4.

Chemical Kinetics

 Studies the rates and mechanisms of

chemical reactions.

1
4.1. The Rates of Chemical Reactions
Rate of reaction:- Change in the concentration/ pressure of
reacting species per unit time
aA + bB  cC + dD

𝑑[𝐴]
Rate of change of concentration of the reactant 𝐴 =
𝑑𝑡
 It is a negative quantity

𝑑[𝐷]
Rate of change of concentration of the product 𝐷 =
𝑑𝑡
 It is a positive quantity

 Rate of change of concentration of reacting species depends on

the coefficient of the species in the balanced chemical equation

2
Example: N2 + 3H2  2NH3

 The rate of consumption of H2 is three times more than the

consumption of N2 .
 The rate of formation of NH3 is two times more than the rate of
consumption of N2.
 For the entire reaction there is only one rate which is a positive
quantity.
 For hypothetical reaction: aA + bB  cC + dD

1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =  = − =− = =
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡

Example: If rate of formation of NH3 = 0.16 mMs-1

 rate of consumption of N2 = 0.08 mMs-1
 rate of consumption of H2 = 0.24 mMs-1
 The rate of the reaction= 0.08 mMs-1
3
4.2. Reaction Rate laws

 The rate of reaction is proportional to the concentrations of the

reactants raised to a power.
Example: For the reaction: aA + bB  Product,

𝒓𝒂𝒕𝒆 = 𝒌[𝑨] [𝑩]

 k is called rate constant
It is
 a positive value.
 independent of concentrations
 depends on temperature
  and  are order of the reactions with respect to A and B,
respectively.
4
 Order of a reaction shows the effect of the concentration of each
species on the rate of the chemical reaction.
 The values may be zero positive or negative including fractions

 Some reactions may have indefinite order.

 Overall order of a reaction: The sum of individual orders.

 Rate law: An equation that expresses the rate of reaction as a

function of the concentrations of all the species present in the
overall chemical equation.
 It is determined experimentally.

5
Example: A reaction having a rate law;  = 𝑘[𝐴]½ [𝐵]
 is ½ order in A, 1st order in B, and the overall order is3/2 .

Integrated rate laws

 An integrated rate law shows how the concentration of a
component in a reaction changes with time.

4. 2.1. nth order reactions

a) First-order reaction
1 𝑑[𝐴]
Consider: aA  P =− = 𝑘[𝐴]
𝑎 𝑑𝑡
𝒅[𝑨]
= −𝒂𝒌 𝑨 = −𝒌[𝑨]
𝒅𝒕
𝑑[𝐴] [𝐴] 𝑑[𝐴] 𝑡
= −𝑘𝑑𝑡 𝐴 o [𝐴]
= −𝑘 0
𝑑𝑡
[𝐴]

𝑨 = 𝑨 o𝒆−𝒌𝒕 𝒍𝒏 𝑨 = 𝐥𝐧 𝑨 o − 𝒌𝒕 6
[A]o = initial concentration of A at t = 0. [A] = concentration of A at t
A plot of ln[A] against t gives a straight line with a slope of –k.

Half-life time (t½): The time taken for the concentration of a reactant
to fall to half of its initial value.
For a first order reaction,
𝑙𝑛2 0.693
𝑡½ = =
𝑘 𝑘
 t1/2 is independent of initial concentration.

Time constant (): The time required for the concentration of a

reactant to fall to 1/e of its initial value.
For a first-order reaction,
𝐴o
1 1
𝑘 = −𝑙𝑛 𝑒
= −𝑙𝑛 =1 =
𝐴o 𝑒 𝑘

7
b) Second-order reaction:

i. Consider aA  P, be a 2nd order reaction.

𝑑[𝐴] 2
= −𝑎𝑘 𝐴 = −𝑘[𝐴]2
𝑑𝑡
[𝐴] 𝑡
𝑑[𝐴] 𝑑[𝐴]
2
= −𝑘𝑑𝑡 2
= −𝑘 𝑑𝑡
[𝐴] [𝐴]
𝐴o 0

𝟏 𝟏
= + 𝒌𝒕
[𝑨] 𝑨o

𝟏
𝒕½ =
𝒌𝑨 o
 t½ depends on the initial concentration of A.
8
General expression for t½
For a reaction: A  P
1
𝑡½ =
𝑘 𝐴 o n−1
ii. Consider aA + bB  P, be a second order reaction.

𝑑[𝐴]
= −𝑘[𝐴][𝐵]
𝑑𝑡

1𝑑 𝐴 1 𝑑[𝐵]
=− =−
𝑎 𝑑𝑡 𝑏 𝑑𝑡

∆[𝐵] 𝑏 𝐵 o−[𝐵] 𝑏
= =
∆[𝐴] 𝑎 𝐴 o−[𝐴] 𝑎

𝑏 𝑏
𝐵 = 𝐵 𝑜 − 𝐴 o + [𝐴]
𝑎 𝑎
9
 𝑑[𝐴] 𝑏 𝑏
= −𝑘[𝐴] 𝐵 o− 𝐴 o + [𝐴]
𝑑𝑡 𝑎 𝑎
[𝐵]
1
𝑙𝑛 [𝐴] 𝐵 o = 𝑘𝑡
𝑎 𝐵 o−𝑏 𝐴 o
𝐴 o

Exercise: Derive the integrated rate law for a) zero order

b) -1order and c) ½ order reactions

4.2.2. Reversible/Opposing reactions

Consider a first order reversible reaction:
k1
A B
k-1

f = k1[A], b = k-1[B]

[B] = -[A]
Therefore,
[B] = [B] o + [A] o – [A]
10
 [A] is reduced by the forward reaction (at a rate k[A]) and
increased by the reverse reaction (at a rate k'[B]). The net rate of
change is:

𝑑[𝐴]
= −𝑘1 𝐴 + 𝑘−1 𝐵 = 𝑘−1 𝐵 o + 𝑘−1 𝐴 o − 𝑘1 + 𝑘−1 [𝐴]
𝑑𝑡

𝑑[𝐴]
At equilibrium: = 0, 𝐴 = 𝐴 𝑒
𝑑𝑡

𝑘−1 𝐵 o + 𝑘−1 𝐴 o = 𝑘1 + 𝑘−1 𝐴 e

Therefore,
𝑑[𝐴]
= 𝑘1 + 𝑘−1 𝐴 e − [𝐴]
𝑑𝑡

𝑨−𝑨e
Solution: 𝒍𝒏 = − 𝒌1 + 𝒌−1 𝒕
𝑨 o− 𝑨 e
11
If there is no B initially, at any time [A] + [B] = [A]o.
𝑑[𝐴]
= − 𝑘1 + 𝑘−1 [𝐴] + 𝑘−1 𝐴 o
𝑑𝑡

Solution:
𝒌−1 + 𝒌1𝒆− 𝒌1+𝒌−1 𝒕
[𝑨] = 𝑨 o
𝒌1 + 𝒌−1

4.2.3. Consecutive/Sequential reactions

 Some reactions proceed through the formation of an intermediate
(B), as in the consecutive unimolecular reactions.
k1 k2
i. A B C

𝑑[𝐴] 𝑑[𝐵] 𝑑[𝐶]

= −𝑘1[𝐴] = 𝑘1 𝐴 − 𝑘2[𝐵] = 𝑘2[𝐵]
𝑑𝑡 𝑑𝑡 𝑑𝑡
12
)

Let [B]o = 0, [C]o = 0, [A] + [B] + [C] = [A]0

Solutions
𝐴 = 𝐴 o𝑒 −𝑘1𝑡
𝑘1 𝐴 o −𝑘 𝑡
𝐵 = 𝑒 1 − 𝑒 −𝑘2𝑡
𝑘2 − 𝑘1
−𝑘 𝑡
𝑘1 −𝑘 𝑡
𝑘1
𝐶 = 𝐴 o 1−𝑒 1 − 𝑒 1 + 𝑒 −𝑘2𝑡
𝑘2 − 𝑘1 𝑘2 − 𝑘1
Steady-state approximation
At steady-state:
𝑑[𝐵]
=0
𝑑𝑡
𝑘1[𝐴] = 𝑘2[𝐵]
𝑘1 𝑘1
𝐵 = 𝐴 = 𝐴 o𝑒 −𝑘1𝑡
𝑘2 𝑘2
𝑑[𝐶]
= 𝑘2 𝐵 = 𝑘1 𝐴 o𝑒 −𝑘1𝑡
𝑑𝑡 13
Exercise
a) Show that [B] is maximum at a time tmax which is given by
𝑘2
𝑙𝑛
𝑘1
𝑡max =
𝑘2 − 𝑘1
b) What is [B]max?
k1
ii A + B k2
I C
k -1

 Pre-equilibrium can arise when the rate of decay of the

intermediate back into reactants is much faster than the rate at
which it forms products; thus, k-1>> k2.
When A, B, and I are in equilibrium,
[𝐼] 𝑘1
𝐾= 𝐾=
𝐴 [𝐵] 𝑘-1
𝑑[𝐶] 𝑘1𝑘2
= 𝑘2 𝐼 = 𝑘2𝐾 𝐴 𝐵 = 𝐴 [𝐵]
𝑑𝑡 𝑘−1

14
:

4.2.3. Parallel/Side reactions

k1
B
A
k2
𝑑[𝐴] C
a) = −𝑘1[𝐴] − 𝑘2[𝐴] = − 𝑘1 + 𝑘2 [𝐴]
𝑑𝑡

Solution: 𝐴 = 𝐴 o𝑒 − 𝑘1+𝑘2 𝑡

𝑑[𝐵]
b) = 𝑘1[𝐴] = 𝑘1 𝐴 o𝑒 − 𝑘1+𝑘2 𝑡
𝑑𝑡
𝑘1 𝐴 o
Solution: [𝐵] = 1 − 𝑒− 𝑘1+𝑘2 𝑡
𝑘1+𝑘2

𝑑[𝐶]
c) = 𝑘2[𝐴] = 𝑘2 𝐴 o𝑒 − 𝑘1+𝑘2 𝑡
𝑑𝑡

𝑘2 𝐴 o
Solution: [C] = 1 − 𝑒− 𝑘1+𝑘2 𝑡
𝑘1+𝑘2

[𝑩] 𝒌1
From [B] and [C], =
[𝑪] 𝒌2 15
4.2.4. Chain reactions
 Reactants are converted into reactive intermediates (usually
radicals).
 The intermediates further react to give products.
Steps:
i. Initiation: Free radicals are formed from ordinary molecules.
ii. Propagation: The free radicals attack other molecules producing
free radicals and products.
iii. Inhibition: The free radicals attack the products thereby
decreasing the rate.
iv. Termination: Free radicals combine to give normal molecules,
thereby stopping the reaction.

16
Consider the reaction:
CH3CHO (g)  CH4 (g) + CO (g)  = 𝑘[CH3CHO]3/2 experimentally determined
Proposed reaction mechanism

 Test the proposed mechanism if it leads to the observed rate law.

Steady-state approximation:
 The rate of change of the intermediates is zero.

17
Solution:

At steady- state

Rate of formation of CH4 is therefore,

Where
½
𝑘i
𝑘 = 𝑘p
2𝑘t
 It is in agreement with the three-halves order observed
experimentally.
18
4.2.5. Acid Base Catalysis
 The mechanism for acid catalysis may be illustrated by the
following reaction
k1
+
a) AH + S SH+ + A
k-1
+
k2
b) SH products

Reaction b is of two types

+
k2
i. SH + H2O H3O+ + product
k2
+
ii. SH + A AH+ + Product

Case i.
𝑑𝑃 𝑘2
=
𝑑𝑡 [𝑆𝐻+]
19
Steady state approximation:
𝑑[𝑆𝐻+]
= 0 = 𝑘1 𝑆 𝐴𝐻+ − 𝑘−1 𝑆𝐻+ 𝐴 − 𝑘2[𝑆𝐻+]
𝑑𝑡
𝑘−1[𝑆][𝐴𝐻+]
[𝑆𝐻+] =
𝑘−1 𝐴 +𝑘2
𝑑𝑃 𝑘1𝑘2 𝑆 [𝐴𝐻+]
= 𝑘2 𝑆𝐻+ =
𝑑𝑡 𝑘−1 𝐴 +𝑘2
Cases:
i. If k2 >> k-1[A]
𝑑𝑃
= 𝑘1 𝑆 [𝐴𝐻+]
𝑑𝑡
Therefore, the rate depends on the concentration of the catalyst

ii. If k2 << k-1[A]

𝑑𝑃 𝑘1𝑘2 𝑆 [𝐴𝐻+]
= 𝑘2 𝑆𝐻+ =
𝑑𝑡 𝑘−1[𝐴]
20
ii. If k2 << k-1[A]
𝑑𝑃 𝑘1𝑘2 𝑆 [𝐴𝐻+]
= 𝑘2 𝑆𝐻+ =
𝑑𝑡 𝑘−1[𝐴]
For the acid dissociation,
AH+ A + H+

𝐴 [𝐻+] 𝐴 [𝐻+]
𝐾= 𝐴𝐻+ =
[𝐴𝐻+] 𝐾

𝑑𝑃 𝑘1𝑘2 𝑆 [𝐻+]
=
𝑑𝑡 𝑘−1𝐾
 The rate specifically depends on the concentration of H+
Exercise
Determine the rate law considering case bii.

21
5.3. Enzyme Catalysis
Michalis – Menten Equation
 Consider the following mechanism
k1
a) E + S ES
k-1
k2
b) ES E + product
Let; 𝑟𝑎𝑡𝑒 = = 𝑘2[𝐸𝑆]
At steady state,
𝑑[𝐸𝑆]
=0
𝑑𝑡

𝑘1 𝐸 𝑆 = 𝑘−1 𝐸𝑆 + 𝑘2[𝐸𝑆]
𝐸 o = 𝐸 + [𝐸𝑆]

𝑘1 𝐸 o 𝑆
[𝐸𝑆] =
𝑘−1 + 𝑘2 + 𝑘1[𝑆]
22
 𝐸 o[𝑆] 𝐸 o[𝑆]
[𝐸𝑆] = 𝑘 [𝐸𝑆] =
−1+𝑘2+[𝑆] 𝐾𝑚+[𝑆]
𝑘1
Where
𝑘−1+𝑘2
𝐾m = = Michalis constant
𝑘1
Hence,
𝒌2 𝑬 o[𝑺] 𝒌2 𝑬 o
𝒓𝒂𝒕𝒆 = = =
𝑲𝒎 + [𝑺] 𝟏 + 𝑲m
[𝑺]
Cases
1. If [S] >> Km
Rate = k2[E]o = max
Rate becomes independent of [S]
2. If [S] << Km
𝒌𝟐
𝑹𝒂𝒕𝒆 = = 𝑬 o[𝑺]
𝑲m
Other form:
𝟏 𝟏 𝑲m 𝟏
= +
 max max 𝑺o

23
4.3. Analysis of kinetic results
a) The Isolation Method: If the reaction rate depends on more
than one reactant, keep all except one at high concentration.
 The rate depends on the reactant of the lowest concentration.
For a reaction: A + B + C  E + F

Rate = k[A][B][C]
 If [B] >> [A] and [C] >> [A], [B] and [C] during the reaction remains
constant.
 k[B][C] = k
 Accordingly,  = k[A]
 The order of the reaction with respect to A can be determined by
determining the rate at different [A].
 The other orders can be determined using similar procedure.
24
b) The initial rate method: Consider a reaction:
A + B + C  Products
 Change the initial concentration of one reactant, say A, while
keeping the others constant.
Order of the reaction with respect to A can be determined
 = k[A]
Its initial rate, o = k[A]o
𝒍𝒐𝒈o = 𝒍𝒐𝒈𝒌 + 𝐥𝐨𝐠 𝑨 o
c) Half-life method:
It is applicable if  = 𝑘[𝐴]𝑛
i. For n = 1, t½ is independent of [A]o.
ii. For n  1
2𝑛−1 −1
𝑙𝑜𝑔𝑡½ = 𝑙𝑜𝑔 − 𝑛 − 1 log 𝐴 o
𝑛−1 𝑘
 n (order of a reaction) is determined from the slope.
25
d) Relaxation method:
 Allow the reaction to reach equilibrium and then perturb (e.g.
temperature jump).
 The rate of restoration to equilibrium gives information on the
rate constants.
Consider:
k1
A B
k-1
Let: xe = equilibrium concentration of B,
a = initial concentration of A, x = concentration of B at time t.
At equilibrium,
𝑑𝑥
= 𝑘1 𝑎 − 𝑥e − 𝑘−1𝑥e = 0
𝑑𝑡
Let x = x -xe , departure from equilibrium.
𝑑∆𝑥 𝑑𝑥 𝑑𝑥
= −0=
𝑑𝑡 𝑑𝑡 𝑑𝑡
26
At any time t,
𝑑𝑥
= 𝑘1 𝑎 − 𝑥 − 𝑘−1𝑥
𝑑𝑡
Using x = x + xe
∆𝑥 𝑑∆𝑥 𝑡
∆𝑥o ∆𝑥
=− 𝑜
𝑘1 + 𝑘−1 𝑑𝑡
where xo = initial departure from equilibrium.

Solution:
∆𝒙 = ∆𝒙o𝒆− 𝒌1+𝒌−1 𝒕
Let  be the relaxation time, the time corresponding to
∆𝑥 1
=
∆𝑥o 𝑒
Hence,
1
=
𝑘1 + 𝑘−1
27
The rate of restoration to equilibrium is given by
𝒕
∆𝒙
=𝒆 
−
∆𝒙o

 The rate is proportional to the displacement and follows a 1st

order kinetics.
 From the value of  measured at different x values, the sum, k1
+ k-1 can be known.
 Individual rate constants are determined from the
thermodynamic equilibrium constant, K, where
𝑘1
𝐾=
𝑘−1
 K can be calculated from equilibrium concentrations.

28
4.4. Theories of reaction rate
4.1. Collision Theory
 The rate of a chemical reaction is equal to the number of head-
on collisions per unit volume per unit time multiplied by the
fraction of all collisions that have the required energy to yield
products.

Consider the bimolecular elementary reaction:

A + B P
 = 𝑘2 𝐴 [𝐵]
 The rate is proportional to:
 the rate of collision and therefore to the mean speed of the
molecules,
their collision cross-section,, and
the number densities of A and B (NA[A], NA[B]).
29
 Collision density (ZAB): Number of collisions per unit volume per
unit time.
½
8𝑘𝑇
𝑍AB =  𝑁A2 𝐴 [𝐵]
𝜋𝑀
Where  = collision-cross section = d2 (d = radius of target area)
 All collisions within  do not lead to products.
 Only those within reaction cross-section (*) lead to products.
* = P where P is a steric factor.
Hence,
8𝑘𝑇 ½
𝑍AB = 𝑃 𝑁A2 𝐴 [𝐵]
𝜋𝑀
 Let f be fraction of collisions that satisfy the energy requirement.
This makes the rate to be proportional to the Boltzmann factor,
e-Ea/RT
30
 𝑑[𝐴] 𝑍AB
− = 𝑓
𝑑𝑡 𝑁A
 Dividing by the Avogadro’s number converts the number of
molecules to molar concentrations.
Hence,
8𝑘𝑇 ½ − 𝐸a
 = 𝑃 𝑁Ae 𝑅𝑇 𝐴 [𝐵]
𝜋𝑀
Therefore,
8𝑘𝑇 ½ − 𝐸a
k2 = 𝑃 𝑁Ae 𝑅𝑇
𝜋𝑀
8𝑘𝑇 ½
Let 𝐴 = 𝜎 𝑁𝐴 - Arrhenius parameter
𝜋𝑀
𝑬
−𝑹𝑻a
𝒌2 = 𝑷𝑨𝒆
The result is similar with the transition state theory.

31
4.2. Transition State theory
 The rate of a reaction is equal to the rate with which reactants
pass over the energy barrier multiplied by the concentration of the
activated complex.

Consider the elementary reaction:

mA C* P

C* is the activated complex.

𝑑𝐴
=− = 𝑘2 𝐴 𝑚 = 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑎𝑠𝑠𝑎𝑔𝑒 𝑜𝑣𝑒𝑟 𝑒𝑛𝑒𝑟𝑔𝑦 𝑏𝑎𝑟𝑟𝑖𝑒𝑟 × 𝐶∗ = 𝑘∗[𝐶∗]
𝑑𝑡

∗ [𝐶∗]
𝐾C =
𝐴m

Where 𝐾𝑐 ∗ is the equilibrium constant for the formation of the

complex.
32
 The rate of passage of the complex through the energy barrier is
proportional to the vibrational frequency of the complex along the
reaction coordinate.
𝑘∗ = 
 = vibrational frequency, k* = rate constant of the complex
decomposition,  = transmission coefficient (~1)
𝑘𝑇
= where h = Planck constant, k = Boltzmann constant
ℎ
Therefore,
∗
𝑘𝑇
𝑘 =
𝑕
Hence,
𝑘𝑇 𝑘𝑇𝐾C∗
= 𝐶∗ = 𝑘2 𝐴 m = 𝐴 m
ℎ ℎ

Therefore,
𝑘𝑇𝐾C∗
k2 = Eyring equation
ℎ
33