Chemical Reaction Engineering

Introduction
• Chemical Process – economic production of finished
goods from raw materials.
• Chemical Process – (Unit Operations + Unit Process)
in correct sequence.
• Unit Process – heart of entire sequence, maximum
attention given to this step in development stage.
• Chemical Reactor
• Design of Chemical Reactor – fluid flow, heat
transfer, mass transfer, economics and
thermodynamics.
 CO + 2H2 CH3OH
1. Reaction will proceed (Feasible) – thermodynamics
2. How fast or how long the reaction will take place – Chemical Kinetics (Reaction Engineering)

• Chemical Kinetics studies the rate of chemical reactions

• Effect of parameters such temperature, pressure, composition of reactants
• Reaction mechanism, Speed of reaction, Type of rate equation
• Design of Reactor

• Thermodynamics gives information about feasibility of reaction (extent of reaction)

• Heat absorbed or liberated in course of reaction

Both kinetics and thermodynamics is required for the design of reactor

 Classification of Chemical Reactions
• Based on number of phases – homogenous and
heterogeneous reaction
Ex: H2SO4
C2H5OH + CH3COOH CH3COOC2H5 + H2O
V2O5
SO2 + 0.5 O2 SO3
• Catalytic and Non- Catalytic Reaction
Ni
C2H4 + H2 C2H6 NO + 0.5 O2 NO2
Heat
• Based on molecularity of a reaction: number of
molecules taking part in the rate determining step
– Decomposition of Cyclobutane: Unimolecular reaction
– Decomposition of Hydrogen Iodide: Bi molecular reaction
• Based on heat effects: Endothermic and Exothermic reactions
Dissolution of NaOH, H2SO4 in water – Exothermic reaction
Dehydration of ethyl alcohol – Endothermic reaction
• Based on order of a reaction as first order reaction, second
order reaction, third order reaction etc.
Decomposition of nitrogen pentoxide is first order reaction
Saponification of ester

CH3COOC2H5 + NaOH CH3COOC2H5 + H2O

Example of third order reaction
2NO2 + H2 N2O + H2O
• Based on the reversibility of reactions
• Reversible and irreversible reactions
H+
C2H5OH + CH3COOH CH3COOC2H5 + H2O
C6 H 6  HNO3  C6 H 5 NO2  H 2O
Rates of Chemical reaction
Homogenous System – based on unit volume of
reacting fluid.
Rate of reaction is defined as change in moles of reactant or
products per unit time and unit volume of reacting fluid.
Factors affecting rates of reaction
i. Nature of reactants and products
ii. Concentration of reactants
iii. Temperature of system
iv. Pressure of system
v. Nature of catalyst
vi. Surface area of reactants
vii. Rate of heat and mass transfer
For homogenous reactions factors that affect rate of reaction is pressure, temperature and
composition
mol
 rA  f temperatur e, concentrat ion 
Dependant terms Dependant terms l sec
A R
n E
 rA  k c A  rA  k0 e RT
c An
E
k0e RT Temperature dependant term E – Activation Energy
k – specific rate constant
c An Concentration dependant term n – Order of reaction with respect to A
Reaction mechanism
It refers to the step by step process by which reactants react among themselves in the process
of product formation
2A  B  R  S
Step 1: A  B  AB
Step 2: A  AB  A2 B
Step 3: A2 B  AB  R
Step 4: AB  S
Elementary Reaction
Reactions in which there is a direct correspondence between rate law and stoichiometric
equation a b
aA  bB  rR  rA  k c AcB
Non - Elementary Reaction
Reactions in which there is no direct correspondence between rate law and stoichiometric
equation
 
aA  bB  rR  rA  k c c A B 𝛼 ≠ 𝑎; 𝛽 ≠ 𝑏
 Sl No. Elementary Reaction Non - Elementary Reaction

1 Single step reactions Multi step reactions

2 Simple in nature
3 Order agrees with
Stoichiometry
4 Order can be Integer
only
Complex in nature
Order doesn’t agree with
Stoichiometry
Order can be a fractions

Molecularity of reaction
The number of chemical species which react simultaneously to bring in a chemical reaction

If one molecule is transformed, the reaction is called as unimolecular.

If two molecules participate to cause a chemical change, the reaction is called as bi-molecular
Reactions requiring simultaneous collision of three or more molecules is rare.
Molecularity of reaction can be a whole number and never can be a zero or fraction and it is a
theoretical quantity.
Order of reaction
• Rate of reaction is directly proportional to number of collisions
• Number of collisions is directly proportional to number of molecules

aA  bB  .....  rR  sS  ..... n  a  b  ......

dc A a b
 rA    kc AcB .....
dt
Order of the reaction is the sum of powers to which concentration terms are to be raised in
the rate expression
For a bi-molecular reaction of type
dc A 1
A  B  R  rA    kc A 2 cB .....
dt
Then molecularity is 2 and order of the reaction is 1.5
Difference between order and Molecularity
Sl No. Molecularity Order

1 Molecularity is defined as number Order of the reaction is the sum of

of ions atoms participating in rate powers to which concentration terms
determining step are to be raised in the rate expression

2 Molecularity is a theoritical Order of a reaction is an experimentally

quantity determined quantity.
3 Molecularity of a reaction must be Order of reaction can be zero whole
a whole number and never is a zero number or fraction
or fraction

For the reaction B  2 D  3R

2
If rate of reaction is measured in terms of B, then rate of reaction will be  rB  k c cB B D
2
If rate of reaction is measured in terms of D, then rate of reaction will be  rD  k c cD B D
If rate of reaction is measured in terms of R, then rate of reaction will be 2
− 𝑟 𝐵 −𝑟 𝐷 𝑟 𝑇 k B k D kT 𝑟 𝑇 =𝑘𝑇 𝑐 𝑐 𝐵 𝐷
= =  
1 2 3 1 2 3
Temperature dependant term of Rate Equation
 rA  f1 (temperatur e). f 2 (compositio n)
 k . f 2 (compositio n)

Temperature dependency from Arrhenius law

• Chemical reaction proceeds through the collision between the molecules.
• Reactant molecules get converted into products – reactions would occur instantaneously
• Weaken the bond between atoms or molecules of reactants which require definite energy
• Minimum amount of energy which the colliding molecules must have to bring in a
chemical reaction is called as Activation energy. (barrier the molecules has to overcome
to get converted into products.
For many particularly elementary reactions, temperature dependence of rate constant is given
by
E
k  k0 .e RT

k0 –Frequency factor R –Gas constant = 8.314 J/mol K

E –Activation Energy (J/mol) T –Absolute Temperature- K

• Activation Energy is minimum amount of energy that must be possessed by reacting
molecules so that they can get converted into products.
E
•
e RT Corresponds to the fraction of molecules colliding together to have minimum
energy to bring in a chemical reaction.
• Activation Energy is determined experimentally by carrying out reaction at different
temperatures.
E
k  k0 .e RT

• Data for rate constant with respect to

temperature

ln k  ln k0  E
RT

• Measuring rate constants at two different temperatures

ln k1  ln k0  E ln k 2  ln k 0  E
RT1 RT2
1 1
ln k 2  ln k1   E E ln( k 2 / k1 )   E 
RT2 RT1 R T T 
 2 1
 1 1 1 1 
ln( k 2 / k1 )   E  ln( k 2 / k1 )  E 
R T T  R T T 
 2 1  1 2
a b
Consider the rate of reaction given by r  kc c
A B
E
RT a b 𝑎 𝑏 −𝐸
r  k0e ccA B 𝑘=𝑘 𝑐 𝑐 0 𝐴 𝐵 𝑟 =𝑘𝑒 𝑅𝑇

−𝐸 −𝐸 −𝐸
ln 𝑟 =ln 𝑘 ln 𝑟 1 =ln 𝑘 ln 𝑟 2 =ln 𝑘
𝑅𝑇 𝑅𝑇1 𝑅𝑇2

−𝐸 𝐸
ln 𝑟 2 − ln 𝑟 1= +
𝑅𝑇2 𝑅𝑇1

1 1
ln( r2 / r1 )   E 
R T T 
 2 1
1 1
ln( r2 / r1 )  ln( k 2 / k1 )   E   
R T T
 2 1
Significance of Activation Energy
• Activation Energy is minimum amount of energy that must be possessed by reacting
molecules so that they can get converted into products.
• Reactant molecules must pass through energy rich activated state before they can react.
• Quantity of energy required by the reactants to overcome this activated state or energy
barrier is called as Activation energy.
• Difference between energies of reactants and products is called as heat of reaction.
• Energy of activation for any reaction is the difference in energy of activated complex and
energy of reactants.
• From Arrhenius law a plot of ln k vs
1/T gives a straight line with large
slope for large E and small slope for
small E
• Reaction with high activation
energy are temperature sensitive
rather than reactions with low
activation energy are temperature
insensitive.
• Any given reaction is temperature
sensitive at low temperatures than
at high temperatures.
 Other Theories for Temperature dependency
E
• Collision Theory k  k 0T .e RT 0  m  1
' m

• Transition State Theory

Temperature dependency from Collision Theory

• During reaction reactant molecules collide with each other.
• Colliding molecules must possess a certain amount of energy which are
effective.
• Frequency of molecular collisions that are effective
1 E
k  T .e 2 RT

• Collision theory was found to be satisfactory especially for number

of bi – molecular gas phase reactions
• It fails in case of uni-molecular reactions.
Temperature dependency from Transition State Theory
• Also known as absolute reaction rate theory
• Reacting molecules first form un-stable intermediate called activated
complex before getting converted into products
• There exist an equilibrium between activated complex and reactant in
which rate of decomposition is same for all reactions
E
k  T .e RT
1. Given the reaction 2 NO2 + ½ O2 → N2O5. What is
the relation between rate of formation and rate of
disappearance of these three components.
2. A certain reaction has the rate given by
-rA = 0.005 cA2 (mol/cm3.min)
If concentration is expressed in (mol/l) and time in hours.
What would be value of rate constant.
3. On doubling the concentration of reactant the
reaction rate triples. Find the reaction order.