PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.

: 1
1. INTRODUCTION :
Chemical kinetics, a branch of physical chemistry, deals
(i) Rate of reaction i.e. time required to convert a definite amount of reactant into products.
(ii) mechanism of reaction, i.e. the path through which reactants are converted into products.
2. RATE OF REACTION :
Rate of reaction is defined as change in concentration of reactant or product per unit time at a given instant. i.e.
Rate of reaction =-
dc
P
dt
or, rate of reaction = +
dc
P
dt
rate of disappearance of A = -
dC
dt
A
rate of reaction = -
1
a
dC
dt
A
rate of disappearance of B = -
dC
dt
B
rate of reaction = -
1
b
dC
dt
B
rate of disappearance of C = +
dC
dt
C
rate of reaction = +
1
C
dC
dt
C
rate of disappearance of D = +
dC
dt
D
rate of reaction = +
1
d
dC
dt
D
So, -
1
a
dC
dt
A
= -
1
b
dC
dt
B
= +
1
C
dC
dt
C
= +
1
d
dC
dt
D
Where dC
R
and dC
P
are change in concentration of reacrants and products,
respectively. ve sign suggests decrease in the concentration of reactants while
+ve sign suggests increase in the concentration pf products with time, as shown
by the graph.
Let us suppose a general reaction : aA + bB cC + dD
where, a , b, c and d are the no. of moles of A, B, C and D respectively
thus, at any instant :
concentration
time
reactants
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by:
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Meq. Appr oach
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 2
3. FACTORS AFFECTING RATE OF REACTION :
(a) Nature of reaction (b) Temperature
(c) Concentration of reactants (d) Catalyst
(e) Surface area of solid reactant (f) Presence of light
There are certain other factors like light, electrical field etc. also for certain particular reactions.
(a) Nature of reaction: Ionic reactions are very fast generally instantaneous, while molecular reaction are
slow due to time required in breaking and reforming bonds.
(b) Temperature : On increasing the temperature, rate of molecular collision increases and so rate of reaction
increases. I t has been found that for every 10 rise in temperature, rate of reaction increases by
2 to 3 times i.e.,

K
K
t+10
t
= 2 to 3,
K
K
t+10
t
is called temperature coefficient
In general, r
t
=r
0
x
t
10

............. (1)
Where, r
t
= final rate of reaction r
0
= initial rate of reaction
x = temperature coefficient
t
= change in temperature
Example
Rate of a chemical reaction increases by 200 times on increasing the temperature by 60 K, find the temperature
coefficient of the reaction increases.
(c) Concentration of reactants : On increasing the concentration of reactants, rate collision increases
and so rate of reaction increases.
(d) Catalyst : A substance when present even in very small quantity changes the rate of reaction appreciably
and the phenomenon catalysis.
Thus catalysts are of two type :
(a) Positive catalysts : They increase the rate of reaction. e.g.,
2KClO
3
2KCl + O
2
(Slow)
2KClO
3
2KCl + O
2
(Fast)
Thus, MnO
2
is a +ve catalyst.
(b) Negative Catalysts : They decrease the rate of reaction. e.g.,
2H
2
O
2
2H
2
O + O
2
(Fast)
2H
2
O
2
2H
2
O + O
2
(Slow)
Thus, Glycerine is a ve catalyst.
CHARACTERISTICS OF CATALYSTS :
1. A catalyst takes part in the reaction but is not consumed in the reaction. Thus, even a very small
quantity of catalyst can cause a large change in the rate of reaction. e.g., one mole of colloidal Platinum
in 10
8
L can catalyse decomposition of H
2
O
2
.
2. The chemical nature of the catalyst remains unchanged at the end of the reaction, although its physical
nature may change. e.g.,
KClO
3
+ MnO
2
(Crystal) KCl + O
2
+ MnO
2
(amorphous)
MnO
2
Glycerine

PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 3

3. A catalyst can never start a reaction.
4. A catalyst changes the mechanism of the reaction and provides a new path of lower activation energy.
Thus, Ea < Ea.
5. A catalyst has no effect on equilibrium, but only shortens the time to reach the equilibrium .
6. A catalyst, particularly enzymes catalyst is highly specific in nature.
7. There is an optimum temperature for a catalysts at which its efficiency is maximum.
TYPE OF CATALYSIS :
There are two types of catalysis
(1) Homogeneous Catalysis
(2) Heterogenous Catalysis
1. Homogeneous Catalysis: In homogeneous Catalysis reactants, products and catalyst, all exist in the
same phase as homogeneous mixture. e.g.,
2SO
2
+ O
2
2SO
3
2. Heterogeneous Catalysis : When catalyst and reactant from two phases, it is called heterogenous
catalysis. e.g.,
KClO
3
(S) KCl (S) + O
2
(g)
Catalytic Promoters : A substance which itself is not a catalyst but when present with catalyst increases
the rate of reaction is called catalytic promotor.
N
2
+ 3H
2
2NH
3
(slow)
N
2
+ 3H
2
2NH
3
(slow)
N
2
+ 3H
2
2NH
3
(fast)
N
2
+ 3H
2
2NH
3
(more fast)
Thus, in the above example, Fe is catalyst while Mo is catalytic promoter.
Catalytic Position :
A substance which destroys the catalytic activity of a catalyst is called catalytic poison. e.g., The rate of
formation of SO
3
, in contact process is slowed down considerably if some arsenic compounds are present
even in traces. Hence arsenic compounds act as poison for platinum catalyst. A catalytic poison is preferably
cover the active surface of the catalyst.
No
MnO
2
(S)
Mo
Fe
Fe
Mo
Rate
time
o
Rate
time
o
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 4
Autocatalyst :
If one of the product formed in the reaction acts as a catalyst, it is called autocatalyst e.g., in the oxidation of
oxalic acid by acidified KMnO
4
, manganous ion act as catalyst, and so it is called autocatalytic and the phenomenon
auto catalysis.
2MnO
4

+ 5C2O
4
2
+ 16 H
+
2Mn
2+
+ 10CO
2
+ 8H
2
O
(e) Surface area of solid reactants:- On increasing the surface area of solid reactants, more and more
reactant molecules involve in the reaction and so rate of reaction increases.
(f) Presence of light :- I t provides the necessary activation energy and the reactions starts
(Photochemical reactions).
4. RATE LAW :
the rate of any chemical reaction is directly proportional to the product of molar concentration/active mass of
reactants each raised to some power which may of may not be equal to their stoichiometric coefficients.
For instance,
aA + bB products
According to law, rate [A]
x
[B]
y
, where x a & y b
And x + y = overall order of reaction
a + b = Molecularity of reaction
or, rate = k[A]
x
[B]
y
Here k is a constant called rate constant or velocity constant of a reaction.
If [A]x = [B]y = 1
Rate = k, Therefore rate constant may be defined as the rate reaction when the concentration of
reactants becomes unity.
Characteristics of rate constant :
! At a given temperature, it becomes equal to the rate of reaction when the concentration of reactants
become unity.
! It is independent of concentration (whether initial or final)
! It remains constant throughout the progress of the reaction.
! +ve catalyst may increases the value of k.
! Unit of k = (mole/lit)
1-n
sec
1
! k value of a reaction increases with increasing temperature.
! If two reactions take place in parallel pathway i.e.
the overall reaction is
A B + C
then k = k
1
+ k
2
.
A
B
C
k
1
k
2
k
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 5
5. ORDER OF REACTION AND MOLECULARITY :
Order of reaction is the sum of the power on concentration terms appearing in the rate equation of a
reaction.
Molecularity of a reaction is the number of molecules involved in the effective collision of the reaction.
Effective collision means that collision which can provide Sufficient amount of energy to convert reactants
into products.
Let us suppose, the following one step reactions:-
(1) A Products
(2) 2A Products
(3) A + B Products
(4) A + 2B Products
(5) A + B + C Products
The rate of reaction (1) C
A
then, order of reaction (1) = 1 (First order)
The rate of reaction (2) C
A
2
then, order of reaction (2) = 2 (Second order)
The rate of reaction (3) C
A
C
B
then, order of reaction (3) with respect to A = 1 and with respect
to B = 1 and so overall order = 2.
The rate of reaction (4) C
A
C
B
2
, similarly overall order if reaction (4) and (5) are 3. The rate of reaction (5)
C
A
C
B
C
C
Overall order of reaction = 3.
Now Molecularity of reaction (1) = 1 (unimolecular)
Molecularity of reaction (2) and (3) = 2 (bimolecular)
Molecularity of reaction (4) and (5) = 3 (termolecular)
NOTE : (a) For one step reaction, order of reaction and molecularity are same provided any reagent is
not present in excess.
(b) Generally the maximum value of order of reaction and molecularity are 3.
Difference between order of reaction and molecularity :-
(1) Order or reaction is determined experimentally.
Molecularity of reaction in determined by theoretically proposed mechanism.
(2) Order of reaction may be fractional, zero and even negative besides +ve integers.
Examples :
(a) Zero order reactions :
In Zero order reaction, rate of reaction does not depend upon the concentration of reactant, i.e.,
dc/dt C
0
Notes :
(i) Most of the photochemical reactions are Zero order reaction.
(ii) The gaseous decomposition on metal surface at high pressure (above saturation pressure) are Zero
order reactions e.g.,
(i) 2NH
3
N
2
+ 3H
2
(ii) 2HI H
2
+ I
2
w
Au
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 6
(b) Fractional order reactions :
CH
3
CHO (g) CH
4
(g) + CO (g)
rate of [CH
3
CHO]
3/ 2
order of reaction = 3/2
(c) Negative order reactions :
In the case of negative catalyst, on increasing the concentration of the catalyst, rate of reactions decreasesand
so order is ve.
Molecularity of a reaction will never be Zero, fractional or negative.
(3) Order of reaction of even a complex reaction is always single valued and is determined by the slowest
step of the reaction.
Example : (a) Let us suppose, an hypothetical reaction.
3A + 2B C + D
Follows the following steps :
(i) A + B E (Fast)
(ii) E + A F (Slow)
(iii) F + A + B C + D (Fast)
So, rate of reaction C
E
C
A
.
But, since fast reaction attains the equilibrium, so equilibrium constant for reaction (i)
K
c
=
C
C C
E
A B

rate of reaction C
A
K
C
C
A
C
B
C
A
2
C
B
So, the above reaction is a third order reaction.
6. PSEUDO-UNIMOLECULAR REACTION :
In olden days, order of reaction and molecularity were used as synonymous words. Thus a unimolecular
reaction. Should be of 1st order, a bimolecular reaction should be of 2nd order. But we know that this is not
always true. So first order reaction with higher molecularity were called pseudounimolecular reactions.
Example : hydrolysis of ester :
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
rate of reaction [Ester] [H
2
O]
order of reaction = 1, But molecularity = 2
7. FIRST ORDER REACTION :
Let us suppose, a first order reaction
A Products.
Let a Mole/L os the initial concentration of A and in time t, x mole/L of A
has converted into products, so rate of reaction, at time t, is given by, :
dx
dt
(a - x)
1
dx
dt
= k(a - x)
t
[A]

0
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 7
Where, k = constant, called rate constant, or velocity constant or specific reaction rate constant. It is a
constant for a particular reaction at a given temperature.

dx
a-x
= kdt
dx
a-x
= k dt
[ln(a x)]
x
o
= k[t]
t
o
ln(a x) + ln a = k(t 0) k = 1/t ln a/a x
This is called first order equation.
It initial concentration = a = C
0
or N
0
and concentration after time t = (a x) = C = N
First order equation can be written as
Thus concentration of the reactant A varies exponentially with time (See graph). These equation is called
Wilhemys equation.
Also first equation is different from
Where (a x
1
) and (a x
2
) are the concentration of the reactant at time t
1
and t
2
respectively.
(1) Unit of K :
For the order reaction,
dx
dt
= k(a x)
n
k =
dx
(a-x)
1
dt
=
[conc]
[Conc] [time
n n

k = [Conc]
1-n
[time]
1
If Conc = mole litre
1
k = mole
1-n
litre
n-1
time
1
For Zero order reaction, n = o, k = mole litre
1
time
1
First order reaction, n = 1, k = time
1
Second order reaction, n = 2, k = mole
1
litre time
1
Thus, we find that, only for 1st order reaction, value of k is independent of the unit of concentration.
(2) Rate of reaction :
Rate of reaction is a constant and is equal to velocity constant.
dx
dt
= k(a x)
o
= k
N = N
o
e
kt
C = C
o
e
kt
or
t
2
t
1
log
10
a x
2
k =
2.303
a x
1
k =
2.303
t
log
a - x
a

x
o

t
o
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 8
Rate of 1st order reaction is directly proportional to Concentration of reactant.
dx
dt
= k(a x)
Rate of 2nd order reaction is directly proportional to square of conc. of reactant. e.g.
dx
dt
= k(a x)
2
Thus, we find that only a Zero order reaction can be completed.
(3) Time required to complete a half of reaction: (half-life)
For Zero order reaction :t
1/ 2
= a/2 i.e. t
1/ 2
a.
For 1st order reaction : t
1/ 2
= 0.693/k i.e. t
1/ 2
= constant
Half life of first order reaction is
T
1/ 2
= T
50
= ln2/ k = 0.693/ k
Here T
1/ 2
can be denoted by T
50
i.e. time required for 50% completion of reaction, then
! At t = T
50
, x = a/2, (a x) = a/2
T
50
= 1 t
50
! At t = T
75
, = x = 3/4a, (a x) = a/4 [where T
75
is the time required for 75% completion of
reaction]
Hence T
75
= 2 T
50
! Also T
87.5
= 3 t
50
:
T99.9 10 T
50
.
Thus completion of 50% reaction and each subsequent 50%
(i.e. 75%, 87.5%, 63.75% ..........99.9%) completion takes equal time.
For 2nd order reaction, t
1/ 2
=
1
ak
i.e. t
1/ 2

1
a
First order reaction
concentration
o
t
1/ 2
Zero order reaction
concentration
o
t
1/ 2
First order reaction
concentration
o
t
1/ 2
dx
dt
Zero order reaction
(a x)
o
dx
dt
First order reaction
(a x)
o
dx
dt
Second order
reaction
(a x)
o
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 9
In general, t
1/ 2

1
a

n - 1
(4) For Ist order reaction,
k = = loga log (a x)
log (a x) = + log a
So, the slope = and intercept = log a.
(5) Average life of 1st order reaction :
1/k is known as average life T
av
of first order reaction
T
av
=
1
k
=
T
50
0.693
= 1.443 T
50
Examples of the reactions of first order :
(i) Decomposition of Nitrogen Pentoxide :
The compound, nitrogen pentoxide, is a volatile solid which decomposes in the gaseous state as well as
in the form of its solution in an inert solvent like carbon tetrachloride, chloroform etc. according to the
equation
N
2
O
5
N
2
O
4
+ 1/2 O
2
2NO
2
When the reaction is carried out in the solution, N
2
O
4
and NO
2
remain in the solution and the volume of
oxygen gas collected is noted at different intervals of time. It is obvious that
Volume of oxygen gas Amount of N
2
O
5
collected at any time (V
t
) decomposed (X)
i.e. x V
t
Volume of oxygen gas Amount
Collected at infinite time of N
2
O
5
time (V ) (Which is done by initially
heating the reaction vessel) taken (a)
i.e. x V
Substituting these values in the first order equation viz.
k =
kt
2.303
kt
2.303

log (a x)
t
o
kt
2.303
slope =
OA = log a
A
t
log
a
2.303
a x
kt
2.303
t
log
2.303
a x
a
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 10
we get
The constancy in the value of K proves the reaction to be the first order.
(ii) Hydrolysis of Ethyl acetate :
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
In the reaction, acetic acid is one of the products, the amount of which can be found by titration against
standard NaOH solution. But being an acid-catalysed reaction, the acid present originally as catalyst,
also reacts with NaOH solution. Hence a little careful thought reveals that for the same volume of
reaction mixture withdrawn at different time,
Volume of NaOH solution used in Amount of acid present only as catalyst
the beginning i.e. at zero time (V
0
) (as no CH
3
COOH is produced at t = 0) (i)
Volume of NaOH solution used at Amount of acid present only as catalyst +
any instant of time (V
t
) amount of CH
3
COOH produced (ii)
Combing results (i) and (ii), we find that
Amount of CH
3
COOH produced
at any instant of time (V
t
V
0
) (iii)
But amount of CH
3
COOH produced Amount of CH
3
COOC
2
H
5
produced
at any instant of time that has reacted (X) (iv)
Hence, x (V
t
V
0
)
Further,
Volume of NaOH solution used after the reaction Amount of acid present as
has taken place for a long time, say 20 hours or so, catalyst + Max. Amount
called infinite time (V ) of CH
3
COOC
2
H
5
(a) (v)
Combining results (i) and (v), we find that
Maximum amount of CH
3
COOH produced (V V
0
)
But
Maximum amount of CH
3
COOH produced Initial concentration of CH
3
COOC
2
H
5
(a) (vi)
Hence a (V V
0
)
From equations (iv) and (vi), we have
(a x) (V V
0
) (V
t
V
0
)
or (a x) (V V
0
) (vii)
substituting the values of a and (a x) from equations (vi) and (vii) in the first order equation,
H
+

k =
t
log
V 2.303
V V
t
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 11
we get
k = or
(iii) Inversion of Cane-Sugar (Sucrose) : The hydrolysis of sucrose in presence of mineral acid
takes place according to the equation.
C
12
H
22
O
11
+ H
2
O C
6
H
12
O
6
+ C
6
H
12
O
6
Glucose Fructose
(dextro - rotatory) (laevo - rotatory)
An important characteristic of the reaction is that sucrose is dextro-rotatory whereas the
products-glucose and fructose are dextro-rotatory respectively. Further the laevo-rotation of fructose is
more (being-92 ) than the dextro-rotation of glucose (being +52.5 ) so that the mixture as a whole is
laevo-rotatory. Thus on hydrolysis, the dextro-rotatory sucrose gradually changes into the laevo-rotatory
mixture. It is for this reaction that the reaction is called inversion of sucrose.
The kinetics of the above reaction is studied by noting the angle of rotation at different intervals of time
with the help of a polarimeter.
Suppose
Reading of the polarimeter at zero time = r
0
Reading of the polarimeter at any time t = r
t
Reading of the polarimeter at infinite time = r
It is evident that the reading at zero time will be positive and would decrease with the passage of time,
pass through zero and ultimately become negative.
Angle of rotation at any instant of time i.e. (r
0
r
t
) amount of sucrose hydrolysed (x) i.e.
x (r
0
r
t
) (i)
Angle of rotation at infinite time i.e. (r
0
r ) the initial concentration of sucrose (a) i.e.
x (r
0
r ) (ii)
From results (i) and (ii), we have
a x (r
0
r ) (r
0
r
t
)
i.e. (a x) ( ( ( ( ( r
t
r ) (iii)
Substituting the value of a and (a x) from equation (ii) and (iii) in the first order equation,
k =
we get
H
+
(laevo - rotatory)
t
log
2.303
a x
a
k =
t
log
2.303
r
0
r
r
t
r
r
t
0
90
r
0
180
90
r
t
log
2.303
a x
a
k =
t
log
V - V
0
2.303
V V
t
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 12
7. ACTIVATION ENERGY :
A mixture of methane and oxygen does not burn at room temperature. But if a burning match stick is put in the
mixture, it burns rapidly. This clearly suggests that in order to initiate a reaction a certain minium amount of
energy is required. This energy is called threshold energy.
According to theory of reaction rates, for a chemical reaction to take place, reactant molecules must make
collisions among themselves. But all collisions are not responsible to convert reactants into products. Only
those collision can convert reactants into products which can provide threshold energy. Such collisions are
called effective collision.
Since reactants molecules themselves have energy, so the different between the energy of reactants and
threshold energy should must be provided by effective collisions. This additional energy is called activation
energy (E
a
). Thus, higher the activation energy, slower the rate of reaction. The relation between different
forms of energy can be shown by the diagrams.
In Fig (1), energy of reactants (E
R
) is greater than energy of products (E
P
) hence H = ve so this is an
exothermic reaction. Similarly in fig (2), E
R
< E
P
,so H = +ve, This is an endothermic reaction. Thus, we
find that activation energy of endothermic reaction is greater than that of exothermic reaction. So rate of
reaction of exothermic reaction is greater than that of endothermic reaction.
8. ARRHENIUS EQUATION :
Arhenius proposed an equation to determine activation energy (E
a
) at a given temperature (T);
K = Ae
E / RT
A = Frequency factor.
On simplifying this equation, we have
log K = log A E
a
/2.303RT
Thus, a plot of log K against 1/T will give a straight line. The slope of
this line is equal to Ea /2.303RT and intercept is equal to log A
At two different temperature the above reaction becomes,
log
k
k
=
E
a
2.303R
(T -T
(T T
2
1
2 1
1 2
)
)
Where k
1
= velocity constant at temp T
1
and k
2
= velocity Constant at temp T
2
.
9. PHOTOCHEMICAL REACTION :
Certain reaction occur on exposure to visible light, are called photochemical reactions e.g. photosynthesis,
! The rate of a photochemical reaction is affected by the intensity of light whereas temperature has little
effect.
Ea
2.303R
slope =
1/T
l
o
g

K
PHYSICAL CHEMISTRY By: Shai l endra Kumar Page No.: 13
! Photochemical reactions take place via free radical mechanism.
! Free energy change (G) of a photochemical reaction may not be negative as the part of the light
energy absorbed by the reactants changes into free energy by the product.
e.g. H
2
+ Cl
2
2 HCl G is positive for this reaction.
! Photosensitizer is a substance when added to a reaction mixture helps to initiate the photochemical
reaction without undergoing any chemical change. This process is photosensitization.
e.g. Chlorophyll acts as photosensitizer is photosynthesis.
! Vision involves geometrical isomerisation of a compound retinal (an unsaturated aldehyde) present in
the eye by absorbing the light falling on it.
Quantum yield or Quantum Efficiency of a photochemical reaction :
Quantum yield or quantum efficiency of a photochemical reaction is defined as
=
No. of reactant molecules reacting in a given time
No. of photons (quanta) of light absorbed in the same time
! Photosynthesis of HBr has low value of while photosynthesis of HCl has very high value of .
Luminiscence : The emission of light during a process other than by the action of heat i.e., emission of
cold light is called luminiscence. This can be of the following different types :
(i) Chemiluminescence : The emission of cold light during a chemical reaction is called chemiluminescence
e.g., glow worm i.e., fire files glow due to oxidation of protein, luciferin present in them. The glow thus
produced in the living organism is called bioluminescence.
(ii) Florescence : Some substances when exposed to light absorb it and immediately start re-emitting it.
The glow continues so long as the light falls on the substance. The glow thus produced is called
fluorescence and the substances producing the glow are called fluorescent substances e.g., fluorite
(CaF
2
).
(iii) Phosphorescence : Some substances like ZnS continue to glow for some time even after the light is
cut off. Such substances are called phosphorescent substances and the phenomenon is called
Phosphoresence.
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