CHEMICAL KINETICS

Kinetics (Ancient Greek: "kinesis", movement or to move)

Chemical kinetics also known as Reaction kinetics is the

study of rate of chemical processes.

Rate of a Reaction
Rate is defined as r = change in concentration (ΔC)
time (Δt)

the rate of formation or loss of any species –

reactant, intermediate or product.
It is important to specify which species we are talking about.
The concentration is increasing with time e.g. a product
The concentration is falling with time e.g. a reactant.

Concentration

Time
Thus rate of reaction can be expressed in terms of the rate of
consumption or disappearance of the reactant or the rate of
formation of the product.
N2 + O 2 2NO

Considering the stoichiometry of the reaction the rate of the

reaction can be expressed as
 For a general reaction

Where -a, -b, c, d are the stoichiometric coefficients and is

negative for reactants and positive for products
 Rate can be expressed in three different ways
(i) Initial rate
(ii) Average rate
iii) Instantaneous rate
Rate changes with time hence expressing
the rate as an instantaneous rate is preferable.
Instantaneous rate means rate at a particular
instant (infinitesimal change in time) i.e.
Concentration

Rate = ± d[concentration]
dt

Time
Unit of Rate of Reaction
Concentration time−1
e.g. mol L−1 sec−1 or mol dm−3 sec−1
Gaseous reactions: Pressure time−1 e.g. torr sec−1

For a 0th order reaction: Rate = k

k = rate = [conc.] time−1

For a 1st order reaction: Rate = k [conc.]

k = rate/[conc.] = [conc.] time−1/[conc.] = time−1

For a 2nd order reaction: Rate = k [conc.]2

k = rate/[conc.] 2 = [conc.] time−1/[conc.] 2 = [conc.]−1 time−1

For a nth order reaction: Rate = k [conc.]n

In 1864 Peter Waage and Cato Guldberg pioneered the
development of Chemical Kinetics by formulating the law
of mass action.

Peter Waage Guldberg

Law of Mass Action
The rate of an elementary reaction (a reaction that
proceeds through only one transition state or one
mechanistic step) is proportional to the product of the
concentrations of the participating molecules.
Rate Law
The rate of a homogeneous reaction is proportional to the
product of the concentrations of the reactants raised to some
power.
Thus for a general reaction

or

‘k’ is the proportionality constant known as rate constant or

specific rate or velocity constant.
It is independent of concentrations and time
Has a specific value at a given temperature
 Reaction Orders and Rate
• The reaction order, n, determines how the rate
depends on the concentration of the reactant.

The rate law for the

reaction can be written:
▪ Rate = k[A]0 = k
▪ Rate = k[A]1
▪ Rate = k[A]2
Order of a Reaction
The sum of the powers of the concentration terms (α + β) in
the rate equation is known as the overall order of the
reaction.
α, β are called the partial orders w. r. t the reactants A and
B respectively.
The order of a reaction generally has a value 0 to 3
Order can also have fractional value e.g. decomposition of
acetaldehyde: CH3CHO → CH4 + CO, rate = k
[CH3CHO]3/2 order = 3/2 or 1.5
Order is different from the stoichiometric coefficient and
needs to be determined experimentally.
Methods for Determination of Order of a Reaction

1. Differential Method

2. Isolation Method

3. Method of Integration

4. Half-life Method
1. Differential Method
In this method rates are measured directly by determining
the slopes of the conc. – time curves and the information is
obtained on how the rate is related to the concs.

The rate of a “nth’ order reaction is given as

A double logarithmic plot of log r with log C gives a straight

line of slope ‘n’ (order) and intercept ‘log k’
 Slope =

log
n

r
log
k
log
C rate can not be
If a straight line plot is not obtained then the
expressed as above and the reaction does not have an order
w. r. t. that particular reactant.
The rate can be measured in two different ways
1.By various runs at different initial concentrations
2.By single run but measuring the rate at different time
1. With different initial concentrations
Various runs are carried out at different initial concentrations
of the reactant and initial rates are measured by measuring the
initial slopes.
r1 r1
r2
r2 r3

log
r4 Slope = nC

r
r3
[C]

r4

log
k
t log
This procedure avoids the possible complications
C due to the
interference by products (e.g. inhibition or autocatalysis)
The order thus determined is called order w.r.t. conc. or true
order (nC)
2. At different time
In this procedure a single run is carried out and the slopes are
measured at different times. So this gives variation of rate
with respect to time.
r1 r1
r2
r2 r3

log
r4 Slope = nt
[C]

r3

r
r4

log
Ti k log
me
C
The order thus determined is called order w.r.t. time (nt)
If r1 and r2 are the rates at two different initial concentrations
C1 and C2 then
2. Isolation Method
If all the reactants except one are present in excess, the
apparent order will be the order w.r.t. the one “isolated”
reactant.
If a reaction rate is expressed as: Rate = k [A]α [B]β [C]γ
B and C are taken in excess of A and the order w.r.t A is
determined which will be ‘α’.
The order w.r.t. B and C can also be determined by similar
procedure.

This method is often used in conjunction with other

methods.
Sometimes taking a large excess of concentration of a
particular reactant may change the mechanism of a
composite reaction.
3. Method of Integration

This method needs to first make a tentative guess on what

might be the order of the reaction and the corresponding
differential equation is integrated. The constant value of ‘k’
if obtained suggests the correctness of the guess.

1. First-Order Reaction
The reaction can be of any type such as
A → P,
 Slope = k/2.303

Slope = − k

t
a0

t
2. Second-Order Reaction
The reaction can be any type such as
A→P A + B→ P
Rate = k (a0 − x)2 Rate = k (a0 − x)2 if a0 = b0
Rate = k (a0 − x) (b0 − x)

Slope = k

t
3. Zero-Order Reaction [A]0
Let’s consider the reaction
Slope = − k
A→P
Rate = k (constant)

[A]
t

Rate

[A]
4. nth-Order Reaction
Let’s consider the reaction A→P
4. Method of Half-Life

For a reaction the half-life t1/2 of a particular reactant is defined

as the time required to reduce the concentration to half of its
initial value.
a0
t1/4 : the time required to reduce
the concentration to one-fourth of
the initial value 3a0/4
(75% completion of reaction)
a0/2
t3/4 : the time required to reduce
the concentration to three-fourth a0/4
of the initial value
(25% completion of reaction)
t3/4 t1/2 t1/4
For a 1st order reaction

At t1/2 (a0 – x) = a0/2 ⇒ x = a0/2

For 1st order reaction the half-life is independent of the

initial concentration of the reactant.
For a 2nd order reaction
For a 2nd order reaction involving a single reactant or two
reactants of equal initial concentrations and reacting according
to the stoichiometry
A+B→P

At t1/2 (a0 – x) = a0/2 ⇒ x = a0/2

For a Zero order reaction

At t = t1/2 [A] = [A]0/2

kt1/2 = [A]0 – [A]0/2

t1/2 = [A]0/2k

t1/2 ∝
[A]0
For a zero order reaction the half-life is directly
proportional to the initial concentration of the
reactant.
For a nth order reaction
If (t1/2)1 and (t1/2)2 are the half lives at two initial
concentrations (a0)1 and (a0)2, respectively then
Factors Affecting the Rate of a Reaction

1. Concentration of the reactants

Physical state
2. Nature of reactants Surface area
Molecular nature

❖ Rate of reactions with reactants in

gaseous phase > solution phase > solid phase

❖ Larger the surface area, larger is the area of contact

hence faster is the rate of the reaction
Molecular nature of the reactant

More is the structural similarity between the reactant

and the product ⇒ faster is the reaction (Not always)

Lesser the rearrangement of bonds needed in the reaction

⇒ faster is the reaction

NO + ½ O2 → NO2 ..……………..(1)

CH4 + 2O2 → CO2 + 2H2O ……..………..(2)

3. Effect of Temperature

Temperature has a marked effect on the reactions

(i) Can initiate a reaction
(ii) Increases the rate of the reaction

For a reaction the thermodynamic requirement is ΔG = −ve

ΔG = ΔH − TΔS

If temperature (T) is increased,

the term TΔS increases relatively by a larger extent as
compared to that of ΔH hence ΔG can become −ve and the
reaction can be initiated
Rate of reaction increases with increase in temperature

Rate of reaction
→
Temperature (T) →

Enzymatic Reactions
Rate of reaction

Rate of reaction
Explosive Reactions
→

Temperature (T) → Temperature (T) →

 For most of the reactions the rate of the reaction doubles or
triples by raising the temperature by 10 K

Temperature Coefficient Rate constant at (T+10) K

= Rate constant at T K
Why does temperature speed up a reaction ?

A chemical reaction takes place due to intermolecular

collisions. On increasing temperature, the kinetic energy of
reacting molecules increases and hence collision frequency
increases.
Z ∝ √T

Increase in collision frequency alone can’t explain the large

increase in rates with temperature
Collision theory along with Maxwell’s distribution of energies
is necessary to explain the effect of temperature on the rate of
a chemical reaction
Fraction of colliding
molecules (dN/N)
→

Energy → T.
E
Collision between molecules possessing energy equal to or
greater than the threshold energy is called effective collision
Number of molecules possessing lower energies decreases,
whereas the number of molecules possessing higher energies
increases with increase in temperature

TK
Fraction of colliding

(T + 10) K
molecules (dN/N)

A’

B’
→

A
B

D C
Energy →
T.
E double or more,
Number of effective collisions become
which results in the observed increase in the rate
Arrhenius Equation
ln A

− Ea/R
ln k
→

(1/T) →
‘A’ and ‘Ea’ are called Arrhenius parameters
A: Pre-exponential factor or Frequency factor or
Limiting rate constant
Ea: Activation energy
A higher activation energy signifies that the rate constant
depends strongly on temp.
 Activation Energy
Molecules need a minimum amount of energy to react.
Visualized as an energy barrier - activation energy, Ea

Even though reaction is exothermic, the reaction still needs an activation energy.
The lower the Activation barrier, the faster the reaction
If the activation energy (Ea) and pre-exponential factor (A)
are independent of temperature
4. Presence of a Catalyst
A catalyst is a substance that may increase or decrease the
rate of a reaction
Increase in rate ⇒ +ve catalyst or promoter
Decrease in rate ⇒ −ve catalyst or inhibitor
Energy

Ea1 Ea2
→

R
P
Reaction Coordinate →
 Catalyst provides an alternative pathway

By providing an alternative pathway (or mechanism) with

lower activation energy.
Homogeneous Catalyst- In the same phase as the reactants.
Acid-base catalysis, Enzymatic catalysis
Heterogeneous Catalyst- In a different phase, for example a solid
catalyst for a gas phase reaction.

• Enzymes are catalysts in biological systems.

• The substrate fits into the active site of the enzyme much like a key
fits into a lock.
A catalyst affects both the forward and backward reaction
equally.

Thus it doesn’t change the state of equilibrium, it only hastens

the approach of equilibrium.
Rate of reaction →

Rate of forward reaction

Rate of backward reaction

t2 t1
Time →
 Theories of Chemical Reactions

There are various theories proposed to explain chemical

reactions.

The most important theories are

1.Collision Theory

2. Transition-State Theory or Activated Complex Theory

or Absolute Reaction Rate Theory
 Collision Theory

❖ This is the oldest theory based on kinetic theory of

collisions.

❖ Originally suggested for gas phase reactions.

❖ This suggests that we can understand the rates of

reactions by analysing the molecular collisions.

❖ All assumptions of kinetic theory of gases are applicable

 Assumptions
❖ The molecules/atoms are hard spheres

❖ The molecular motions are explained by classical

mechanics or Newtonian mechanics

❖ The size of the molecules is negligible as compared to the

typical distance between them

❖ Due to the kinetic energy of molecules, they move around

and collide with each other

❖ The molecular collisions are perfectly elastic i.e. energy is

conserved
The velocity of the molecules is distributed according to
Maxwell distribution
The mean velocity of a molecule is given as

kB = Boltzmann constant, T = Temperature,

m = mass of a molecule
Considering collision between two types of molecules A and B
of mass mA and mB then the mean relative velocity is given by

Where
The rate of the reaction can be calculated from the rate at
which the reactant molecules are colliding
So the collision rate or collision number (number of
collisions per unit volume per unit time) is expressed as

= Collision cross section

The collision between A and B will result in a reaction when
the energy of the collision is sufficient to overcome the
energy barrier Ea(effective collision)

According to Boltzmann distribution the fraction of

collisions with energy of Ea is proportional to e−Ea/RT

So the number of effective collisions per unit volume per unit

time = number of product molecules formed per unit volume
per unit time

Number of moles of product formed per unit volume per unit

time
The rate expressed in moles/unit volume/unit time is

If the reaction is first order w.r.t. both A and B

A+B→P
r = k [A] [B]
Comparing the two equations we get

‘k’ is the bimolecular rate constant or

second order rate constant
Comparison with the Arrhenius Equation
According to Arrhenius equation

According to Collision Theory

= steric factor
 Transition State Theory/ Absolute Reaction Rate Theory/
Activated Complex Theory
Suggested by Eyring, Evans and Polyani in 1935
The reactants form some sort of complex with a structure
somewhere between the reactant and the product and called
as Transition-state or Activated complex
T.
T. S
S

Ea
Energy
Ea
Energy

→
→

R P
P R
Reaction Coordinate → Reaction Coordinate →
 Run concentration (mole dm-3) Initial rate (mole dm-3 S-1)

[A] [B]

1 0.50 1.0 2.0

2 0.50 2.0 8.0
3 0.50 3.0 18.0
4 1.0 3.0 36.0
5 2.0 3.0 72.0
the table represents the data obtained for a reaction between A and B, Calculate (i) the
order of reaction with respect to A, (ii) ) the order of reaction with respect to B, (iii) Write
the rate equation for the reaction and calculate the rate constant.
Solution: Let the rate equation be , Rate = k[A]m [B]n …… (1), where m and n are the order
with respect to A and B, respectively.
(i) Calculation of M: In cases of runs 3, 4, 5 it is found that the concentration of B is
constant. Therefore, in these cases reaction rate is dependent on the concentration of
only. The rate equation can be written
Rate∞ [A]m ……. (2)
It is also found that (in cases of runs 3, 4, 5) rate of reaction become double as the
concentration increase to double or rate of rate increase3 times if the concentration increase
four times i.e, rate of reaction is directly proportional to the concentration of A. therefore,
 Examples:
For the reaction A+B = C, the following results are obtained at a constant temperature:

Run concentration (mole dm-3) Initial rate (mole dm-3 S-1)

[A] [B]
1 0.20 0.10 0.20
2 0.40 0.10 0.80
3 0.40 0.20 0.80
Calculate (i) Write the rate equation for the reaction (ii) calculate the rate constant, (iii)
find the initial rate of the reaction when [A]o = 0.60 mole dm-3and [B]o = 0.30 mole dm-3.
The initial rates measured for a reaction at different initial concentration are tabulated below:
Run concentration (mole dm-3) Initial rate (mole dm-3 min-1)

[A] [B]
1 0.150 0.25
2 0.150 0.50
3 0.075 0.50
4 0.075 0.25
Calculate (i) Write the rate equation for the reaction (ii) calculate the rate constant, (iii) find
the initial rate of the reaction when [A]o = 0.120 mole dm-3and [B]o = 0.220 mole dm-3.
Alkaline hydrolysis ester is given by the reaction
CH3COOC2H5 + NaOH = CH3COONa + C2H5OH

Time (min) 0 5 15 25 35

Volume of alkali solution(cm-3) 16.0 10.5 6.25 4.5 3.52

(i) From the above data determine whether the order of reaction is 1st or 2nd?
(ii) Derive the integrated equation for above stated reaction.
(iii) Find out the relationship with the half life and initial concentration for the above
stated reaction.
(iv) calculate the time required for the completion of 90% of the reaction.