Chemical Kinetics 455

60
Chapter

11

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Chemical Kinetics

The branch of physical chemistry which deals with (3) Very slow reactions : These reactions are
the rate at which the chemical reactions occur, the
mechanism by which the chemical reactions take place
and the influence of various factors such as
concentration, temperature, pressure, catalyst etc., on
ID
extremely slow and take months together to show any
measurable change.
Examples
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the reaction rates is called the chemical kinetics. (i) Rusting of iron :
Types of chemical reactions Fe 2 O3  xH 2 O  Fe 2 O3 . xH 2 O
Hy drated ferric oxide (Rust)

On the basis of reaction rates, the chemical

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reactions have been classified into the following three (ii) 2 H 2  O 2   2 H 2 O
Room temperatu re

types, Rate of a reaction

(1) Very fast or instantaneous reactions : These The rate (speed or velocity) of a reaction is the
reactions occur at a very fast rate generally these change in concentration in per unit time.
reactions involve ionic species and known as ionic x dx  x 2  x 1 
or  
reactions. It is almost impossible to determine the rates t dt  t 2  t1 
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of these reactions.
where x or dx is the concentration change, i.e.,
Examples (x 2  x 1 ) in the time interval t or dt, i.e., (t 2  t1 ) .
(i) AgNO3  NaCl  AgCl NaNO 3 (Precipitation Concentration is generally expressed in active mass, i.e.,
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(PPt.)
mole L–1
reaction)  The rate measured over a long time interval is
(ii) HCl  NaOH  NaCl  H 2 O (Neutralization called average rate and the rate measured for an
ST

(acid) (base) (Salt) infinitesimally small time interval is called

reaction) instantaneous rate and
Instantaneous rate  (Average rate) t 0
(2) Moderate reaction : These reactions proceed
with a measurable rates at normal temperature and it  For the reaction aA  bB  cC  dD
is these reactions are studied in chemical kinetics. Rate of disappearance of a reactant is negative
Mostly these reactions are molecular in nature. d [ A]
  Rate of disappearance of A
dt
Examples
d [ B]
  Rate of disappearance of B
(i) Decomposition of H 2 O2 : 2 H 2 O2  2 H 2 O  O2 dt
(ii) Decomposition of N 2 O5 : 2 N 2 O5  2 N 2 O4  O2 Rate of formation of a product is positive
d [C ]
 Rate of formation of C
dt
 456 Chemical Kinetics
d [D] (4) Presence of catalyst : The function of a
 Rate of formation of D
dt catalyst is to lower down the activation energy. The
 In terms of stoichiometric coefficient rate may greater the decrease in the activation energy caused by
be expressed as the catalyst, higher will be the reaction rate.
Reaction
dx 1 d[ A] 1 d[B] 1 d[C] 1 d[D] path
    Without
catalyst
dt a dt b dt c dt d dt Ea
 The rate of reaction is always positive.
 The rate of chemical reaction decreases as the Ea Reaction
path
reaction proceeds. with
catalyst
Unit of conc. Reactants
 Unit of rate of a reaction = =mole L–1

Potential
Energy of Reaction

Energy
Unit of time

60
Products
time –1
In term of gaseous reaction the unit is atm time-1 A catalyst changes the reaction
path
and
Rate in atm time-1= Rate in mole L1 time 1  RT (5) Effect of sunlight : There are many chemical
reactions whose rate are influenced by radiations

E3
Factors affecting rate of a reaction particularly by ultraviolet and visible light. Such
The rate of a chemical reaction depends on the reactions are called photochemical reactions. For
following things example, Photosynthesis, Photography, Blue printing,
Photochemical synthesis of compounds etc.
(1) Nature of reactants
The radiant energy initiates the chemical reaction
(i) Physical state of reactants : This has by supplying the necessary activation energy required
considerable effect over rate of reaction.
Gaseous satae  Liquid state  Solid state
                
Decreasing rate of reaction


(ii) Physical size of the reactants : Among the

ID for the reaction.
Law of mass action and Rate constant
The rate at which a substance reacts is directly
proportional to its active mass and the rate at which a
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solids, rate increases with decrease in particle size of reaction proceeds is proportional to the product of the
the solid. active masses of the reacting substances.
(iii) Chemical nature of the reactants  For a reaction, aA  bB  product
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(a) Reactions involving polar and ionic  dx   dx 

Rate     [ A]a [B]b ;    k [ A]a [B]b
substances including the proton transfer reactions are  dt   dt 
usually very fast. On the other hand, the reaction in Where k is called rate constant or velocity
which bonds is rearranged, or electrons transferred are constant.
slow. dx
When [ A]  [B]  1 mol / litre , then k
(b) Oxidation-reduction reactions, which dt
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involve transfer of electrons, are also slow as Thus, rate constant k is also called specific
compared to the ionic substance. reaction rate.
(c) Substitution reactions are relatively much  The value of rate constant depends on, nature
slower.
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of reactant, temperature and catalyst. It is independent

(2) Effect of temperature : The rate of chemical of concentration of the reactants.
n 1 1 n
reaction generally increases on increasing the  litre   mol 
 Unit of rate constant     sec 1     sec 1
temperature. The rate of a reaction becomes almost  mol   litre 
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double or tripled for every 10 o C rise in temperature. Where n  order of reaction.

Temperature coefficient of a reaction is defined as Rate law : Molecularity and Order of a reaction
the ratio of rate constants at two temperatures Molecularity is the sum of the number of molecules
differing by (generally 25°C and 35°C) 10°C. of reactants involved in the balanced chemical equation.
k at (t  10 o C ) k 35 o C Molecularity of a complete reaction has no significance
  Temperatur e coefficien t  
k at t o C k 25 o C and overall kinetics of the reaction depends upon the
rate determining step. Slowest step is the rate-
(3) Concentration of reactants : The rate of a
determining step. This was proposed by Van't Hoff.
chemical reaction is directly proportional to the
concentration of the reactants means rate of reaction Example : NH 4 NO 2  N 2  2 H 2 O (Unimolecular)
decreases with decrease in concentration. NO  O3  NO 2  O 2 (Bimolecular)
 Chemical Kinetics 457
2 NO  O 2  2 NO 2 (Trimolecular) AB 3  A  A2 B3 (fast)
The total number of molecules or atoms whose (Here, the overall order of reaction is equal to
concentration determine the rate of reaction is known as two.)
order of reaction.  Molecularity of a reaction is derived from the
Order of reaction = Sum of exponents of the conc. terms in mechanism of the given reaction. Molecularity can not be
rate law greater than three because more than three molecules may
For the reaction xA  yB  Products not mutually collide with each other.
 Molecularity of a reaction can't be zero,
The rate law is Rate  [A]x [B[y
negative or fractional. order of a reaction may be zero,
Then the overall order of reaction. n  x  y
negative, positive or in fraction and greater than three.

60
where x and y are the orders with respect to Infinite and imaginary values are not possible.
individual reactants.  When one of the reactants is present in the large
 If reaction is in the form of reaction mechanism excess, the second order reaction conforms to the first
then the order is determined by the slowest step of order and is known as pesudo unimolecular reaction.
mechanism. (Table 11.1)

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2 A  3 B  A2 B3
A  B  AB (fast)
AB  B2  AB 3 (slow) (Rate determining step)
Table : 11.1 Order and molecularity of some reaction
S. Chemical equation Molecularit Rate law Order w.r.t.
No
.

1. aA  bB  product
y

a+b
ID  dx 
   k [ A]a [B]b
First
reacta
nt
a
Second
reactant

b
Overal
l

a+b
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 dt 
2. aA  bB  product a+b  dx  2 zero, if B is in 2
   k [ A]2 [B]0 excess
 dt 
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Pt, 
3. 2 H 2 O2   2 H 2 O  O2 2  dx  1* ----- 1
(Bimolecula    k [H 2 O2 ]
 dt 
r)

4. CH 3 COOC 2 H 5  H 2 O 
H
 2  dx  1* Zero, if H2O is 1
(Bimolecula    k [CH 3 COOC 2 H 5 ] in excess
CH 3COOH  C2 H5 OH  dt 
r)

5. C12 H 22 O11  H 2 O 
H
 2  dx  1* Zero, if H2O is 1
   k [C12 H 22 O11 ]
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Sucrose (Bimolecula  dt  in excess

C6 H12 O6  C6 H12 O6 r)
Glucose Fructose
 Zero, if OH–
6. (CH 3 )3 CCl  OH  2  dx  1* 1
   k [(CH 3 )3 CCl ]
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(Bimolecula  dt  does not take

(CH 3 )3 COH  Cl 
r) part in slow
step

7. CH 3 Cl  OH  CH 3 OH  Cl  2  dx  1 1 2
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(Bimolecula    k [CH 3 Cl ][OH  ]

 dt 
r)

8. C6 H 5 N 2 Cl  C6 H5 Cl  N 2 1  dx  1 ---- 1
(Unimolecul    k [C6 H 5 N 2 Cl ]
 dt 
ar)

9. CH 3 CHO  CH 4  CO 1  dx  1.5 ---- 1.5
(Unimolecul    k [CH 3 CHO ]3 / 2
 dt 
ar)
10. H 2 O2  2 I   2 H   2 H 2O  I2 5  dx  1 1 2
   k [H 2 O 2 ][I  ] (H+is medium)
 dt 
11. 2O3  3O2 2  dx  1 -1 with respect 1
   k [O 3 ] [O 2 ]
2
(Bimolecula  
dt to O2
r)
 458 Chemical Kinetics
*Pseudo-unimolecular reactions.
Table : 11.2 Rate constant and other parameters of different order reactions
Orde Rate constant Unit of rate Effect on rate by (Half-life
r constant changing conc. to m period) T50=
times
–1
0 x conc. time No change a
k0 
t (mol L–1 s–1) 2k 0
1 2 . 303  a  k t time–1 (s–1) m times 0 .693
k1  log 10   , C  C0 e 1
t  a  x  k1

60
k1 t 2 .303 (a  x1 )
N  N 0e , k1  log10
(t2  t1 ) (a  x 2 )
2 1 1 1 x conc–1 time–1 m2 times 1
k2      (for the case (mol L–1) s–1
t  (a  x ) a  ta(a  x ) k 2a
L mol–1 s–1
when each reactant has equal

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concentration)
2.303  b(a  x ) 
k2  log 10   (for the case
t(a  b)  a(b  x ) 
when both reactants have different
concentration)
3

n
k3 

kn 
1
2t
 1



1 
(a


 x )2

1
a
1
 2



1 
; n2
ID
conc–2 time–1
(mol L–1)–2 s–1
L2 mol–2 s–1
conc(1–n) time–
1
m3 times

mn times
3
2k 3 a 2

2n 1  1
(n  1)t  (a  x )n 1 (a)n 1  (n  1)kn (a)n 1
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(mol L–1)(1–n)
s–1
L(n–1) mol(1–n)
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s–1
Methods for determination of order of a reaction (2) Half-life method : This method is employed
only when the rate law involved only one concentration
(1) Integration method (Hit and Trial method)
term.
(i) The method can be used with various sets of
t 1 / 2  a 1 n ; t 1 / 2  ka 1 n ; log t1 / 2  log k  (1  n) log a
a, x and t with integrated rate equations.
A plotted graph of log t1 / 2 vs log a gives a straight
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(ii) The value of k is determined and checked for

all sets of a, x and t . line with slope (1  n) , determining the slope we can
find the order n. If half-life at different concentration
(iii) If the value of k is constant, the used
is given then,
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equation gives the order of reaction.

n 1
(iv) If all the reactants are at the same molar 1 1 (t1 / 2 )1  a2 
(t1 / 2 )1  ; (t1 / 2 )2  ;  
concentration, the kinetic equations are : a1n 1 a 2n 1 (t1 / 2 )2  a1 
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2.303 a log 10 (t1 / 2 )1  log 10 (t1 / 2 )2  (n  1) [log 10 a2  log 10 a1 ]

k log 10 (For first order
t (a  x )
log 10 (t1 / 2 )1  log 10 (t1 / 2 )2
reactions) n 1
(log 10 a 2  log 10 a1 )
1 1 1 
k  (For second order
t  a a  x 
 This relation can be used to determine order of
reaction ‘n’
reactions)
Plots of half-lives Vs concentrations (t1/2  a1–n)
1  1 1 
k   2 (For third order Zero 1st order 2nd 3rd
2 t  (a  x ) 2
a 
t1/2 
t1/2 

t1/2 
t1/2 

order order order

reactions)

Conc. Conc. 1/a 1/a2

 Chemical Kinetics 459
This method can be used irrespective of the
(3) Graphical method : A graphical method
number of reactants involved e.g., consider the
based on the respective rate laws, can also be used.
reaction, n1 A  n2 B  n3 C  Products .
(i) If the plot of log( a  x ) Vs t is a straight line,
This method consists in finding the initial rate of
the reaction follows first order.
the reaction taking known concentrations of the
1
(ii) If the plot of Vs t is a straight line, the different reactants (A, B, C).
(a  x )
reaction follows second order. Suppose it is observed as follows,
1 (i) Keeping the concentrations of B and C
(iii) If the plot of Vs t is a straight line, constant, if concentration of A is doubled, the rate of
(a  x )2
reaction becomes four times. This means that, Rate

60
the reaction follows third order.
 [A] 2 i.e., order with respect to A is 2
(iv) In general, for a reaction of nth order, a
1 (ii) Keeping the concentrations of A and C
graph of Vs t must be a straight line.
(a  x )n 1 constant, if concentration of B is doubled, the rate of
reaction is also doubled. This means that, Rate  [B]
Plots from integrated rate equations

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i.e., order with respect to B is 1
Zero order 1st order 2nd order 3rd order
Conc. [A]

(iii) Keeping the concentrations of A and B

log. [A]

1 1


constant, if concentration of C is doubled, the rate of



[ A] [ A ]2 reaction remains unaffected. This means that rate is

t t t
independent of the concentration of C i.e., order with
t
respect to C is zero. Hence the overall rate law
Plots of rate Vs concentrations [Rate = k(conc.)n

Zero order
]

1st 2nd 3rd

IDexpression will be, Rate = k[A]2 [B] [C]0
 Overall order of reaction = 2 + 1 + 0 = 3.
Theories of reaction rate
Rate 
Rate 

Rate 
Rate 

order order order (1) Collision theory

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(i) The basic requirement for a reaction to occur
is that the reacting species must collide with one
Conc. Conc. (Conc.) (Conc.) another. This is the basis of collision theory for
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2 3
reactions.
(4) Van't Haff differential method : The rate of (ii) The number of collisions that takes place per
reaction varies as the nth power of the concentration second per unit volume of the reaction mixture is
Where 'n' is the order of the reaction. Thus for two
known as collision frequency (Z). The value of collision
different initial concentrations C1 and C 2 equation,
frequency is very high of the order of 10 25 to 10 28 in
can be written in the form,
dC 1 dC 2 case of binary collisions.
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 kC1n and  kC 2n
dt dt (iii) Every collision does not bring a chemical
change. The collisions that actually produce the product
Taking logarithms,
are effective collisions. The effective collisions, which
 dC 1 
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log 10    log 10 k  n log 10 C1 …..(i) bring chemical change, are few in comparison to the
 dt  total number of collisions. The collisions that do not
 dC 2  form a product are ineffective elastic collisions, i.e.,
and log 10    log 10 k  n log 10 C 2 …..(ii)
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 dt  molecules just collide and disperse in different

directions with different velocities.
Subtracting equation (ii) from (i),
 dC1   dC 2  Fraction of
log 10    log 10   molecules
n  dt   dt  capable of
Fraction of

…..(iii)
molecules

log 10 C1  log 10 C 2 bringing

effective collisions
 dC 1 dC 2
and are determined from
dt dt
concentration Vs time graphs and the value of 'n' can Energy E
Distribution of energies at a
be determined. definite temperature
(5) Ostwald's isolation method (Initial rate
method)
 460 Chemical Kinetics
(iv) For a collision to be effective, the following two Where f is fraction of effective collision and Z is
barriers are to be cleared, the collision frequency.
(a) Energy barrier : “The minimum amount of (vii) The physical meaning of the activation
energy which the colliding molecules must possess as to energy is that it is the minimum relative kinetic energy
make the chemical reaction to occur, is known as
which the reactant molecules must possess for
threshold energy”.
changing into the products molecules during their
 In the graph 'E' corresponds to minimum or
collision. This means that the fraction of successful
threshold energy for effective collision.
collision is equal to e  Ea / RT called Boltzmann factor.
 There is an energy barrier for each reaction. The
reacting species must be provided with sufficient energy to (viii) It may be noted that besides the
requirement of sufficient energy, the molecules must

60
cross the energy barrier.
(b) Orientation barrier : The colliding molecules be properly oriented in space also for a collision to be
should also have proper orientation so that the old successful. Thus, if Z AB is the collision frequency, P is
bonds may break and new bonds are formed. For the orientation factor (Steric factor) then,
example, NO 2 (g)  NO 2 (g)  N 2 O4 (g). During this
k  PZ AB .e  Ea / RT . If we compare this equation with
reaction, the products are formed only when the

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colliding molecules have proper orientation at the time Arrhenius equation. k  A e  Ea / RT
of collisions. These are called effective collisions.
We know that pre-exponential form 'A' in
Collisions not properly oriented Arrhenius equation is, A  PZ AB .
O O O Concept of activation energy
Molecule Molecule O

O
N

NO2 +
O N
O
NO2
s
approach
O
N O N

Collision
s
Separate
O

Properly oriented collisions form products

O
NO2
N

NO2
No product
N
O
ID The excess energy (Over and above the average
energy of the reactants) which must be supplied to the
reactants to undergo chemical reactions is called
activation energy (Ea ) ,
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O O O O O O Ea  E(Threshold energy )  E(Reactants)
Molecule Bond
N N N N N N
s
approach Formatio Activation energy = Threshold energy – Average
O O O O n O O
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kinetic energy of the reacting molecules.

NO2 Product
+ NO2 Collision N2 O 4
(a) Zero activation energy = Fraction of effective
Fig. 11.1
collision (f) will be very large = Very fast reaction
(v) Thus, the main points of collision theory are (Instantaneous reaction).
as follows, (b) Low activation energies = Fraction of effective
(a) For a reaction to occur, there must be collision (f) will be large = Fast reactions.
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collisions between the reacting species. (c) High activation energies = Fraction of
(b) Only a certain fraction of the total number of effective collision (f) will be small = Slow reaction.
collisions is effective in forming the products. The activation energy (Ea ) depends upon the nature
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(c) For effective collisions, the molecules should of chemical bonds undergoing rupture and is
possess sufficient energy as well as orientation. independent of enthalpies of reactants and products.
(vi) The fraction of effective collisions, under According to the concept of activation energy, the
ST

ordinary conditions may vary from nearly zero to about reactants do not change directly into the products. The
one for ordinary reactions. Thus, the rate of reaction is reactant first absorb energy equal to activation energy
proportional to : and form activated complex. At this state, the molecules
must have energy at least equal to the threshold energy.
(a) The number of collisions per unit volume per
This means that the reaction involves some energy
second (Collision frequency, Z) between the reacting
barrier which must be overcome before products are
species
formed. The energy barrier is known as activation
(b) The fraction of effective collisions (Properly energy barrier.
oriented and possessing sufficient energy), f i.e.,
Threshold Activated
dx energy complex
Rate   fZ Et (Et)
dt
Energy
Ea barrier
(activation
energy)
Er Reactants Energy of
E the
(Er) reaction
Ep Products (Ep)

Progress of reaction
 Chemical Kinetics 461

log k
Ea
Slope  
2 .303 R

1/T
(2) Transition state theory
(i) According to transition state theory the Rate constants for the reaction at two different
activated complex is supposed to be in equilibrium with temperatures T1 and T2 ,
the reactant molecules. k2 1
Ea 1 
   

60
log …..(iii)
(ii) Once the transition state is formed it can k1  1
2 .303 R
T T2
either return to the initial reactants or proceeds to where k 1 and k 2 are rate constant at temperatures
form the products.
T1 and T2 respectively (T2  T1 ) .
(iii) Assuming that once formed the transition state
proceeds to products we can say that rate is Mechanism of the reaction

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proportional to concentration of transition state. (1) Reaction involving first order consecutive
Mathematically, Rate  Transition state reactions
Rate= Constant × Transition state (i) In such reactions, the reactions form a stable
(iv) The activation energy for the forward intermediate compound before they are finally
reaction, (Eaf ) and the activation energy for the reverse converted into the products.

reaction (Ear ) are related to the enthalpy (H ) of the

reaction by the equation H  Eaf  Ear .
(a) For endothermic reactions, H  0, so that
ID (ii) For example, reactants (R) are first converted to
intermediate (I) which is then converted to product (P) as
R 
k1
I 
k2
P
Therefore, the reaction takes place in two steps,

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Ear Eaf both of which are first order i.e.,
(b) For exothermic reaction, H  0, so that Step I : R 
k1
I ; Step II : I 
k2
P

Ear  Eaf . This means that I is produced by step I and consumed

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by step II. In these reactions, each stage will have its

Arrhenius equation own rate and rate constant the reactant concentration
Arrhenius proposed a quantitative relationship will always decrease and product concentration will
between rate constant and temperature as, always increase as shown in fig.
k  A e  Ea / RT …..(i) P
Concentration

The equation is called Arrhenius equation.

In which constant A is known as frequency factor. I
D

This factor is related to number of binary molecular

collision per second per litre. R
Ea is the activation energy. Time
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T is the absolute temperature and Concentration profile of reactants (R),

intermediate (I) and products (P) as a
R is the gas constant function of time
Both A and Ea are collectively known as (2) Reaction involving slow step : When a
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Arrhenius parameters. reaction occurs by a sequence of steps and one of the

Taking logarithm equation (i) may be written as, step is slow, then the rate determining step is the slow
Ea step. For example in the reaction
log k  log A  …..(ii)
2 .303 RT R 
k1
I; I 
k2
P , if k1  k 2 then I is
The value of activation energy (Ea ) increases, the converted into products as soon as it is formed, we can
value of k decreases and therefore, the reaction rate say that
decreases. d [ R ] d [ P ]
When log k plotted against 1 / T , we get a straight   k1 [R]
dt dt
line. The intercept of this line is equal to log A and
(3) Parallel reactions : In such type of reactions
 Ea
slope equal to . the reactants are more reactive, which may have
2 . 303 R
different orders of the reactions taking place
Therefore Ea  2.303 R  slope .
simultaneously. For example, in a system containing
 462 Chemical Kinetics
NO 2 and SO 2 , NO 2 is consumed in the following two (iv) The rate of photochemical reactions depend
upon the intensity of radiation’s absorbed.
 N 2O4 ; NO 2  SO 2 
reactions, 2 NO 2 
k1
 NO  SO 3
k2
(v) The G values for light initiated reactions
The rate of disappearance of NO 2 will be sum of
may or may not be negative.
the rates of the two reactions i.e., (vi) The temperature does not have marked effect
d[ NO 2 ] on the rate of light initiated reactions.
  2k1 [ NO 2 ]2  k 2 [ NO 2 ][SO 2 ]
dt (2) Mechanism of some photochemical
Photochemical reaction reactions
Absorption of radiant energy by reactant (i) Photochemical combination of H2 and Cl2 : A
molecules brings in photophysical as well as mixture of H 2 and Cl 2 on exposure to light give rise to

60
photochemical changes. According to Einstein's law of the formation of HCl, showing a chain reaction and
photochemical equivalence, the basic principle of photo thereby producing 10 6 to 10 8 molecules of HCl per
processes, each reactant molecule is capable of photon absorbed.
absorbing only one photon of radiant energy. The
H 2  Cl 2   2 HCl
sunlight
absorption of photon by a reactant molecule may lead

E3
to any of the photo process. The mechanism leading to very high yield of HCl
as a result of chemical change can be as follows.
Reactant molecule
Chlorine molecules absorb radiant energy to form an
Absorption of
photon (As per
excited molecule which decomposes to chlorine free
Einstein law) radicals (Cl) to give chain initiation step.
Excitation of Knock out the
Light absorption step : Cl2 

hv
Cl2*
electronic level

Excited molecule
electron from the
reactant species
Photoelectric effect
ID ........(i)
Chain initiation step : Cl2*  Cl   Cl 
........(ii)
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The chlorine free radical then combines with H 2
Photophysical Photochemical
process molecule to form HCl and H  free radical. The H  free
process
(i) Oxidation radical so formed again combines with another Cl2
(i) Fluorescence (ii) Reduction
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(ii) Phosphorescence (iii) Dissociation molecule to give HCl and Cl  free radical back resulting
(iv) Double into chain propagation step.
decomposition
Chain propagation step : Cl   H 2  HCl  H 
(v) Isomeric
transformation
The chemical reactions, which are initiated as a ........(iii)
(vi) Photosensitization
result of absorption of light, are known as photochemical H   Cl 2  HCl  Cl 
reactions. In such cases, the absorbed energy is The combination of two Cl  free radicals leads to
D

sufficient to activate the reactant molecules to cross chain terminating step.

the energy barrier existing between the reactants and
Chain terminating step : Cl   Cl   Cl 2
products or in other words, energy associated with
........(iv)
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each photon supplies activation energy to reactant

(ii) Photochemical combination of H2 and Br2 :
molecule required for the change.
The combination of H 2 and Br2 to form HBr in
(1) Characteristics of photochemical reactions
presence of light is also an example of chain reaction
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(i) Each molecule taking part in a photo process

like photochemical combination of H 2 and Cl2 . Here
absorbs only one photon of radiant energy thereby
hc two Br2 molecules absorb photon, however, inspite of
increasing its energy level by hv or
 chain reaction only one molecule of HBr is formed for
(ii) Photochemical reactions do not occur in dark. each 100 photon absorbed by 100 molecules of Br2 .
(iii) Each photochemical reaction requires a H 2  Br 2   2 HBr
light

definite amount of energy which is characteristic of a

Mechanism
particular wavelength of photon. For example,
reactions needing more energy are carried out in Light absorption step : Br2  hv  Br2*
presence of UV light (lower  , more E/Photon). A ........(i)
reaction-taking place in UV light may not occur on Chain initiation step : Br2*  Br   Br 
exposure to yellow light (lower  and lesser E/Photon) ........(ii)
 Chemical Kinetics 463
Chain propagation step : Br *  H 2  HBr  H  
after the chain initiating step X 2 
hv
2X 
........(iii) Cl  H2  HCl  H is exothermic whereas
H *  Br2  HBr  Br  Br  H 2  HBr  H is endothermic.
........(iv)
 Drapper’s effect : H 2  Cl2  2 HCl , Such
Chain termination step : Br   Br   Br2 ........(v)
reactions are accompanied by the increase in the
The lower values of HBr formation per photon of volume. This is called Drapper’s effect. The reason is
light absorbed has been attributed to the fact that step that the reaction is exothermic and heat released
(III) is highly endothermic and thus before step (III) raises the temperature and gas expands resulting in
can take place most of the bromine free radicals the increase in volume.
recombine as per step (V) to give Br 2 molecule and
 Actinometer : A device which is used to measure

60
thus providing less feasibility for step (IV) i.e. steps the intensity of radiation is konwn as actimometer.
regenerating free radicals. Also the decomposition of e.g., Uranyl oxalate actinometer.
HBr increases with increase in temperature.  Amount of the substance left after ‘n’ half lives
(3) Quantum yield (or quantum efficiency) : The A0
quantum efficiency or yield   of a photochemical  .

E3
2n
reaction may be expressed as,
No. of molecules reacted or product formed
 Free energy change (G) for thermochemical
 reactions is always negative but remember, G for
No. of photon absorbed
photochemical reaction may not always be negative.
(4) Application of photochemistry :
It may be +ve also because a part of the light energy
Photochemistry has significant role in our daily life.
Some of the photochemical reactions commonly known
as cited below,
(i) Photosynthesis in plants
(ii) Photography
ID absorbed is converted into the free energy of the
products.
 Negative catalysts or inhibitors are those
substances which decrease the rate of a reaction.
 Example of fourth order reaction,
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(iii) The formation and destruction of ozone layer
4KClO3 ⇌ 3 KClO4  KCl
(iv) Photoetching in electronic industry  Grothus-Draper law : When light falls on a
(v) Many polymerization reactions.
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substance, a part of light is absorbed, a part is

(vi) Modern printing technology reflected and a part is transmitted. only that part of
(vii) Free radical combinations to obtain many light which is absorbed causes a particular reaction
compounds. to occur.
 Stark’s Einstein law of photochemical equivalence
According to this law, every atom or molecule taking
part in photochemical reaction absorbs only one
D

quantum of radiaton.
 Kinetics of fast reactions can be studied by (i)
Relaxation method (ii) Flash photolysis technique
 Different reactions have different rates because
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etc.
their activation energies are different. Lesser the
 Enzyme catalysed reactions are faster than metal
activation energy faster is the reaction.
catalysed reactions, the former has lower activation
1
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 The reaction, NO  O2  NO 2 , exhibits a small energy.

2
negative temperature coefficient and the rate of
reaction decreases with increase of temperature.
 Fuels in contact with oxygen do not burn by
themselves. This is because they need activation energy
(provided by the flame) to initiate the reaction. Thus,
fuels are thermodynamically unstable ( G is –ve) but Rate of a reaction
kinetically stable.
 Quantum efficiency of the photochemical 1. The rate of a chemical reaction
reaction, H 2  Cl 2  2 HCl is very high while that
hv [MP PMT 1973; CPMT 1982]
(a) Increases as the reaction proceeds
of H 2  Br2 
hv
2 HBr , is very low. This is because
(b) Decreases as the reaction proceeds
 464 Chemical Kinetics
(c) May increase or decrease during the reaction
(d) Remains constant as the reaction proceeds
2. The rate of a reaction that not involve gases is not
dependent on [CPMT 1988; AFMC 1995]
(a) Pressure (b) Temperature
(c) Concentration (d) Catalyst
3. The rate at which a substance reacts depends on
its
[MP PMT 1987; BHU 1999; KCET 2005]
(a) Atomic weight (b) Equivalent weight

60
(c) Molecular weight (d) Active mass
4. The rate law for the reaction
RCl  NaOH (aq)  ROH  NaCl is given by Rate
 K1 [RCl ] . The rate of the reaction will be[IIT 1988]
(a) Doubled on doubling the concentration of

E3
sodium hydroxide
(b) Halved on reducing the concentration of alkyl
halide to one half
(c) Decreased on increasing the temperature of
the reaction

5.
(d) Unaffected by increasing the temperature of
the reaction
If doubling the concentration of a reactant `A'
increases the rate 4 times and tripling the
concentration of `A' increases the rate 9 times,
ID
U
the rate is proportional to [AIIMS 1991]
(a) Concentration of `A'
(b) Square of concentration of `A'
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(c) Under root of the concentration of `A'

(d) Cube of concentration of `A'
6. The rate of chemical reaction at constant
temperature is proportional to
(a) The amount of products formed
(b) The product of masses of the reactants
(c) The product of the molar concentration of the
D

reactants
(d) The mean free path of the reaction
7. The concentration of a reactant decreases from
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0.2 M to 0.1 M in 10 minutes. The rate of the

reaction is
(a) 0.01 M (b) 10 2
3 1
(d) 1 mol dm 3 min 1
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(c) 0.01 mol dm min

8. When a reaction is progressing
(a) The rate of the reaction goes on increasing
(b) The concentration of the products goes on
decreasing
(c) The concentration of the reactants goes on
decreasing
(d) The reaction rate always remains constant