Chemical

Kinetics
• Thermodynamics- Does a reaction take place?

• Kinetics- how fast does a reaction proceed?

• Studies the rate at which a chemical process occurs.

• Besides information about the speed at which reactions

occur, kinetics also sheds light on the reaction
mechanism (exactly how the reaction occurs).
 Chemical Kinetics
• The branch of chemistry, which deals with the
study of reaction rates and their mechanisms,
called chemical kinetics.
• Thermodynamics tells only about the feasibility of
a reaction whereas chemical kinetics tells about
the rate of a reaction.
• For example, thermodynamic data indicate that
diamond shall convert to graphite but in reality
the conversion rate is so slow that the change is
not perceptible at all.
 Chemical Kinetics

Reaction Rates How we measure rates.

How the rate depends on amount of
Rate Laws reactants.
How to calculate amount left or time to
Integrated Rate Laws reach a given amount.
Half-life How long it takes to react 50% of reactants.
How rate constant changes with
Arrhenius Equation temperature.
Link between rate and molecular scale
Mechanisms processes.
 Reaction
Rates

Rates of reactions can be

determined by monitoring the
change in concentration of
either reactants or products as
a function of time. [A] vs t
 Chemical Kinetics
• Kinetic studies not only help us to determine
the speed or rate of a chemical reaction but
also describe the conditions by which the
reaction rates can be altered.
• The factors such as concentration,
temperature, pressure and catalyst affect the
rate of a reaction.
 Rate of a Chemical Reaction
• The speed of a reaction or the rate of a
reaction can be defined as the change in
concentration of a reactant or product in unit
time. It can be expressed in terms of:
• (i) the rate of decrease in concentration of
any one of the reactants, or
• (ii) the rate of increase in concentration of
any one of the products.
 The Rate of a Chemical Reaction

Consider a hypothetical reaction, assuming that the volume of

the system remains constant
R→P
One mole of the reactant R produces one mole of the product
P. If [R]1 and [P]1 are the concentrations of R and P
respectively at time t1and [R]2 and [P]2 are their
concentrations at time t2 then,
Δt = t2 – t1

Δ[R] = [R]2 – [R]1 & Δ [P] = [P]2 – [P]1

The square brackets in the above expressions are

used to express molar concentration.
 The Rate of a Chemical Reaction

• Rate of disappearance of R
= Decrease in concentration of R = − Δ [R]
Time taken Δt

Rate of appearance of P
= Increase in concentration of P = + Δ [P]
Time taken Δt

Since, Δ[R] is a negative quantity (as concentration of

reactants is decreasing), it is multiplied with –1 to
make the rate of the reaction a positive quantity.
 The Rate of a Chemical Reaction
Consider the following chemical reaction -

2 Fe3+(aq) + Sn2+ → 2 Fe2+(aq) +Sn4+(aq)

t = 38.5 s [Fe2+] = 0.0010 M

Δt = 38.5 s Δ[Fe2+] = (0.0010 – 0) M

Δ[Fe2+] 0.0010 M
Rate of formation of Fe2+= = = 2.6x10-5 M s-
Δt 38.5 s
 General Rate of Reaction
aA+bB→cC+dD
Rate of reaction = rate of disappearance of reactants

1 Δ[A] 1 Δ[B]
=- =-
a Δt b Δt Eqn.1

= rate of appearance of products

1 Δ[C] 1 Δ[D]
= = Eqn.2
c Δt d Δt

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]

or - =- = = Eqn.3
a Δt b Δt c Δt d Δt
 Average rate & Instantaneous rate
 Average rate depends upon the change in conc. of
reactants or products and the time taken for that
change to occur.
Equations 1-3 represent the average rate of a
reaction, rav.
The rate of reaction at a particular moment of
time is called as the instantaneous rate, rins.
It is obtained when we consider the average rate at
the smallest time interval say dt ( i.e. when Δt
approaches zero).
 Average rate & Instantaneous rate
• Mathematically for an infinitesimally small time
interval, dt, instantaneous rate is given by –
• rav = −Δ[R ] = Δ[P ]
Δt Δt
As Δt → 0 or

rins. = - d[R] = d[P]

dt dt
Unit of rate of reaction:– mol L-1 s-1
 Factors affecting the Rate of a Chemical
Reaction
1-Nature of reactant : Ionic substance react much faster than
covalent substances.
2-Concencentration of Reactants
: Rate of reaction is directly
proportional to conc. of reactants
(partial pressure in case of gaseous
- phase reactions).
3-Temperature : Rate of reaction increases with increase
in temperature.
4-Presence of Catalyst : A catalyst alters the Rate of a reaction.
5-Surface Area of the Reactants:
Rate of rean. ∝ surface area.
 Rate Law or Rate Expression and Rate
Constant
• The expression which relates of rate of
reaction to concentration of the reactants is
known as rate law. It is also called as rate
equation or rate expression.
• Consider a general reaction
aA + bB → cC + dD
• where a, b, c and d are the stoichiometric
coefficients of reactants and products.
 Rate Law
A rate law expresses the relationship between the reaction rate and the
concentrations of reactants raised to some power.
For gas-phase reactants use PA instead of [A].

• Rate laws are always determined

experimentally
For a general reaction: a A + b B cC + dD
• Reaction order is always defined in
rate law: rate = k [A] [B] m n
........ terms of reactant (not product)
concentrations

k = rate constant • The order of the reaction is not

m and n = reaction related to the stoichiometric
coefficient of the reactant in the
orders (not related to balanced chemical equation
a, b,...)
 Rate Law or Rate Expression and Rate
Constant
• The rate expression for this reaction is -

Rate of reaction ∝ [A]x[B]y

or

Rate of reaction = k [A]x[B]y

• where exponents x and y may or may not be equal
to the stoichiometric coefficients (a and b) of the
reactants.
 Rate Law or Rate Expression and Rate
Constant
• Thus, rate law is the expression in which reaction
rate is given in terms of molar concentration of
reactants with each term raised to some power,
which may or may not be same as the
stoichiometric coefficient of the reacting species in
a balanced chemical equation.
• Note:Rate law for any reaction cannot be predicted
by merely looking at the balanced chemical
equation, i.e., theoretically but must be determined
experimentally.
Rate Law or Rate Expression and Rate Constant

• Rate Constant (k) : For a general reaction

aA + bB → cC + dD
Rate of reaction = k [A]x[B]y

Where k is known as rate constant

When [A] = [B] = 1 mol/L, than
Rate of reaction = k

thus rate constant of a chemical reaction may be

defined as the reaction rate when the
concentration of each reactant is unity.
Rate Law or Rate Expression and Rate Constant

 The value of rate constant is definite and

constant for a particular reaction at given
temperature.

 Rate constant is independent of

concentration of reactants it depends only
upon temperature and presence of catalyst.
 Order of a Reaction
• The sum of powers of the concentration of the
reactants in the rate law expression is called the
order of that chemical reaction.
• For a general reaction
aA + bB → cC + dD
Let Rate of reaction = k [A]x[B]y
Here ,
x = order of reaction w.r.t. A
y = order of reaction w.r.t. B
Overall order of reaction(n) = x + y
 Reaction Order
• The sum of the exponents in rate = k[A]0 = k (1) = k
the reaction rate equation. zero order
(rate independent of [A])
Rate = k[A]n[B]m
rate = k [A] first
Overall reaction order = n + m
order
overall (rate a [A])
k = rate constant
rate = k [A]2
[A] = concentration of reactant A
second order overall (rate
[B] = concentration of reactant B a [A]2)
 Order of a Reaction
Examples of observed rate laws for some reactions follow.
 Order of a Reaction
 Order of a reaction can be 0, 1, 2, 3 and even a
fraction.
 Depending upon order of reaction, reactions are
termed as zero, first or second order reactions.
 A zero order reaction means that the rate of
reaction is independent of the concentration of
reactants.
 Order of reaction cannot be predicted by merely
looking at the balanced chemical equation, i.e.,
theoretically but must be determined
experimentally.
 Order of a Reaction& Units of Rate
Constant
For a nth order reaction- A → Product
Rate = k [A]n

a
Rate concentration 1
k = = x
[A]n time (concentration)n

k = (concentration)1-n time-1
 Practice Problems
1.

2.

3. For the reaction

A + B   Products
The following initial rates were obtained at various given intial
concentrations
S. No [A] [B] Rate (mol lt–1 sec–1)
1. 0.1 0.1 0.05
2. 0.2 0.1 0.10
3. 0.1 0.2 0.05
Write rate law and find the rate constant of the above reaction.
 Molecularity of a Reaction

Molecularity of a reaction is simply the

number of reacting species (atoms, ions or
molecules) involving is an elementary
reaction which must collide simultaneously.
Let us consider the following reactions,
 Molecularity of a Reaction

Q.Why the reactions having molecularity

greater than three is rare ?

Ans:- Since the chances of collision and

reaction of more than three molecules at a
time are very less, the molecularity greater
than three is rare.
 Molecularity of a Reaction

Molecularity in case of complex reactions?

Molecularity of a complex reaction has no meaning.

Actually a complex reaction is the series of two or
more elementary reactions and thus, it completes in
several steps. The slowest step or slowest reaction
determines the rate of the reaction. Hence we find
out the molecularity of the slowest elementary
reaction of a complex reaction which is, in general,
similar to the overall order of the complex reaction.
 Molecularity vs. Order
Molecularity of Reaction Order of Reaction
It is the number of atoms, ions or It is the sum of the power of
molecules that must collide with one concentration terms on which the rate
another simultaneously so as to of reaction actually depends or it is
result into a chemical the sum of powers of the
reaction. concentration terms in the rate law
equation.
Molecularity of reaction Order of reaction can be zero.
Cannot be zero.

It is a theoretical concept. It is determined experimentally.

It is always a whole number. It can even have fractional values.
The overall molecularity of complex Order of reaction is for overall
reaction has no significance. reaction.
Individual step has its own
molecularity.
 Integrated Rate Equations
Zero Order Reactions

Zero order reaction means that the rate of the reaction

is proportional to zero power of the
concentration of reactants. Consider the reaction,
R→P
 Integrated Rate Equations

Integrating both sides between proper limits

[R] ̶ [Ro] = ̶ kt

Or [R] = ̶ kt + [Ro]

y = mx + c
Integrated Rate Equations
 Integrated Rate Equations
First Order Reactions
First order reaction means that the rate of the reaction is
proportional to first power of the concentration of reactants.
Consider the reaction,
R→P
 Integrated Rate Equations
Integrating both sides between proper limits

ln[R] ̶ ln [Ro] = ̶ kt
Or
ln [Ro ] ̶ ln [R] = kt
Or
kt = ln
Or k= ln

Or k= log10
 Integrated Rate Equations

k= log10
 Integrated Rate Equations

1. The thermal decomposition of HCOOH is a first order reaction

with a rate constant of 2.4 x 10─3 s ─1 at a certain temperature.
Calculate how long will it take for three-fourth (3/4) of initial
quantity of HCOOH to decompose ? (log 0.25 = − 0.6021 )

2.A first order reaction has a rate constant of 0.0051 min─1 . If we

begin with 0.10 M conc. of the reactant, how much conc. of the
reactant will remain is solution after 3 hrs?

3. The rate constant for a reaction of Zero order in A is 0.0030

mol L─1 s─1 . How long will it take for the initial conc. of A to fall
from 0.10 M to .075 M ?
 Half-Life of a Reaction
The half-life of a reaction is the time in which the
concentration of a reactant is reduced to one half of
its initial concentration. It is represented as t1/2
t1/2 for a Zero Order Reactions
 Half-Life of a Reaction
t1/2 for a First Order Reactions

Thus for a first order

reaction, half-life
period is constant, i.e.,
it is independent of
initial concentration of
the reacting species.
 Half-Life of a Reaction
Practice Problems
1. A first order reaction takes 40 minutes for 30 %
completion . calculate its t1/2 value.

2. The decomposition of phosphine PH3 . Proceeds acc. to

following eqn:
4 PH3 (g) ---> P4(g) + 6H2 (g) ;
It is found that he reaction follows the following rate equation:

Rate = K [PH3] ;
The half lite of PH3 is 37.9 S at 1200C
(a) How much time is required of 3/4th of PH3 to decompose ?
(2) What fraction of original sample of PH3 remains behind
after 1 minute ?
 Pseudo - first order reaction
Reactions which are not truly of the first order but under certain
conditions reactions become that of first order are called
pseudo unimolecular reaction.
For example: Hydrolysis of ester in presence of acid
CH3COOC2H5 + H2O  CH3COOH + C2H5OH
From this reaction, the rate expression should be
r = k [ester] [H2O]
Since, hydrolysis takes place in the excess of H2O and
concentration change of H2O is negligible practically.
therefore, r = k’ [ester]
Where k’ = k[H2O].
 Methods of determining the order of a
reaction

Reaction Differential Integrated rate Characteristic Slope Units of rate

Order rate law law kinetics Plot of constant
kinetic
s plot

Zero  d[A] [A]=[Ao]-kt [A] vs t -k Mole l-1 sec-1

k
dt

First  d[A] [A]=[Ao]e-kt In[A] vs t -k sec-1

k [A]
dt

Second  d[A] [Ao] 1/[A] vs t k L mole-1 sec-1

k [A] 2 A 
dt 1  k  [A]
 An overview of zero-order, first-order
and simple second-order reactions
zero first second
order order order
rate law rate = rate = k rate = k [A]2
k [A]
units for mol/L s 1/
L/mol s
k s
integrated rate [A]t = kt + ln[A]t = -kt + 1/[A]t = kt +
law in straight- 1/[A]0
[A]0 ln[A]0
line form
plot for straight [A]t vs t ln[A]t vs t 1/[A]t vs
line t
slope, y- -k, -k, k, 1/[A]0
intercept [A]0 ln[A]0
half-life [A]0/2k (ln 2)/k 1/k [A]0
 Graphical Representation

Conc. [A] log [A] 1/ [A]

t t t
zero order first order second order

Graphical representation for concentration of integrated rate equation versus time

 Theories of chemical kinetics

1. Collision theory

2. Transition state theory

 Collision theory
Reaction occurs when reacting species have sufficient energy
to collide and proper orientation in space.

Energy barrier:
The minimum energy which the colliding particles possess in
order to bring about the chemical reaction is called threshold
energy
The energy difference between threshold energy & average
energy of reacting molecules is called activation energy

Orientation barrier:
Colliding molecules should be in their proper orientation at
the time of collision.
 Transition State Theory
In the activated complex theory, we consider two reactants
approaching and their potential energy rising and reaching a
maximum.

H Ea  Ea`

Activation energy - the energy needed to form activated

complex is called energy of activation. It is very low for some
reactions and very high for others.
 Some Points about Ea

1. Ea is always positive.

2. The larger the value of Ea, the slower the

rate of a reaction at a given temperature.

3. The larger the value of Ea, the steeper the

slope of (ln k) vs (1/T). A high activation
energy corresponds to a reaction rate that
is very sensitive to temperature.
 Effect of temperature on rate of chemical reaction

For a chemical reaction with rise in temperature by 10°,

the rate constant is nearly doubled

k(T+10)
The ratio kT is called the temperature
coefficient and its value is 2 or 3
Effect of temperature on rate of chemical reaction

Arrhenius equation

The temperature dependence of the rate of a chemical reaction

can be accurately explained by Arrhenius equation
-Ea/ RT
k = A.e
A is frequency factor or Arrhenius constant, Ea is activation
energy

or

Plot of log k vs 1/T is a straight line & slope = ̶ Ea/2.303R

 Effect of temperature on rate of chemical reaction

Plot of ln k vs 1/T is a straight line & slope =-Ea/R

 Effect of temperature on rate of chemical reaction

At temperature T1 Eqn.1

At temperature T2 Eqn.2

k1 and k2 are the values of rate constants at temperatures T1 and T2

respectively. Subtracting equation (2) from (1), we obtain
 Illustrative Example

The specific reaction rate for a reaction increases by a factor 4 if

the temperature is changed from 27o C to 47o C. Find the activation
energy for the reaction.
Solution:
 K2  Ea  T2 - T1 
log10  =  
 K1  2.303 R  T1T2 
Ea  320 - 300 
log4 =  
2.303×1.987  300×320 

0.60205×2.303×1.987×300×320
Ea =
20

= 13222.98 cals
Ea = 13.311 K cals
 Reaction Mechanism
The sequence of events that describes the actual process by which reactants become
products.

Reactions may occur all at once or through several discrete steps.

Each of these processes is known as an elementary reaction or elementary process.

Postulatin
Measurin ga
Formulati
g the rate reasonabl
on of rate
of e
law
reaction mechanis
m
 Activation Energy
The minimum amount of energy required to
Molecules must possess a initiate a reaction: the activation energy, Ea.
minimum amount of energy
to react. Why?
Ea varies with the reaction.
In order to form
products, bonds must Just as a ball cannot get over a hill if it does
be broken in the not roll up the hill with enough energy, a
reactants. Bond reaction cannot occur unless the molecules
breakage requires possess sufficient energy to get over the
energy. activation energy barrier.

Molecules moving too

slowly, with too little
kinetic energy, don’t
react when they collide.
 Energy Diagrams

Exothermic Endothermic

(a) Activation energy (Ea) for the forward reaction

(b) Activation energy (Ea) for the reverse reaction
(c) DH
 Molecular orientation and effective
Effective Collisions collisions
Not all collisions that occur with NO + NO3 2 NO2
energy equal to, or exceeding, the
activation energy lead to products.

Molecular orientation is critical!

-E /RT
k = Ae a

the frequency factor = product of collision

frequency Z and an orientation probability
factor p (A = Zp)
 Catalysis

Catalyst: A substance that changes the rate of a reaction

without being consumed in the reaction.

• Provides an easier way to react.

• Lower activation energy.
• Still make the same products.
• Enzymes are biological catalysts.

Inhibitor: A substance that decreases the rate of reaction (a

negative catalyst).
How catalyst change reaction rate

• Catalysts are
the one way to
lower the
energy of
activation
for a particular
reaction by
altering the
path of the
reaction.

• The lower
activation
energy allows
the reaction to
proceed faster.
 Catalyst
Catalysts increase the rate of a reaction by decreasing the activation energy
of the reaction.

Catalysts change the mechanism by which the process occurs.

 Catalyst
There are two types of catalyst: Homogeneous – one that is
One way a catalyst can present in the same phase as the reacting molecules.
speed up a reaction is
by holding the Example: Hydrogen peroxide decomposes very slowly in the
reactants together and absence of a catalyst:
helping bonds to break. 2H2O2(aq)  2H2O(l) + O2(g)
In the presence of bromide ions, the decomposition
occurs rapidly in an acidic environment:
2Br–(aq) + H2O2(aq) + 2H+(aq)  Br2(aq) + 2H2O(l)
Br2(aq) + H2O2(aq)  2Br–(aq) + 2H+(aq) + O2(g)

Br– is a homogeneous catalyst because it is regenerated at

the end of the reaction.
The net reaction is still…2H2O2(aq)  2H2O(l) + O2(g)
Heterogeneous – one that is present in a different phase as the reacting molecules.
Example:
C2H4(g) + H2(g)  C2H6(g)
In the presence of a metal catalyst (Ni, Pt or Pd) the reaction occurs quickly at room
temperature.
 Rate Law and Mechanism
A mechanism is a collection of elementary steps devised to
explain the reaction in view of the observed rate law.
For the reaction, 2 NO2 (g) + F2 (g)  2 NO2F (g), the rate law
is,
rate = k [NO2] [F2] .
Can the elementary reaction be the same as the overall
reaction?
If they were the same the rate law would have been
rate = k [NO2]2 [F2],
Therefore, the overall reaction is not an elementary
reaction.
 Rate-determining Step in a Mechanism

Slowest step:
The rate determining step is the slowest elementary step
in a mechanism, and the rate law for this step is the rate
law for the overall reaction.
 Illustrative Problem

The hypothetical reaction A2+ B2  2AB

follows the following mechanism
A2  A + A (fast)
A + B2  AB + B (slow)

A B  AB (fast)

The order of the overall reaction is

(a) 0 (b) 1

(c) 2 (d) 3/2

 Solution

The order depends on slowest step

 Rate(slow step) = k[A][B2 ]

= k[B2 ].k` [A2 ]1/ 2
= k"[A2 ]1/ 2[B2 ]
1 3
Overall order   1 
2 2
Hence, the answer is (d).
Illustrative Problem

At 380° C, the half-life period for the first order

decomposition of H2O2 is 360 min. The energy of
activation of the reaction is 200 kJ mole-1. Calculate the
time required for 75% decomposition at 450° C.
 Solution

0.693
k380 = =1.925×10-3 min-1
360

k 450 200×103  1 1 
 log =  - 
k380 2.303×8.314  653 723 

k 450
log =1.55  k 450 = 6.83×10-2
1.925×10-3

0.693
t 1 at 450°C = =10.15 min
6.83×10-2
2

t75% = 2t 1 = 20.29 min.

2
 Kinetics at surfaces-
Adsorbent-The solid that Adsorption
takes up a gas, vapour or a
The phenomenon of higher
solute from a solution, e.g.
concentration of any species of solid,
silica gel, charcoal, clay,
liquid or gas at the surface than in
etc.
the bulk of a material, is known as
adsorption.
Adsorbate-The gas, vapour
or the solute, which is held
to surface of the solid. e.g.
poisonous gases

Desorption-The process of
removal of adsorbed
substances from the
surface on which it is
absorbed
 Adsorptio
n
Exother
mic
process

∆𝐺=∆𝐻−𝑇∆𝑆Spontaneo
us
 Adsorption vs Absorption
Absorption Adsorption
• It is the phenomenon in which • It is the phenomenon in which
the particles of gas or liquid the higher conc. of particles of
uniformly distributed gas or liquid on surface than in
throughout. bulk.
• Bulk phenomenon • Surface phenomenon
• Occurs at uniform rate • Rapid in beginning but slowly
• Anhydrous CaCl2 absorbs water decreases.
• Silica gel absorbs water vapour.
Types of Adsorption

Physisor Chemis
ption orption
PROPERTIES PHYSISORPTION CHEMISORPTION
Bonding Weak, long range Strong, short range
forces, forces, Chemical
van der Waals bonding involving
interactions. orbital overlap and
charge transfer.
Enthalpy 20-40 kJ mol-1 80-240 kJ mol-1

Saturation Multi-layer Mono-layer

Nature reversible irreversible
Effect of Occurs at low Occurs at high
temperature temperature and temperature and
decreases with increases with increase
increase in in temperature.
temperature.
Effect of Increases with Decreases with
pressure increase in pressure of increase of pressure
adsorbate.
Activation Not needed High activation energy
energy is needed.
Surface No Yes
specificity
 Factors Affecting Adsorption

• Nature of gas - easily liquefiable gases easily gets

adsorbed.

• Nature of adsorbent- More the surface area per unit

mass of the adsorbent, more will be the adsorption.

• Temperature- adsorption increases as temperature

decreases.

• Pressure- magnitude of adsorption increases with

increase in pressure.
 L
Types of isotherms
a
n
g
Temkin
m
isother
u
Dubin
i m
in–
r Freun
Radus
dlich
hkevic
ih isothe
s rm
isothe BET
rmo isother
t m
h
e
r
 Langmuir Adsorption
isotherm
In 1916, Dr.
Irving Langmuir
presented this
Objective of Langmuir
History

model.
Langmuir was
awarded the Nobel Equation
Prize in 1932
Adsorption can be
physisorption or
chemisorption
Estimate the
adsorption capacity
of adsorbent used
 Basic assumptions of Langmuir
Model
The surface is homogeneous

All sites are equivalent

Mono-layer adsorption only

No interactions between
adsorbate molecules on
adjacent sites
Heat of adsorption is
constant and equivalent for
all sites
Adsorbate molecules have
tendency to get adsorb and
desorb from surface
 Langmuir Equation

Based on these assumptions Langmuir derived the following

equation
 Langmuir adsorption isotherm-Derivation
• Case I- Single molecule adsorption
When adsorption is in a dynamic equilibrium

A(g) + M(surface site) DAM

the rate of adsorption rads = kads (1-Ɵ) P A
the rate of desorption rdes = kdes Ɵ
at equilibrium rads = rdes Þ kads (1-Ɵ) P = kdes Ɵ case I

rearrange it for Ɵ
(k ads / k des ) P

1  (k ads / k des ) B0 P

k ads Cs B0 P
B0   
let k des C 1  B0 P
B0 is adsorption coefficient
 Case II- Single molecule adsorbed dissociative
on one site D
A-B(g) + M(surface site) A-M-B
the rate of A-B adsorption rads=kads (1- Ɵ A )(1- Ɵ B)PAB=kads (1- Ɵ )2PAB
q=qA=qB
the rate of A-B desorption rdes=kdesqAqB =kdesq2
A B
at equilibrium rads = rdes Þ kads (1-q ) PAB= kdesq
2 2 A B

rearrange it for q case II

(kads / k des ) PAB

1  (k ads / k des ) PAB

k Cs ( B0 PAB )1/2
B0  ads  
Let. k des Þ C 1  ( B0 PAB )1/2
• Case III- Two molecules adsorbed on two sites

A(g) + B(g)
D + 2M(surface site) A-
M + B-M
the rate of A adsorption rads,A = kads,A (1-
qA- qB) PA
A B

the rate of B adsorption rads,B = kads,B (1-

qA- qB) PB case III

the rate of A desorption rdes,A = kdes,A qA

the rate of CBs ,A desorption
B0 ,A PA rCs ,B = k B0des,B
,B PB qB
A    B des,B
C 1  B0 ,A PA  B0 ,B PB C 1  B0 ,A PA  B0 ,B PB
k ads,A k ads,B
0 ,A 
Bat equilibriumand B0 ,B  rads ,A = rdes ,A and Þ
k des ,A k des ,B
rads ,B = rdes ,B
Þ kads,A(1-qA-qB)PA=kdes,AqA and kads,B(1-
qA-qB)PB=kdes,BqB
 Langmuir-Hinshelwood Mechanism
2 or more reactants adsorb on surface without dissociation

• Diffusion of the reactants towards the surface

• Adsorption of reactants at the surface

• Interaction between the reactants

• Desorption of products from the surface

• Diffusion of products from the surface

Langmuir-Hinshelwood Mechanism
This mechanism deals with the surface-catalysed reaction in which 2 or more
reactants adsorb on surface without dissociation
A(g) + B(g) DA(ads) + B(ads) P (the desorption of P is not r.d.s.)
A B
P "
The rate of reaction ri=k[A][B]=kqAqB +

From Langmuir adsorption isotherm (the case III) we know

 B0 ,A PA
 A  1  B0 ,A PA  B0 ,B PB

 B0 ,B PB
We then have  B 
 1  B0 ,A PA  B0 ,B PB
 B0 ,A PA  B0 ,B PB  kB0 ,A B0 ,B PA PB
ri k  



 1  B0 ,A PA  B0 ,B PB  1  B0 ,A PA  B0 ,B PB  1  B0 ,A PA  B0 ,B PB

When both A and B are weakly adsorbed (B0,APA<<1, B0,BPB<<1),

ri kB0 ,A B0 ,B PA PB k' PA PB
2nd order reaction
When A is strongly adsorbed (B0,APA>>1) and B weakly adsorbed (B0,BPB<<1 <<B0,APA)

1st order w.r.t. B

Langmuir-Hinshelwood Example
Langmuir Equation-Applications