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 Chemical Engineering Department
Chemical Reaction Engineering (CH314)
Lecture-4

Kinetics of Homogenous
Reactions

Dr. Imran Nazir Unar

Lecture Objectives

• Discussion of Rate Laws

• Understanding of ORDER of Reactions
• Arrhenius Law
• Kinetic Expressions: Rate Constant and Activation Energy
RATE LAWS
Power Law Model
 The rate law is an expression relating the rate of a reaction to the
concentrations of the chemical species present, which may include reactants,
products, and catalysts.
 Many reactions follow a simple rate law, which takes the form.

 It means, rate is proportional to the concentrations of the reactants each raised

to some power.
 The constant of proportionality, k, is called the rate constant.
RATE LAWS
Power Law Model
A  B  P

 
 rAC CA B α order in A
  β order in B
 rA  kC C A B
Overall Rection Order  α  β
Rate Constant
(Constant of proportionality)
RATE LAWS
Power Law Model
 Other reactions follow complex rate laws.

 These often have a much more complicated dependence on the chemical

species present, and may also contain more than one rate constant.
 Complex rate laws always imply a multi-step reaction mechanism.

 An example of a reaction with a complex rate law is

RATE LAWS
Power Law Model
2A  B  3C
 A reactor follows an elementary rate law if the reaction orders just happens to
agree with the stoichiometric coefficients for the reaction as written.
 e.g. If the above reaction follows an elementary rate law, then

 rA  k AC C B
2
A

 2nd order in A, 1st order in B, overall third order

RATE LAWS
Power Law Model
 Rate Laws are found from Experiments.
2A  B  3C
 Rate Laws could be non-elementary. For example, reaction could be:
 Second Order in A
 Zero Order in B
 Overall Second Order
 rA  k AC A2

rB  k B C 2
A

rC  kC C 2
A
RATE LAWS
Relative Rates of Reaction
 Let we have a reaction:  Example: 2A  B  3C
aA  bB  cC  dD
mol
 We can also write it as  Given  rA  10
(by taking α common)
dm 3  s

b c d  Then
A B  C  D rA rB rC
 
a a a  2 1 3
 The relative rate equations are:  rA mol
 rB  5
2 dm 3  s
rA rB rC rD
   3 mol
a b c d rC  rA  15
2 dm 3  s
RATE LAWS
Reversible Elementary Reaction
 Let we have a reaction: kA
A+2B 3C
k-A
 Then rate expressions become:
What we call this???
 2 C  3
 rA  k AC C B  k  AC  k A C A C B 
2
A
3
C
C

 k A k A 
 2 CC3  Dimension of K moles moles
 k A C A C B     rA   3 CA 
 Ke  dm s dm 3
  rA  mole dm 3 s dm 6
 Reaction is: First Order in A k   2   
 A B   mole dm  mole dm 
2 2
C C 3 3 mole s
Second Order in B
Overall third Order
RATE LAWS
Examples of Reaction Rate Laws
RATE LAWS
Finding Reaction Rate Laws – Algorithm
 How to find Rate Expression?  rA  f  X 

 Step 1: Rate Law  rA  g  Ci 

 Step 2: Stoichiometry  Ci   h  X 

 Combine to get  rA  f  X 
TEMPERATURE DEPENDENCE OF REACTION RATES
Arrhenius Law
 For any reaction with a non-zero activation energy, the
rate constant is dependent on temperature.
 The temperature dependence is often modelled by the
ARRHENIUS EQUATION.
 E RT
k  AeOR

 E Activation Energy for the reaction

T  k  A
 A A constant known as the
 Pre-exponential factor OR k T 0 k 0
 Frequency Factor OR
A 10
13
 Arrhenius Constant.
 A and E are known as Kinetic Parameters. T
TEMPERATURE DEPENDENCE OF REACTION RATES
Arrhenius Law
 This temperature dependence means that in order to measure an accurate value
for k, the temperature of the reaction mixture must be maintained at a constant,
known value.
 If activation energies are to be measured as part of the kinetic study, rate
constants must be measured at a series of temperatures.
 It is found experimentally that the rate constants for many chemical reactions
follow the Arrhenius equation.

 These parameters (A and E) may be determined from experimental rate data by

plotting lnk against 1/T.
 This is known as an Arrhenius plot, and has an intercept of lnA and a slope of –
Ea/R.
TEMPERATURE DEPENDENCE OF REACTION RATES
Modified Arrhenius Law
 For most reactions, the Arrhenius equation works fairly well over at least a
limited temperature range.
 However, there are often deviations.
 These are generally due to the temperature dependence of the pre-exponential
factor.
 Then we apply “Modified Arrhenius Law”.

 Some time Pressure has also effects on latest research has even modified this
law as n
T 
k    Ae  E RT P n
 To 
ACTIVATION ENERGY
Why is there an Activation Energy?
 We see that for the reaction to occur, the reactants must overcome an energy
barrier or activation energy EA.

 The energy to overcome their barrier comes from the transfer of the kinetic
energy from molecular collisions to internal energy (e.g. Vibrational Energy).

1. The molecules need energy to disort or stretch their bonds in order to break them and
thus form new bonds
2. As the reacting molecules come close together they must overcome both stearic and
electron repulsion forces in order to react.
ACTIVATION ENERGY
Concept 1. Law of Mass Action
 The rate of reaction increases with increasing concentration of reactants owing
to the corresponding increase in the number of molecular collisions.

 The rate of disappearance of A, –rA, depends on temperature and concentration.

For many irreversible reactions, it can be written as the product of a reaction rate
constant, kA, and a function of the concentrations (activities) of the various
species involved in the reaction:
 rA   k A  T   fn  C A , C B  

 For example for the elementary reaction

AB +C ®
¬ A + BC
- rAB =kABCABCC =AAB e- E RT
CABCC
 E = Activation Energy, (kJ/mol)
ACTIVATION ENERGY
Concept 2. Potential Energy Surfaces and Energy Barriers
AB +C ®
¬ A\ B\ C ® A + BC
¬
 As two molecules, say AB and C, approach each other, the potential energy of
the system (AB, C) increases owing repulsion of the molecules.
 The reaction coordinate is a measure of progress of the reaction as we go form
AB and C to A and BC as shown in Figure 1 below.

Fig. 1: Progress along reaction path. (a) Symbolic reaction; (b) Calculated from Computational software
Thank You

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