Effect of Temperature on Reaction Rate:

The rate of a reaction invariably increases with

the increase of temperature. But the rates of
increase are different for different reactions.
Arrhenius observed that the variation of ln(rate
𝟏
constant, k,) of reaction with is linear and the
𝑻
result can be presented with the equation
𝑬
k = Ae-Ea/RT or, lnk = lnA - 𝑹𝑻𝒂
A is called Arrhenius factor, or preexponential
factor, Ea is activation energy of the reaction.
Both A and Ea are known as Arrhenius
parameters.

The above equation can be derived from the van’t

Hoff”s equation of effect of temperature on the
equilibrium constant, K,.
𝒅𝒍𝒏𝑲 𝜟𝑬
= , 𝛥𝐸 is the enthalpy of reaction
𝒅𝑻 𝑹𝑻𝟐
𝒌𝒇
𝒅𝒍𝒏( ) 𝜟𝑬 𝐸𝑓 −𝑬𝒃 𝐸𝑓 𝑬𝒃
𝒌𝒃
or, = = = 𝟐 −
𝒅𝑻 𝑹𝑻𝟐 𝑹𝑻𝟐 𝑹𝑻 𝑹𝑻𝟐

kf and kb are the rate constants of the forward and

backward reactions. Ef and Eb are the activation
energies of forward and backward reactions
respectively
1
Activation energy, Ea, of a reaction can be defined as
the minimum amount of energy per mole, in excess of
average molecular energy, which enables the
molecules to undergo reaction.

The above equation can be split into

𝒅𝒍𝒏𝒌𝒇 𝐸𝑓 𝒅𝒍𝒏𝒌𝒃 𝑬𝒃
= + C1 and = + C2
𝒅𝑻 𝑹𝑻𝟐 𝒅𝑻 𝑹𝑻𝟐

Experimentally it is found that the constants are

zero, so we can write
𝒅𝒍𝒏𝒌𝒇 𝐸𝑓
= 𝟐 , on integration
𝒅𝑻 𝑹𝑻

𝐸𝑓
ln𝒌𝒇 = − + A, A is constant or, 𝒌𝒇 =Ae-Ea/RT
𝑅𝑇

𝐸𝑓
ln𝒌𝒇 Slope = − 𝑅

1/T
Now, writing this equation at two different
temperatures (T1 and T2) and subtracting we have

𝑘2 𝑬𝒂 1 1
ln( )=− ( - )
𝑘1 𝑅 𝑇2 𝑇1

2
Theories of Reaction Rates: A number of
theories have been put forward to explain the
kinetics of reactions. They are mainly:

(i) Arrhenius theory

(ii) Collision theory
(iii) Transition state or absolute reaction rate
theory

Collision theory of reaction rate: The basic

assumptions of this theory are:
(i) Molecules are considered as hard sphere.
(ii) Reaction occurs as a result of collision
between reactant molecules.
(iii) All collisions do not lead to product
formation.
(iv) Collisions between the molecules having
activation energy, Ea, or greater can produce
product.

If the collision between the reactant molecules is

only the requirement for reaction, the rate of
reaction should be equal to the frequency of
collision. But the calculation shows that it is much
smaller than that. Only a few % of collisions are
effective.
3
Again, an increase of temperature by 100 C,
frequency of collision increases by 2-3% only,
but reaction rate is increased by mostly 200-
300%. To overcome this anomaly, Arrhenius
suggested that only the active molecules can take
part in a reaction. At a particular temperature, an
equilibrium exists between the active and normal
molecules given by Maxwell-Boltzmann energy
distribution equation
𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒉𝒂𝒗𝒊𝒏𝒈 𝒆𝒏𝒆𝒓𝒈𝒚 𝑬𝒂 𝒐𝒓 𝒈𝒓𝒆𝒂𝒕𝒆𝒓
𝑻𝒐𝒕𝒂𝒍 𝒏𝒖𝒎𝒃𝒆𝒓𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆
= e-Ea/RT

Fraction of molecules having energy 𝑬𝒂 or greater is e-Ea/RT

So, as the temperature increases the number of

molecules having energy Ea also increases.

If the total number of collisions per sec at unit

concentration is Z, the number of molecules
undergoing reaction per sec, which is equal to the rate
constant, k, is given by

k = Ze-Ea/RT……..1

If we consider a bimolecular reaction between two

gaseous molecules A and B, then according the kinetic

4
theory of gases, the frequency of collision between A
and B, ZAB is given by
8𝑘 𝑇
ZAB = σ( 𝐵 )½ NA2 [A] [B]…….. 2
𝜋µ

Where, σ = collision cross-section, 𝑘𝐵 = Boltzmann

constant, µ = reduced mass of the colliding molecules
1 1 1
( = + ) and NA= Avogadro’s number, [A] and
µ 𝑚𝐴 𝑚𝐵
[B] are the concentrations of A and B respectively, the
values of ZAB is generally of the order of 4.0x1013 -
4.0x1014 cm3mol-1s-1.
For a unimolecular reaction of reactant, A, the
frequency of collision can be written as
4𝑘 𝑇
ZAA = σ( 𝐵 )½ NA2 [A]2 …….. 3
𝜋𝑚

Alternative Method: Consider a reaction as;

A +B → product
According to the collision theory, the rate of change of
A molecules in unit volume is equal to the product of
frequency of collision, ZAB, and the fraction of
molecules having activation energy, Ea, i.e. Boltzmann
factor, e-Ea/RT,
𝒅𝑵𝑨
- = ZAB e-Ea/RT…….1
𝒅𝒕

Dividing above equation by Avogadro’s number, NA,

𝒅[𝑨]
- = ZAB e-Ea/RT/ NA…….2
𝒅𝒕

5
From the kinetic theory of gas frequency of collision
is expressed by
𝟖𝑘 𝑻
ZAB = σ( 𝐵 )½ NA2 [A] [B]
𝜋µ

Where, σ = collision cross-section {σ =π(RA+RB)2=

πd2}, 𝑘𝐵 = Boltzmann constant, µ = reduced mass of
1 1 1
the colliding molecules ( = + ) and NA=
µ 𝑚𝐴 𝑚𝐵
Avogadro’s number, [A] and [B] are the
concentrations of A and B respectively.

Now, inserting the value of ZAB in equation-2

𝒅[𝑨] 8𝑘 𝑇
- = σ NA( 𝐵 )½ e-Ea/RT[A][B]…..3
𝒅𝒕 𝜋µ
Again, considering the reaction to be an elementary
one, the equation can be written as
𝒅[𝑨]
- = k[A][B]……….4
𝒅𝒕
Comparing equation-3 and 4
8𝑘 𝑇
k = σNA( 𝐵 )½e-Ea/RT
𝜋µ
8𝜋𝑘 𝑇
or, k = NAd2( 𝐵 )½e-Ea/RT……5
µ
8𝜋𝑘𝐵 𝑇 ½
N Ad (
2 ) is called frequency factor
µ
when, both A and B are the same, i.e. unimolecular
reaction, then frequency of collision is given by
4𝑘 𝑇
ZAA = σ( 𝐵 )½ NA2 [A]2
𝜋𝑚
Similarly, the rate constant will be

6
 4𝑘𝐵 𝑇 ½ -Ea/RT
k = σNA( ) e
𝜋𝑚
4𝜋𝑘 𝑇
or, k = NAd2( 𝐵 )½e-Ea/RT…..6
𝑚
4𝜋𝑘 𝐵 𝑇 ½
NA d (
2 ) is called frequency factor
𝑚

The frequency factor or preexponential factor, A or

8𝜋𝑘 𝑇 4𝜋𝑘 𝑇
ZAB is (NAd2( 𝐵 )½ or NAd2( 𝐵 )½) of a reaction
µ 𝑚
can be determined by using experimental values of rate
constant at different temperatures by using equation 5
or 6. The experimental values of A or ZAB are found to
be reasonably in agreement with those of calculated
from kinetic theory of gas for a few simple elementary
reactions.

But with increase of complexity of the reactant

molecules, the deviation between experimental and
calculated values of frequency factor (A or Z)
increases rapidly. To overcome this discrepancy, the
equation is rewritten as

k = PZe-Ea/RT

P is known as probability factor or steric factor, whose

value varies between 10-5 to 10-10 depending on the
complexities of reactant molecules.

7
Catalyst: A catalyst is a substance which by virtue of
its presence in a reacting system accelerates or retards
the rate of reaction, itself remaining unchanged in
property and mass. If the activation energy of a
reaction is high, the reaction rate is low. A catalyst
lowers the activation energy of the reaction by
providing an alternative path that avoids the slow rate
determining step of the uncatalyzed reaction and
results in a higher reaction rate at same temperature.
The catalysts occur in living things are called enzymes.

Characteristic of a catalyst:
(i) It should remain unchanged in mass and property at
the end of reaction.
(ii) A small amount of it can bring about a large
change.
(iii) It will not change the position of equilibrium.
(iv) It can’t start a reaction.
(v) It is specific in its reaction.

Types of catalysts:
(i) Positive catalyst- Its presence increases the reaction
rate. e.g. 2KNO3(s)+heat→2KCl(s)+3O2(g) catalyst is
MnO2(s), 2SO2(g)+O2(g)→2SO3(g) Catalyst is NO(g).

(ii) Negative catalyst-Its presence decreases the

reaction rate. e.g. 2H2O2(l)→2H2O(l)+O2(g) catalyst is

8
H3PO4(l), 2Na2SO3(s)+O2(air)→2Na2SO4(s), catalyst
is glycerin
.
(iii) Auto-catalyst- It is a product produced in a
reaction and then catalyzes the same reaction. e.g.
Mn2+-(aq) ion produced in the reaction 5C2O42-
(aq)+16H+(aq)+2MnO4(aq)→2Mn2+(aq)+10CO2+8H2O(l)
catalyzes the same reaction.

On the basis of physical states of reactants and catalyst,

the phenomenon can be again of two types:

Homogeneous catalysis-When both reactants and

catalyst are in one phase. e. g. 2SO2(g) + O2(g) →
2SO3(g) is catalyzed by NO(g).

Heterogeneous catalysis-When both reactants and

catalyst are in one than one phases. e. g. N2(g) + 3H2(g)
⇋ 2NH3(g) is catalyzed by Fe(s).

Mechanism of catalysis: Catalyst provides an

alternative path of a reaction, so that it can take place
at lower activation energy increasing the rate of a
reaction. So, catalyst has to interact with one of its
reactants to form a reactive reaction intermediate in
one step which later reacts with the other reactant(s)
with product formation and release of the catalyst.
Hence, there must be at least two steps in a catalytic
9
reaction. The mechanisms of few catalytic reactions
are as follows:

(i) Oxidation of SO2 to SO3 catalyzed by NO: In this

reaction, first catalyst NO combines with O2 forming
NO2. Then NO2 combines with SO2 forming SO3 with
the release of catalyst NO.
Uncatalyzed 2SO2(g) + O2(g) → 2SO3(g)

Catalyzed 2NO(g) + O2(g) → 2NO2(g)

2[NO2(g)+SO2(g) → NO(g)+SO3(g)]
_______________________________
2SO2(g) + O2(g) → 2SO3(g

(ii) Depletion of O3 layer in stratosphere catalyzed

by Cl atoms: The depletion of O3 at stratosphere is
caused by the following reaction:
O3(g) + O(g) → 2O2(g)
As the activation energy of the reaction is relatively
high, the rate of this of reaction is slow. But in presence
of Cl atoms (produced from photo-decomposition of
CFC) the rate of this reaction is increased about 100
times, and the reaction is assumed to occur in two steps
as follows:
Step-1 O3(g) + Cl(g) → ClO(g) + O2(g)
Step-2 ClO(g) + O(g) → Cl(g) + O2(g)
_____________________________
O3(g) + O(g) → 2O2(g)
10
(iv) Oxidation of iodide to iodine by
peroxidisulphate (persulphate) ion is catalyzed
with Fe2+: The uncatalyzed reaction is very slow
presumably it involves the collision of two negative
ions. The reaction can be catalyzed by Fe2+ ion and the
mechanism is thought to be
2Fe2+ + S2O82- → 2SO42- + 2Fe3+
2I- + 2Fe3+ → I2 + 2Fe2+
__________________________________

S2O82- + 2I- → I2 + 2SO42

Examples of some Catalysts

Industry Reaction Catalyst, Temp.,

and Pressures.
HNO3 NH3(g) +5O2(g) → 4NO(g) + 6H2O(g) Pt/Rh alloy, 9000 C,
1-8 atm.
H2SO4 SO2(g) + O2(g) ⇋ SO3(g) Pt, V2O5-Pt, 4500 C,
2 atm.
Hydrogenation
of vegetable oil C=C + H2(g) → -C-C- Ni

NH3 N2(g) + 3H2(g) ⇋ 2NH3(g) Fe(Promoted by Al2O3 or

Mo),4500 C, 200 atm.
Refining Reforming Pt/SiO2
Cracking SiO2/Al2O3
Synthetic Petroleum CO(g) + H2(g) → Liquid hydrocarbon & Co-Fe-Ni
alcohols
Methanol
Fermentation C6H12 O6(aq) → C2H5OH(aq) + CO2(g) Zymase enzyme
Refining motor NO (g) +CO(g) → N2O(g)+CO2(g) Pt-Rh
car exhaust NO(g) +CnH2n+2 → N2O(g) + CO2(g)+H2O
Polyethylene nC2H4(g) → -(CH2-CH2)n- Halides of organo-
Cr & Ti
Plastic C3H6(g) + NH3(g) + O2(g) → acrylonitrile Bi2O3-Mo2O3

11
 Class Assesment, 1st Year BS (Hons) 2019-20
Subject- Chemistry
Name -……………………………
Class Roll No……………Merit Position……
Put X marks beside the letter of correct answer

Consider the following reaction and answer the

question1-10: 2A+B→3C+D 1x12

Q.1 The rate of the reaction is given by

(A) d[A]/dt (B) -d[B]/2dt
(C) d[C]/3dt (D) -d[D]/dt

Q.2 The rate equation of the reaction is

(A) Rate = k [A]2[B] (B) Rate = k [A]nA[B] nB
(C) Rate = k [C]nC[D]nD (D) Rate = k [C]3[D]

Q.3 The unit of rate of a reaction is

(A) mol dm-3s-1 (B) mol dm-3
(C) mol dm-3s (D) none of these

Q.4 The order of a reaction can be

(A) 1, 2, 3 only (B) 0, 1, 2, 3 only
(C) 0, 1, 2, 3 and fractional (D) fractional only

12
Q.5 If above reaction is 1st order with respect to A and
1st order with respect to B, the unit of the rate constant
will be
(A) mol dm-3s-1 (B) mol-1 dm3s-1
(C) mol-2 dm6s-1 (D) s-1

Q.6 If above reaction is 1st order with respect to A and

1st order with respect to B, the reaction will occur at
least in
(A) one step (B) two steps
(C) three steps (D) four steps

Q. 7 If the activation energy of the above reaction is

reaction is very high, the rate of the reaction will be
(A) very (B) fast
(C) very slow (D) unpredictable

Q.8 The rate of above reaction is doubled if

temperature of reaction mixture is increased by only
100 C, the reason behind this is
(A) The more fraction of reactant molecules gains Ea
(B) frequency of collision increases
(C)Activation energy is decreased
(D) both (A) and (B)

Q.9 Above reaction is 1st order with respect to A and

1st order with respect to B, if the concentrations of A
and B are doubled, the rare of reaction will increase by
13
(A) 2 times (B) 4 times
(C) 6 times (D) 8 times

Q.10 If above reaction is 1st order with respect to A

and 2nd order with respect to B, The rate equation of
the reaction is
(A) Rate = k [A]2[B] (B) Rate = k [A]nA[B] nB
(C) Rate = k [A]2[C] 2 (D) Rate = k [A] [B]2
Q.11 The rate equation for the reaction NO2 + CO →
NO + CO2 is found to be, Rate = k[NO2]2. Which of
the following statement about this reaction is wrong?
(A) The reaction is second order.
(B) The reaction is bimolecular.
(C) The reaction is not elementary.
(D) The order of the reaction with respect to CO is zero.

Q. 12 The rate equation for the acid catalyzed reaction

CH3COCH3+I2→CH3COCH2I+HI is found to be
Rate= k[CH3COCH3][H+].Which of the following
statement is incorrect?
(A) The order of the reaction with respect to I2 is zero.
(B) The rate of the reaction is doubled if [H+] is doubled.
(C) The rate determining step involves a collision
between a I2 molecule and an CH3COCH3 molecule.
(D)The rate of the reaction is proportional to
concentration of CH3COCH3.

14
Q. 13 The best way of freezing (or quenching) of a
chemical reaction is
(A) diluting the reaction mixture (B) cooling the reaction mixture
(C) heating the reaction mixture
(D) simultaneous cooling and diluting the reaction mixture

Q. 14 A chemical reaction can quickly be completed by

(A) diluting the reaction mixture
(B) cooling the reaction mixture
(C) heating the reaction mixture.
(D) simultaneous heating and diluting the reaction mixture

Q.15 The best method to study of kinetics of the acid

catalyzed reaction CH3COCH+I2→CH3COCH2I+HI is
(A) conductometric method
(B) titroimatric method
(C) spectrophotometric method
(D) mass loss measurement method

Q.16 The best method to study of kinetics of the

reaction CH3COOC2H5(aq)+NaOH(aq)→
CH3COONa(aq)+C2H5OH(aq) is
(A) conductometric method
(B) titroimatric method
(C) spectrophotometric method
(D) mass loss measurement method

15
To answer the questions number from 13 and 14,
consider a reaction A → P
Q. 17 Draw a graph to show the change of
concentration of A with time if the reaction is (i)zero
order, (ii) 1st order and (iii) 2nd order with respect to A.

Q.18 Draw a graph to show the change of rate of the

reaction with [A] if the reaction is (i) zero order, (ii) 1st
order and (iii) 2nd order with respect to A.

Q.19 In a set of experiments to determine the

rate of the reaction between persulphate ions
and iodide ions S2O2-8+21-→2SO2-4+I2,in
aqueous solution, following data were
obtained:
16
 Initial rate /
Expt. [S2O82-]/ [I-]/ mol dm-3 mol dm-3s-1
No. mol dm-3
1 0.100 0.100 0.36
2 0.200 0.100 0.72
3 0.200 0.200 1.44
Deduce the order of reaction with respect to
each of the reagents and hence write the rate
equation for the reaction.

Q.20 Calculate the rate constant of above

reaction including unit. 1

Q.21 Calculate the activation energy of a the reaction

if rate constants of it at different temperatures are as
follows:
k/10-3s-1 2.46 10.6 45.1 160.4 576
Temp./oC 0 10 20 30 40
17
18