BASARA GNANA SARASWATHI CAMPUS KAKATIYA HILLS

Sec: Star SC Nuclear Chemistry Date: 20-10-2020

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Rate of reaction: Let us consider a reaction from A to B. Here A is reactant and

B is product.
A ⎯⎯→ B

The initial concentration of reactant A is ‘a’. When the reaction proceeds

concentration of reactants decrease while the concentration of products
increase w.r.t time.
Definition: The change in concentration w.r.t time is known as rate of
reaction.
(or)
The decrease in the concentration of reactants (or) increase in the
concentration of products w.r.t time known as rate of reaction. It is denoted
by ‘r’ (or) ‘R’
change in concentration
r=
time
decrease in concentration of reactants
=
time
increase in concentration of products
=
time
Units: M time −1
or
atm time−1

FACTORS INFLUENCING REACTION RATE

It could be easily expected that the rate of a reaction will depend on the
reactivity or nature of the involved substances. However, for a single step
reaction, between some given substances, the rate depends on the following
additional factors.
1. Temperature
Rates of all single reactions increase with rise in temperature.
Temperature co-efficient: (  )
 It is the ratio between two rate constants which differ by 10 o
C of temperature.

Denoted by  .

Let kt be the rate constant at t o C and k t +10 be rate constant at (t + 10) oC .

 From definition of temperature co-efficient, we can write.

k t +10
=
kt

Note: Temperature coefficient generally lies in between 2-3 i.e., for every rise
in number 10 oC of temperature rate of reaction

2. Concentration of reactants
Increase in the concentration of each and every reactant of a reaction
increases the rate of the reaction. Conversely, a decrease in concentration of
a reactant decreases the reaction rate.
As a reaction proceeds, the concentration of the reactants must inevitably
decrease and hence its rate must also progressively decrease. Thus rate of a
reaction will depend on the state of progress of the reaction. Nearer it is to
the end state, slower will its rate be. We have, therefore to modify or definition
of a reaction rates as follows for greater precision.
Rate of a reaction, at a particular instant of time during the course of the
reaction, is the instantaneous rate of change of concentration of any of its
reactants or products with respect to time.
3. Catalyst
Many reactions proceed faster in presence of catalysts. Some may take place
faster even under the influence of light or electricity or any other energy
providing aid.
Catalyst also does effect the rate constant because the addition of catalyst
would bring change in the path of the reactant

k2 E − E'a
log = a
k1 2.303RT

Ea is activation energy in absence of catalyst

E'a is activation energy in presence of catalyst

4. Reaction Medium
 Reactions may take place at different rates in gaseous or liquid media.
Reactions between polar or ionic reactants have different rates in solvents of
different dielectric constant.
5. Surface Area
Larger surface areas of a solid reactants and catalysts tend to increase the
rate of a reaction.
LAW OF MASS ACTION
Statement
The rate of a reaction is proportional to the product of effective concentration
of the reacting species, each raised to a power which is equal to the
corresponding stoichiometric number of the substance in the chemical
equation.
At a given temperature, the rate of a simple reaction at each instant is
proportional to the product of the instantaneous concentrations of the
reactants raised to powers which are numerically equal to the numbers of
their respective molecules in the stoichiometric equation describing the
reaction.

xA + yB ⎯⎯→ P

r   A B
x y

r = k  A B
x y

Where k = rate constant (or) velocity constant (or) Gyroscopic constant.

Limitations

1. When concentration of the reactants are high it is found that the

concentration of a reactant has to be multiplied by a certain factor to
get the active mass consistent with the law of mass action formation.
Such a factor is called activity coefficient and the modified active mass
obtained by multiplying the concentration by the activity coefficient is
called the activity of the substance.

2. When the reaction mechanism is different than suggested by the

stoichiometric equation given for it, the power numbers in the rate
 equation may differ from the stoichiometric numbers. These numbers
are then found out experimentally.
Characteristics of Rate Constant

1. Rate constant determines the speed of the reactant i.e., the reaction
with more ‘k’ value takes place very fast and vice versa.

2. The rate constant of a reactant is a characteristic property of that

reactant i.e., rate constant is a constant value at constant
temperature.

3. Rate constant of a reaction is independent of concentration of

reactants.

4. The rate constants of two different reactions must have two different
values.

Units for the Rate Constant ‘k’

The concentrations for the purposes of the law of mass action are expressed
as moles per litre (moles- litre−1 ) or as molarities (M). Rate of a reaction, which
is change of concentration per unit time, is expressed, in units of moles per
litre per second (moles - litre−1 sec −1 ) or molarity units per second ( M.sec−1 ) .

From the rate equation

dx
= k CaA .CBb . . . . . .
dt
the dimensional equation would be
a b
 Mole  −1  Moles   Moles 
  sec = k     ........
 Litre   Litre   Litre 

From this dimensional equation, the units of k can be written as

1−( a + b +.......)
 Moles 
.sec −1 or M (
1− a + b +......)
 Litre  sec −1 .
 

Molecularity
The total number of co-efficients of atoms in an elementary step of a reaction
is known as molecularity.
1. Molecularity of a reaction is always a positive integer.
2. Molecularity of a reaction is neither a fraction nor a negative value.
3. Molecularity of a reaction is never equal to zero
4. The determination of molecularity can be done by using mechanism of
a reaction.
ORDER
It is the sum of the powers of reactions which are raised to the co-efficients
of species in the rate law is known as order.
Properties
i) An order of a reaction is always estimated from rate law.
ii) The determination of order of a reaction is an experimental method.
iii) The order of a reaction is an integer and sometimes zero.
iv) The order of a reaction may be a fraction (or) negative value.
v) Similar to molecularity, higher order is not possible due to lack of
probability of collision.
ZERO ORDER REACTION
The reaction in which rate of reaction is independent on original
concentration of the reactant is known as zero order.
Examples
h
1. H2 + Cl2 ⎯⎯⎯ → 2HCl

2. Pt(or)Au
2NH3 ⎯⎯⎯⎯ ⎯
→ N2 + 3H2

3. Mo
4PH3 ⎯⎯⎯ → P4 + 6H2

Rate Expression
A ⎯⎯→ P
At t = 0 sec a 0
After t sec a–x x

dx d(A) d
r= =− = + [P] = k[A]0
dt dt dt
Integrated form
dx
 = k[A]0
dt

  dx = kdt
  dx = k  dt
 x = kt + C ……(1)
If t = 0 and x = 0, then C = 0
Sub C = 0 in (1)
 x = kt + C
x
 k=
t
 x
 k0 =
t
Units
x concentration
k0 = = = M time−1
t time
= mol L−1 time−1
Graph
x
k0 =
t
x = k0t
y = mx

Half life
Time taken to complete half of original concentration of reactant is called half
 
life  t 1  .
 2 
a
t = t 1 and x =
2
2
x
k0 =
t
a
= 2
t 12
a
t1 =
2
2k 0
y = mx
ANOTHER FORM OF ZERO ORDER
x
k0 =
t
a − (a − x)
=
t
[A]0 − [A]t
=
t
kt = [A]0 − [A]t
[A]t = [A]0 − Kt
[A]t = −kt + [A]0
y = mx + C

FIRST ORDER REACTION

If the rate of reaction depends on concentration of only one reactant in known
as first order reaction.

Examples
1) 2N2O5 ⎯⎯→ 4NO2 + O2

r = k[N2O5 ]1

2) 2N2O ⎯⎯→ 2N2 + O2

r = k[N2O]1

3) C2H5Cl ⎯⎯→ C2H4 + HCl

r = k[C2H5Cl]1
H+
4) CH3COOC2H5 + H2O ⎯⎯⎯ → CH3COOH + C2H5OH

r = k[CH3COOC2H5 ]1[H2O]

5) SN1 in organic reactions

Rate Expression
A ⎯⎯→ P
At t = 0 sec a 0
After t sec a–x x
 dx −d[A] +d
r= = = [P] = k[A]1 = k[a − x]1
dt dt dt

Integrated Form:
−d
 [A] = k[A]
dt
d
 [A] = −k[A]
dt
1
 d[A] = −k dt
[A]

Integrate on both sides w.r.t

a to a–x on L.H.S
o to t on R.H.S
a −x t
d[A]
 
a
[A] o 
= −k.dt

 ln[A]aa −x = −kt
 ln(a − x) − ln(a) = −kt
 a 
 ln   = kt
a −x
1  a 
 k = ln  ……(1)
t  a − x 
2.303  a 
 k= .log   ……(2)
t a −x
kt  a 
 = log  
2.303 a −x
mx = y

kt  a 
 = log  
2.303 a −x
Let a =  A 0 and (a − x) =  A t

−kt  At
 = log
2.303  Ao
−kt
 = log  At − log  Ao
2.303
 −kt
 log  At = + log  Ao
2.303

y = mx + c

Exponent Form
1. From …… (1)
l a
k = ln
t a−x
a
kt = ln
a−x
a−x
−kt = ln
a
a−x
= e−kt
a
a − x = ae−kt
(a − ae − kt ) = x
a(l − e − kt ) = x

2. From …… (2)
2.303 a
k= log
t a−x
a−x −kt
log =
a 2.303
a−x
= 10−kt/2.303
a
x = a 1 − 10−kt/2.303 

UNITS
2.303 a
k= log
t a−x
1
k= = time−1
time

Half Life: The time taken to complete half of the original concentration of
reactant
 a
Let t = t1/2 and x=
2 substitute in ……(2)
2.303 a
k= log
t1/2 a − a /2
2.303
k= log 2
t1/2
2.303(0.301)
t1/2 =
k
0.693
t1/2 =
k
Half life does not depend on initial concentration of a reactant.

Average life: The reciprocal of rate constant of first order reactant is known as
average life denoted by (  )
1
 =
k

Amount of substance left after n-half lives

a
The amount of substance that is left after n-half lives =
2n
Total time
Where n =
time taken for one half life
1 st a 2nd a 3rd a nth a
a ⎯⎯⎯→ ⎯⎯⎯ → ⎯⎯⎯ → .................. ⎯⎯⎯ → n
2 4 8 2
The amount of substance reacted after ‘n’ half lives.
a
=a−
2n

EXPERIMENTAL DETERMINATION OF FIRST ORDER REACTION

Ester hydrolysis
When ester undergoes hydrolysis in the presence of mineral acid like HCl and
H2SO4, it forms carboxylic acid and alcohol. This is known as ester
hydrolysis.

The rate law can be written as

1 o
r = k CH3COOC2H5  H2O

The above reaction is also known as pseudo first order reaction because water
is present in excess amount.
The volume of ester can be calculated on the basis of volume of carboxylic
acid by titrating against NaOH.

Vo - volume of mineral acid only

 Vt - volume of mineral acid + volume of carboxylic acid at time ‘t’
V - volume of mineral acid + volume of total carboxylic acid.

a  ( V − Vo )
x  ( Vt − Vo )
( a − x )  ( V − Vo − Vt + Vo )
( a − x )  ( V − Vt )
2.303 a
k= log
t a−x
2.303 V − Vo
k= log 
t V − Vt

Hydrolysis of sucrose
Sucrose undergoes hydrolysis in the presence of mineral acids like HCl,
H2SO4 and forms 1 mole of glucose and 1 mole of fructose. In this reaction a
dextro rotatory compound of sucrose is converted to laevo rotatory mixture.

Hence this process is also known as inversion phenomenon (or) inversion of

cane sugar.
+
H
C6H12O6 + H2O ⎯⎯⎯→ C6H12O6 + C6H12O6

Sucrose glucose fructose

ro = Initial optical rotation
rt = Rotation at time t
r = Rotation at the end
a  ( ro − r )
x  ( ro − rt )
( a − x )  ( ro − r − ro + rt )
( a − x )  ( rt − r )
2.303 r −r 
k= log  o  
t  rt − r 
SECOND ORDER REACTIONS
1. General reaction equations
i) 2A ⎯⎯→ Products

or ii) A + B ⎯⎯→ Products

2. Rate laws
dx
= k  A
2
i)
dt
 dx
ii) = k  AB
dt

3. Rate constant relationship

i) When the reaction is of the type

2A ⎯⎯→ Products

Or when the reaction is of the type

A + B ⎯⎯→ Products

and it is started with equal concentrations of A and B, let ‘a’ moles per litre
be the initial concentration of A (or of A as well as B for the second type of
reaction) and (a–x) moles per litre be the concentration of A, or of A as well as
B, at time t = t, then the rate equation (in either case) will be
dx
= k (a − x )
2

dt
Separating the variables and integrating over the time interval t = 0 to t = t,
we shall have
x =x t =t
dx
 (a − x )
x =0
2
=  k dt
t =0

x =x
 1 
=  kt t =0
t =t
a − x 
  x =0

1 1 1 1
− =k t= −
a−x a C t C0

1 1
= kt +
a−x a
1 1
or t= −
k ( a − x ) ka

1  x 
also t=
ak  a − x 

Graphical Representation of Second order reaction characteristics

A graph of 1/(a – x) or 1/CA versus t will be straight lines with positive slope.
ii) When reaction is of the type
A + B ⎯⎯→ Products

and initial concentrations of A and B are unequal and say, ‘a’ moles litre and
‘b’ moles / litre respectively and let ‘x’ moles/litre of each reactant be
converted to the products after a time ‘t’. The reaction rate equation will then
be
dx
= k ( a − x )( b − x )
dt
Integrating the equation between the limits t = 0 and t = t gives
1 b (a − x )
ln = kt
a − b a (b − x )

2.303 b (a − x )
or log = kt
a −b a (b − x )

If a start is made with large excesses of A, then ‘a’ will be much larger than
‘b’ as well as ‘x’. Then we can replace (a-b) and (a-x) by ‘a’ and we have
1 b
ln = kt
a b−x

b
or ln = akt
b−x

b
or ln = k 't
b−x

Hence a second order reaction between two reactants, when a large excess of
one reactant is used, becomes kinetically a reaction of first order in respect
of the reactant taken in smaller quantity.
Some examples of second order reactions
100C
i) 2O3 ⎯⎯⎯⎯ → 3O2

ii) 2N2O ⎯⎯⎯⎯

200C
→2N2 + O2

iii) 2Cl2O ⎯⎯→ 2Cl2 + O2

iv) Saponification of esters in solutions

CH3COOC2H5 + NaOH ⎯⎯→ CH3COONa + C2H5OH

v) Conversion of ammonium cyanate to urea in solution

NH4CNO ⎯⎯→CO(NH2 )2

vi) 2NO2 + F2 ⎯⎯→ 2NO2F

r = k[NO2 ]1[F2 ]1

vii) NO2 + CO ⎯⎯→ NO + CO2

r = k[NO2 ]2

viii) NO + O3 ⎯⎯→ NO2 + O2

r = k[NO]1[O3 ]1

xi) SN 2 in organic reactions

Reactions of Higher Orders

Such reactions when involving only one reactant may be represented by the
general reaction equation,
nA ⎯⎯→ Products.

Rate equation for them will be of the form

dx
= k CnA
dt
and then
log(dx /dt) = log k + n log CA

Accordingly a straight line graph can be obtained by plotting the logarithm of

rate of reaction, versus logarithm of reactant concentration and the slope of
this line will equal ‘n’. If we make the hypothetical assumption that the rate
constant ‘k’ has the value which does not depend on the order of the reaction,
the dependence of rates on orders of reactions can be depicted as shown in
the figure.
 Rate equation for a reaction can also be set in the form of equation as
dx
= k (a − x )
n

dt
Integrating the equation
1  1 1 
 − =k t
( n − 1)  ( a − x )n−1 a n−1 
Half change time for such reactions is given by
1
t1 =
2 ( n − 1) a n−1. k
 t 1 is inversely proportional to a n−1
2

Note The kinetic relationships are based on the assumption that the changes
in the concentrations of reactants are due to the reactions alone and no
volume changes occuring during the reactions. This true in most cases but
not in all.
DETERMINATION OF ORDER OF A REACTION
The reaction is carried out at a constant temperature in a thermostat.
Concentrations of one or more of the reactants of reaction products are
measured after increasing intervals of time by a suitable technique. This data
can be analysed by a number of procedures. The more common and simple
methods are described here.
1. Integration method: The experimental data is substituted in the equations for
different orders. When we get the calculated values of the rate constant ‘k’
comes out reasonably constant, the corresponding equation decides the order
of the reaction.
a
First order 2.303 log = kt
a−x
1 1
Second order − =k t
a−x a
 1  1 1 
Third order  − 2=k t
2  (a − x ) 2
a 
 

2. Graphing method: Straight line graphs can be obtained for a first order reaction
by plotting log (a – x) verses t and for a second order reaction by plotting 1/(a-
x) verses t. So the experimental data can be tried with these functions. Third
order reactions will give linear plot for 1/ (a – x ) verses t.
2

3. Half change time method: In general the dependence of the half change time of a
reaction with equal initial concentrations of reactants, or for a single reactant
is given by
1
t1 
2
a n −1

Accordingly if n = 0, t 1 is proportional to a
2

n = 1, t 1 is constant and independent of a

2

1
n  1, t 1 is proportional to
2 a n−1

If t1 and t 2 are half change times when the initial concentrations are a1 and a 2
, then
n−1
t1  a 2 
= 
t2  a1 

t1 a
or log = ( n − 1) log 2
t2 al

Thus the order of the reaction can be obtained.

The same relationship holds for times for any other defined fraction of
1
reaction such as or 10%.
4
4. Van Hoff’s differential method: In this method the average rates of reactions for a
10% or small initial fraction of the change are compared for two different sets
of equal initial concentrations of all reactants. Then
 x  n
  = r1 = k C1
 t 1

 x 
and 
n
 = r2 = k C2
 t 2

Then,
 n
r2  C2 
= 
r1  C1 

Taking logarithms on both sides,

n log (C2 /C1 ) = log ( r2 /r1 )

log ( r2 / r1 )
 n=
log ( C2 /C1 )

5. Varying the ratio of the reactants by a known factor:

Consider the general equation
dx
= k.CaA .CBb
dt
dx
After finding the value for some values of CA and CB , the value of one of
dt
dx
them say CA is doubled and that of CB is kept constant, the new value of is
dt
found again. Then
 dx 
 dt 
k ( 2 C A )  ( CB )
a b
 Second expt.
= = 2a.
  k ( C A )  ( CB )
a b
dx
 
 dt first expt.

Thus the value of ‘a’, the order of the reaction with respect to the reactant A,
is evaluated. A similar process gives the order ‘b’ of the reaction with respect
to reactant B. The overall order of the reaction is equal to (a + b).
6. Ostwald’s isolation of flooding method: In this method, the experiment is run a
number of times each time taking all the reactants except one in large excess.
This reactant is thus isolated and all the other reactants are flooded. The
kinetics of the reaction then gives the order of the reaction with respect to the
reactant. The orders found for other reactants are then added upto get the
overall order of the reaction.
i) Side reactions: Hence the same reactant or set of reactants participate
simultaneously in the formation of two or more different sets of products. If
one of these reactions gives the major amount of products, it is called the
main or major reaction and the other are called side reactions. If, however,
the simultaneous reactions consume comparable quantities of the reactants,
then all reactions are said to be parallel reactions.
 dCB
= k1 CA
dt
dCC
= k 2 CA
dt
dCA
− = ( k1 + k 2 ) CA
dt
dx
= ( k1 + k2 ) CA = k CA
dt
For A ⎯⎯⎯
k
→B 1

r = k1[A]

For A ⎯⎯⎯
k
→C 2

r = k 2 [A]

r1 k1[A]
=
r2 k 2 [A]

r1 k1
=
r2 k 2

Total rate of reaction

r = r1 + r2

r = k1[A] = k 2[A]

r = ( k1 + k 2 ) [A]

For a reaction of this type the ratio of the molar amounts of B and C formed
upto any stage during the reaction, will be of the respective rate constants
and will be independent of the length of time for which the reaction has been
going on.
Amount of B formed in time t k
= 1.
Amount of C formed in the same time k 2

k1[A]
% of [B] =  100
( k1 + k 2 ) [A]
k1
% of [B] =  100
k1 + k 2
 k2
% of C =  100
k1 + k 2

Ex: 1. Nitration of benzoic acid gives a mixture of ortho meta and para
benzoic acids
2. Dual decay of radioactive elements in some cases.

ii) Reversible reactions: Reversible reactions are simultaneously reactions in

which the reactants of the forward reaction are being consumed and
reproduced simultaneously. The overall rate of the reaction progressively
decreases and becomes zero at the equilibrium point.
Ex: There are several examples of reversible reactions, which eventually
reach steady equilibrium eventually reach
steady equilibrium states

1) H2 + I2 2HI

2) N2 + 3H2 2NH3

3) CH3COOC2H5 + H2O CH3COOH + C2H5OH.

kf
A kb
B

Forward Backward
kf kb
A ⎯⎯⎯ →B B ⎯⎯⎯ →A

rf = k f [A] rb = k b [B]

r = rf − rb

dx  d   −d
 =  −  A −  B 
dt  dt   dt 

dx
= k f [A] − k b [B]
dt

A B

t = 0 [A]0 0

t=t [A]0 − x x
Both forward and backward reactions are of 1st order.

dx
= k f [A]0 − x  − k b x...............(1)
dt

At equilibrium

rf = rb

rf − rb = 0

dx
=0
dt

x = x eq

(
0 = k f [A]0 − xeq − k b xeq )
kb xeq = kf [A]0 − xeq 

k b x eq = k f [A]0 − k f x eq

(kf + k b ) x eq = k f [A]0

k f [A]0
x eq = ............(2)
kf + kb

(
kb xeq = kf [A]0 − xeq )
k b x eq
kf =
[A]0 − x eq

Substituting in equation (1)

dx  k f [A]0 − x eq
= k f ([A]0 − x ) − 
( )  x
dt  x eq 
 

k f [A]0 x k f .x eq x
= k f [A 0 ] − k f (x) − +
x eq x eq

k f [A]0 x
= k f [A]0 −
x eq

dx k f [A]0
dt
=
x eq
x eq − x ( )

1  x eq 
  dx = dt
k f [A]0  x eq − x 
 
 Integrate on both sides

x eq 1
k f [A]0 x eq − x
dx = dt 
x eq
 − ln(x eq − x) = t + C
k f [A]0 

By applying boundary conditions

t=0 x =0

x eq
(− ln x eq ) = C
k f [A]0

x eq x eq
t= ln
k f [A]0 x eq − x

From equation (2)

1 k f [A]0 x eq
t= ln
k f [A]0 ( k f + k b ) x eq − x

1 x eq
 t= ln
kf + kb x eq − x

2. Consecutive or Successive Reactions: The reactions in which one or more products

of a preceding reaction step, either alone or along with some of the other
molecular species present, become reactants for another forward reaction
step are called consecutive reactions. If the rate constants of succeeding
reaction steps are comparable in magnitude, the reaction rate equation may
become quite complicated. If a particular reaction step is much slower than
the rest, it becomes the rate controlling step for the whole reaction (principle
of bottle neck). A simple case will be of a reaction with just two first order
steps.
k k
A ⎯⎯⎯
1
→ B ⎯⎯⎯
2
→C

At t=0 a 0 0 moles/litre
At t=t x y z moles/litre
The controlling rate equations are
dx
− = k1x
dt
 dy
+ = k1 x − k 2 y
dt
dz
+ = k2 y
dt

k1 k2
A ⎯⎯⎯ → B ⎯⎯⎯ →C

[A]0 0 0

[A] [B] [C]

[A0 ] = [A] + [B] + [C]

d
− [A] = k[A]
dt

Rate of change of B = rate of disappearance of A – rate of appearance of C.

−d +d
= [A] − [C]
dt dt

= k1[A] − k 2 [B]

d
[B] = k1[A] − k 2[B]
dt

d
[B] + k 2[B] = k1[A]
dt

[A] = [A]0 .e − k1t

d
[B] + k 2[B] = k1[A]0 e−k1t
dt

Multiply the expression with e+ k t 2

d  + k 2t
= k1[A]0 e ( 1 2 )
− k −k t
 dt [B] + k 2 [B] e
 

Assume B in excess

d  + k 2t
= k1[A]0 e ( 1 2 )
− k −k t
 dt [B]  e
 

e + k 2t .d[B] = k1[A]0 e ( 1 2 ) dt
− k −k t

Integrate on both sides

e + k 2t d[B] = k1[A]0 e ( 1 2 ) dt
− k −k t

 e−( k1 −k2 )t ) 
e+ k2t [B] = k1[A]0  +C
 − ( k1 − k 2 ) 
 
t = 0, [B] = 0

k1[A 0 ]
e0 [0] = +C
− k1 − k 2 

k1  A 0 
C=
k1 − k 2

 e−(k1 −k2 )t 1 
e+ k2t [B] = k1[A0 ]  + 
 −(k1 − k 2 ) k1 − k 2 

 e−(k1 −k2 )t 1 
= k1[A0 ]  + 
 (k 2 − k1 ) k1 − k 2 

Divide with e+ k t 2

 e−k1t e − k 2t 
[B] = k1[A]0  +  ……(1)
 k 2 − k1 k1 − k 2 

We know that [A]0 = [A] + [B] + [C]

 e−k1t e − k 2t 
[A]0 = k[A] + k1[A]0  +  + C
 k 2 − k1 k1 − k 2 

As we know [B] is in excess.

d
[B] = 0
dt

d k [A ]
[B] = 1 0  −k1e−k1t + k 2 − e− k2t 
dt k 2 − k1

k1[A 0 ]
0=  −k1e−k1t + k 2e− k2t 
k1 − k 2  

For the above reaction,

−k1e − k1tmax + k 2e − k 2tmax = 0

k1.e − k1tmax = k 2 .e − k 2tmax

k1
= e  2 1  max
− k −k t

k2

k1
ln = − k 2 − k1  t max
k2

1 k
t max = ln 2 …….(2)
k 2 − k1 k1
 k2
 k  k1 −k2
[B]max = [A0 ]  2 
 k1 

At any time ‘t’ during the reaction, the values of x, y and z can be shown to
be
x = a e − k1t

y=
k1a
k 2 − k1
(
e−k1t − e−k2t )
z=
a
k 2 − k1
 ( ) (
k 2 1 − e− k1t − k1 1 − e− k2t )
In consecutive reactions of above type, the concentration of A goes on
decreasing all the time while that of C goes on increasing all the time.
Concentration of B first increases and later on decreases and eventually
disappears simultaneously with that of A. Accumulation of the intermediate
B can be conspicuously seen if it happens to be a coloured substance.
Ex:
1. Oxidation of H3PO3 by K2S2O8 in presence of HI.

H2S2O8 + 2HI ⎯⎯→ H2SO4 + H2SO4 + I2 ( fast )

 A B

H3PO3 + I2 + H2O ⎯⎯→ H3PO4 + 2HI (slow )

C

The colourless solution acquires the characteristic brown iodine colour of

intermediate B and eventually becomes colourless again.
2. Saponification of ethyl succinate by NaOH solution
CH2COOC2H5 CH4COONa
| + NaOH ⎯⎯→ | + C2H5OH
CH2COOC2H5 CH2COOC2H5
 A B

CH2COONa CH2  COONa

| + NaOH ⎯⎯→ | + C2H5OH
CH2  COOC2H5 CH2  COONa
 C

A consecutive overall reaction with more than two steps can be called chain
reaction.

Molecular Collision Theory

1. All the processes occurring in nature by themselves are those in which
involved systems undergo a decrease of free energy. These processes are
 called as spontaneous reactions and hence, the first necessary condition for any
reaction is that it should be thermodynamically possible.

2. Suppose a chemical reaction is thermodynamically feasible, the next

consideration would be as to how such a reaction may be brought about.
Since all chemical reactions can take place between individual molecules and
the reacting molecules must approach each other near enough to influence
the inter-atomic and inter-molecular forces such that rupture and re-making
of inter-atomic bonds could occur. Such approach of molecules is known as
a collision. So a collision between reacting molecules is a second requisite for a chemical
reaction involving more than one molecule in each reaction step.

3. Let us consider a simple reaction such as thermal dissociation of gaseous

hydrogen iodide. It is a reaction of second order and involves binary
collisions between molecules of the same kind. Suppose we have one mole of
HI present per litre of reaction at 283 °C, the number of binary molecular
collisions, Z1,1, can be calculated from the formula

RT
Z1,1 = 2n2a 2
M
where ‘n’ the number HI molecules present per c.c.
6.02  1023
= or about 6 1030
1000
, diameter of HI molecule = 3.5 10−8 cm.
R, the gas constant = 8.3 107 ergs/mole.deg.

M, the gm-molecular wt. of HI = 128 gm

T = 556 K and  = 3.143
Z1,1  3  10+31

The number of colliding molecules per c.c. and second

= 2  3 1031 = 6 1031

The observed specific reaction rate of the reaction is 3.5  10−7 L.mol −1.sec −1

dx 3.5  10−7  6  1023

= k HI =
2
 molecules per c.c. per sec.
dt 1000

= 2.1  1014 molecules per c.c. per sec.

Thus the number of molecules result into formation of products per c.c. per
sec. is much smaller than the number of molecules participating in binary
 collisions per c.c. per sec. Through the intermolecular collisions are essential for any
reaction, every collision does not result into a completion of the reaction step.

4. Molecules in a gas widely different in their energies. The thermal dissociation

of HI is increases rapidly on raising the temperature but rise in temperature
causes only a slight increase in the frequency of molecular collisions
(proportional to T ) but the reaction rate increase is several fold more than
the increase in collision frequency.
A 10 °C rise at room temperature could cause an increase in the total number
of binary of collisions by about 1.5 % but the same change in temperature
will double the number of molecules with an energy of 12.5 kilo-calories per
mole or more their number at the lower temperature. Svante Arrhenius
suggested that collision of only such molecules, which possessed energy equal
to or above a certain value characteristic of the reaction, could succeed in
producing the reaction products. This minimum energy which the reacting
molecules have to possess between themselves for a reaction was called by
Arrhenius the energy of activation, Ea for the reaction. The probability of a
molecule having an energy equal to or greater than a critical value Ea at two
temperatures T1 and T2 is depicted by a shading of the areas.

Obviously the more important effect of rise in temperature is an increase in

the proportion of molecules with energies equal to or greater than Ea ,
Arrhenius activation energy for the HI dissociation calculated from the
change in value of specific reaction rate with temperature found to be 44.0
kcal per mole. The fraction of the total molecules with energies of 44.0 kcal
per mole or more, according to Maxwell distribution, is given by
 Ea 44.0103
− −
e RT = e RT

and equals nearly 5  10−18 . Thus, out of a total of 6 1031 molecules per c.c.
taking part in collisions per sec. as calculated earlier, activated molecules
amount to 5 10−18  6 1031 or 3.0  1014 per c.c. and it is only these which are
expected to take part in the formation of products. This number is very close
to the number 2.11014 per c.c. calculated on the basis of observed reaction
rate. Hence, according to the collision theory of reaction rates, the third requirement
for a reaction to occur is suitable activation of the molecules.

5. When the observed reaction rates are much smaller than those calculated on
the basis of collision between activated molecules, it is further postulated that
in these reactions, a suitable orientation of molecules of reacting substances is a fourth
requirement for the occurrence of a reaction and factors like steric hindrances may be having
an influence in deciding the success of collision. On the basis of this approach,
it is deduced that,
k =  Z e − Ea /RT

where ‘k’ is the specific reaction rate, 'Ea ' is activation energy, ‘Z’ is collision
number and '  ' is the probability of a collision between activated
molecules resulting into products. The collision number ‘Z’ is the collision
intensity of the reaction. This can be increased by an increase in
Ea
−
concentration of reactions or by a rise in temperature. The other factor e RT

is a measure of the collision efficiency and thus can be improved by use of a

catalyst which reduces the activation energy need and improves collision
orientations.

This analysis of a spontaneous reaction rate based on a kinetic collision

approach has assumed three things.
1. Molecules have definite structures and collisions between reacting molecules
lead to the reaction.
2. All the collisions will not results in products only molecules which have
enough of activation energy can lead to the formation of products.
3. For a reaction to occur between colliding molecules, shapes of molecules also
play a role. Proper presentation of molecules for reaction at the moment of
collision is accounted for by the orientation and probability effects.

Transition State Theory

The collision theory of reaction rates failed to give a convincing explanation

of differences in the rates of similar reactions. Polanyi, Pelzer and Eyring
worked to develop another independent theory. According to this theory, all
reactants exist in an intermediate unstable combination before they pass on
to the state of products of the reaction. This unstable combination has
higher potential energies than the reactants or the products of the reaction
and is more complex in structure than either the reactants or the products.
Because of its high energy and complex structure, the reaction intermediate
has been called an activated complex. Since the activated complex is capable
of slipping back into the reactants or going further on to the products, it is
also called the transition state. Thus the explanation for reaction rates
developed by H. Eyring and others is called transition state or activated
complex theory. It is also known as theory of absolute reaction rates.
Reactants Activated complex or Transition state ⎯⎯→ Products

A+B (AB)* ⎯⎯→

Products
The activated complex has some stability of existence and its existence may
be for as short a time as 10−13 sec and is never more than 10−8 sec. Only such
molecules of reactants can form the activated complex on colliding between
them enough energy to build up the energy of the activated complex.

The energy difference between the energy of the activated complex and the
average energy of the reactants is called the activation energy or threshold
energy of the reaction step.

Reaction Rates and Temperature Changes

Rates of all single reactions increase when the temperature is raised. A
temperature rise of 10 ° from 25 ° to 35 °C about doubles the rates of most
reactions. At 45 °C it will be twice as much as at 35 °C and four times its
value at 25 °C and so on. The ratio of the specific reaction rate of a reaction
at a certain temperature to its rate for the same concentrations of reactants
at 10 °C lower temperature is called the temperature co-efficient of the
reaction.
The changes in reaction rates take place because of an increase in the specific
reaction rate k with increase in temperature. The values k1 and k 2 of a reaction
at temperatures T1 and T2 Kelvin are related by the empirical Arrhenius
equation or Arrhenius reaction rate law
k = A e − Ea /RT

k2 Ea 1 1
or log =−  − 
k1 2.303R  T2 T1 

Here R is the gas constant (1.987 calories per mole per degree) and Ea is
Arrhenius activation energy or Arrhenius constant for the reaction. A graph
1
between and log k should be a straight line with a negative slope.
T