CHEMICAL KINETICS

Books:
Physical Chemistry by Peter Atkins and Julio De Paula.
Chemical Kinetics by Puri and Sharma
 Thermodynamics vs. Kinetics
Thermodynamics:
Is the reaction feasible? (G = ve?)
Which product is stable? (at equilibrium)

Ea

Kinetics:
How fast (rate) is the chemical process!
Mechanism of reaction! (any intermediate!)
 Thermodynamics vs. Kinetics

Thermodynamics favors the process (G: -ve )

Kinetics makes this reaction nearly impossible
(Requires a very high pressure and temperature over long time)
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 (C)
time (t)

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
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
 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
Unit of Rate of Reaction
Concentration time1
e.g. mol L1 sec1 or mol dm3 sec1
Gaseous reactions: Pressure time1 e.g. torr sec1

For a 0th order reaction: Rate = k

k = rate = [conc.] time1

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

k = rate/[conc.] = [conc.] time1/[conc.] = time1

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

k = rate/[conc.] 2 = [conc.] time1/[conc.] 2 = [conc.]1 time1

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

k = rate/[conc.] n = [conc.] time1/[conc.] n = [conc.]1n time1
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 + O2 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
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
Order of a Reaction
The sum of the powers of the concentration terms ( + )
in the rate equation is known as the overall order of the
reaction.
, 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.

This method was first introduced by vant Hoff in 1884.

The rate of a nth order reaction is given as

logarithmic plot of log r with log C gives a straight line of

slope n (order) and intercept log k
 Slope = n

log r
log k
log C
If a straight line plot is not obtained then the rate can not be
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
r4 Slope = nC
r3
r4
[C]

log k
t log C
This procedure avoids the possible complications 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
r4 Slope = nt
r3
[C]

r4

log k
Time
log C

The order thus determined is called order w.r.t. time (nt)

These two procedures can be combined and can be obtained a graph
where both nC and nt can be determined.

Slope = nC

Slope = nt

log C
If nt > nC as the reaction proceeds the rate falls off more rapidly
than if the true order applied to the time course of the reaction i.e.
some substance produced in the reaction is acting as an inhibitor

If nt < nC rate is falling off less rapidly with time than expected on
the basis of true order i.e. some activation of reaction exists or
autocatalysis is taking place.
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] [B] [C]
B and C are taken in excess of A and the order w.r.t A is
determined which will be .
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.

The reaction can be of any type such as

A P, A + B P, A+B+ CP
2AP nA P
1. First-Order Reaction

Slope = k/2.303

Slope = k

t
a0

t
2. Second-Order Reaction
The reaction can be any type such as
2A 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
Lets consider the reaction
Slope = k
A P

[A]
Rate = k (constant)

Rate

[A]
4. nth-Order Reaction
Lets consider the reaction AP
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) 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

When there is only one reactant the half-life of the reactant is
also the half-life of the reaction.
But this is not true particularly for reactions of higher order
with more than one type of reactants and of unequal initial
concentrations and/or different stoichiometry.

A + B P A + 2B P
At t=0 a0 b0 0 a0 b0 0
At t=t (a0 x) (b0 x) x (a0 x) (b0 2x) x
Rate = k (a0 x) (b0 x) Rate = k (a0 x) (b0 2x)
At t1/2 of A, (a0 x) = a0/2 but it is not necessary that in this
time (b0 x) = b0/2 and vice versa. Under such conditions the
half life of each reactant needs to be determined independently.
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
Rate of Homogeneous Reactions is higher than the
Heterogeneous Reactions
Rate depends on the physical state of reactants , e.g. liquid
/gaseous/solid
Rate depends on the number of collisions or encounters
between the reacting species
Surface area of the reactant
Heterogeneous reaction occurs at interface of two phases of
reactants
If one reactant is Solid , rate increases with increase in surface
area of solid phase reactant
Surface area increases , area of contact between reactants
increases - rate of encounter between reactants increases - Rate
increases
Surface area of a solid can be increased by Sub-division i.e.
dividing the bigger particles in smaller
Surface area of the reactant
Surface area of the reactant
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 G = ve

G = H TS

If temperature (T) is increased,

the term TS increases relatively by a larger extent as
compared to that of H hence G 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

Explosive Reactions Rate of reaction

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.

Increase in collision frequency alone cant explain the large

increase in rates with temperature
Effect of Concentration
Reacting molecules must Collide with proper Orientation &
sufficient Energy
Above factors increases as conc. increases & hence Rate
increases
Effect of Catalyst
A substance that increases the reaction rate without
undergoing a chemical change itself
Provides an alternate reaction mechanism faster
than mechanism in absence of catalyst
Lowers the activation energy for a chemical
reaction
Effect of Catalyst

C is catalyst ,
R 1 & R2 reactants,
P1 & P 2 products,
I is intermediate
Reaction Mechanism
Molecularity
 Molecularity Order

Number of reacting species which Sum of powers to which

concentrations are raised in the rate
collide to result in reaction law expression
Only positive integral values e.g
Zero, fractional or even be -ve
1,2,3 & never ve
Theoretical concept & value is Experimental fact & derived
from rate
derived from mechanism of law
reaction
Collision theory along with Maxwells distribution of energies
is necessary to explain the effect of temperature on the rate of
a chemical reaction

molecules ((dN/N)
Fraction of colliding

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
molecules ((dN/N)
Fraction of colliding

(T + 10) K

A
B

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

EaR
ln k

(1/T)
A and Eaare 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 doesnt 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
provided 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 eEa/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.S
T.S

Energy
Energy

Ea Ea

R P
P R
Reaction Coordinate Reaction Coordinate
 The reactants A and B and the activated complex (AB ) in the T. S.
are in quasi-equilibrium with each other and characterised by the
pseudo-equilibrium constant (K)
The rate of the product formation is influenced by the rate of
decomposition of the activated complex. The concentration of the
activated complex that are becoming product can be calculated
using equilibrium theory
Molecules that have passed through activated complex configuration
in the direction of product cant turn back and form reactant

The energy distribution among the reactant molecules is in

accordance with the Maxwell distribution.

The activated complex has one special vibrational degree freedom

associated with the mode of product formation along the reaction
coordinate i.e. it has been converted to a translational degree of
freedom along the reaction coordinate
Lets consider a simple bimolecular reaction
K k

Rate of the reaction = k [AB]

In AB one of the vib. degree of freedom = translational degree of
freedom which is responsible for the product formation

The rate at which the activated complex moves across the energy
barrier is proportional to the vibrational frequency

The rate constant (k) is related to the vib. frequency () as

k = where = kappa = transmission coeff. and 0 < 1

For convenience the value of is taken = 1 and we know kBT = h
Comparing the above two equations
The equilibrium constant K can be expressed in terms of
standard Gibbs free energy change of activation

Eyring Equation
Comparison with the Arrhenius Equation

According to Arrhenius equation

Comparing the above two equations

If the enthalpy of activation is close to the energy of activation then