CHM 305

Chemical Kinetics

Department of Chemistry
Obafemi Awolowo University, Ile-Ife, Nigeria
 Introduction:
• Chemical Kinetics (or Reaction Kinetics): the study of reaction rates and
mechanism of chemical reactions.
• Reaction rates study provides information on the rates of a reaction under
certain conditions and what factors can influence the rate of reaction
• The mechanism of reaction deals with step-by-step processes taking place in
a chemical reaction (such as bond breaking & bond formation). It also
involves an interpretation of the empirical laws in terms of a reaction
mechanism.
• The ultimate objective of a kinetic study is to arrive at a reaction mechanism.
• Applications of Chemical kinetics: drug design, industrial synthesis of
compounds, environmental clean-ups, fast electronics, lasers, biological
processes, etc.
REVIEW OF RATE EQUATIONS
 Rate of Reaction
……a measure of how fast a reactant is used up or a product is formed.
• The rate, speed or velocity of a reaction may be expressed in terms of
the concentration of any one of the reactants or any one of the
products of the reaction.

• E.g A + B C

→Slope = -d[A]/dt

Curve showing the concentration of a product, and the concentration of a reactant as a

function of time. Source: https://www.google.com/url?sa=i&url=https%3A%2F%2Ffanyv88.com%3A443%2Fhttps%2Fbyjus.com%2Fjee%2Fchemical-
kinetics%2F&psig=AOvVaw2PHFL70llK5Gxyn9xeiwUO&ust=1612948652783000&source=images&cd=vfe&ved=0CAIQjRxqFwoTCLCQgKW8
3O4CFQAAAAAdAAAAABAl
 Rate of Reaction (cont’d)
𝑑[𝐴] 𝑑[𝐶]
• Instantaneous rate: − = - slope or = slope
𝑑𝑡 𝑑𝑡
• Relative rate:
For any reaction aA + bB → cC + dD,
rates are related by:
1 𝑑[𝐴] 1 𝑑[𝐴] 1 𝑑[𝐴] 1 𝑑[𝐴]
= − = =
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡

e.g Consider the hypothetical reaction: X(g) + 2Y(g) → XY2g)

∆[Y ]
= − 5.0 × 10−2 mol L−1 sec−1
∆t
What is the rate of formation of XY2(g)?
1 𝑑[𝑌] 𝑑[𝑋𝑌2]
Solution: Since from the balanced equation, - =
2 𝑑𝑡 𝑑𝑡
1 −5.0 × 10−2 𝑑[𝑋𝑌2]
− x mol L−1 sec−1 = .
2 𝑑𝑡 𝑑𝑡
𝑑[𝑋𝑌2]
჻ Rate of formation of XY2 , = 2.5 × 10−2 mol L−1 sec−1
𝑑𝑡
Order of Reaction
For a reaction  A   B   C......  Pr oduct

From rate law, rate α [A]α[B]β[C]γ

Rate = k[A]α[B]β[C]γ ….. (k = rate constant, [ ] ≡ concentration)
The reaction is αth order with respect to A, βth order with respect to B, γth
order with respect to C….
• The overall order, n = (α+β+ γ +……)
E.g (1) : , Rate is first order in N2O5 , n = 1
(2) : 2HI → H2(g) + I2(g) Rate = k[HI]2 , Rate is second order in HI, n = 2
 Order and Reaction Stoichiometry:
• In many cases, this is not necessarily a simple relationship between the
stoichiometric coefficient in a reaction and the order. This is because
the reaction occurs by a complex mechanism involving a number of
steps.

• Consider the following reactions:

CH3CHO → CH4 + CO , Rate = k [CH3CHO]3/2

2 3 2  k [ Hg2 2 ][Tl 3 ]
Hg2  Tl  2 Hg  Tl , Rate 
[ Hg 2 ]

Hence, rate laws must be determined experimentally from measurements of reaction rates and cannot be
deduced from the reaction stoichiometry.
Molecularity
-the sum of stoichiometry coefficients of reactants involved in the
stoichiometrically balanced equation of the reaction.
A  Pr oduct , molecularity =1 (Unimolecular reaction)

A  B  Pr oduct , 2 A  Pr oduct , molecularity = 2 (Bimolecular reaction)

2 A  B  Pr oduct , molecularity = 3 (Termolecular reaction)

Note: molecularity ≠ reaction order

E.g Hydrolysis of ester in the presence of an acid as a catalyst

CH 3COOC2 H 5  H 2O 
[H ]
 CH 3COOH  C2 H 5OH

Since [H2O] remains constant as in the case of inversion of cane sugar, it does not affect the rate of reaction and the reaction is first order wrt ester. Hence

molecularity is 2, overall order is 1.

Methods of Determining Reaction Order?
1.The Method of Integration
2.Half-life Period Method
3.The Differential Method
4.Isolation Method
1. The Method of Integration:
Integrated form of rate expression is used. Rate equations for reactions
can be obtained from the differential form of rate equation.

This produces rate equations that can be tested to ascertain the order
of the reaction………
 (a) Zero-order reactions:
Rate is independent of the concentration of such reactant.
e.g 2 HI ( g )  H 2( g )  I 2( g )

d [ HI ]
Rate of disappearance of HI, Rate    k [ HI ]0  k
dt

k = specific rate constant for the zero order reaction

For A  Pr oduct

t = 0, a 0

t = t a-x x

dx dx
rate of formation of product, rate   k [A]0 ,  k (1)
dt dt

integrating eqn 1,

xx t t


x 0
dx  k 
t 0
dt  kt  x

Rate law: kt = x (2)

Unit of k = x/t = mol dm-3s-1

Zero-order reaction (cont’d)

Graphical Test for equation (2) gives:

Rate law: 𝑘𝑡 = 𝑥

• Plot of concentration of product versus time

(b) First-order reaction:
For A → Product
t = 0, a 0
t = t, a-x x (conc after time t)

Rate = k[A]
Rate of formation of product is:
dx
Integrating gives:  k (a  x ) (3)
dt
dx
rearranging the variables gives  kdt (4)
(a  x )
xx t t
dx

x 0
(a  x )
 k  dt
t 0

Applying the boundary conditions, the rate equation is (6)

First-order Kinetics (cont’d)
Graphical method of testing the these equations with experimental results
• Equation (6) can be written as:
• Using equation (6)
𝑙𝑛(𝑎−𝑥)=−𝑘𝑡 + ln𝑎
−𝑘
or log 𝑎 − 𝑥 = 𝑡 + log 𝑎
2.303

−𝑘
Slope= 2.303
 Second order reactions:
There are 2 possibilities: Rate may be proportional to
(1) the product of two equal initial concentrations i.e 2A → Product
(2) substances and the two concentrations are not initially equal
A  B 
k
 product

Case 1: For A → Product

t = 0, a 0
t = t, a-x x
Rate  k [ A]2
dx
 k (a  x )2 (8) x
dt
dx  1 
k t 0  
x t
  k  dt
t
Rearranging and integrating, ›››   (9)
0 (a  x ) 2 0  ( a x ) 0
 Second order reactions (cont’d)
On applying the boundary conditions, the rate equation is thus
x or 1 1 (10)
kt  kt  
a (a  x ) (a  x) a

Graphical Test:
Second order reactions (cont’d)
Case 2: Rate is proportional to the product of two different reactants
and the concentrations are not initially the same.
A + B → Product
t= 0 a b 0
t= t a-x b-x x (concentrations after time t)
dx
Rate is  k ( a  x )(b  x ) (11)
dt dx
Rearranging gives kdt  (12)
( a  x )(b  x )

Breaking this into partial fraction, we have 1  1 1  (13)

kdt     dx
a  b  (b  x ) ( a  x ) 
1 b( a  x )
Integration gives the rate equation as
kt  ln (14)
(a  b) a(b  x)
Second order reactions (cont’d)
• Graphical test gives:

1 b( a  x ) 1 b
Since equation 14 can be written as ln  kt  ln
(a  b) a (b  x) a b a
Third-order reactions:
(i) For A +2B → Products
If the reaction is first order in both A and B; and a and b are initial concentrations of A &B respectively,
dx
 k ( a  x )(b  2 x )
dt
1 a(b  2 x)
k  ln
t (b  2a ) b(a  2 x)

(ii) For A + B + C → Product (with equal initial concentrations)

t =0 a a a 0
t=t a-x a-x a-x x

𝑑𝑥 3
Rate, =𝑘 𝑎−𝑥
𝑑𝑡

1 1 1
Rate equation: 𝑘𝑡 = 2 −
2 𝑎−𝑥 𝑎2
Reaction of nth order
For nA → Product

If n ≠1, the general equation is

1  1 1 
k  n 1
 n1 
t (n  1)  (a  x ) a 
If n =1, the rate equation is
1 a
k  ln
t ax
Exercise:
𝒌
For a reaction 𝐧𝐀 𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝒅𝑪
with differential rate equation − = 𝒌𝒄𝒏 where c =
𝒅𝒕
concentration at time t and c0 = initial concentration,
1 1 1
show that for n = n, 𝑘 = −
(𝑛−1)𝑡 𝑐 𝑛−1 𝑐0 𝑛−1
 Practice Questions
1. For a gaseous reaction between A and B, the half-life period (t1/2)
were measured and data reported are
PA (mm) 400 200 200
PB (mm) 20 40 20
t1/2(min) 40 40 20
Find the order with respect to A and B. Suggest rate law and evaluate the
rate constant.
2. A second-order reaction in which both the reactants were at same
initial concentration was 50% completed in 500 sec. How long will it take
to complete 75% of the reaction? Determine the rate constant also.
 (2) Half-life Period method
• Reaction rates can be expressed in terms of half-life or half-life period. Half-

life (t½) is the time required for the concentration of a reactant to decrease to

half its initial value.

• t = t½ when x = a/2 i.e. time taken for 50% of the reactant to be consumed

2𝑛−1 −1
• Generally, a reaction of nth order has 𝑡1 = 𝑓𝑜𝑟 𝑛 ≠ 1
2 𝑛−1 𝑘𝑎𝑛−1
To determine reaction order using Half-life method…..
Consider two experiments of the same reaction with initial concentration
of 𝑎1 and 𝑎2 , and (𝑡½ )1 and (𝑡½ )2 as the corresponding half-life periods
respectively, then,
1 1
(𝑡½ )1 ∝ and (𝑡½ )2 ∝
(𝑎1 )𝑛−1 (𝑎2 )𝑛−1
Therefore,
(𝑡½ )1 (𝑎2 ) 𝑛−1
=
(𝑡½ )2 (𝑎1 )
• Taking the logarithm of both sides,
(𝑡½ )1 𝑎2
log = 𝑛 − 1 log
(𝑡½ )2 𝑎1
 Example 1:
• In a reaction when initial concentration doubles, the half-life is reduced to half. What
is the order of the reaction?
Solution:
When initial conc = 2a1, (t½) becomes (t½)/2
(𝑡½ )1
Therefore, a2 = 2a1 and (𝑡½ )2 = 2

(𝑡½ )1 𝑎1 𝑛−1
From the general equation, =
(𝑡½ )2 𝑎2

(𝑡½ )1 2𝑎1 𝑛−1

Substituting, we have (𝑡½ )1 =
2
𝑎1

2 = (2)𝑛−1

Taking the log of both sides, log 2 = 𝑛 − 1 log 2

∴ 𝑛=2

Order of reaction is 2. Hence, second-order reaction.

 3. Differential method ,

Also called initial rate method (developed by van’t Hoff). Actual rates of
reactions are determined by measuring the slopes of concentration-time
curve. If rate is determined at various initial concentrations of the reactant, plot of log
of rate versus log of concentration will give a straight line.

c
 Differential method cont’d
Consider the reaction A+B+C+…..→Product
Rate  k [ A] [ B] [C ] ..

• If a = initial concentration of reactant A, at constant concentrations of

B,C,…
And measuring the initial rate for several runs varying the initial conc of
one reactant at a time,
,

log r2  n log a2  log k r

log( 1 )
Solving this simultaneously, r2
n
a1
log( )
a2
4. Isolation Method
• Principle: This method is based on the fact that ‘if any reactant is used
in large excess, its concentration virtually remains constant, and thus
it will not affect the rate of reaction’.
• All reactants are used in very large concentration except one (say A).

• Large excess implies at least their concentrations (initial) should be at

least 10 times initial concentration of A or preferably 100 times larger
than concentration of A.

• Under these conditions, the order with respect to A may be

determined may be determined by any method earlier described
Further examples:
1. A zero order reaction is 50% complete in 20 min. How much time will it take to
reach 90% completion?
Solution:
If the initial concentration, is a (mol dm-3), x = a/2 mol dm-3.===half-life
𝑎
For zero-order reaction, 𝑡½ =
2𝑘
𝑎 (𝑚𝑜𝑙𝑑𝑚−3 ) 𝑎
𝑘= = mol dm−3 s−1.
2(20×60 𝑠) 2400

When the reaction is 90% complete, x = 0.9a mol dm-3.

𝑥 𝑎 0.9𝑎
Since 𝑘= , =
𝑡 2400 𝑡

∴ 𝑡 = 2160𝑠 = 36 𝑚𝑖𝑛