on method
1 AXA  Y
 A dX A  dY
dY
dX A 
A
C Ao 1  A X A  dY
 k t
A 1 Y
C Ao
ln1   A X A   kt
A
C Ao V
ln  kt
A Vo
 First-order
reactions
Consider the reaction type A  Pr oducts
1 dN A 1 dN Ao (1  X A )
 rA     k CA
V dt Vo (1   A X A ) dt
C Ao  dX A  C Ao (1  X A )
k
(1   A X A )  dt  (1   A X A )
dX A
 k dt
(1  X A )
int egrate the above eqn
t  0; X A  0
t  t; X A  X A

 ln(1  X A )  k t
we know that
V  Vo (1   A X A )
V  Vo
XA 
 A Vo
V
XA 
 A Vo
 V 
 ln1  X A    ln1    k t
  A Vo 
 Second-order
reactions
Consider the reaction type 2 A  Pr oducts
A  B  Pr oducts with C Ao  C Bo
1 dN A C Ao  dX A 
 rA     k C 2
(1   A X A )  dt 
A
V dt
2
C Ao  dX A  2  1 XA 
 k C Ao  
(1   A X A )  dt  1   A A
X

Solve the above eqn then we will get

(1   A ) X A
  A ln(1  X A )  k C Ao t
1 XA
(1   A )V  V 

  A ln1    k C Ao t
Vo  A  V  Vo  A 
 Problems

1. The half-life period of a reaction of the first order is 5 minutes.

Calculate its rate constant in seconds.
2. Show that the decomposition of N2O5 at 67oC is a first order reaction.
Calculate the value of the rate constant.

Time, min 0 1 2 3 4
3. TheChalf life of a first0.16
N2O5, mol/l 0.113 A →
order reaction B is 200.056
0.08 min. what0.040
percent of A
remains after 100 min?
4. The decomposition of a component is second order. When the initial
concentration of that component is 5x10-2 mol/L, it is 30 %
decomposed in 30 min. calculate the value of rate constant.
5.In case of a first order reaction, show that the time required for 75%
conversion is double the time required for 50 % conversion.
6.For the reaction A → Products, the following data were obtained at 25oC,
in which the concentration of A is given at different intervals of time.

Time, min 0 10 20 30 40
find the order of reaction and calculate the rate constant and the
CA, mol/l
half life period. 0.860 0.740 0.635 0.546 0.405
7.The decomposition of NH3 on tungsten wire at 856 oC yielded the
following results

Find the order of the reaction and calculate the rate constant.
Time, s 200 400 600 1000
Total pressure, 228 250 273 318
(torr)
8. In a gaseous phase reaction, the time for half change (t1/2) for the
various initial partial pressures (p) of the reactant was given as follows

t , (min) 200 300 400

Find the order1/2
of the reaction.
9. The first orderpAo , (torr)
reversible 150phase reaction
liquid 99.8 A↔
75.3
R takes place in a
batch reactor. After 8 minutes, the conversion of A is 33.3 % while
equilibrium conversion is 66.7 %. Find the rate equation to represent
this reaction. Take CAo = 0.50 mol/l and CRo = 0
10. The liquid phase reaction A → R+S with CAo = 0.1823 mol/l, CRo = 0 and
CSo = 55 mol/l proceeds as follows.

Find the rate expression for this reaction

Time, (min) 0 36 65 100 160 ∞
CA, (mol/l) 0.1823 0.1453 0.1216 0.1025 0.0795 0.0494
11. Consider the reaction type A → Products takes place in a batch reactor
and the results are tabulated.

Time, (min) 0 1 2 3 4 5 6
CA, (mol/l) 0.041 0.034 0.027 0.023 0.021 0.018 0.016

Time, (min) 7 8 9 10 15 20
CAUse the differential
, (mol/l) 0.015 methods of analysis
0.0136 0.012 to determine
0.0014 the order of
0.0009 0.0007
the reaction and also the rate constant.

12.For the series reaction

with k1 = k2. Find the maximum concentration of R and the time at
which it is reached.
A 
k1
R k
2 S