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Chemical Kinetics
 Extent of a Speed of a
Feasibility of
Chemistry is always chemical chemical
a reaction
concerned with change. reaction reaction

Chemical Equilibrium
By means of a
chemical reaction
Thermodynamics Chemical Kinetics
 Chemical Kinetics

It deals with the Along with feasibility

rate of a chemical and extent, it is
reaction and the equally important to
know the rate and the
mechanism by
factors controlling the
which it proceeds. rate of a chemical
reaction.

Chemical
Kinetics
Thermodynamics vs Chemical Kinetics

Thermodynamics tells only about

the feasibility of a reaction.

However, chemical kinetics

tells about the speed
with which it proceeds.
Rate of a Chemical Reaction

Example:
Burning of
Some reactions are rapid LPG fuel
 Rate of a Chemical Reaction

Some reactions proceed with moderate Speed

Inversion of cane sugar

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose

Decomposition of hydrogen peroxide

2H2O2 2H2O + O2
 Rate of a Chemical Reaction

Example:
Rusting of
Some reactions are very slow iron
 Rate of a Chemical Reaction
Rate can be expressed as

The rate of change

of concentration,
The rate of decrease in
with time, of different
concentration (disappearance)
chemical species
of reactants
taking part in a chemical
reaction.

The rate of increase in

Known as rate of reaction concentration (appearance)
w.r.t. that species of products
 Rate of a Chemical Reaction

For a gaseous reaction at

constant temperature,

Concentration ∝ Partial pressure

of species

Rate is expressed as the rate

of change in partial pressure
of a reactant or a product.
 Types of Rate

Types of rates

Average Instantaneous
rate rate
 Average Rate of Reaction
For the reaction,

R P

Total change in concentration

Average
rate
= Total time taken

Cfinal ⎻ Cinitial
= tfinal ⎻ tinitial

ΔC
=
Δt
 Average Rate of Reaction

R P

Rate of disappearance of reactant (R)

[R]initial = Initial concentration
of reactant at tinitial Decrease in concentration of R
[R]final = Final concentration
Average
rate
=
Time taken
of reactant at tfinal
[R]final < [R]initial
[R]final ⎻ [R]initial
Average
rate
= tfinal ⎻ tinitial
 Average Rate of Reaction

R P

Rate of appearance of product (P)

[P]initial = Initial concentration Average Increase in concentration of P

of product at tinitial rate
[P]final = Final concentration
of product at tfinal
[R]final < [R]initial Average
rate
= Time taken
[P]final ⎻ [P]initial
= tfinal ⎻ tinitial
 Average Rate of Reaction

As we know,
During a
reaction

The concentration The concentration

of the reactant of the product
decreases. increases.

[R]f < [R]i [P]f > [P]i

 Average Rate of Reaction

For reactant R,

Average [R]final ⎻ [R]initial Δ[R]

The rate is defined in
rate = tfinal ⎻ tinitial = ⎻
Δt
a manner so that

It is always a For product P,

positive quantity
Average [P]final ⎻ [P]initial Δ[P]
rate = tfinal ⎻ tinitial = +
Δt
 Average Rate of Reaction

R P

1 mol of R 1 mol of P

Rate of
disappearance of R
= Rate of
appearance of P

Average rate of Δ[R] Δ[P]

reaction, ravg
= −
Δt
= +
Δt
 Average Rate of Reaction (Graph)
[R]0

[R1]
Concentration of R vs time ravg

Concentration
– {[R2] − [R1]}

of reactants
Δ[R]
Rate = =− Δ[R]
(t2 − t1) Δt
[R2]
Δt

t1 t2
Time
 Average Rate of Reaction (Graph)

(P)

ravg
Concentration of P vs time

Concentration
[P2]

of products
+ {[P2] − [P1]} Δ[P]
Rate = = +
(t2 − t1) Δt Δ[P]

[P1]
Δt

t1 t2
Time
 Instantaneous Rate of Reaction

Instantaneous rate of
Rate of reaction disappearance of R
at a particular
d[R]
instant RInstantaneous = –
dt

Instantaneous rate of
appearance of P
R P
d[P]
ravg = -
Δ[R]
=+
Δ[P] RInstantaneous = +
dt
Δt Δt
Relation Between Rates
of Different Species
Involved in a Reaction
 Rate of Reaction

Example N2 (g) + 3H2 (g) 2NH3 (g)

d[N2]
These all are
Rate of reaction
w.r.t. N2
= –
dt
correct rate
expressions.
Rate of reaction d[H2]
w.r.t. H2
= –
dt

Rate of reaction d[NH3]

However, they
are not equal w.r.t. NH3 = +
dt
 Rate of Reaction

N2 (g) + 3H2 (g) 2NH3 (g)

1 Rate of
Rate of
consumption of N2
= 3 consumption of H2

1 mol N2 reacts
with 3 mol H2 to 1 Rate of
produce 2 mol NH3. = 2 formation of NH3
 Rate of a Chemical Reaction

By By dividing
As the
convention, the individual
overall
the rate of a rates with their
rate of
reaction is stoichiometric
reaction
expressed coefficients
 Rate of a Chemical Reaction

aA + bB cC + dD

Average rate 1 Δ[A] 1 Δ[B] Instantaneous d[A] 1 d[B]

of reaction, = – = – rate of = – 1 = –
a Δt b Δt a dt b dt
ravg reaction, rinst

Δ[C] + 1 d[C] + 1 d[D]

= + 1 = + 1 Δ[D] = =
c Δt d Δt c dt d dt
 Important

The value of the rate of

reaction is independent on the
stoichiometric coefficients of
substances involved in a reaction.

However, the rate w.r.t. any

species is dependent of
its stoichiometric coefficient.
 Unit of Rate of a Chemical Reaction

We know,
Unit of ΔC mol/L
1 L = 1 dm3 = 10-3 m3 = 103 cm3 Unit of
rate
= = s
Unit of Δt
ΔC
Rate =
Δt
= mol L−1 s−1
Where,
ΔC: Change in concentration
of any species
Δt: Time change corresponding = mol dm−3 s−1
to the concentration change
 Note!
For a gaseous reaction at a constant
temperature, rate is expressed as

dp
rinst = dt

Where,
p: Partial pressure of the
component

Unit of rate equation = atm s−1

 Factors Affecting Rate of a Chemical Reaction

1 Effect of concentration

Effect of nature of
2
reactant and product
Kinetic studies help us
determine the speed of
a reaction and describe 3 Effect of Pressure
the conditions that can
alter the reaction rate.
Effect of temperature 4

5 Effect of catalyst
 Effect of Concentration
From law of mass action, we know

Rate of
reaction ∝ Concentration
of reactants

The rate of reaction is often

found to be proportional to the
concentrations of the reactants Generally, rate of reaction
raised to a power. decreases with passage of time,

Due to decrease in
concentration of reactants
 Rate Law or Rate Expression

Simple rate laws can

be obtained by starting
Instantaneous with pure reactants.
rate
For these reactions,

It is an equation that expresses

the rate of reaction as a
function of the concentration
Rate ∝ (concentration)order
of all the species present in the
overall chemical equation for
the reaction at some time.
Rate = k (concentration)order
 Rate Law or Rate Expression

Rate of reaction ∝ [A]x [B]y

aA + bB cC + dD

Rate of reaction = k [A]x [B]y …(1)

k: Proportionality constant (rate
constant)
x and y: May or may not be equal to Where a, b, c, and d are stoichiometric
stoichiometric coefficients coefficients of reactants and products
(a and b) of reactants
 Rate Law

Rate of reaction = k [A]x [B]y …(1)

It is the expression in which the
reaction rate is given in terms of the
Eq. 1 can also be written as molar concentration of reactants.

d[A]
⎻ dt = k [A]x [B]y
With each term raised to some power

Which may or may not be the same

Differential as the stoichiometric coefficient
rate equation of the reacting species
 Rate Law

It can only be established Reactant Product

by experiments.

It may differ for the same reaction Rate = kk [Reactant]order

under different conditions.
 Note!

For homogeneous gas phase

reactions, it is often more convenient to
express the rate law in terms of partial
pressure, which is related
to molar concentration as:

p
J
= RT[J]
 Rate Constant

Rate = k[Reactant]order

It is the rate of reaction when the Rate

concentration of reactant is unity. k = [Reactant]n

It is also known as the

specific reaction rate Where n is the order of the reaction
 Rate Constant

The rate constant (k) Unit of

mol L−1
depends only on concentration
temperature and not
on concentration.

Unit of rate (Concentration)1 time−1

Rate dC
k= Rate =
[Reactant]n dt

Unit of k mol1−n Ln−1 s−1

 Order of a Reaction

Experimentally,
aA + bB + cC Products

R ∝ [A]p [B]q [C]r

The power to which

the concentration of a
species is raised in a
rate law is the order
of the reaction with
respect to that species.
Where,
p: Order of reaction w.r.t. A
q: Order of reaction w.r.t. B
r: Order of reaction w.r.t. C
 Order of a Reaction

aA + bB + cC Products
R ∝ [A]p [B]q [C]r

Rate ∝ [A]p [B]q [C]r

Thus p, q, and r indicate

Order of a Reaction:
It is the sum of powers
of the concentration of
the reactants in the rate
law of a chemical
reaction.
how sensitive the rate is
to change in concentration
of A, B, and C, respectively.
Sum of the
(p + q + r)
exponents
 Remember!
aA + bB + cC Products

Rate ∝ [A]p [B]q [C]r

‘p’ may or may not be equal to ‘a’.

‘q’ may or may not be equal to ‘b’.

‘r’ may or may not be equal to ‘c’.

Characteristics of Order of a Reaction

The order of a reaction can be

1 zero or any whole number.

It can be a
2 fractional number.

It can even be negative with

3 respect to a particular reactant.

Overall order can

never be negative.
 Order of a Reaction

Example:

2N2O5 (g) 4NO2 (g) + O2 (g)

Rate law = k [N2O5]1

Overall
order
= 1
 Order of a Reaction

Example:

5Br− (aq) + BrO−3 (aq) + 6H+ (aq) 3Br2 (l) + 3H2O (l)

Rate law = k [Br− ] [BrO3− ] [H+]2

Overall
order
= 1+1+2 = 4
 Order of a Reaction

A balanced equation does not The reaction involves

necessarily give us a true picture only a single step.
of how the reaction takes place.
For an elementary reaction,

Rarely, a reaction gets The sum of

Order of the
completed in one step. stoichiometric = reaction
coefficients
 Remember!
For the elementary reaction,

H2 (g) + I2 (g) 2HI (g)

Rate = k [H2] [I2]

Overall
order
= 2
 Remember!
For a complex reaction,

The reaction Steps involved:

involves more
than one step. 2NO ⇌ N2O2 Step 1

N2O2 + H2 N2O + H2O Step 2

The order is experimentally
calculated.
N2O + H2 N2 + H2O Step 3

For example:

2NO + 2H2 N2 + 2H2O Rate = k [NO]2 [H2]

Methods to Analyse Rate of a Reaction

1 Initial rate method

Integrated rate
2
law method

3 Graphical method

Unit method 4
 Initial Rate Method

aA + bB + cC Products [R]0 rinitial

It is instantaneous rate
at the start of the
The method involves reaction (t = 0).
finding the initial rate
rinst

Concentration
of reactant R
of the reaction
d[R]

dt

By taking known
concentrations of
different reactants.
t
Time
 Initial Rate Method

Involves comparison
aA + bB + cC Products
of different initial
rates of a reaction

By varying the
Rate = k [A]p [B]q [C]r
concentration of one
of the reactants
The concentration of A is
While other reactants changed, by keeping the
are kept constant concentrations of B and C
same as before.
 Initial Rate Method

Two different initial concentrations [A0]1 p

r1
of A, [A0]1, and [A0]2 are taken.
r2
=
[A0]2
The initial rates of the
reaction are determined as,

r1 = k′ [A0]1p The value of ‘p’ can be

calculated by measuring the
values of r1, r2, [A0]1, and [A0]2.
r2 = k′ [A0]2p
Following the same method, q
and r can also be calculated.
k′ = k [B]q [C]r
Methods to Analyse Rate of a Reaction

The rate law tells about

the dependency of the rate of
the reaction on the
concentration of reactant(s).

But it does not tell how the

concentration changes with time
 Integrated Rate Law Method

This method, quantitatively, Zero-order

gives the concentration of reaction
reactant(s) as a function of time.
Integrated
rate law for

First-order
The form of the integrated rate reaction
equation depends on the order of
reaction.
 Zero-Order Reaction
For a zero-order
For a general reaction reaction
Where,
A Product(s)
n : Order = 0
k : Rate constant
[A] : Concentration of
reactant A
According to the rate law,

Rate of
reaction
= k [A]n
Rate = k
 Plot of Rate vs Time
For a zero-
Rate = k [A]0 order reaction

Rate = k[A]n

Zero-order
d[A]
− = k[A]0
Rate

dt

d[A]
⎻ = k
Concentration dt
 Zero-Order Reaction

Rate = k [A]0
When Concentration
of A = [A]0
time = 0
⎻ d[A] = k dt
Initial
concentration
Integrating both sides from time (t) = 0 to t

[A]t t

⎻∫ d[A] = ∫
k dt
When Concentration
= [A]t
0 time = t of A
[A]o
 Zero-Order Reaction
[A]t t

⎻∫ d[A] = k dt ∫
[A]0 0

[A]t t
Integrated rate { ⎻ [A] }
[A]0
= k{ [t] }
0
law of zero-order

[A]0 ⎻ [A]t = kt
Plot of Concentration of Reactant vs Time

[A]t = [A]0 − kt
… (1)

[A]0
Zero-order

Slope = -k
[A]

t
 Rate Constant for Zero-Order Reaction

Unit of k = mol1−n Ln−1 s−1

[A]0 − [A]t
k =
t

Unit of k Concentration1 time−1

So, Unit of k mol L−1 s−1

 Time of Reaction Completion (tC)
At this time, the reactants
are consumed [A]0 − [A]t
completely. k =
t

So, at tc,
[A]tc = 0
[A]0 − 0
k =
tc
Zero-order
[A]

[A]0
tc =
k
t tC
 Half-Life Period (t1/2)

When the concentration At

of reactants becomes half
of its initial concentration t = t1/2

[A]o
[A]t =
It means that the reaction 2
is half-completed.
 Half-Life Period (t1/2)

[A]0 − [A]t Putting concentration value at t1/2 in eq. (1),

k= … (1)
t
[A]o ⎻ {[A]o/2}
t1/2 = k

[A]o
t1/2 =
2k

t1/2 ∝ [A]0
Plot of t1/2 vs Concentration

t1/2 ∝ [A]o

Zero-order

t1/2

Concentration
 Examples of Zero-Order Reaction

Pt
i 2NH3 (g) N2 (g) + 3H2 (g)
Generally,
the decomposition of Au
gases on metal surfaces ii 2HI (g) H2 (g) + I2 (g)
at high concentration
follows zero-order Ni
iii 2PH3 (g) 2P (g) + 3H2 (g)
kinetics.

hν
iv H2 (g) + Cl2 (g) 2HCl (g)
 Zero-Order Reaction

In a zero-order reaction equal concentration

of reactants get consumed in equal time.

t1/2 A0 t1/2
A0 0
2

tc
Example

t = 10 s t=5s t = 2.5 s
[R] 100 90 85 82.5
 Zero-Order Reaction

Generally, in a zero-order reaction, Replace k by nk in all the previous formulas.

nA Product
Rate = nk

Rate = k [A]o
[A]0 ⎻ [A]t = nkt

d[A]
⎻ = k [A]0
n dt tc =
nk
 First-Order Reaction
Rate = k [A]n
For a general reaction,
For a first-order
Where,
A Product reaction,

n : Order = 1
According to the rate law, k : Rate constant
[A] : Concentration of
reactant A
Rate (R) = k [A]n

Rate = k [A]
 Plot of Rate vs Time

R = k [A] Rate = k [A]n

R = k [A]
First-order
Rate

d[A]
⎻ = k [A]
dt
Concentration
 First-Order Reaction

A Products
d[A]
⎻ dt
= k [A]

Time = 0 a 0

d(a − x)
⎻ = k (a − x)
dt
Time = ‘t’ a–x x
 First-Order Reaction

x t
dx
∫ a−x
0
= k
∫ dx
dx 0

dt
= k (a − x)
Integrating both sides,

As ‘a’ is a constant value, a

ln
a−x = kt

dx
a−x
= k dt

a
2.303 log
a−x = kt
 First-Order Reaction

The integrated rate law of first-order reaction

a 1 [A]0
ln
a−x = kt … (1)
t
ln = k
[A]

[A]0 2.303 [A]0

ln = kt
… (2) t
log
[A]
= k
[A]
 First-Order Reaction

2.303 [A]0
log k
t [A] =

kt
log[A]0 − log[A] = 2.303

kt
log [A] = log[A]0 −
2.303
Plot of log [A] vs Time
kt
log[A] = log[A]0 −
2.303

First-order

log [A]

t
 First-Order Reaction

[A]0 Multiplying eq. (2) by -1,

ln = kt … (2)
[A] [A]0
— ln = — kt
[A]

[A]
ln
[A]0
= — kt

Eliminating natural log from both the

sides,

[A] ⎻ = [A]0 e—kt … (3)

 Plot of [A] vs Time

[A] = [A]0 e−kt

First-order

[A]

t
 Half-Life Period for First-Order Reaction
Putting the value of x in eq. (1),
a
ln = kt …(1)
a−x a
ln
a−
a = kt1/2
Reaction will be 2
half-completed.

1
a
t1/2 = ln2
At k
x = 2
t = t1/2
0.693
t1/2 ⎻ = k
 Plot of t1/2 vs Concentration

0.693
t1/2 =
k
First-order
Does not depend
on the concentration

t1/2
of reactants

Concentration
 Unit of Rate Constant (k)

Rate = k [Conc.]

Unit of rate mole L−1 sec−1

Unit of conc. mole L−1

Unit of k sec−1
 Note!

In the first-order reaction, an

equal percentage of reactants
get consumed in equal time.

Example

t=5
[R] 100 sec 90

t = 5 sec

72.9 t = 5 sec
81
 Note!

Generally, for a first-order reaction, Replace k by nk in all

the previous formulas.

nA Product 2.303 [A]0

t
log = nk
[A]

Rate = k [A]
[A] = [A]o e—nkt

d[A]
⎻ n dt
= k [A]
0.693
t1/2 = nk
 Examples

1 Decomposition of H2O2 takes place.

MnO2
2H2O2 (aq) 2H2O (l) + O2 (g)

All radioactive decays are

2
always first-order kinetics.

226Ra
88
222Rn
86
+ 4
2He
 Pressure Measurement

As we know,
n
PV = nRT
So, P = V
RT

n
V: Volume P ∝ V
n: Number of moles
P: Pressure
R: Gas constant
T: Temperature P ∝ Concentration
 Pressure Measurement

A (g) B (g)
+ C (g)
So, for the reactions
involving gaseous
reactants and products
Progress of a reaction involving
gaseous reactants/products
can be monitored by

Pressure is considered
to monitor the reaction
instead of concentration Measuring the total pressure at a
fixed volume and temperature
 Pressure Measurement

In terms of
concentration A B + C A (g) B (g) + C (g)

At time t, a−x x x
t=0 P0 0 0

t=t P0 − Pr Pr Pr

P0: Initial pressure

Pr: Pressure due to amount of
reactant consumed up to time ‘t’
 Pressure Measurement

The pressure measurement

can be done in two ways

(i) Partial pressure of the reactant

(ii) Total pressure of the reaction system

 Pressure Measurement
In terms of
concentration A B + C Total pressure
Pt
at time ‘t’
At time t, P0 − Pr Pr Pr

According to Dalton’s law,

Pt = (P0 − Pr) + Pr + Pr

Pt = P0 + Pr

Pr = Pt − P0
 Pressure Measurement

As, Concentration ∝ Pressure

a ∝ P0

a−x ∝ P0 − Pr

a P0
a−x
= …(1)
P0 − Pr
 Pressure Measurement
For the first-order reaction,
a [A]0
kt = ln
a−x = ln
[A]
a P0
= …(1)
a−x P0 − Pr Substituting values from eq. (1) in
the first law expression,

Pt = (P0 − Pr) + Pr + Pr P0 [PA]0

Pt = P0 + Pr
kt = ln
P0 − Pr = ln
[PA]

Substituting the value of Pr,

P0
kt = ln
2P0 − Pt
 Unit of Rate Constant (k)

Rate = k [Concentration]n Unit of k: mol1−n Ln−1 s−1

Unit of For zero

mol L−1 s−1
mol L−1 order (n = 0)
concentration

For first
s−1
Unit of rate mol L−1 s−1 order (n = 1)

For second
mol−1 L1 s−1
Unit of k mol1−n Ln−1 s−1 order (n = 2)
Half-Life Period for nth Order Reaction

1
So, t1/2 ∝ an – 1

Any reaction of any order

will follow this relation.
 Half-Life Period for nth Order Reaction

For first-order reaction,

1
t1/2 ∝ [A] n – 1
0 t1/2 is independent
of [A] 0

For zero-order reaction,

For second-order reaction,
t1/2 ∝ [A] 0
t1/2 ∝ 1
[A] 0
 Pseudo Order Reactions

The order of a reaction is

sometimes altered by conditions.
Depending upon the
conditions, a second-order
reaction can behave as a
first-order reaction.
A reaction whose order is different
from the actual order due to excess
concentration of one of the reactants
is known as pseudo order reaction.
 Pseudo First-Order Reaction

For a second-order reaction,

If the concentration of one reactant,
A + B Product(s)
A, is taken in excess,

The change in concentration of A

Rate = k [A][B]
is negligible during the reaction.
Pseudo First-Order Reaction

So, it can be considered

as constant.

Now, the reaction rate

depends on the concentration
of the other reactant (B) only.

The reaction becomes

a first-order reaction.
 Pseudo First-Order Reaction

Rate = k [A] [B]

The reactions that are actually of

A + B Product(s) second (or higher) order but
behave as first-order reactions

Rate = k′ [B]
Pseudo first-order reactions

Where k′ = k[A]
 Examples of Pseudo First Order Reaction
Hydrolysis of Ethyl Acetate

0.01 mol of ethyl H+

CH3COOC2H5 + H2O CH3COOH + C2H5OH
acetate + 10 mol H2O

t=0 0.01 10 0 0

t=t 0.01-x 10-x x x

 Hydrolysis of Ethyl Acetate
CH3COOC2H5 + H2O CH3COOH + C2H5OH

Rate = k [CH3COOC2H5] [H2O] Rate = k′[CH3COOC2H5]

As the change of [H2O] during the reaction is

negligible (≈ 0.01 mol out of 10 mol consumed),
Pseudo first-order reaction

k [H2O] = Constant = k′
 Hydrolysis of Ethyl Acetate

C12H22O11 + H2O C6H12O6 + C6H12O6

Water
Sucrose Glucose Fructose
(excess)

Rate = k [sucrose] [water]

Rate = k′ [sucrose]
Hydrolysis of Ethyl Acetate

Hydrolysis of
cane sugar
 Graphical Representation

1 3

Rate vs concentration
of reactant(s)
Rate vs Concentration of Reactant(s)
For a general reaction,

A Product(s)

Rate law,

Rate = k [A]n

d[A]
dt
= k [A]n
 Rate vs Concentration of Reactant(s)
For nth order reaction
Zero-order First-order
Rate = k [A]n

Rate

Rate
Concentration Concentration

Second-order Second-order

Rate
Rate

Concentration (Concentration)2
Concentration of Reactant(s) vs Time (For Zero-Order)

[A] = [A]0 − kt

[A]0

[A]
[A]0
k
Time
Concentration of Reactant(s) vs Time (For First-Order)

[A] = [A]0 e−kt

kt

[A]
log[A] = log[A0] −
2.303

Time
[A]0
[A]

log [A]
log

Time Time
 t1/2 vs Concentration of Reactant(s)

[A]0 0.693 1
t1/2 = t1/2 = t1/2 =
2k k k[A]0

Zero-order First-order Second-order

t1/2

t1/2

t1/2
Concentration Concentration 1/Concentration
 Unit Method

For an nth order reaction, we know that, Unit of k: mol1−n Ln−1 s−1

Rate
k= For zero
[Concentration]n mol L−1 s−1
order (n = 0)

Unit of k = mol1 − n Ln − 1 s−1 For first

s−1
order (n = 1)

In this method, the order

of a reaction can be
For second
determined by observing mol−1 L1 s−1
order (n = 2)
the unit of the rate constant.
 Effect of the Temperature on Rate of Reaction

The effect of Can be

Generally, for a chemical temperature mathematically Temperature
reaction with rise in on reaction expressed coefficient
temperature by 10°, rate using
the rate constant
is nearly doubled.
 Arrhenius Equation (With and Without Catalyst)
Without catalyst

k = Ae -Ea/RT … (1)

With catalyst
Potential

Ea
energy

Ea′
kcat = ′
Ae -Ea/RT … (2)

R
P
k: Rate constant without catalyst
Reaction coordinate
kcat: Rate constant with catalyst
Ea: Activation energy without catalyst
Ea′: Activation energy with catalyst
 Trying to Interpret Arrhenius Theory

Example

Elementary reaction

A2 + B2 2AB

According to Transition state theory,

The reaction can take place

1 only when a molecule of A2
and a molecule of B2 collide.
 Trying to Interpret Arrhenius Theory

The collision leads to the

2
formation of an unstable state.

Transition state
It exists for a very short
Potential
energy

time and gradually a product

is formed from this.

Reaction coordinate
This is called Transition-state
complex/ Activated complex
 Reaction and Transition State Complex

A B A B A B

+ +
A B A B A B

Transition state
Reactants complex/Activated Products
complex
Trying to Interpret Arrhenius Theory

Energy required to form

3
the activated complex

Activation energy
 Plot of Potential Energy vs Reaction Coordinate
A B
A2 + B 2 2AB
Activated
complex A B

Endothermic
Activation

Potential energy
or exothermic energy (Ea)

The final enthalpy A B

of the reaction depends A B A 2 + B2 A B

upon the nature of
A B 2AB
reactants and products.
Reaction coordinate
 Enthalpy Change During a Reaction
For exothermic
A+B C+D △H < 0
We know enthalpy reaction
change for a reaction
Activated
complex

△H = ΣHP − ΣHR

Potential energy
Ea

ΣHP = Summation of enthalpies of ∑HR

product(s) Reactants ΔH
ΣHR = Summation of enthalpies of ∑HP A+B
Products
reactant(s) C+D
Progress of the reaction
 Enthalpy Change During a Reaction
For endothermic
A+B C+D △H = ΣHP − ΣHR > 0
reaction

Activated
complex

Potential energy Ea

∑HP Products
ΔH C+D
∑HR
Reactants
A+B
Progress of the reaction
 Enthalpy Change During a Reaction
For a reversible
exothermic reaction
Ea E
Reactants ⇌ Products f ab

Enthalpy (H)
∑HR
Reactants
ΔH
Enthalpy change can
also be expressed in terms ∑HP
of activation energy, Products

Progress of reaction
(or reaction coordinate)
△H
= E af− E a
b
Eaf = Activation energy of the forward reaction
Ea = Activation energy of the backward reaction
b
 Enthalpy Change During a Reaction
For a reversible
exothermic reaction
Ea E
Reactants ⇌ Products f ab

Enthalpy (H)
∑HR
Reactants
ΔH
Enthalpy change can
also be expressed in terms ∑HP
of activation energy, Products

Progress of reaction
(or reaction coordinate)
△H
= E a− E a
f b
Eaf = Activation energy of the forward reaction
Eab = Activation energy of the backward reaction
 Remember!

Greater the height

of the energy barrier

E
Potential energy

∑HR Greater will be the

activation energy
∑HP

Reaction coordinate
Slower will be the
reaction rate
Decrement in Energy After Transition State

Endothermic
or exothermic

The final enthalpy of the

reaction depends upon the
nature of reactants and products.
 Activation Energy vs Threshold Energy

Threshold Activation
energy energy

Potential energy
Eaf Ea Threshold
b

The minimum energy

energy that the The extra energy Reactants (or enthalpy)
colliding required by a
reactant Products
reactant to
molecules participate in a
must possess reaction. Progress of reaction
for the chemical (or reaction coordinate)
reaction
to occur.
Energy of
ET = Ea + reactant molecule
 Maxwell–Boltzmann Statistics and Arrhenius Theory

All molecules in the reacting

species do not have the
The distribution of kinetic energy may be
same kinetic energy.
described by plotting the fraction of
molecules (NE / NT) with a given kinetic
energy (E) versus kinetic energy.
It is difficult to predict the
behaviour of any one
molecule with precision.
Where,
NE is the number of molecules with
Statistics is used to predict energy, E
the behaviour of a large NT is the total number of molecules
number of molecules.
 Maxwell–Boltzmann Statistics and Arrhenius Theory

When temperature is raised Area under the

curve constant
The maxima of the curve moves
to the higher energy value

Fraction of
molecules
Most probable
Curve broadens out kinetic energy

Kinetic energy
Greater proportion of molecules
possess much higher energies
 Maxwell–Boltzmann Statistics and Arrhenius Theory

Increasing temperature T1
This area shows
fraction of
T2 additional
molecules

Fraction of
molecules
Increases the fraction of which react
molecules This area shows
at (T2)
the fraction
of molecules
that react at T1
Which collide with
energies greater than Ea
activation energy (Ea) Kinetic energy
Maxwell–Boltzmann Statistics and Arrhenius Theory

k = A e─E
- Eaa/RT
/RT

By increasing the
temperature or
decreasing the
activation energy,
The fraction of molecules the rate of reaction
that have kinetic energy increases.
greater than Ea
Calculation of Activation Energy (Ea)

Calculation of
activation energy (Ea)

By measuring rate
Graphically constant (k) at two
different temperatures
 Graphically
Arrhenius equation
-Ea/RT
k = Ae

Taking natural logarithm on both sides

ln k = ln [A e-Ea/RT ]

Ea
ln k = ln A - RT .…(1)

Plotting ln k versus (1/T), can give a straight line

Ea 1
ln k = ln A - R × T
 Plot of ln k vs 1/T
Ea 1
ln k = ln A - × …(1)
R T
Intercept = ln A

Straight line
Ea
Slope = -
R
Ea
ln k Slope = -
R

From the Ea can be

graph calculated
0 1
T
Rate Constant at Different Temperatures
At temperature T1, Arrhenius equation:
Ea
ln k1 = ln A - RT1
…(1)

k1: Rate constant at temperature T1

At temperature T2, Arrhenius equation:

Ea
ln k2 = ln A - RT2
…(2)

k2: Rate constant at temperature T2

 Rate Constant at Different Temperatures
Subtracting eq (1) from eq (2)

Ea Ea
ln k2 - ln k1 = RT1
- RT2

Ea … (1)
ln k1 = ln A - k2 Ea 1 1
RT1 ln
k1
= R T1
─
T2
. . . (3)

Ea
ln k2 = ln A - … (2)
RT2
k2 Ea 1 1
log
k1
= 2.303R T1
─
T2
. . . (4)
Rate Constant at Different Temperatures

If the rate constant k1 and k2 and

the corresponding temperatures
T1 and T2 are known.

Ea can be calculated
 Catalyst

Catalyst is a substance
that can alter the Types of catalyst
rate of reaction

Without undergoing any Positive catalyst Negative catalyst

permanent chemical change

Increases the Decreases the

This phenomenon rate of a reaction rate of a reaction
shown by a catalyst is
known as catalysis
 Catalysis
Example

Thermal decomposition of
H2O2 is accelerated

Generally, by the term

“catalysed reaction”
By the presence of MnO2

The presence of a positive

catalyst is assumed 2H2O2 + MnO2 2H2O + O2 + MnO2
 General Characteristics of Catalyst

A catalyst does not initiate Only a small amount of

1 any reaction; it simply 2 catalyst can catalyse a large
speeds up the reaction. amount of reactants.

A catalyst does not alter It does not alter the Gibbs

3 4
the position of equilibrium energy (ΔG) of a reaction

Catalyses spontaneous
It only reduces the time reactions but not non-
taken to reach the equilibrium
spontaneous reactions
 Function of Catalysts

Different pathway
A catalyst provides
an alternate pathway
or reaction mechanism

Activation energy Activation energy

By reducing the activation decreases increases
energy between reactants and
products and hence, lowering
the potential energy barrier. Positive Negative
catalyst catalyst
(inhibitor)
 Positive Catalyst

Reaction path
without catalyst

Reaction
path with Ea
Potential energy

catalyst without
Ea with catalyst catalyst

Reactants

Products

Reaction coordinate
 Negative Catalyst

Ea in the
presence of
negative
Ea without catalyst
Potential energy

catalyst (inhibitor)

Reactant

Products

Reaction coordinate
 Collision Theory

Though Arrhenius equation

is applicable under a wide
range of circumstances

A more advanced
theory was developed

With greater insights into the

energetic and mechanistic
aspects of reactions
 Collision Theory

The reactant molecules are

assumed to be hard spheres
Rate of reaction

A reaction occurs when molecules,

having sufficient energy, collide
with each other
Collision Activation Orientation
frequency energy factor
It is based on the kinetic
theory of gases
 Activation Energy

Not all collisions result

in product formation
E
a
Potential Energy

∑HR

A few reactant molecules

∑HP acquire activation energy
Reaction coordinate

Activation energy is
inversely related to
the rate of a reaction
 Collision Theory

For a bimolecular elementary reaction

A + B Products

Rate = ZAB e -Ea/RT … (1)

ZAB: Collision frequency of reactants, A and B

e -Ea/RT : Fraction of molecules with energies
equal to or greater than Ea
 Collision Theory
-Ea/RT
Rate = ZAB e … (1)

Rate expression predicts the value Not all collisions

of rate constant fairly accurately
lead to product
for simple atoms/molecules
formation i.e., only
few collisions are
effective.

For complex molecules, significant

deviations are observed
 Collision Theory

The collisions in which molecules

collide with sufficient threshold
energy and proper orientation

So as to facilitate the breaking

of bonds between the reacting
species and the formation of
new bonds to form products
 Collision Frequency

Collision frequency can be

The number of increased by increasing the
collisions per concentration and temperature
second per unit
volume
of the reaction
mixture is Both factors contribute towards
more number of collisions per
unit time per unit volume

Known as collision
frequency (Z)
 Effective Collision

How can we predict

if the collisions are
effective or not?

Conditions

Sufficient
kinetic energy

Proper orientation
 Sufficient Kinetic Energy
The minimum amount of
energy

Potential energy
Ea ET
R
The colliding molecules
P
must possess to participate
in a chemical reaction Reaction coordinate

Energy of
Threshold
Threshold energy So, if colliding ≥ energy
molecule

Only the molecule that satisfies this condition can cross the energy barrier.
 Proper Orientation

Energy alone does

not determine the
effectiveness of a collision
Conditions

Sufficient The reacting molecules

kinetic energy must collide in a
proper orientation to make
Proper orientation the collision effective.
 Proper Orientation
Proper collision

Reactants Transition Product

state

A2 B2 2AB
+
 Proper Orientation
Improper collision

The proper orientation of No reaction

the reactant molecules leads
to bond formation

Transition No products
Reactants
state are formed
Whereas improper orientation
makes them simply bounce back
and no products are formed.
 Effective Collision

To account for proper orientation Final expression of rate becomes

Rate = P ZAB e -Ea/RT

A factor “P” is introduced

Fraction of molecules
Orientation
Collision factor
frequency
with sufficient energy.
Probability or steric factor