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CHEMICAL
KINETICS
 2 MARKS

1. CH EM I CA L K I N ET I CS
Kinetics is the study of the rates of chemical processes in an effort to understand what it is that
influences these rates and to develop theories which can be used to predict them. A knowledge
of reaction rates has many practical applications, for example in designing an industrial process,
in understanding the intricate interplay of the chemical reactions that are the basis of life.
At a more fundamental level we want to understand what happens to the molecules in a chemical
reactionăthat is what happens in a single reactive encounter between two reagent molecules. By
understanding this we may be able to develop theories that can be used to predict the outcome
and rate of reactions.

2 . RA T ES, RA T E L A WS, RA T E CON ST A N T S A N D ORDER OF REA CT I ON

In this Section we will introduce the language and terms used to describe the rates of chemical
reactions. At this stage we will not be concerned with the theory of reactions or mechanisms, but
just stand back and describe the overall rates.

Concentration c
2 .1 Ra t e o f r e a c t i o n
The rate is defined as
c
change in concentration, c, in time t t
t
time, t
It is important to specify which species we are talking about. The rate can be positive or negative :
a positive rate means that the concentration is increasing with time e.g. a product; a negative rate
means that the concentration is falling with time e.g. a reactant.
The rate may vary with time (and concentration), so it is usual to define the rate over a very small
time, t. We think of the rate as the derivative of concentration with respect to time.

d  concentration 
rate 
dt
This derivative is the slope of a graph of concentration against time, taken at a particular time.
Symbolically, concentration is often indicated by square brackets. So [A] means the concentration
of species A, and [Br2] means the concentration of bromine, and so on.

Re l a t i o n t o s t o i c h i o m e t r i c e q u a t i o n s
Consider the reaction whose stoichiometric equation is
O2 + 2H 2  2H 2O
The stoichiometric equation shows how the number of moles of reactants and products are re-
lated; it must be balanced.
This equation says that to form two moles of water, one mole of oxygen and two moles of hydrogen
must react. It follows that the rate of consumption of hydrogen is twice that of oxygen.

d H2  d O2 
2
dt dt

CHEMICAL KINETICS
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The rate of formation of water is twice the rate of loss of oxygen, as two moles of water are formed
from one mole of oxygen. As water is the product, the rate of change of its concentration is positive
i.e. the concentration is increasing with time; however, the rates of change of the concentrations
of both hydrogen and oxygen are negative as these concentrations are decreasing with time. In
derivative form :

d H2O d O 2  1 d  H2 O d O2 
ă  2 or, equivalently  
dt dt 2 dt dt
With all these „rates‰, different for each species, how can we define the „rate of the reaction‰ ?
The usual procedure is to include the stoichiometric coefficients in the definition of the rate. These
coefficients are the numbers in front of the species in the balanced chemical equation. So the
stoichiometric coefficients is 1 for oxygen and 2 for both hydrogen and water.
The rate of reaction, r, is defined for any species A as

1 d A 
r [1]
vA dt

where vA is the stoichiometric coefficient of species A in the balanced chemical equation. In

addition the stoichiometric coefficients are given negative signs for reagents and positive signs for
products. This definition ensures that the rate is always positive and the same for a given reaction
no matter which species is considered.

2 .2 Or d e r o f Re a c t i o n
The speed of a chemical reaction, in general depends on the concentration of reading species of
the reaction. This is known as law of mass action and is stated as follows :
The ra te of a chemica l rea c tion is p roportiona l to the p roduct of effective conc entra tions
(a ctive ma sses) of the rea ting spec ies, ea ch ra ised to a power tha t is equa l to the c orre-
spond ing stoic hiometric number of the substanc e a ppea ring in the c hemic a l rea ction.
Thus, for a general reaction aA + bB  cC + dD ... (2a)
We have
r  [A]a [B]b
or r = k [A]a [B] b ... (2b)
where k is the constant of proportionality.
If the rate of a reaction is determined experimentally, it is found that equation (2b) is not always
applicable. However, the experimental results can be fitted to satisfy a relation of the type of
equation (2b) where the exponents may or may not be equal to the respective stoichiometric
coefficients. In general, we may write the rate as
r = k [A]a´ [B]b´ .... (2c)
where the dimensionless exponents a´ & b´ may or may not be equal to a & b respectively. The
constants a´ & b´ may have positive, negative integral or fractional values or zero value. The
constant a´ is known as the order of the reaction with respect to A, b´ as the order of the reaction
with respect to B and so on. The sum (a´+ b´) is known as the overall order of the reaction (which

CHEMICAL KINETICS
 4 MARKS

does not have much of significance)). If (a´ + b´) = 1, the reaction is said to be of first-order; if
(a´ + b´) = 2, the reaction is said to be second order and so on. The dependence of reaction rate
on concentration is of great use as it helps in proposing the mechanism of a reaction.
The constant k, which appears in equation (2c) is known as rate constant or more formally, the
specific reaction rate constant, since it is numerically equal to the rate of the reaction provided
all concentrations were set equal to unity. Each reaction is characterized by its own reaction rate
constant. From equation (2c), we find that the units of k is (mol lă1)n să1 where n = 1 ă (a´ + b´).
The expression of equation (2c), which relates the rate of reaction, with the concentrations of
reacting species is known as the differentia l ra te la w.
It ma y be empha sised onc e a ga in here tha t the ra te equa tion with its ra te consta nt a nd
order of various rea c ting spec ies is a n experimenta l finding a nd ca nnot be predic ted
from the stoichiometry of the ba lanced rea ction.
For example, the solution reaction

N N
+ Bră
Ph Br N N+

PhCh2Br DABCO Ph

is found to have the rate law.

r = k[PhCH 2Br] [DABCO]
The reaction is second order overall, and first order with respect to both PhCH 2Br and DABCO.
Some reactions have very much more complex rate laws. For example, in the gas phase, the
reaction
H 2 + Br 2  2HBr
has the rate law
3
ka  H2  Br2  2
r
 Br2   kb  HBr 
For this reaction, no order with respect to Br2 , and no overall order, can be defined.

2 .3 Re l a t i o n t o e q u i l i b r i u m c o n s t a n t s
{To be read after completing the chapter ÂÂChemical equilibriumÊÊ}
Chemical equilibrium is a dynamic state, not one in which all reaction has stopped. The forward
and back reactions continue just as they do when a system is away from equilibrium, but when
equilibrium has been reached these forward and backward rates are equal. As a result, there is
no change in the concentration of any of the species, even though the reactions are still going on.

CHEMICAL KINETICS
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Suppose we have a reaction of the form

A + B  C + D
Also suppose that rate of the forward reaction is kf[A] [B] and that the rate of the back reaction
is k r [C] [D] (these are assumptions, we cannot say from the stoichiometric equation that these
will be the rate laws). At equilibrium these two rates are equal

kf  A eq  Beq  kr Ceq  Deq

where the „eq‰ subscripts have been added to emphasize that this relation is only true at equi-
librium.
Rearranging gives
kf  C eq  D eq

kr  Aeq  Beq
The quantity of the right is the equilibrium constant Keq, so it follows that

kf
K eq 
kr

The equilibrium constant is therefore the ratio of the rate constants of the forward and backward
reactions.

3. Units of k :
In general, the rate law for a nth order reaction can be taken as :

dc
 kcn
dt
where k : rate constant & n : order of reaction

dc / dt
 k
cn
units of k  (mol/L) 1ăa (time) ă1

(1) For a first order reaction (n = 1)

units of k  (time) ă1
 units are : secă1, mină1, hrsă1 etc.

(2) For a second order reaction (n = 2)

Units of K  (mol/L)ă1 (time)ă1
 units are : L/mol/s.

(3) For (n = 3)
Units of k = L 2 molă2 să1

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(4) For a ÂzeroÊ order reaction (n = 0) :

Units of k  mol/L/S
general form
k = (mol/L) 1ăn (time)ă1.

4 . SI M PL E RA T E L A WS
A first order rate law is one in which the rate is proportional to the concentration raised to the
power 1 (hence „first‰)
r = k1st [A]1
k1st is called a first order rate constant. The rate equation, and the reaction it describes, is said
to be first order in A or it is said that the order with respect to A is one. As the units of r are
concentration timeă1 and the units of [A] are concentration, the units of k 1st are found as

r conc.time1
r  k1st  A 
1 k
so 1 st    time1
 
A conc.

Hence first order rate constants have units of timeă1 .

A second order reaction has the concentration raised to the power of 2.
r = k2nd[A] 2
k2nd is called a second order rate constant. The rate equation, and the reaction it describes, is said to
be second order in A, or the order with respect to A is two. The units of k2nd are found to be conc.ă1
time ă1.

1) N t h Or d e r Re a c t i o n
Let the reaction
A  B
be n th order reaction then
r = k [A]n
where k is constant.
r = rate of reaction

 dA
 k A
n

dt

 dA
  An =  kdt
Let at t = 0, [A] = a
and t = t, [A] = a ă x

t
a x  dA
then a   kdt
 A n 0

CHEMICAL KINETICS
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1  1 1 
     kt
  n  1   a  xn 1 an 1 
a

1  1 1 
t1 /     tó  1nă1
or 2 k  1  n   a / 2 n1 a n1  a
 

1  2n 1 
=  n 1  1
k  n  1  a 
tó

1
Thus t1 / 
2
a 
n 1

Let in two different conditions, initial concentration be a 1 & a2 .

 t   a 
1
/2 1
n1
2
Then
 t  a 
1
/2 2
n1
1

where subscript 2 & 1 stands for condition 1 & 2.

t /   a
1
2
1
n 1
2

t /  a 
1
2
2
n 1
1

Thus through this equation we can know the half life time at given concentration if its half life
time at some other concentration is given.

2) Fi r s t o r d e r r a t e l a w
For reaction of the form A  products, a first order rate law takes the form
r = k1st [A]1
writing the rate in the differential form this becomes

d A 
  k1st  A  ........ [7]
dt
we need the minus sign as A is a reactant and so its concentration decreases
with time i.e the slope of a graph of [A] against time will be negative.
The variables [A] and t in Eq. [7] can be separated to give :
1
d[A]   k1st dt
[A]

CHEMICAL KINETICS
 8 MARKS

which can be integrated [A]

[A] 0
1
 A  d  A    k1st dt
ln [A] = ă k1st t + const. t
The constant of integration can be removed by supposing that at Plot of [A] against time
for a f irst ord er
t = 0 [A] = [A]0, the initial concentration of A; so 1n[A]0 = const. reaction.[A] falls exponen-
Substituting this gives the final form tially from [A]0 towards
zero.
ln [A] = ă k1st t + ln[A] 0 .....[8]
This can also be expressed as
[A] = [A]0 exp (ă k1st t)

Fe a t u r e s o f a Fi r s t Or d e r Re a c t i o n
1. A first order reaction must follow above form of rate for all time instants.
This means if we are given value of a (initial concentration) and values of x at different time
instants [i.e. (a ă x) as value of reactants after t], the values of k can be calculated for different
time instants by using the above first order law. If the reaction for which the data were given
is a first order reaction, then all values of k will approximately equal to each other.
2. The time for half reaction for a first order reaction is independent of initial concentration of
reactants (i.e. a) and is given as follows :
If t1/2 be the time for half reaction, or the half life then a ă x = a/2

a
 kt1 / 2  2.303 log
a/2

 k t1/2 = 2.303 log 2 = 0.693 Ct

0.693
 t1 / 2 
k

3. The concentration of reactants in a first order reaction

decreases exponentially with time (see figure)
Note that plot of log Ct vs t is linear. It is important to note
that equation of this straight line is of the form : O t
y = mx + b. Comparing it with Ist order rate law as follows :

log Ct C0
kt  2.303 log
Ct
A
 k 
 log Ct    t  log C 0 is the equation of line.
2.303 

 k 
Note that slope of the line =   and Y intercept (OA) = log C 0
 2.303 
O t
CHEMICAL KINETICS
 MARKS 9

Ex a m p l e 1
The half life of first order decomposition of nitramide is 2.1 hour at 15ĈC.
NH 2NO2 (aq)  N2 O(g) + H2O(l )
If 16.2 gm of NH 2NO 2 is allowed to decompose, find :
(a) time taken for nitramide to decompose 99%;
(b) volume of dry N2 O gas produced at this point at STP.
Solution :
(a) Using first order kinetics, we have :

C0
kt  2.303 log
Ct

0.693 100
  t  2.303 log
2.1 100  99

 t = 13.96 hours.
(b) 16.2 gm of NH2NO 2  0.1 mol
& 1 mole NH 2NO 2  1 mole of N2 O
As 99% of NH2 NO2 is decomposed
 0.099 mol of NH 2NO2 is decomposed
0.099 mol of N 2O are produced  22.4 ï 0.099 = 2.217 L of N2O at STP.

A n a l y s i s o f s o m e i m p o r t a n t f i rs t o r d e r r e a c t i o n s :
1. Decomposition of Hydrogen peroxide (H 2O 2)
2 H2O2  2 H2O + O 2
The rate of this first order reaction is measured by titrating a fixed volume of H2O2 (undecomposed)
against a standard solution of KMnO 4. Here KMnO4 acts as oxidising agent and H2O 2 as reducing
agent. The volumes of KMnO4 used for H2O2 after regular intervals of time are as follows :

Time instants t= 0 t1 t2 t3 t4 t5

Vol. of KMnO 4 V0 V1 V2 V3 V4 V5

volume of KMnO4 at t = 0 corresponds to volume of H2O2 initially present

 a  V0
volume of KMnO4 at time instants t 1, t 2, t3 , .... corresponds to volume of
H2O 2 remaining after t1, t2 , t3, ...
 a – x  Vt
now it being a first order reaction, follows first order kinetics, so

CHEMICAL KINETICS
 10 MARKS

V0
kt  2.303 log
Vt

Now using the above expression, if we calculate the values of k for different time intervals t1,
t2, ... (for actual numerical data), the values of k should be same if the reaction follows first order
kinetics.

2. Decomposition of Nitrogen Pentoxide

The compond, introgen pentoxide, is a volatile solid which decomposes in the gaseous state as well
as in the from of its soluction in an insert solvent like carbon tetrachloride, chloroform etc.
according to the equation

1
N 2O 5  N 2O 4  2NO 2  O2
2

2NO2

When the reaction is Carried out in the solution, N2 O4 and NO2 remain in the solution and the
volume of oxygen gas collected is noted at different internals of time It is obvious that

volume of oxygen gas Amount of N2O 4


collected at any time (Vt) left decomposed (x)

i.e. substituting these values in the first order equation viz

2.303 a
k log
t a x

2.303 v
we get k= log
t v  v t

The constancy in k proves it first order reaction.

3. H y d r o l y s i s o f e s t e r s (CH 3COOC2 H 5 )
CH 3COOC2 H5) (ester) + H2 O + HCl (H+)  CH 3COOH + C2H 5OH
The reaction rate is measured by titrating the acid (CH3COOH) produced against a standard
alkali solution. Note that when a test sample is prepared from the reacting mixture, there are two
acids : one is mineral acid H + (HCl or any other) and second is CH 3COOH produced. So volume
of alkali used gives titration value for both acids. The data is collected in the following manner.

Time instants t= 0 t1 t2 t3 t4 t

Vol. of NaOH V0 V1 V2 V3 V4 V

CHEMICAL KINETICS
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at t = 0. V0 is the voume NaOH used to neutralise the mineral acid present (H+) being used as
catalyst. (at t = 0, no CH3COOH is yet produced)
at t =  (i.e. at the end of hydrolysis), V is the volume of NaOH used to neutralise whole of
CH 3COOH plus vol. of HCl present. At t = , volume CH3COOH corresponds to volume of ester
taken initially.
 a  V - V 0 (as V 0  vol. of HCl)
at t = t 1 , t2 , t3, ...., V1, V 2 , V3, ...... corresponds to vol. of HCl plus vol. of CH 3COOH being produced.
 x  Vt - V 0
 a – x  (V – V 0) ă (V t - V0 )

V  V0
kt  2.303 log
V  Vt

5. GA S PRESSU RE
The pressure, p, that a gas exerts is related to the volume V, the number of moles n, and the
temperature, T, by the ideal gas equation.
pV = nRT
This can be rearranged to give

n p

V RT
the fraction n/V is a measure of concentration; in SI it would be in moles m ă3. The relationship
tells us that at constant temperature pressure is directly proportional to concentration.
In a reaction we will generally have a mixture of gases, and so we can talk about the partial
pressure, p, of each gas i. The partial pressure of a gas is the pressure that the gas would exert
if it occupied the volume on its own. DaltonÊs Law states that the total pressure, PT , is the sum
of the partial pressures :
PT = P1 + P 2 + P 3 + .....
Each partial pressure follows an ideal gas law

ni p
 i
V RT
where ni is the number of moles of gas i. Therefore the partial pressure of species i is a measure
of its concentration.
In a reaction involving gases the only measurable pressure is the total pressure exerted by the
system. However, to make kinetic measurements we need to know the concentration, that is the
partial pressure, of the individual species. We need, therefore, to find some way of relating these
two. An example of how this is done is considered here.
Consider the reaction between NO and O2 in the gas phase
2NO + O 2  2NO2

CHEMICAL KINETICS
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Overall three moves of gas go to two, so as the reaction proceeds there is a measurable decreases
in the total pressure. The total pressure is the sum of the partial pressures

PT = PNO + P NO + PO
2 2

There are three unknown quantities on the right, and only one measurable quantity, the total
pressure; to solve this we are going to have to introduce some extra restrictions.
Suppose that at time zero there is no NO2 present, and that the NO and O2 are mixed in a
2 : 1 ratio, just as the stoichiometry of the reaction. If the initial partial pressure of O2 is PO ,0
2
then the initial partial pressure of NO is 2pO ,0 and so the initial total pressure, p0 , is 3PO ,0 . This
2 2
is the situation set out on line 1 of the Table

pO pNO pNO pT
2 2
1 pO 2p O 0 3p O  p0
2,0 2,0 2,0
2 pO ă p O 2p O ă 2p O 2pO 3pO ă p O
2,0 2 2 ,0 2 2 2,0 2
1 2 p ă 2p
3 p ă p O 2pO p0 ă pO
3 O 2 3
O O2 2 2

4 pT ă 2 pO
3

Suppose after time t the partial pressure of O2 has fallen by p O2; due to the stoichiometry of the
reaction the partial pressure of NO2 will fall by 2p O and the partial pressure of NO 2 will
2
increase by 2pO2. This is the situation set out on line 2 of the Table.
Our aim now is to find pO2 in terms of measurable quantities. There are two steps. In going from
line 2 to line 3 in the Table we have used the fact that p0 = 3pO2,0 to substitute for p O2,0 . From
line 3 we then see that pT = p0 ă pO from which it follows that p O = p 0 ă pT. This value of
2 2
p O is used in going from line 3 to 4.
2
So, finally, on line 4 we have an expression for pO in terms of measurable quantities :
2

pO = pT ă 2 p 0.
2 3

Ex a m p l e 2
The gas phase decomposition
2N 2O5  4NO2 + O 2
follows the first order rate law. At a given temperature the rate constant of the reaction
is 7.5 ï 10ă3 să1. The initial pressure of N2O 5 is 0.1 atm.

CHEMICAL KINETICS
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(i) Calculate the time of decomposition of N2O 5 so that the total pressure becomes 0.15
atm.
(ii) What will be the total pressure after 150 seconds?
Solution :
(i) The decomposition reaction is represented by
2N2O5 (g)  4NO2 (g) + O 2 (g)
initial p0 0 0
After time t p0 ă 2x 4x x
Total pressure = p0 ă 2x + 4x + x + x = p0 + 3x = 0.15 atm
or, 3x = 0.15 ă 0.10 = 0.05

0.05
or, x  0.0166 atm
3

Pressure of N2 O5 after 1 seconds,

p = p0 ă 2 ï 0.0166 = (0.1 ă 0.0332) = 0.067 atm
Now applying first order rate law

2.303 p 2.303 0.1

t log 10 0  3
log10  53.4 seconds
k p 7.5  10 0.067

(ii) After 150 seconds,

2.303 0.1
150  3
log 10
7.5  10 p

0.1 150  7.5  103

or, log10   0.4885
p 2.303

0.1
p  0.03247
3.0696

p0 ă 2x = p = 0.03247
2x = (0.1 ă 0.03247)
= 0.06753
x = 0.033765
Total pressure = p0 + 3x = 0.1 + 0.101295
= 0.201 atm

CHEMICAL KINETICS
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Ex a m p l e 3
At a certain temperature the half change period for the catalytic decomposition of ammonia
were found as follows :
Pressure (Pascals) : 6667 13333 26666
Half life period in hours : 3.52 1.92 1.0
Calculate the order of reaction.
Solution :

t 
1/
2 1 a 
 2
n 1

t 
1
/2 2
 a1 
where n is order of reaction

From the given data,

n1
3.52  13333 
 (a  initial pressure)
1.92  6667 

= (2) nă1

3.52
log   n  1  log 2  0.3010   n  1
1.92

0.2632 = 0.3010 ï (n ă 1)
n = 1.87
= 2

Ex a m p l e 4
Some PH3 (g) is introduced into a flask at 600ĈC containing an inert gas. PH3 proceeds to
decompose into P4(g) and H 2(g) and the reaction goes to completion. Total pressure is given
below as a function of time. Find the order of the reaction and calculate the rate constant,
Time (sec) 0 60 120 
Pressure (mm Hg) 262.40 272.90 275.51 276.40
Solution :
4PH3 (g) + Inert gas  P 4 (g) + 6H2 (g) + inert gas
t= 0 P Pi 0 0 0
t= t (P ă x) Pi x/4 6x/4 Pi
t =  0 Pi p/4 6p/4 Pi

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At t = 0, 262.40 = P + Pi ...(1)
t = 60 sec 272.90 = PPH3(left) + PP4(g) + PH2(g) + P i
t = 120 sec 275.51 = PPH3(left) + PP4(g) + PH2(g) + P i
t=  276.40 = PPH4(left) + PH2(g) + Pi

P 6P ...(2)
276.40    Pi
4 4
276.40 ï 4 = 7P + 4Pi ... (3)
On solving equations (2) and (3), we get
P = 18.66 mm, Pi = 243.74 mm
At 60ĈC

x 6x
272.90   P  x   Pi  
4 4

7x
272.90 = 18.66 ă x + 243.74 +
4
x = 14 mm

2.303  a  2.303 18.66

k log   log
t  a  x  60 18.66  14

k = 2.32 ï 10ă2 sec

Similarly at 120 sec. k = 2.30 ï 10ă2 secă1.
Since, value of ÂkÊ are same, hence the reaction belongs to first order.

6. I N V ERSION OF CA N E SU GA R
The inversion of cane-sugar (sucrose) catalysed with dil HCl.

H
C12H12 O11 + H 2O   C6 H12O6 + C6H 12O6
The progress of the reaction is followed by noting the optical rotation of the reaction mixture with
the help of polarimeter at different time intervals and the change in rotation is proportional to
the amount of sugar decomposed.
Let ro , rt, r be the angle of rotation during zero, t and infinite time respectively.
Then ro ă r   a; rt ă r   a ă x

2.303  ro  r 
 k log  
t  rt  r 

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Ex a m p l e 5
Cane sugar is gradually converted into dextrose and laevulose by dilute acid. The rate of
inversion is observed measuring the polarization angle, at various times, when the following
results are obtained :
Time (sec) 0 10 20 30 40 100 
Angle 32.4 28.8 25.5 22.4 19.6 ă 6.1 ă 14.1
Show that the reaction is of first order. Calculate the value of t, when the solution is
optically inactive.
Solution :
In case the inversion of cane sugar is a first order change, then

2.303  A 0 2.303 r  r
k log10  log10 0
t A  t rt  r

(i) When t = 10, r0 = 32.4, rt = 28.8, r = 14.1

2.303 32.4    14.1 

k log10
10 28.8    14.1

2.303 46.5
= log10
10 42.9
= 0.008 mină1
(ii) When t = 20, r0 = 32.4, rt = 25.5, r  = ă 14.1

2.303 32.4    14.1 

k log10
20 25.5    14.1 

2.303 46.5
= log10
20 39.6
= 0.008 min ă1.
(iii) When t = 30, r0 = 32.4, rt = 22.4, r  = ă 14.1

2.303 32.4    14.1 

k log10
30 22.4    14.1

2.303 46.5
= log10
30 36.5
= 0.008 mină1
Thus, the reaction is of first order as the value of k is constant.
The solution will be optically inactive when half of the cane sugar is inverted.
0.693 0.693
t 1/    86.6 min
2 k 0.008
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Ps e u d o Fi r s t Ord e r Re a c t i o n
There are circumstances where a second order reaction might appear, in an experiment, to be first
order. That is when one of the reactants in the rate equation is present in great excess over the
other in the reaction mixture.
As an example, letÊs look again at the mixed second order rate law that we treated in the last
section.

d B 
We had the rate law,   k B A  , with a reaction whose stoichiometry is, 2A + B  P + etc
dt

(P = product)
Sometimes [A]0 > > [B] 0.
For example, say we prepare the system such that,
[A] 0 = 2.0 M and
[B] 0 = 0.001 M
Then, when the reaction has run to completion, (at time = infinity),
[A] inf = [A] 0 ă 2 [B]0 = 2.0 ă 0.0001 = 1.998  2.0
So [A] is approximately constant throughout the entire reaction.
Then the rate law becomes,

d B
  kB A    kB  A 0 ...(1)
dt

which is effectively a first order rate reaction. This rate equation has the solution,

k A 0
 B   B0 e ...(2)

where the „effective‰ first order rate constant is k[A]0 .

You can actually solve this problem as a mixed second order rate problem, as we did in the last
section, but it is lot more work.
Pseudo first order reactions are sometimes used to find the rate constant of a second order
reaction when one of your two components is very expensive and the other one is relatively cheap.
You can use an excess of the inexpensive reagent and use a small amount of the expensive one.
Notice that you can still obtain the second order rate constant by dividing the effective first order
rate constant by the concentration of the excess component.

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Co m p a r i n g r a t e c o n s t a n t s
As the half life of a first order reaction is independent of concentration it is easy simply to look
at the rate constant and get an immediate feel for how fast it is. For example, the reaction

2N2O 5  4NO 2 + O2
has a first order rate constant of about 2000 să1 at 400 K; the half life is therefore 0.3 ms, which
makes the reaction quite fast.
On the other hand the second order reaction
2NOBr  2NO + Br2 (gas phase)
has a rate constant at 280 K of 0.8 molă1 dm3 să1. Is this „faster‰ or „slower‰ than the first order
reaction above ? To answer this we need to know the concentration of the reactants. Suppose that
the pressure of NOBr is 0.1 atmospheres, corresponding to a concentration of 4.4 ï 10ă3 mol dm ă
3
; using the above expression we find that the half life is 280 s ă so, under these conditions, the
reaction is much slower than the decomposition of N2O 5.
The key point to understand here is that we cannot compare directly the rates of reactions of
different orders by comparing their rate constants; concentration has to be taken into account.

7. EL EMEN T A RY REA CT I ON AN D I TS M OL ECU L A RI T Y

Most chemical reactions proceed through a series of elementary reactions. An elementary reaction
is one that is proposed as taking place in a single step. These elementary steps are classified
according to the number of molecules, which they involve. A process in which only one molecule
is involved is known as unimolecular process. One involving two molecules is called bimolecular
and so on. It is well known that in elementary reactions, the products are formed when the
reactant molecules come close and collide together. Since the collisions in which more than three
particles come together simultaneously are very rare, the elementary process with molecularity
greater than three are not known.
If a reaction involves more than one step, the overall reaction is obtained by adding these elementary
steps. In such a case, it is wrong to decide the molecularity of the overall reaction on the basis
of its stoichiometry and rate law equation.
It was stated earlier that the order of a reaction, in general, cannot be predicted from the
stoichiometry of the overall reaction. However, the order of an elementary step can be predicted
from its molecularity. In fact, the order of an elementary step is always equal to its molecularity.
This follows from the following analysis.

7 .1 U n i m o l e c u l a r El e m e n t a r y Pr o c e s s
In this process, a single reactant gives a product, A  B. This is achieved when A molecules
collide to form an activated complex (an activated complex is the one whose energy is quite high)
by transferring energies. The activated complex further decomposes independentally.

A + A  A* (activated complex of A)
A  A* (effective reaction)

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It is obvious that the number of activated complexes produced would depend on the number or
concentration of A molecules.
A*  B

d  A
r  k A 
dt
Hence, the unimolecular elementary process is necessarily a first order reaction.
1. O3  O2 + 0
2. N2O5  N2O + 2O 2

7 .2 B i m o l e c u l a r El e m e n t a r y Pr o c e s s
Let the elementary process be represented as
A + B  products
Now, for a molecule of A to react with a molecule of B it should come close to A and collide with
it. The rate at which collisions between A & B molecules occur is directly proportional to the
concentrations of A and B. Thus, the rate of the reaction will be given as
r = k [A] [B]
which is the expression of the second-order process. Hence, a bimolecular elementary process is
necessary a second-order reaction.
The above arguments can be extended to a trimolecular reaction. Hence a trimolecular elementary
process will follow third order rate law.
1. 2 HI  H 2 + I2
2. NO + O3  NO2 + O2

7.3 T rim o lec ul ar

2 NO + O2  2 NO2

Note (1)
For a reaction : A  B in the rate law : r = k [A]m [B]n
Neither the order of reaction ( m + n) nor the molecularity of a reaction can be predicted from
stoichiometric coefficient of a balanced reaction. The order of reaction is always to be determined
experimentally and molecularity is determined theoretically after studying the reaction mechanism.
However as a theoretical idea sometime, we can have an approximate order of reaction equal to
molecularity (i.e., the number of molecules taking part in slowest elementary step for complex
reactions).

Note (2)
Order of a reaction can be fraction also. For example consider the following reaction :
(i) H2 + Br 2  2 HBr
rate = k [H2] [Br2]ó (determined experimentally)
order of reaction = 1 + ó= 3/2
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(ii) CH3CHO (g)  CH4 + CO

rate = k [CH3CHO] 3/2 (determined experimentally)
order of reaction = 3/2
Also note that sum of stoichiometric coefficient (1 + 1 = 2) is not equal to the order of reaction.
Order and Molecularity of a Reaction : A Distinction
Order wrt
S.N. Chemical Equation Mole Rate Law First Second Overall
cularity Reactant Reactant

 dx 
  k A  B 
a b
1. aA + bB  Product a + b  a b a +b
 dt 

 dx 
  k A  B
2 0
2. aA + bB  Product a + b  2 Zero, if B is in excess 2
 dt 

 dx 
3. P4 
2H2 O2   2H2 O  O2 2    k  H 2O 2  1* ă 1
 dt 
(Bimolecular)

 dx 
4. CH3 COOC2 H5 + H 2 O 2    k CH3 COOC2 H5  1* Zero, if H 2O is in excess 1
 dt 
H
(Bimolecular)
  CH 3 COOH +
C 2H5OH

 dx 
5. H
C 12H22O 11 + H 2O   2    k C12 H22 O11  1* Zero, if H 2Ois in excess 1
 dt 
sucrose

C 6H12O6 + C 6H12 O6
glucose (fructose)
 dx 
6. (CH3 )3 CăCl + OH ă  2    k  CH 3 3 C-Cl  1 Zero, OH ă does not take 1
 dt 
(Bimolecular)
(CH3 )3 + OHă  part in slow step
ă
CH3 OH + Cl

 dx 
 dt   k CH3 Cl  OH 

7. CH3 Cl + OHă  2 1 1 2
 
(Bimolelcular)
CH3 OH + Clă

 dx 
8. 
C 6H5N2 Cl   1    k  C6 H5 N2Cl  1 ă 1
 dt 
(Unimolecular)
C 6H5Cl + N2

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S.N. Chemical Equation Mole Rate Law First Second Overall

cularity Reactant Reactant

 dx  3

 dt   k CH3 CHO
/2
9. 
CH3 CHO  1 1.5 ă 1.5
  
(Unimolecular)
CH4 + CO

 dx 
  k H2 O2   I 

10. H2O 2 + 2I ă + 2H + 5  1 1 (H + is medium) 2
 dt 
 2H2O + I2

* Pseudo ă unimolecular reactions

8. ST U DY I N G DI FFEREN T TY PES OF REA CT I ON S

8 .1 Pa r a l l e l (o r Si m u l t a n e o u s ) Re a c t i o n s
Rea c tions in which two pr oducts a re formed from sa me set of rea c ta nt(s) by different
pa ths a re ca lled pa ra llel or simulta neous. For example, ăDăglucose and ăDăglucose are
formed in solution from the aldehydic form of Dăglucose following different paths as :

ăDăglucose
Aldehydic form of Dăglucose

ăDăglucose
k1 B
A
or
k2 C

The various differential rate laws are

d A 
  k1 A   k2 A    k1  k2  A  .... (a)
dt

d B 
 k1  A  ..... (b)
dt

d C 
 k2  A  ...... (c)
dt
Now, let us assume that at t = 0, only A was present. After a very small time, let us say, 2 second,
x mole/l of B and y mole/l of C was formed.

d  B x d  C y
Then  and 
dt 2 dt 2

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d B 
dt  x
d C  y
dt

From equation (b) and (c)

d B
dt  k1
d C  k2
dt

x k1
 
y k2
This means that at any given instant of time, the ratio of amount of B formed to that of C formed
till that instant is a constant.

Ex a m p l e 6 k1 B

k 1 = a hr ă1; k 1 : k 2 = 1 : 10 A
k
C  2 C
Calculate
A  after one hour from the start of the reaction, assuming only A was present in
the beginning.
Solution :

 d  A
  k1  k2   A 
dt
Separating the variables give

 d A 
  k1  k 2 dt
A 
Integrating equation within limits,

At d  A t
 A A    k1  k2   dt
0
0

 A0   k  k t
ln  1 2
A t 

 B  1
k1 = a hr ă1 and k2 = 10 a hră1
 C 10 , since
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We can write, [A0] = [A t] + [B] + [C]

 At    B   C  k  k t
ln  1 2
At 

[C]
1  [C]   B 1 
ln 10  11 a   ; k1  a hr  1 , k2  10a hr  1 , t  1hr 
[A t ]   C 10 

 11 C 
ln  1  10 A   11 a
  t 
The equation can be written as

 C  10 e11a
 A t  11
 1 

8 .2 Se q u e n t i a l r e a c t i o n s
Suppose that we have two sequential reactions which for simplicity we will assume are both first
order.

k1
A  B [1]
k
B 
2

 C [2]

We can imagine two extreme (limiting) cases :

(1) Rate constant of process [1] is very much greater than that of process [2] :
k1 >> k2
In this case A i converted rapidly into B, leading to an accumulation of B which is more
slowly converted into C. The rate at which the product C is formed depends on the rate of
process [2] ă it is said that step [2] is the rate determining step.
(2) Rate constant of process [2] is very much greater than that of process [1].
k2 >> k1 .
In this case A is converted slowly into B, and then B reacts to form C almost as soon as B
is formed. The rate at which the product C is formed depends on the rate of process [1] ă step
[1] is now the rate determining step. In this limit there is very little B present at any time
as the moment it is produced it reacts.
If either of these limiting cases applies then the kinetics is greatly simplified, as the overall
rate of production of the product depends only on the step with the smallest rate constant.
The same is true for more complex schemes of sequential reactions.
k1 k2 k4
k
A  B   C 
3
 D  
E

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If the step from B to C has the smallest rate constant, then the rate of formation of the product
E depends only on k2 .
k k
A 
1
B 
2
C
The differential rate equations are

 d A 
Rate of disappearance of A,  k1  A  ...... (a)
dt

d B 
Rate of change of B,  k1  A   k2 B  ........ (b)
dt

d C
Rate of formation of C,  k2  B ........ (c)
dt
Integrating equation (a) within the limits we get,
t
[A] t = [A] 0 eăk, ....... (d)
In order to get the value of B at any instant of time, we need to integrate equation (b). Since this
is a differentia equation, we integrate it in the following manner.
First bringing k2 [B] to the left side of the equation

d B 
 k2 [B]  k1 A  ........ (e)
dt
From equation (8e), we get

d  B
 k2 [B]  k1 A 0 e k1t
dt
Integration of this equation is not possible as we are unable to separate the two variables, [B] and
t. Thus, the equation is to multiplied on both sides by an integrating factor ek2t.

 d B 
 k2 B    k1 A  0 e 2 1
k k t
ek2 t 
 dt 

d B
 k2  B ek2t  k1  A 0 e
k2  k1  t
ek2t ..... (f)
dt

Left hand side of the equation (f) is equal to

d
dt
B  e  k2 t
(a differential of [B]e k2t).

d
dt
 B e   k A  e
k2 t
1 0
k2  k1 t

 
d  B ek2t  k1  A  0 e
 k2  k1 
dt ..... (g)

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Integrating equation (g) within the limits, 0 and t,

B  ek2t t

  
d B  ek2 t  k1  A 0  e  k2  k1  t dt
0 0

t
 ek 2 k1 t  k1
 B e k2 t
 k1  A0    A 0 e k2  k1  t  1 
k
 2  k 1 0  k2  k1 

k1
B    A  e k2t  ek2 k1 t 1
 k2  k1  0

k
B    A   ek1t  ek2t 
 k2  k1  0  ..... (8h)

In general, the concentration of A decreases exponentially, the concentration of B initially increases

up to a maximum and then decreases thereafter, and the concentration of C increases steadily.

Time when [B] becomes maximum

d B
 k1 [A]  k2 [B]  0
dt
k1 [A] = k2 [B]
Substituting equation (8d) and equation (8h), we get

 k1 t k2 k1
k1 [A]0 e  [A]  e k1 t  e k2 t
 k2  k1  0 
Rearranging, we get

 k2  k1   e k1t  e  k2t 

 
k1t
k2 e

k1  k  k t
1 1 e 1 2
k2

1 k
tmax  ln 1 ....(8i)
 k1  k2  k2

Maximum concentration of B
k1
[B]  [A]0  ek1t  e k2t 

 2 1
k  k

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k1  k  k2 k1 
 B   A   k  1k  1n 
 k2  k1  0  e 1 2  e  1 2
k  k
k2 

  k  k1 k 
k2

k1  ln  k2   k2  k2  ln  2   k1  k2  
 B   A e  1  e
k
 1

 k2  k1 0  
 

 k1 k2 
[B]max 
k1
[A]   k2  k1  k2   k2

 k1  k2  
 k2  k1  0  k    .... (j)
  1   k1  

In order to get the concentration of [C], we substitute [B] equation (8h) to (8c) and then integrate
within the limits.

d  C k2 k1
 k2  B   A0  e k1t  e  k2t 
dt  k2  k1 

k2 k1
d C    A  e  k1t  e  k2t  dt
 k2  k1  0 

Upon integrating within the limits, 0 to t,

 C t
k2 k1
 d C  A 0   e k1t  e k2t  dt
0  2 1
k k 0

t
 e  k1t e  k2t 
C   k2 k1 A 0   
 k2  k1    k1  k2  0

k2 k1   e k1t  1   e k2t  1 
C   A      
 k2  k1  0    k1    k2 

k2 k1   1  e k1 t   1  e k2 t 
C  A       
 k2  k1  0   k1   k2 

A 0
C 
 k2  k1   2  1 
 k 1  e k1t  k 1  e  k2t 
   ....... (k)

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9. RA DI OA CT IV I T Y
All radioactive decay follows first order kinetics. The only difference from chemical reactions is
that temperature does not influence the rate of radioactive decay.
In radioactive decay the term used for identifying the reaction rate is the number of nuclei rather
than concentration.
A  B

 d NA
  NA .... (a)
dt

 is similar to k in chemical reactions and is known as decay or disintegration constant and

NA is the number of nuclei of A at a given instant of time.

N0
ln   t; Nt  N0 e  t .... (b)
Nt

0.693
tó 

A term called average life time is introduced here which is given by 1/.

1
 tav 

Average lifetime means the life time of a single isolated nuclei. If NA = 1, and this nuclei decays

 dN A
in one second, then according to the equation (11a), 
dt

If a nucleus of A decays after 2 seconds, then

 dN A 1
   . The average lifetime of the nucleus is therefore 1/.
dt 2

1 tó
t av    1.44 tó
 0.693

Ac tivity of a ra dioactive element is the ra te at whic h it deca ys a nd is given by  N.

A = N
Since according to equation (11b)
N t = N0 eăt
Multiplying by , we get
N t = N 0 eăt
At = A0 eăt,

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 d NA  dN A
 q  A  q  N ( and A will not be equal)
dt dt

Specific a c tivity is the a ctivity of a unit ma ss of a ra dioa c tive substa nce.

Units of radioactivity
1 curie = 3.7 ï 1010 disintegrations per second(dps) = 3.7 ï 1010 Bq.
1 Becquerel = 1 disintegrations per second(dps)

Amount of radioactive substance left after n half-lives :

Let us start with the amount of radioactive substance in the beginning as A0.

A0
Then, amount of radioactive substance after first half-life =
21

A0
Amount of radioactive substance after second half-life =
22

A0
And amount of radioactive substance after n half-life =
2n

Ex a m p l e 7
The mean lives of a radioactive substance are 1620 years and 405 years for -emission and
 -emission respectively. Find out the time during which three fourth of a sample will decay
if it is decaying both by  -emission and -emission respectively.
Solution :
For successive , -emissions,

1 1  5  1
average        yr
1620 405  1620 

Following first-order kinetics,

2.303 N
 log 0
t Nt

2.303  1620 N0
t log  449.2 years
5 
N0 / 4  .

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The reac t ion c oordinat e and t he reac t ion profile

The minimum energy pathway from reactants to products is called the reaction coordinate. Moving
along this pathway involves changing the positions of all of the atoms involved in the reaction in
a complex way, so the „coordinate‰ is in fact a composite of many motions.
We can plot the energy against the reaction coordinate to give a plot which is know as the reaction
profile, which you have encountered before.

potential energy
transition state

Ea

products

reactants

reaction coordinate

The transition state exists at the potential energy maxima, and the difference in energy between
this maxima and the reactants is called the activation energy E.
The fraction of molecules coming together with sufficient energy to reach the transition state is
exp(ăEa/RT). For a typical value of the activation energy of 50 kJ molă1, this means that only
about 1 in 109 of the molecules which attempt to reach the transition state actually have enough
energy to make it. We can imagine the molecules all queuing up like eager climbers at Everest
base camp (the reactants); many set off towards the summit (the transition state), but few have
the energy to make it, and so slide back down the slope.
As we commented before, actually calculating the form of the potential energy surface is a
challenging task. However, this discussion has allowed us to develop an understanding of the
origin of the energy barrier to reaction, and to introduce the important concepts of the transition
state and the reaction profile.

T h r e s h o l d En e r g y
It is the minimum amount of energy at which reaction takes place.

A c t i v a t i o n e n e r g y (E a )
The energy given to the reactant to reach the threshold value of energy is called as activation
energy is shown in the graph below.

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Threshold Energy
Threshold Energy

Eaf
Eaf Eab E ab

Potential Products
Hr = EafăEab Potential Reactants
Energy Energy
Reactants
Products
Reaction Progress
Reaction Progress
Endothermic Reaction
Exothermic Reaction

where
Eaf = activation energy for forward reaction
Eab = activation energy for backward reaction
H r = Enthalpy of reaction = Eaf ă Eab

1 0 . T H E COL L I SI ON T H EORY OF REA CT I ON RA T ES

We are going to look in detail at reactions which involve a collision between two species.

Species : This is a useful term covers any sort of particle you like-molecule, ion or free radical.

Reactions where a single species falls apart in some way are slightly simpler because you wonÊt
be involved in worrying about the orientation of collisions. Reactions involving collisions between
more than two species are going to be extremely uncommon.

1 0 .1 Re a c t i o n s i n v o l v in g c o l l i s i o n s b e t w e e n t w o s p e c i e s
It is pretty that if you have a situation involving two species they can only react together if they
come into contact with each other. They first have a collide, and then they may react.
Why „may react‰? It isnÊt enough for the two species to collide-they have to collide the right way
around, and they have to collide with enough energy for bonds to break.
(The chances of all this happening if your reaction needed a collision involving more than 2
particles are remote. All three (or more) particles would have to arrive at exactly the same point
in space at the same time, with everything lined up exactly right, and having enough energy to
react. ThatÊs not likely to happen very often!)

1 0 .1 .1 T h e o r i e n t a t i o n o f c o l l i s io n
Consider a simple reaction involving a collision between two molecules-ethene, CH2=CH2 , and
hydrogen chloride, HCl, for example. These react to give chloroethane.

CH 2 = CH 2 + HCl  CH3CH2Cl

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As a result of the collision between the two molecules, the double bond between the two carbons
is converted into a single bond. A hydrogen atom gets attached to one of the carbons and a
chlorine atom to the other.
The reaction can only happen if the hydrogen end of the H-Cl bond approaches the carbon-carbon
double end. Any other collision between the two molecules doesnÊt work. The two simply bounce
off each other.

collision 1 collision 2

collision 3 collision 4

Of the collisions shown in the diagram, only collision 1 may possibly lead on to a reaction.
You may be wondering why collision 2 wonÊt work as well. The double bond has a high concentration
of negative charge around it due to the electrons in the bonds. The approaching chlorine atom is
also slightly negative because it is more eletronegative than hydrogen. The repulsion simply
causes the molecules to bounce off each other.
In any collision involving unsymmetrical species-you would expect that the way they hit each
other will be important in deciding whether or not a reaction happens.

1 0 .2 T h e e n e r g y o f t h e c o l l i s io n
Ac tivation Ener gy
Even if the species are orientated properly, you still wonÊt get a reaction unless the particles
collide with a certain minimum energy called the a c tivation energy of the reaction.

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Activation energy is the minimum energy

required before a reaction can occur. You can Energy
show this on an en er gy pr o fil e for the
reaction. For a simple over-all exothermic Activation
reaction, the energy profile looks like this : Energy E A

Note : The only difference if the reaction was

Reactants
endothermic would be the relative positions of
the reactants and pr od uc ts lines. For an
endothermic change, the products would have a
Products
higher energy than the reactants, and so the
green arrow would be pointing upwards. It
makes no difference to the discussion about Progress of reaction
the activation energy.

If the particles collide with less energy than the activation energy, nothing important happens.
They bounce apart. You can think of the activation energy as a barrier to the reaction. Only those
collisions which have energies equal to or greater than the activation energy result in a reaction.
Any chemical reaction results in the breaking of some bonds (needing energy) and the making of
new ones (releasing energy). Obviously some bonds have to be broken before new ones can be
made. Activation energy is involved in breaking some of the original bonds.
Where collisions are relatively gentle, there isnÊt enough energy available to start the bond-
breaking process, and so the particles donÊt react.

1 1 . RA T E CON ST A N T S A N D T H E A RRH EN I U S EQU A T I ON

The Arrhenius equation
Rate constants and rate equations
You will remember that the rate equation for a reaction between two substances A and B looks
like this :
order of reaction order of reaction
with respect to A with respect to B

rate = a b
k[A] [B]

rate in rate constant concentrations

-3
mol dm-3s-1 in mol dm

The rate equation shows the effect of changing the concentrations of the reactants on the rate of
the reaction. What about all the other things (like temperature and catalysts, for example) which
also change rates of reaction? Where does these fit into this equation?

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These are all included in the so-called rate constant-which is only actually constant if all you are
changing is the concentration of the reactants. If you change the temperature or the catalyst, for
example, the rate constant changes.
This is shown mathematically in the Arrhenius equation.
activation energy
rate constant

E
ă A
k = Ae RT kelvin temperature

the gas consant

frequency factor
or
pre-exponential factor mathematical
quantity,e

What the va rious symbols mea n

Starting with the easy ones...
Temperature, T
To fit into the equation, this has to be measured in kelvin.
The gas constant, R
This is a constant which comes from an equation, pV = nRT, which relates the pressure, volume
and temperature of a particular number of moles of gas. It turns up in all sort of unlikely places!
Activation energy, EA
This is the minimum energy needed for the reaction to occur. To fit this into the equation, it has
to be expressed in joules per mole-not in kJ molă1 .
And then the rather trickier ones...
e
This has a value of 2.71828... and is a mathematical number, a bit like pi and is called exponent.
–(EA/ RT )
The expression, e
For reasons that are beyond the scope of any course at this level, this expressions counts the
fraction of the molecules present in a gas which have energies equal to or in excess of activation
energy at a particular temperature.
The frequency factor, A
You may also find this called the pre-exponential factor or the steric factor.
A is a term which includes factors like the frequency of collisions and their orientation. It varies
slightly with temperature, although not much. It is often taken as constant across small temperature
ranges.
You may also come across it in a different form created by a mathematical operation on the
standard one:

EA
ln k  ln A 
RT

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1 2 . T H E EFFECT OF T EM PERA T U RE ON REA CT I ON RA T ES

1 2 .1 T h e f a c t s
What happens?
As you increase the temperature the rate of reaction increases. As a rough approximation, for
many reactions happening at around room temperature, the rate of reaction doubles for every
10ĈC rise in temperature.
You have to be careful not to take this too literally. It doesnÊt apply to all reactions. Even where
it is approximately true, it may be that the rate doubles every 9ĈC or 11ĈC or whatever. The number
of degrees needed to double the rate will also change gradually as the temperature increases.

1 2 .2 T h e e x p l a n a t i o n
1 2 .2 .1 I n c r e a s i n g t h e c o l l i s io n f r e q u e n c y
Particles can only react when they collide. If you heat a substance, the particles move faster and
so collide more frequently. That will speed up the rate of reaction.
That seems a fairly straighforward explanation until you look at the numbers.
It turns out that the frequency of two-particle collisions in gases is proportional to the square root
of the kelvin temperature. If you increase the temperature from 293 K to 303 K (20ĈC to 30 &
deg. C), you will increase the collision frequency by a factor of :

303
 1.017
293
ThatÊs an increase of 1.7% for a 10Ĉ rise. The rate of reaction will probably have doubled for that
increase in temperature-in other words, an increase of about 100%. The effect of increasing
collision frequency on the rate of the reaction is very minor. The important effect is quite different.

For Example
What happens if you increase the temperature by 10ĈC from, say, 20Ĉ C to 30Ĉ C (293 K to 303 K)?
The frequency factor, A, in the equation is approximately constant for such a small temperature
change. We need to look at how e ă (E A /RT) changes - the fraction of molecules with energies equal
to or in excess of the activation energy.
LetÊs assume an activation energy of 50 kJ molă1 . In the equation, we have to write that as 50000
J molă1. The value of the gas constant, R, is 8.31 J K ă1 molă1.
At 20ĈC (293 K) the value of the fraction is
EA 50000
 
8.31  293
e RT e
= 1.21 ï 10 ă9
By raising the temperature just a little bit (to 303 K), this increases :
EA 50000
 
8.31  303
e RT e
= 2.38 ï 10 ă9

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You can see that the fraction of the molecules able to react has almost doubled by increasing the
temperature by 10ĈC. That causes the rate of reaction to almost double. This is the value in the
rule-of-thumb often used in simple rate of reaction work.

Note : This approximation (about the rate of a reaction doubling for a 10 degree rise in
temperature) only works for reactions with activation energies of about 50 kJ molă1 fairly close
to room temperature.
The rate constant goes on increasing as the temperature goes up, but the rate of increase falls
off quite rapidly at higher temperatures.

1 3 . T H E EFFECTS OF CAT A L Y ST S ON REACT I ON RA T ES

1 3 .1 T h e f a c t s
What are catalysts?
A catalyst is a substance which speeds up a reaction, but is chemically unchanged at the end of
the reaction. When the reaction has finished, you would have exactly the same mass of catalyst
as you had at the beginning.
Some examples
Some common examples which you may need for other parts of your syllabus include :
reaction catalyst
Decomposition of hydrogen peroxide manganese (IV)
oxide, MnO2
Nitration of benzene concentrated sulphuric acid
Manufacture of ammonia by the Haber Process iron
Conversion of SO2 into SO3 during the Contact vanadium (V) oxide,
Process to make sulphuric acid V 2O 5

Hydrogenation of a C=C double bond nickel

1 3 .2 Ca t a l y s t s a n d a c t i v a t i o n e n e r g y
To increase the rate of a reaction you need
to increase the number of successful Energy Activation Energy
collisions. One possible way of doing this without catalyst
is to provide an alternative way for the
reaction to happen which has a lower Activation Energy
activation energy. with catalyst
Adding a catalyst has exactly this effect Reactants
on activation energy. A catalyst provides
an alternative route for the reaction.
That alternative route has a lower Products
activation energy. Showing this on an
energy profile :
Progress of reaction
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A w ord of c aut ion!

Be very careful if you are asked about this in an exam. The correct form of word is
„A catalyst provides an alternative route for the reaction with a lower activation energy.‰
It does not „lower the activation energy of the reaction‰. There is a subtle difference between the
two statements.
If particles collide with enough energy they can still react in exactly the same way as if the
catalyst wasnÊt there. It is simply that the majority of particles will react via the easier catalysed
route.

Ex a m p l e 8
If for a first order reaction, rate constant varies with temperature
according to the graph given. At 27ĈC, 1.5 ï 10 ă4 per cent of the

Rate constant
reactant molecules are able to cross-over the potential barrier. At
52ĈC, the slope of this graph is equal to 0.2 kă1 sec ă1, calculate the
value of rate constant at 52ĈC, assuming that activation energy does
not change in this temperature range.
Solution : Temp. (K)

1  RT
1.5  10 4   e Ea /
100
ă Ea/R ï 300
= 1.5 ï 10 ă6 = e
 Ea = 33.43 kJ moleă1
ă Ea/RT
k= e

dk E
 a2 k
d T RT

8.314  325  325

k  0.2 
33.43  1000

k = 8.75 ï 10 ă2 mină1.

Ex a m p l e 9
1 mole of gas changes lineraly from initial state (2 atm, 10 lt) to final state (8 atm, 4lt). Find
the value of rate constant, at the maximum temperature, that the gas can attain. Maximum
rate constant is equal to 20 secă1 and value of activation energy is 40 kJ mole ă1, assuming
that activation energy does not change in this temperature range.
Solution :
Let the equation of straight line is
P = mV + c
Now putting the values, we get
P + V = 12

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From the ideal gas equation,

PV PV
T 
nR R

 12  V  V
T
R
For T to be maximum

dT
0
dV
V = 6 lt
P = 6 atm

36
Value of Tmax =  439 K
0.082
Now putting the values of
A = 20 secă1
Ea = 40 ï 103 J mole ă1
We get
k = A e ăEa/RT

40  103
8.314  439
k  20 e

k = 1.56 ï 10ă3 secă1.

Ex a m p l e 1 0
From the following data, show that the decomposition of hydrogen peroxide in aqueous
solution is a first order reaction. What is the value of the rate constant?

Time in minutes 0 10 20 30 40

Volume (V) in ml 25.0 20.0 15.7 12.5 9.6

where V is the number of ml of potassium permanganate required to decompose a

definite volume of hydrogen peroxide solution.
Solution :
The equation for a first order reaction is

2.303 a
k log
t ax

The volume of KMnO4 used, evidently corresponds to the undecomposed hydrogen peroxide.

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Hence, the volume of KMnO4 used at zero time corresponds to the initial concentration ÂaÊ and the
volume used after time t corresponds to (a ă x) at that time. Inserting these values in the above
equation, we get

2.303 25
when t = 10 min., k = log = 0.022318 mină1 = 0.000373 să1
10 20.0

2.303 25
when t = 20 min., k = log = 0.023265 mină1 = 0.0003871 să1
20 15.7

2.303 25
when t = 30 min., k = log = 0.02311 min ă1 = 0.000385 s ă1
30 12.5

2.303 25
when t = 40 min., k = log = 0.023932 min ă1 = 0.0003983 să1
40 9.6

The constant value of k shows that the decomposition of H2O 2 in aqueous solution is a first order
reaction. The average value of the rate constant is 0.0003879 să1 .

Ex a m p l e 1 1
Two reactions (I) A  Products (II) B  Products follow first order kinetics. The rate of the
reaction (I) is doubled when temperature is raised from 300 K to 310 K. The half life for this
reaction at 310 K is 30 minute. At the same temperature B decomposes twice as fast as A.
If the energy of activation for the reaction for the reaction (II) is half that of reaction (I),
calculate the rate constant of reaction (II) at 300 K. (IIT 1992)
Solution :
(I) A  Products
(II) B  Products
 tófor (I) at 310 K = 30 minute

0.693
 K  I  at 310   0.0231 min 1 ... (1)
30
 rate = K[ ] and both reactions are of I order

KI at 310
Also given 2 ... (2)
K I at 300

K II at 310
Also given 2 ... (3)
KI at 310

E aII 1
Also we have,  ... (4)
E aI 2

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KI at 310 Ea I  310  300 

2.303 log10 
For I KI at 300 R  310  300  ... (5)

K II at 310 Ea II  310  300 

For II 2.303 log10    ... (6)
K II at 300 R  310  300 

Dividing Eqs. (5) by (6)

KI at 310
log 10
KI at 300 E a I
  2
 K at 310 Ea II By eq. (4) ... (7)
log 10 II
K II at 300

K I at 310  K II at 310 
or log10  2 log10  
K I at 300  K II at 300 

2
KI at 310  KII at 310 
or log10   ... (8)
KI at 300  KII at 300 
By Eqs. (2) and (8),

2
 KII at 310 
or  K at 300   2
 II 

By Eqs. (3) and (9),

2 ï K I at 310 K = 2 (KII at 300 K)

2  K I at 310
KII at 300 K = ...(10)
2

By Eqs. (1) and (10),

KII at 300 K = 2  0.0231

K II at 300 K = 3.27 ï 10ă2 mină1

= 0.0327 mină1 .

Ex a m p l e 1 2
In the Arrhenius equation for a certain reaction, the values of A and Ea (energy of activation)
are 4 ï 1013 secă1 an 98.6 kJ molă1 respectively. If the reaction is of first order, at what
temperature will its half life period be 10 minute ?

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Solution :
Given,
K= ? A = 4 ï 1013 sec ă1
E a = 98.6 ï 10 3 J mol ă1 t ó = 10 ï 60 sec
ăEa/RT
 K = Ae
103)/8.314 ï T
 K = 4 ï 1013 eă(98.6 ï

0.693 0.693
Now for I order reaction, K   sec  1
tó 600

0.693  10 3) / 8.314  T
  4  1013 e (98.6
600

0.693 98.6  103

or log e  log e 4  10 13 
600 8.314  T

0.693 98.6  103

or log 10  log10 4  10 13 
600 8.314  2.303  T

T = 311.35 K

Ex a m p l e 1 3
The half life period and initial concentration for a reaction are as follows. What is order
of reaction?
Initial concentration 350 540 158
tó 425 275 941
Solution :
tó (a )1ăn
For I  425  (350)1ăn ...(1)
1ăn
For II  275  (540) ...(2)
1ăn
For III  941  (158) ...(3)
By Eqs. (1) and (2),

1 n
425  350 

275  540 

Taking log,

425 350
log  1  n log
275 540
n = 2

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Ex a m p l e 1 4
d [A]
 B, the rate law expression is 
For the reaction A   K[A]ó . If initial concentration
dt
of A is A0. Calculate :
(a) integrated form of the rate expression.
(b) nature of plot of [A] óvs. time.
(c) half life period.
Solution :

d[A]
(a)   K[A]ó
dt

dA
or   Kdt
[A]ó

on integrating   [A] ó d A  K  dt

ă 2A ó = K t + C ...(1)
ó
at t = 0; A = A0  C = ă 2A0 ...(2)
By Eqs. (2) and (1),
ă 2Aó = Kt ă 2A0ó
or Kt = 2[A0 ó ă A ó] ...(3)

(b) Plot of Aó vs. t will be linear because Eq. (3) yields,

2A ó = ă Kt + 2A0ó

K
or Aó =  t  Aó
0
2

K
or Aó   t  A0ó (similar to y = mx + C)
2
(c) If t = t óA = A0/ 2
 By Eq. (3)

 ó  A ó  1 
K ó  2  A 0   0    2Aó
t 0 1  
  2    2

2[ 2  1]
Któ 
2
0  2
Aó  
2  1 Aó
0

 tó 
2  21 A ó
0
K

CHEMICAL KINETICS
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Ex a m p l e 1 5 :
The rate law for the following reaction :

dx
Ester + H+  Acid + Alcohol, is  K (ester) [H3 O+ ]0
dt
What would be the effect on rate if :
(a) Concentration of ester is doubled ?
(b) Concentration of H+ ion is doubled ?
Solution :
 Rate = K [ester]´ [H3 O+ ]0
(a) r1 = K [ester]´ [H3O+] 0
Let, Initial conc. of ester = a, initial conc. of H3O+ = b
 r1 = K [a] [b]0
If conc. of ester is doubled, i.e., [ester] = 2a, then
r2 = K [2 ï a ]´ [b]0

r1 1
 
r2 2 or r2 = 2r 1

(b) r1 = K [a] [b] 0

If conc. of H3O+ is doubled, i.e., [H3 +O] = 2b
r3 = [a] t [2b]0

r1
  1 or r = r
r3 1 3

Ex a m p l e 1 6
The rate of a certain reaction depends on concentration according to the equation

dC k 1C
  , what will be the order of reaction, where (a) concentration is very-very
dt 1 + k2C
high, (b) very-very low.
Solution :

dC k1 C k1
  
dt 1 + k2C 1
 k2
C
(a) If C is very very high 1/C is smallest and thus negligible.
dC k1
   Constant
dt k2
Thus, order of reaction is zero.

CHEMICAL KINETICS
 MARKS 43

(b) If C is very very low 1 + k2C = k´

d C k1 C
   k''C
dt k'
Thus, order of reaction is unity.

Ex a m p l e 1 7
An organic compound A decomposes following two parallel first order mechanism :
k1
B k1 1
A  and k 1 = 1.3 ï 10ă5 secă1.
k2 k2 9
C
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only
A for one hour.
Solution :

k1 1

k2 9

But k1 = 1.3 ï 10ă5 secă1; k2 = 9 ï 1.3 ï 10ă5 secă1 = 11.7 ï 10ă5 sec ă1.
(k1 + k2) = (1.3 ï 10 ă5) + (11.7 ï 10ă5) sec ă1 = 13 ï 10 ă5 sec ă1 ...(1)

[B] t 1 [C]t
Also,   [B]t  ...(2)
[C]t 9 9

For parallel first order reaction :

d[A]
   k1  k2 [A]
dt

[A]t t t
d[A]
     k1  k2   dt
[A]0
[A] t 0

[A]0   A  t  [B] t  [C] t 

 ln   k1  k2  t; ln     k1  k2  t
[A]t  [A]t 

  Ct 
[ A] t   C  t 
 ln  9    k1  k2 t [from eq. (2)]
  A t 
 
 

 10 Ct 
 ln 1     k1  k2 t
 9 A t 

CHEMICAL KINETICS
 44 MARKS

 10 Ct  5
 ln 1    13  10  60  60  0.468 [from eq. (1)]
 9 A  t 


10  C t C t
 1  1.5968;  0.537
9 A t [A]t

Ex a m p l e 1 8
The rate of formation of NO(g) in the reaction :
2NOBr(g)  2NO(g) + Br2 (g)
was reported as 1.6 ï 10ă4 Msă1 (M = mol L ă1). What is the rate reaction and the rate of
consumption of NOBr ?
Solution :

dx 1 d NOBr 1 d  NO  d B r
Taking the fact    
dt 2 dt 2 dt dt
d  NO 
given  1.6  10 4 Ms 1
dt

dx 1 d  NO 1.6  10 4

hence rate of reaction   Ms1  8  105 Ms1
dt 2 dt 2
d  NOBr  d NO 
and rate of consumption of NOBr    1.6  10  4 Ms  1
dt dt

Ex a m p l e 1 9
The rate constant for the decomposition of a certain substance is
2.80 ï 10ă3 M s ă1 at 30Ĉ C and 1.38 ï 10 ă2 M ă1 s ă1 at 50ĈC. Evaluate the Arrhenius parameters
of the reaction.
(R = 8.314 ï 10ă3 kJ molă1 K ă1)
Solution : Energy of activation Ea and are pre-exponential factor A are Arrhenius parameters
given rate constant k1 = 2.80 ï 10 ă3 M ă1 s ă1 at 30ĈC (303 K)
k2 = 1.38 ï 10 ă2 M ă1 s ă1 at 50ĈC (323 K)

2.303 RT1T2 k
thus energy of activation E a  log10 2
 2 1
T  T k1

2.303  8.314  10 3  303  323 1.38  10 2 

=
 323  303
log 10  2.80  10 3 
 
Ea = 64.91 kJ molă1
ă Ea/RT Ea/RT
also k = Ae  A = ke
10ă3 ï 303)
A = 2.80 ï 10ă3 e64.91/(8.314 ï
= 4.34 ï 108 Mă1 să1
CHEMICAL KINETICS
 MARKS 45

Ex a m p l e 2 0
The acid catalysed hydrolysis of an organic compound A at 30Ĉ C has a time for half change
of 100 min when carried out in a buffer solution at pH 5, and 10 min when carried out at
pH 4. Both times of half-change are independent of the initial concentration of A. If the rate
 d [ A]
constant K is given by  k [A ]a [H  ]b , what are the values of a and b ?
dt
Solution :

 d A  b
The rate equation is  k [A]a H  
dt
During any experiment, pH is constant, hence

 d A
 K [A]a where K [H ]b
dt
Since half life is independent of the initial concentration of A, hence a = 1; Consequently k´ is a
first order rate constant and is given by K´ = 0.693/T50 , Therefore

b b
 
 T50 1 k2 ´ k H  2  H  2
  
 T50 2 k1´ k H  b H  
b
 1  1

b  
 100   10
4   1 
or      or b = 1, pH  log 
 10   10 H  
5
    

Therefore the rate of hydrolysis has a first order dependence on [H+], so that

 d [A]
 k A  [H  ]
dt

Ex a m p l e 2 1
A reaction between substances A and B is represented stoichiometrically by A + B  C.
Observations on the rate of this reaction are obtained in three separate experiment as follows :
Initial concentrations t/h duration of Final
S.No. [A]0 , M [B]0, M experiment concentration
[A]f , M
(1) 0.1000 1.0 0.50 0.0975
(2) 0.1000 2.0 0.50 0.900
(3) 0.0500 1.0 2.00 0.0450

What is the order with respect to each reactant and what is the value of the rate
constant ?

CHEMICAL KINETICS
 46 MARKS

Solution :
 [A]
Let rate law be  k [A]a [B]b where a and b are order w.r.t. A and B respectively. First
t
  [A]
we calculate rate of disappearance of A,
t
Set  (1) (2) (3)
A ă 0.0025 ă 0.0100 ă 0.0050
t 0.50 0.50 2.00

 [A] 
   0.0050 0.0200 0.0025
 t 

[A]0 0.1000 0.1000 0.0500

[B]0 1.0 2.0 1.0

Putting these values in rate law, we have

+ 0.0050 = k [0.1000]a [1.0]b ...(1)
0.0200 = k [0.1000] a [2.0]b ...(2)
0.0025 = k [0.500]a [1.0]b ... (3)
b
on dividing eq. (2) by (1), 4 = 2 which gives b = 2
on dividing eq. (1) by (3), 2 = 2a which gives a = 1

  [A]
thus rate law is = k [A] [B]2
t
if we put the above values of any one set, say (1) rate law

[A]
t 0.0050
k   5  102 M2h 1
[A] [B] 2
 0.1000  1.0 2

Ex a m p l e 2 2
A certain reaction A + B  products is first order w.r.t. each reactant with
k = 5.0 ï 10 ă3 M ă1 s ă1.
Calculate the concentration of A remaining after 100 s if the initial concentration of A was
0.1 M and that of B was 6.0 M. State any approximation made in obtaining your result.
Solution :
Since [B] = 6.0 M, we can consider that its concentration remains constant throughout. Thus
Rate = k [A] [B]
= k [A] 6 = 6k [A]
= k´ [A]

CHEMICAL KINETICS
 MARKS 47

where k´ (= 6k) is new constant and reaction under this condition is supposed to follow first order
kinetics.

2.303 a
k'  log
t a  x 

a K 't 6kt
      log  
 a  x 2.303 2.303

a 6  5.0  10 3  100

log 
 a  x 2.303

 a 
log    1.3026
a  x 

 a 
   20
 a  x

ax 1

a 20

a 0.1
(a ă x) =   0.005M
20 20
Hence concentration of the reactant A after 100s is 0.005 M.

CHEMICAL KINETICS
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