Chemical Kinetics

Svante August Arrhenius

Svante August Arrhenius (1859 –1927) was a Swedish chemist and one of the founders of
the science of physical chemistry. The Arrhenius equation and the lunar crater Arrhenius
are named after him.
In 1884 he worked on the conductivities of electrolytes and presented a dissertation
on electrolytic conductivity to university of Uppsala for the doctorate. The dissertation did
not impress the professor and he received the lowest possible passing grade. Later in 1903,
this work earned him the Nobel Prize in Chemistry. The most important idea in the
dissertation was his explanation of the fact that neither pure salts nor pure water is a
conductor, but solution of salts in water are.
Arrhenius' explanation was that in forming a solution, the salt dissociates into
charged particles (which Michael Faraday had given the name ions many years earlier).
Faraday's belief had been that ions were produced in the process of electrolysis; Arrhenius
proposed that, even in the absence of an electric current, solutions of salts contained ions.
He thus proposed that chemical reactions in solution were reactions between ions. For
weak electrolytes this is still believed to be the case, but modifications (by Peter J. W.
Debye and Erich Hückel) were found necessary to account for the behavior of strong
electrolytes.
In an extension of his ionic theory Arrhenius proposed definitions for acids and
bases, in 1884. He believed that acids were substances which produce hydrogen ions in
solution and that bases were substances which produce hydroxide ions in solution.
In his last years he wrote both textbooks and popular books, trying to emphasize the
need for further work on the topics he discussed.
In September, 1927, he came down with an attack of acute intestinal catarrh, died on
October 2, and was buried in Uppsala.

Introduction
Chemical Kinetics is the branch of science that deals with rate of reaction, factors affecting the
rate of reaction and reaction – mechanism.
Different reactions occur at different rate. In fact a chemical reaction involves
redistribution of bonds – breaking in the reactant molecule(s) and making of bonds in the
product molecule(s). The rate of a chemical reaction actually depends upon the strength of the

53
bond(s) and number of bonds to be broken during the reaction. It takes longer time for the
reactant molecules to acquire higher amount of energy which they do by collision. Hence
reactions involving strong bond – breaking occur at relatively slower rate while those involving
weak bond – breaking occur at relatively faster rate. On the basis of rate, reactions are classified
as.
(i) Instantaneous or extremely fast reaction i.e. reactions with half-life of the order of fraction
of second.
(ii) Extremely slow reactions i.e. reactions with half-life of the order of years.
(iii) Reactions of moderate or measurable rate.
Ionic reactions are instantaneous. If a drop of silver nitrate solution is added to a solution of
the chloride salt of any metal or solution of HCl, a white precipitate of silver chloride appears
within twinkling of eye. This is because of the fact that in aqueous solution an ionic compound
exists as its constituent ions. No bond needs to be broken during the reaction. Hence reaction
takes no time to complete. The half life period of an ionic reaction is of the order of 10–10 s.
Na + + Cl− + Ag+ + NO3− ⎯⎯
→ AgCl  + Na + + NO3−

Free radicals being very unstable (reactive) due to the presence of unpaired electron, reactions
involving free radicals also occur instantaneously. Thus, the reactions, are instantaneous.
•
→ CH3Cl + •Cl
CH3 + Cl2 ⎯⎯
•
CH3 + •CH3 ⎯⎯
→ H3C − CH3

2.1 Rate of Reaction

With the progress of reaction the concentration of reactants decreases while that (those) of
product(s) increases. If the reaction occurs fastly, the concentration (mole L–1) of reactant will
decrease rapidly while that of product will increase rapidly. Thus, the rate of reaction is
defined as the rate at which the concentration of reactant decreases or alternatively, the rate at
which concentration of product increases. That is the change in concentration of any of the
substance (reactant/product) per unit time during the reaction is called rate of reaction. If C be
the change in concentration of any reactant or any product during the time interval t then the
rate may given as
C
Rate = ±
t
(– ve sign applies in the case of reactant whose concentration goes on decreasing with time and
+ ve sign applies in the case of product whose concentration goes on increasing with time).

54
However, the rate of reaction is not uniform. With the
passage of time the concentration(s) of reactant(s) goes on
decreasing and hence according to Law of Mass Action,
the rate of reaction goes on decreasing. Infact, the rate of

Rate
reaction decreases moment to moment. This is shown in
the graph of rate vs time curve of a reaction.
Rate varies from moment to moment so rate of reaction
Time
has to be specified at a given instant of time called
instantaneous rate or rate at any time t. This is as defined
below.
dc
rinst or rt = 
dt
Where dc is the infinitesimal change in concentration during infinitesimal time interval dt
after time t i..e. between t and t + dt. The time interval dt being infinitesimal small, the rate of
reaction may be assumed to be constant during the interval.
The rate of reaction expressed as ± C/t is actually the average rate with time interval
considered.
For the reaction; 2N2O5 ⎯⎯
→ 4NO2 + O2
The rate of reaction at any time t may be expressed by one of the following
−d[N 2 O5 ] d[NO2 ] [O ]
,+ or + d 2
dt dt dt
Where square bracket terms denote molar concentration of the species enclosed.
The above three rates are not equal to one another as is evident from the stoichiometry of
the reaction. For every mole of N2O5 decomposed, 2 moles NO2 and 1/2 mole of O2 will be
formed. Obviously, the rate of formation of NO2 will be four times that of O2 and it is twice the
rate of consumption of N2O5. Thus, their three rates are interrelated as,
d[NO2 ]  d[N 2O5 ]   d[O2 ] 
+ = 2 −  = 4 
dt  dt   dt 
Dividing through out by 4,
1  d[N2O5 ]  1  d[NO2 ]  d[O2 ]
−  = + =+
2 dt  4  dt  dt

Thus, rate of reaction expressed in terms of the various species involved in a reaction will
be equal to one another if each of there is divided by the stoichiometric constituent of the
species concerned. Rate divided by stoichiometric coefficient may be called as rate per mole.

55
 The kinetic experiment has shown that the rate of reaction mentioned above increases same
number of times as the number of times the concentration of N2O5 is increased. That is, rate is
doubled by doubling the concentration of N2O5. This may be mathematically expressed as
Rate  [N2O5]
or Rate = k [N2O5] …(1)
Where k is the proportionality constant called rate constant, velocity coefficient or specific
reaction rate of the reaction, and is a constant for a given reaction at a given temperature.
Equation 1 showing the concentration – dependence of rate is called rate law of the reaction.
Expressing rate in terms of change of concentration of various species, equation may be put as
d[N 2 O5 ]
− = k [N2O5]
dt
d[NO5 ]
+ = k [NO2]
dt
d[O 2 ]
+ = k [O2]
dt
when k, k and k are the rate constants of the reaction. These three rate constants are inter-
related
k ' k ''
= = k '''
2 4
Thus, for a reaction represented by the general equation
aA + bB ⎯⎯
→ cC + dD
1  dCA  1  dCB  1  dCc  1  dCD 
− = − = +  = + 
a  dt  b  dt  c  dt  d  dt 
We have,
k I k II k III k IV
= = =
a b c d
where
kI, kII, kIII and kIV
are the rate constants of the reaction when its rate is expressed in terms A, B, C and D,
respectively.
The rate of reaction at any time t is determined in the following way,
(i) Concentration of any of the reactants or products which ever may be convenient is
determined at various time intervals.
(ii) Then concentration vs time curve is drawn.

56
(iii) A tangent is drawn at the point p of the curve which corresponds to the time t at which rate
is to be determined.
(iv) The slope of the tangent gives the rate of reaction at the required time as shown below.

CR Rt = tan = – tan(180 – ) = – OA
OB
A CP 1
B
P
A OA
rt = tan = OB
 
180 –  B
t Time O t time

(CR and CP denote concentration of reactant and product respectively)

Unit of concentration
Unit of rate = = Concentration time–1 i.e. mole L–1 S–1
Unit of time

2.2 Molecularity
A chemical reaction that takes place in one and only one step i.e., all that occurs in a single step
is called elementary reaction while a chemical reaction occurring in the sequence of two or more
steps is called complicated reaction. The sequence of steps through which a complicated
reaction takes place is called reaction – mechanism. Each step in a mechanism is an elementary
step reaction.
The molecularity of an elementary reaction is defined as the minimum number of
molecules, atoms or ions of the reactants(s) required for the reaction to occur and is equal to the
sum of the stoichiometric coefficient of the reactants in the chemical equation of the reaction.
Thus, the molecularity of some elementary reactions are as mentioned below.
Elementary reaction Molecularity
PCl5 ‡ˆ ˆˆ †ˆ PCl3 + Cl2 1
H2 + I2 ‡ˆ ˆˆ †ˆ 2HI 1+1=2
Reactions with molecularity equal to one, two, three etc., are called unimolecular,
bimolecular, termolecular, etc., respectively.
A complicated reaction has no molecularity of its own but molecularity of each of the steps
(elementary reactions) involved in its mechanism.

57
 For example, consider the reaction: 2NO + 2H2 → N2 + 2H2O, which is complicated
reaction and takes place in the sequence of following three steps.
(i) NO + NO ‡ˆ ˆˆ †ˆ N2O2 (fast and reversible)
(ii) N2O2 + H2 ⎯⎯⎯
r.d.s.
→ N2O + H2O(slow)

(iii) N2O + H2 ⎯⎯
→ N2 + H2O (fast)
The molecularity of each step in the mechanism is two, so what we say is that the reaction
takes in the sequence of three steps each of which is bimolecular. There is another view also.
According to which molecularity of a complicated reaction is taken to be equal to the
molecularity of the slowest step i.e. rate – determining step (r.d.s.) in the mechanism.
For example, the reaction
ROH + HCl ⎯⎯⎯
ZnCl2
→ RCl + H2O

is said to be unimolecular nucleophilic substitution (SN1) since the reaction occurs in the
sequence of the following three steps and the slowest step i.e. r.d.s. is unimolecular.
•• 
(i) R OH + HCl ‡ˆ ˆˆ †ˆ R OH2 + ••Cl− (fast)
•• ••


(ii) R OH2 ‡ˆ ˆˆ †ˆ R  + H2O (slow)
••


(iii) R + ••Cl− ⎯⎯
→ RCl(fast)

Reactions of higher molecularity (molecularity > 3) are rare. This is because a reaction
takes place by collision between reactant molecules and as number of reactant molecules i.e.
molecularity increases the chance of their coming together and colliding simultaneously
decreases.

2.3 Order of a Reaction

The speed of a chemical reaction, in general depends on the concentration of reacting species of
the reaction. An early generalization in this regard is due to Gulberg and Waage. This
generalization is known as law of mass action and is stated as follows.
The rate of a chemical reaction is proportional to the product of effective concentration
(acting masses) of the reacting species, each raised to a power that is equal to the corresponding
stoichiometric number of the substance appearing in the chemical reaction.
Thus, for a general reaction aA + bB ⎯⎯
→ cC + dD …(2a)

58
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 k 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 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 concentration were set equal to unity. Each reaction is characterized by its own
reaction rate constant. From equation (2c), we find that units of k is (mol )n s–1 where n = 1 – (a
+ b).
The expression of equation (2c), which relates the rate of reaction, with the concentration
of reacting species is known as the differential rate law.
It may be emphasized once again here that the rate equation with its rate constant and order
of various reacting species is an experimental finding and cannot be predicted from the
stoichiometry of the balanced reaction.
Although many reactions obey equation (2c), there are numerous others whose rate
expressions are not of such simple form. A few such reactions are listed in Table.

59
Examples of reactions obeying complicated Rate Laws

Overall reaction Experimentally determined rate laws

H2 + I2 ‡ˆ ˆˆ †ˆ 2HI 1 d[HI]
= k1 [H2] [I2] – k–1 [HI]2
2 dt

H2 + Br2 ⎯⎯
→ 2HBr 1 d[HBr] k[H 2 ] [Br2 ]1/ 2
=
2 dt [HBr]
1+ k '
[Br2 ]
−
OCl− + I− ⎯⎯⎯
OH
→ OI− + Cl− d[Cl− ] [OCl − ] [I − ]
=k
dt [OH − ]
+
CH3COCH3 + I2 ⎯⎯→
H
CH3COCH 2 I + HI d[I2 ]
− = k[CH3COCH3 ] [H + ]
dt

Table reveals the following facts.

1. The rate law may not bear a simple relationship to the stoichiometric equation.
2. The rate law may not depend on the concentration of every reactant of the reaction.
3. The rate law may depend on the concentration of species (e.g., catalysts) which do not
appear in the equation for the overall reaction.
These facts clearly indicate that the rate equation cannot be predicted from the form of the
stoichiometric equation for the overall reaction. Hence, the rate equation must be determined
experimentally. In some cases, the order of the reaction is meaningless. For example, for the
hydrogen-bromine reaction, the reaction is of first-order with respect to hydrogen gas but it
would be impossible to assign the order with respect to bromine and to hydrogen bromide. Thus,
the concept of order of reaction has no meaning if a rate law does not have the form as given in
equation (2c).
In the reaction between hypochlorite and iodide ions, though OH– does not appear in the overall
reaction, yet it appears in the denominator of the rate law. This indicates that OH– acts as an
inhibitor. Similarly, the reaction between acetone and iodine does not involve H+ in the overall
reaction, but it appears in the numerator of the rate law. This shows that H + acts as an
accelerator or a catalyst.

60
2.4 Difference Between Order and Molecularity
(i) Order is an experimentally property while molecularity is the theoretical property.
(ii) Order concerns with kinetics (rate-law) while molecularity concerns with mechanism.
(iii) Order may be any number, fractional, integral or even zero whereas molecularity is always
an integer excepting zero.
Example
Reactions Rate Law Order
CH3CHO ⎯⎯
→ CH4 + CO Rate  [CH3CHO]3/2 1.5

NH3 ⎯⎯
→
1 3
N2 + H2 Rate  [NH3]0 0
2 2

2HI ⎯⎯
→ H2 + I2 Rate  [HI]0 0
i.e. Rate = k

Note that a zero order reaction is one in which concentration of reactant remains
throughout constant and as such rate of reaction remains throughout constant equal to the
rate constant.
(iv) Order may change with change in experimental condition while molecularity can’t.
Example

isomerization CH3
H2C

The reaction follows 1st order kinetics at high gas pressure and 2nd order kinetics at low
gas pressure of cyclopropane.

2.5 Kinetics of First Order Reaction

A first order reaction is one whose rate varies as 1st power of the concentration of the reactant
i.e. the rate increases as number of times as the number of times the concentration of reactant is
increased.
Let us consider a unimolecular first order reaction represented by the general equation.
A ___________ Product
A x=0 …t=0
A–x x=x …t=0
The initial concentration of A is a mole L–1 and its concentration after any time t is (a – x)
mole L–1. This means during the time interval t, x mole L–1 of A has reacted.

61
The rate of reaction at any time t is given by the following first – order kinetics.
d(a − x) d(x)
−  (a − x) or  (a – x)
dt dt
dx
or = k (a – x)
dt
da
( = 0 Q a has a given value for a given expt.)
dt
where k is the rate constant of the reaction.
dx
= kdt
a−x
This is differential rate equation and can be solved by integration.
dx
 a − x = k  dt
or – ln (a – x) = k.t + C …(1)
The constant C can be evaluated by applying the initial condition of the reaction i.e. when t = 0,
x = 0. Putting these in equation 1, we get
C = – lna
Putting the value of C in equation 1, we get
1 a 2.303 a
– ln (a – x) = k.t. – lna or k = ln = log …(2)
t a−x t a−x
If [A0] and [A] be the concentrations of reactant at zero time and time t, respectively then Eq. 2
may be put as
1 [A ]
k = ln 0
t [A]
This is the integrated rate expression for first order reaction. Unit of the rate constant
1 a
k = ln
t a−x
kt = lna – ln(a – x)
a – x = ae–kt
x = a(1 – e–kt)
The differential rate expression for nth order reaction is as follows.
dx dx concentration
= k(a − x) n or k = = = conc. 1–n . time–1
dt (a − x) dt (concentration)n time
n

If concentration be expressed in mole L–1 and time in minute, then

k = (mole L–1)1–n min–1
For zero order reaction: n = 0 and hence k = mole L–1 min–1

62
For 1st order reaction: n = 1 and hence
k = (mole L–1)0 min–1 = min–1
For 2nd order reaction: n = 2 and hence
K = (mole L–1)–1 min–1 = mole–1 1 min–1
The rate constant of a first reaction has only time unit. It has no concentration unit. This means
the numerical value of k for a first order reaction is independent of the unit in which
concentration is expressed. If concentration unit is changed the numerical value of k for a first
order reaction will not change. However, it would change with change in time unit. Say, k is 6.0
 10–3 min then it may also be written as 1  10–4 s–1 i.e. numerical decrease 60 times if time unit
is changed from however to minute or from minute to second.
Half-time or half-life period of a first order reaction
The half-time of a reaction is defined as the time required to reduce the concentration of the
reactant to half of its initial value. It is denoted by the symbol t1/2. Thus,
a
When x = , t = t1/2
2
Putting these in equation 2 mentioned above, we get
2.303 a 2.303 2.303
k= log = log 2 =  0.30103
t1/ 2 a t1/ 2 t1/ 2
a−
2
(Q log 2 = 0.30103)
0.693
t1/2 = …(3)
k
Since k is a constant for a given reaction at a given temperature and the expression lacks
any concentration term so from equation 3 it is evident that half-time of a 1st order reaction is a
constant independent of initial concentration of reactant. This means if we start with 4 mole L –1
of a reactant reacting by first-order kinetics and after 20 minute it is reduced to 2 mole L–1 will
also be 20 minute. That is, after 20 minutes from the start of reaction the concentration of the
reactant will be 2 mole L–1, after 40 minutes from the start of reaction of concentration is 1 mole
L–1. After 60 minutes from the start of reaction the concentration of the reactant will be reduced
to 0.5 mole L–1. In order words, if during 20 minutes 50% of the reaction completes, then in 40
minute 75%, in 60 minute 85.5% of the reaction and on will complete as shown with following
plot.

63
 n
Fraction left after n half-lives =  
1
2   100
n 75
Concentration left after n lives a n =   a 0
1
2  

C( %)
50
It is also to be noted that equation 3 helps to
25
calculate t1/2 or k with the knowledge of k or t1/2.
A general expression for t1/2 is as follows 0 20 40 60 80
1 t (min)
t1/ 2 
a n −1
Where n = order of reaction.

2.6 Graphical Representation

Since for nth order reaction
dx dx
= k(a − x) n , or − = k.c n
dt dt
dx
So, from this it is evident that a plot of vs(a – x)n will be straight line passing through
dt
the origin and will have its slope equal to k, the rate constant of reaction.
Thus, for a first order reaction one will get
dx
straight line passing through the origin of i.e.
dt
dx
rate of reaction be plotted against a – x as show dt K = tan
below.
Taking logarithm of the above equation 
dx (a – x)
log = n log (a – x) + log k
dt

dx
This equation demands that a plot of log vs log
dt
B1
(a – x) will be straight line of the slope equal to n, order
log dx
dt 0 = 45° if n = 1,
of reaction and intercept equal to log k. For first order i.e. OA = OB
reaction this slope will be 1 as shown.
Equation 2 may be rearranged as 
−k 
B O log (a – x)n
log (a – x) =   t + log a
 2.303 

64
 k
Thus, a plot of (a – x) vs. t will be straight line with slope equal to − and intercept
2.303
equal to log a, if the reaction is of first order.

ILLUSTRATIONS
Illustration 1
In a reaction with initially 0.12 M, the concentration of reactant is reduced to 0.06 M in 10 hour
and to 0.03 M in 20 hour.
(a) What is the order of reaction?
(b) What is rate constant?
Solution
2.303 a
Assuming 1st order, K = log
 (a − x)
2.303 0.12
For case – 1 K = log
10 0.06
= 0.069 hr–1.
Reaction is of 1st order and rate constant = 0.069 hr–1.
Illustration 2
For a reaction 3A → Products, it is found that the rate of reaction doubles if concentration of
A is increased four times, calculate order of reaction.
Solution
Rate = K [Reactant]n if [Reactant] = q
rate = r1
r1 = K[a] …(1) if [Reactant] = 4 q
n

2r1 = K[4a]n …(2) rate = 2r1

n

Dividing   =   , n =
1 1 1
   
2 4 2

PRACTICE EXERCISE
1. The rate constant for the reaction
CO2 + OH− ⎯⎯
→ HCO3−

In the aqueous solution is 4  10–3 litre mol–1 sec–1. Calculate the n umber of mole of CO2
and OH– used up per second when [CO2] and [OH–] are 10–6 and 10–1 mol litre–1. Also
predict the mole of HCO3– formed per second.
2. For a reaction 3A ⎯⎯ → Products, it is found that the rate of reaction doubles if
concentration of A is increased four times, calculate order of reaction.

65
 Answers
1
1. 4  10–10 mol L–1 sec–1. 2. n =
2

2.7 Half-Life of a nth order Reaction

Let us venture on to find out the t1/2 for a nth order reaction where n  1 .
[A0 ]
t
−d[A] −d[A] 2
d[A] 1/ 2

dt
= k[A]n 
[A]n
= kdt  −  [A]n
= k  dt
[A0 ] 0

A0
 [A]1− n 
[A0 ]


n −n
[A] d[A] = kt1/ 2   = kt1/ 2
[A 0 ]  1 − n  A0 / 2
2

1  1− n  [A]0 1− n  [A]10− n   1 1− n 

  0

[A] −  2   = kt  1 −    = kt1/ 2
1− n 1− n
1/ 2
      2  

1 (2n −1 − 1)
 [1 − 2n −1 ] = kt1/ 2  = kt1/ 2 (order n  1)
(1 − n)[A0 ]n −1
(n − 1) [A 0 ]n −1

Therefore for a nth order reaction, the half life is inversely related to the initial concentration
raised to the power of (n – 1).
[A]0
Note: It can be noted that for a zero order reaction t1/ 2 .
2k

2.8 Examples Of First–Order Reaction

A large number of reactions exhibiting first-order kinetics are known. A few examples are listed
below

(i) (CH3 )3 COOC(CH3 )3 ⎯⎯ → 2CH3COCH3 + C2H6
 1
(ii) N 2 O5 (g) ⎯⎯ → 2NO 2 (g) + O 2 (g)
2

(iii) (CH3 )2 CHN = NCH(CH3 )2 ⎯⎯ → N2 + C6 H14

(iv) SO2Cl2 (g) ⎯⎯ → SO2 (g) + Cl2 (g)
COOH

NO2 NO2
NO2 NO2
(v) 
+ CO2(g)

NO2
NO2
 1
(vi) H 2O2 (soln.) ⎯⎯ → H 2 O(l ) + O 2 (g)
2

66
(vii) All radioactive decays.
There are reactions in which more than one species is involved in the rate determining step,
but the order of the reaction is one. Such reactions are known as pseudo-unimolecular
reactions and they involve solvent molecules or a catalyst as one of the reacting species.
Examples of this type of reactions are:
+
(viii) Acid hydrolysis of an ester: CH3COOC2H5 + H2O ⎯⎯→
H
CH3COOH + C2H5OH
+
(ix) Inversion of cane sugar: C12H22O11 + H2O ⎯⎯→
H
C6H12O6 (glucose) + C6H12O6 (fructose)
+
(x) Decomposition of benzene diazonium: C6 H5 N  NCl− + H2O → C6H5OH + N2 + HCl

2.9 Concentrations Replaced By Other Quantities In First-Order Integrated Rate Law

The rate constant for a first-order reaction, it is necessary to determine the ratio of the
concentration at two different times. Quantities proportional to the concentration terms may be
substituted in these equations, since the proportionality constants cancel. We describe below a
few typical cases where concentration terms are replaced by other easily measurable quantities.
Case – I:
Let there be a first–order reaction of the type, A ⎯⎯ → B + C. Let us assume that all the three
species are gases. We are required to calculate the value of rate constant based on the following
data
Time 0 t 
Partial pressure of A P0 Pt –

Strategy:
We know that for a first-order reaction,
1 A
k = In 0
t At

At t = 0, the partial pressure of A is P0 and at time t, it is Pt. According to the ideal gas law
n n P
P= RT or =
V V RT
n P0  n  Pt
  = ;   =
 V  t =0 Rt  V  t = t RT

n
 
 V  t =0 A 0 P0
 = =
n A t Pt
 
 V t =t

1 P
 k = In 0
t Pt

67
Case – II:
Let there be a first order reaction, A ⎯⎯
→ B+C. Let us assume all three are gases. We are
required to calculate the value of rate constant based on the following data.
Time 0 t 
Total pressure P0 Pt –

Calculate the expression of rate constant.

Strategy:
Total Pressure means the sum of partial pressures of all the gaseous species present in the
system.
A ( g ) ⎯⎯
→ B(g ) + C (g )
At time = 0 P0 0 0
At time = t P0 − x x x

Since at t = 0 the total pressure is P0, it must also be the partial pressure of A at t = 0, since in the
beginning only the reactant will be present. Let the decrease in pressure of A due to reaction till
time t be x. Thus, at time t, the total pressure would be
(P0 – x) + x + x = P0 + x
P0 + x = Pt
x = Pt – P0
(P0 – x) = P0 – (Pt – P0) = 2P0 – Pt
1 P0
k = In
t 2P0 − Pt

Case – III:
Time 0 t 
Partial pressure of A + B + C – Pt P

Calculate the expression of rate constant.

Strategy:
Let the initial pressure of A be P0 and the pressure of A reacted till time t be x.
A (g) ⎯⎯
→ B(g ) + C (g )
At time = 0 P0 0 0
At time = t P0 − x x x
At time =  0 P0 P0

68
 is the time when the reaction is complete.
At time = t, the total pressure will be
(P0 – x) + x + x = Pt
P0 + x = Pt
x = Pt – P0
At time = , the total pressure will be
P
P = 0 + P0 + P0 = 2P0 ; 2P0 = P ; P0 =
2
P
x = Pt – P0 = Pt –
2
P  P 
(P0 − x) = −  Pt −   = P − Pt
2  2 

1  P 
k = In  
t  2(P − Pt ) 

Case – IV:
Time 0 t 
Partial pressure of B + C – Pt P
Calculate the expression of rate constant.
Strategy:
Let the initial pressure of A be p0 and the amount of pressure reacted till time t be x.
At time infinity, the total pressure of B and C will be
P0 + P0 = 2P0 = P
P
P0 =
2
At time t, the total pressure of B and C will be
x + x = 2x = Pt
Pt
x=
2
1 P / 2
k = In
t P / 2 − Pt / 2

1 P
k = In .
t P − Pt

69
Case – V:
A ⎯⎯
→ B+C

Time T 
Partial pressure of B P2 P3
Find k.
Now let us assume that A, B and C are substances present in a solution. From a solution of A, a
certain amount of the solution (small amount) is taken and titrated with a suitable reagent that
reacts with A. The volume of the reagent used is V1 at t = 0 and V2 at t = t.
Time 0 T
Volume of reagent V1 V2
The reagent reacts only with A. Find k.
It can be understood that the volume of the reagent consumed is directly proportional to the
concentration of A. Therefore the ratio of volume of the reagent consumed against A at t = 0 and
t = t is equal to [A]0/[A]t
1 [A]0 1 V1
 k = In = In .
t [A]t t V2

ILLUSTRATIONS
Illustration 3
A ⎯⎯
→ B+C

Time 0 T
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k.
Solution
We can use a similar logic for solving this one. That is
A ⎯⎯ → B + C
At t = 0 V1 0 0
At t = t V1 − x x x
At t =  0 V1 V1

where x is the volume of the reagent for those moles of a which have been converted into B and
C
 V1 + x = V 2
 x = V 2 – V1

70
 V1 – x = 2V1 – V2
1 [A]0 1 V
 k = In = In
t [A]t t (2V1 − V2 )

This is true only if we make an assumption in the beginning of this problem. The assumption is
that the ‘n’ factor of A, B and C with the reagent is same.
This can be made clear as follows. Let y moles of A be converted to B and C. If y moles of
A require x ml of reagent and if the ‘n’ factor of A is n1 with the reagent then the equivalents of
A converted are n1y and in x ml of reagent n1y equivalents of the reagent are present. Now since
the same y moles of B and C are formed and we find the same volume of reagent used for B and
C, it can be calculated that y moles of B and C also contain n1y equivalent each, which implies
that ‘n’ factor of B and C are also ‘n1’.

2.10 Sequential Or Consecutive Reaction

Reaction in which a reactant gives product, which further goes to give another product, are
called sequential or consecutive reaction.
A ⎯⎯
k1
→ B ⎯⎯
k2
→C
The differential rate equation are
−d[A]
Rate of disappearance of A, = k1[A] …(1)
dt
d[B]
Rate of change of B, = k1 [A] − k 2 [B] …(2)
dt
d[C]
Rate of formation of C, = k 2 [B] …(3)
dt
Integrating equation within the limits we get,
[A]t = [A]0 e − k1t ...(4)
In order to get the value of B at any instant of time, we need to integrate equation. Since
this is a differential equation, we integrate it in the following manner.
First bringing k2[B] to the left side of the equation
d[B]
+ k 2 [B] = k1 [A] …(5)
dt
From equation (8e), we get
d[B]
+ k 2 [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 be multiplied on both sides by an integrating factor e k 2 t .

71
  d[B] 
ek 2 t  + k 2 [B]  = k1[A]0 e(k2 −k1 )t
 dt 
d[B]
ek2t + k 2 [B] ek 2 t = k1[A]0 e(k 2 −k1 )t …(6)
dt

Left hand side of the equation (6) is equal to

d
dt
(
[B]e k 2 t ) (a differential of [B]e k2t
.

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

( )
d [B]ek2t = k1 [A]0 e(k2 −k1 )t dt …(7)

Integrating equation (7) within the limits, 0 and t,

[B]ek 2 t t

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

t
 e(k 2 − k 2 )t  k1
[B]e k2t
= k1[A]0   = [A]0 e(k 2 − k1 )t − 1
 2
k − k 1 0 (k 2 − k 1 )

k1
[B] = [A]0 e− k2 t e(k2 −k1 )t − 1
(k 2 − k1 )

k1
[B] = [A]0 e− k1t − e− k 2 t  …(8)
(k 2 − k1 )

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] − k 2 [B] = 0
dt
k1[A] = k2 [B]
Substituting equation (4) and equation (8), we get
k 2 k1
k1[A]0 e− k1t = [A]0 e− k1t − e− k 2t 
(k 2 − k1 )

Rearranging, we get
(k 2 − k1 ) [E − k1t − e − k 2 t
=
k2 e − k1t

k1
1− = 1 − e(k1 −k 2 )t
k2

1 k
tmax = In 1 …(9)
(k1 − k 2 ) k 2

72
Maximum concentration of B
k1
[B] = [A]0 e− k1t − e− k2t 
(k 2 − k1 )

k1  − k1 −k2
In 1 
k
(k1 − k 2 ) (k1 − k 2 ) k 2
[B] = [A]0 e −e 
(k 2 − k1 )  

k1  − k1 In k1 −k2
In 1 
k

[B] = [A]0 e (k1 −k 2 ) k1 − e (k1 −k 2 ) k 2 

(k 2 − k1 )  

k1  In  k 2  k1  k  k2
In  2  
[B] = [A]0 e  k1  (k1 −k2 ) − e  k1  (k1 −k2 ) 
(k 2 − k1 )  
 
 k1 k2

k1 
 2 k  (k1 − k 2 )  k  (k1 − k 2 )

[B]max = [A]0
 k 
− 2 

…(10)
(k 2 − k1 )
 1   k1  

In order to get the concentration of [C], we substitute [B] from equation ( 8) to (3) and then
integrate within the limits.
d[C] k 2 k1
= k 2 [B] = [A]0 e− k1t − e− k2t 
dt (k 2 − k1 )

k 2 k1
d[C] = [A]0 e− k1t − e− k 2 t  dt
(k 2 − k1 )

Upon integrating within the limits, 0 to t,

[C] t
k 2 k1
 d[C] =
(k 2 − k1 )
[A]0  [e− k1t − e− k 2t ]dt
0 0

t
k 2 k1  e − k1t e − k 2 t 
[C] = [A]0  − 
(k1 − k1 )  − k1 − k 2  0

k 2 k1  e− k1t − 1   e− k 2 t − 1  
[C] = [A]0  − 
(k 2 − k1 )  −k1   −k 2  

k 2 k1  1 − e− k1t   1 − e− k 2t 
[C] = [A]0  − 
(k 2 − k1 )  k1   k2  
[A]0
[C] =  k 2 (1 − e− k1t ) − k1 (1 − e− k 2t  .
(k 2 − k1 )  

2.11 Effect of Temperature on the Reaction Rate (Arrhenius Theory)

Temperature has very marked effect on the reaction rate. It has been found that the rate of most
homogeneous reaction are nearly doubled or tripled by 10° rise in temperature.

73
 k t +10
= 2 to 3 (nearly)
kt

The ratio of the rate constant of a reaction at two different temperatures differing by 10°
i.e. kt+10/kt is known as temperature coefficient of reaction rate. This ratio also depends upon
temperature and two temperatures generally selected are 25°C and 35°C. If a reaction has a
temperature coefficient of reaction rate equal to 3, then raising its temperature from 25°C to
65°C, the rate will increase by nearly 3  3  3  3 i.e. 81 times.
In order to explain the effect of temperature on the reaction rate. Arrhenius proposed a
theory of reaction rate which states as follows:
(i) A chemical reaction takes place by collision between the reactant molecules, and collision
to be effective the colliding molecules must posses some certain minimum energy called
threshold energy of the reaction.
(ii) Reactant molecules having energy equal or greater than the threshold are called active
molecules and those having energy less than the threshold are called passive molecules.
(iii) At a given temperature there exists a dynamic equilibrium between active and passive
molecules. The process of transformation from passive to active molecules being
endothermic, increase of temperature increases the number of active molecules and hence
the reaction.
Passive molecules ‡ˆ ˆˆ †ˆ Active molecules, H = +ve
(iv) Concept of energy of activation (Ea)
The extra amount of energy which the reactant molecules (having energy less than the
threshold) must acquire so that their mutual collision may lead to the breaking of bond(s)
and hence the reaction, is known as energy of activation of the reaction. It is denoted by the
symbol Ea. Thus,
Ea = Threshold energy – Actual average energy
Ea is expressed in kcals mole–1 or kJ mole–1

74
The essence of Arrhenius Theory of
reaction rate is that exists an energy
barrier in the reaction path between Threshold enthalpy
Enthalpy (H) Ea1 or energy
reactant(s) and product(s) and for
Ea2
reaction to occur the reactant HR
Reactant
molecules must climb over the top of H = HP – HR = Ea1 = E a2
HP
the barrier which they do by collision. Products
The existence of energy barrier and Progress of Reaction
concept of Ea can be understood from (or reaction coordinate)
the following diagram.
 HR = Summation of enthalpies of reactants

 H P = Summation of enthalpies of products

H = Enthalpy change during the reaction
Ea1 = Energy of activation of the forward reaction (FR)
Ea2 = Energy of activation of the backward reaction (BR)
Notable Points
(i) H = Energy activation of FR – Energy of activation of BR
(ii) In the diagram mentioned above, FR is exothermic (H is –ve) while BR is endothermic
(H is + ve). The minimum activation energy of FR i.e. any exothermic reaction will be
zero while minimum activation energy for BR i.e. any endothermic reaction will be equal
to H.
(iii) Greater the height of energy barrier, greater will be the energy of activation and more
slower will be the reaction at a given temperature.
(iv) Rate = Collision frequency  fraction of the total number of collision which is effective.
or
= Collision frequency  fraction of the total number of collisions in which K.E. of the
colliding molecules equals to Ea or exceeds over it
Collision frequency is the number of collisions per unit volume per unit time. It is denoted
by the symbol Z. Z is directly proportional to T . By 10° rise in temperature. So, it is the
fraction of the total number of effective, collisions that increases markedly by 10° rise in
temperature resulting into marked increase in the reaction rate.

75
 Arrhenius Equation
The variation equilibrium constant of a reaction with temperature is described by Van’t Hoff
equation of thermodynamics which is as follows
dInK p H
=
dT RT 2
If k1 and k2 be the rate constant of FR and BR, respectively then Kp = k1/k2. Further, H =
Ea1 – Ea2. Putting these in the above equation we get,
dInk1 dInk 2 Ea1 Ea 2
− = −
dT dT RT 2 RT 2
Splitting into two parts
dInk1 Ea1
= + Z (For FR)
dT RT 2
dInk 2 Ea 2
= + Z (For BR)
dT RT 2
where Z is constant
Arrhenius sets Z equal to are and without specifying FR and BR, he gave the following
equation called Arrhenius equation.
dInk E
= a2 …(1)
dT RT
From this equation it is evident that rate of change of logarithm of rate constant with
temperature depends upon the magnitude of energy of activation of the reaction. Higher the Ea1
smaller the rate of change of logarithm rate constant with temperature. That is, rate of the
reaction with low Ea increase slowly with temperature while rate of the reaction with high Ea
increases rapidly with temperature. It is also evident that rate of increase of logarithm of rate
constant will go on decreasing with increase of temperature.
Integrating Equation (1) assuming Ea to be constant we get,
Ea
Ink = − + InA …(2)
RT
k Ea
or In =− …(3)
A RT
or k = Ae–Ea/RT
Equation (3) is integrated form of Arrhenius equation. The constant A called pre-
exponential factor since it is somewhat related with collision frequency. It is a constant for a
given reaction. From Equation (3) it is evident that as T → , k → a. Thus, the constant A is

76
the rate constant of reaction at infinitely temperature. The rate constant goes on increasing with
temperature.
So, when T approaches infinity, k will be maximum. That is to say, A is the maximum rate
constant of a reaction.
It is also be noted that the exponential term i.e. e–Ea/RT measures the fraction of total number
of molecules in the activated state or fraction of the total number of effective collisions. If
n Ea and n be the number of molecules of reactant in the activated state and the total number of

molecules of the reactant present in the reaction vessel respectively, then

n Ea
= e− Ea / RT
n
Equation (2) may also be put as
 Ea  1
log k =  −  + log A …(4)
 2.303R  T
Ea
Since and logA both are constants for a given reaction. So from equation 7 it is evident
2.303R
1 Ea
that a plot of log k vs. will be a straight line of the slope equal to − and intercept equal
T 2.303R

to logA as shown below.

−E a OA
= tan = – tan (180 – ) = −
2.303R OB A
OA
 Ea =  2.303R log K
OB
logA = OA
180 –  
Thus, from this plot Ea and A both can be O
1/T
determined accurately.
If k1 be the rate constant of a reaction at two different temperature T1 and T2 respectively
then from equation (4), we may write
Ea 1
log k1 = . + log A
2.303R T2
Ea 1
log k2 = . + log A
2.303R T2

Subtracting
k2 Ea  1 1 
log =  −  …(5)
k1 2.303R  T1 T2 

77
With the help of this equation it is possible to calculate Ea of a reaction provided, rate constants
of reaction at two different temperatures are known. Alternatively one can calculate rate
constant of a reaction at a given temperature provided that rate constant of the reaction at some
other temperature and also Ea of the reaction is known.

ILLUSTRATIONS
Illustration 4
The half time of first of decomposition of nitramide is 2.1 hour at 15°C.
NH2NO2(aq.) ⎯⎯ → N2O(g) + H2O(l)
If 6.2 g of NH2NO2 is allowed to decompose, calculate.
(i) time taken for NH2NO2 is decompose 99%
(ii) volume of dry N2O produced at this point measured at STP.
Solution
2.303 a
Q t= log10
K (a − x)
1 a 2.303 a
If t = , x = ;  t1/ 2 = log10 …(1)
2 2 K a
a−
2
99a 2.303 a
If t = t99%, x = ; t99% = log10 …(2)
100 K 99a
a−
100
log10 100
By Eqs. (1) and (2), t99% =  t1/ 2
log10 2
2
= 2.1
0.3010
= 13.95 hour
99
Also Mole of N2O formed =  mole of NH2NO2 taken
100
99 6.2
=  = 0.099
100 62
 Volume of N2O formed at STP = 0.099  22.4 = 2.217 L.
Illustration 5
In I order reaction, the concentrations of reactants 10 and 20 minute after the beginning of
reaction corresponds to 13.8 and 8.25 (arbitrary units). Calculate the initial concentration of the
reactants and the velocity constant.
Solution
t = 10, (a – x) = 13.8
t = 20, (a – x) = 8.25
t = 0,

78
 2.303 a
Q K= log10
t a−x
2.303 a
 K= log10 …(1)
10 13.8
2.303 a
K= log10 …(2)
20 8.25
By solving Eqs. (1) and (2),
K = 5.1  10–2 minute–1
a = 23.09.
Illustration 6
Calculate the factor by which the rate of I order reaction is increased for a temperature rise of
10°C from 25°C to 35°C. The energy of activation is 35 kcal mol–1.
Solution
Given,
T2 = 273 + 35 = 308 K, T1 = 273 + 25 = 298 K
Ea = 35  10 cal mol ,
3 1
R = 1.987 cal
K 2 Ea [T2 − T1 ]
Q 2.303 log10 =
K1 R T1T2
K 2 35  103 [308 − 298]
 2.303 log10 =
K1 1.987 308  298
K2
 = 6.812
K1
or K2 = 6.812  K1
 The factor by which the rate constant changes is 6.812
Q Rate = K [ ]
 The factor by which rate changes is also 6.812.

Illustration 7
At 380° C, the half life period for the first order decomposition of H2O2 is 360 min. The energy
of activation of the reaction is 200 kJ mol–1. Calculate the time required for 75% decomposition
at 450°C.
Solution
K1 = 0.693/360 min–1 at 653 and
Ea = 200  103 J, K2 = ? at 723 K, R = 8.314 J
 From 2.303 log10 (K2/K1) = (Ea/R) [(T2 – T1)/(T1T2)
K2 = 0.068 min–1
2.303 100
Now t = log10 = 20.39 minute.
0.068 25

79
 PRACTICE EXERCISE
3. Catalytic decomposition of nitrous oxide by gold at 900°C at an initial pressure of 200 mm
was 50% in 53 minute of 73% in 100 minute.
(a) What is the order of reaction?
(b) Calculate velocity constant.
(c) How much will it decompose in 100 minute at the same temperature but at an initial
pressure of 600 mm?
4. The decomposition of N2O5 according to equation 2N2O5 4NO2(g) + O2(g) is a first
order reaction. After 30 minute from start of the decomposition in a closed vessel, the total
pressure developed is found to be 284.5 mm of Hg and on complete decomposition, the total
pressure is 584.5 mm of Hg. Calculate the rate constant of reaction.
5. A 1st order reaction is 50% complete in 30 minute at 27°C and in 10 minute at 47°C.
Calculate the
(a) Rate constant for reaction at 27°C and 47°C
(b) Energy of activation for the reaction.
(c) Energy of activation for the reverse reaction if heat of reaction is – 50 kJ mol–1.
6. The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the
energy of activation by 75%. What will be effect on rate of reaction at 20°C; other things
being equal?

Answers
3. 1.308  10–2 minute–1 4. 5.206 kt 10–3 minute–1
5. 43.85 kJ mol–1, 93.85 kJ mol–1 6. 2.35  1013

2.12 Catalyst
A catalyst is a substance, which increases the rate of a reaction without itself being consumed at
the end of the reaction, and the phenomenon is called catalysis. There are some catalysts which
decrease the rate of reaction and such catalysts are called negative catalyst. Obviously, the
catalyst accelerating the rate will be positive catalyst. However, the term positive is seldom used
and catalyst itself implies positive catalyst.
Catalyst are generally foreign substances but sometimes one of the product formed may act
as a catalyst and such catalyst is called “auto catalyst” and the phenomenon is called auto
catalysis. Thermal decomposition of KClO3 is found to be accelerated by the presence of MnO2.
Here MnO2 (foreign substance) acts as a catalyst.
2KClO3 + [MnO2] ⎯⎯ → 2KCl + 3O2  + [MnO2]

80
 MnO2 can be received in the same composition and mass at the end of the reaction. In the
permanganate titration of oxalic acid in the presence of bench H2SO4 (acid medium), it is found
that the titration in the beginning there is slow discharge of the colour of permanganate solution
but after sometime the discharge of the colour become faster. This is due to the formation of
MnSO4 during the reaction which acts as a catalyst for the same reaction. Thus, MnSO4 is an
“auto catalyst” for this reaction. This is an example of auto catalyst.
2KMnO4 + 3H2SO4 + 5H2C2O2 ⎯⎯ → K2SO4 + 8H2O + 10CO2

General characteristics of catalyst

(i) A catalyst does not initiate the reaction. It simply fastens it.
(ii) Only a small amount of catalyst can catalyse the reaction.
(iii) A catalyst does not alter the position of equilibrium i.e. magnitude of equilibrium constant
G°. It simply lowers the time needed to attain equilibrium. This means if a reversible
reaction in absence of catalyst completes to go to the extent of 75% till attainment of
equilibrium, and this state of equilibrium is attained in 20 minutes then in presence of a
catalyst also the reaction will go to 75% of completion before the attainment of equilibrium
but the time needed for this will be less than 20 minutes.
(iv) A catalyst drives the reaction through a different route for
which energy barrier is of shortest height and hence Ea is P.E. Ea
a
of lower magnitude. That is, the function of the catalyst is H R
Reactants
to lower down the activation.
HP
Products
Ea = Energy of activation in absence of catalyst.
Ea = Energy of activation in presence of catalyst. Reaction Coordinate

Ea – Ea = lowering of activation energy by catalyst.

If k and kcat be the rate constant of a reaction at a given temperature T, and Ea and Ea are
the activation energies of the reaction in absence and presence of catalyst, respectively, the
k cat Ae− E 'a / RT
=
k Ae− Ea / RT
k cat
= Ae(Ea − E 'a ) / RT
k
k cat
Since Ea, Ea is + so kcat > k. the ratio gives the number of times the rate of reaction
k
will increase by the use of catalyst at a given temperature and this depends upon E a – Ea1.
Greater the value of Ea – Ea1, more number of times kcat is greater than k.
The rate of reaction in the presence of catalyst at any temperature T1 may be made equal to
the rate of reaction in absence of catalyst but for this sake we will have to raise the temperature.

81
Let this temperature be T2 this
− Ea / RT2
e− E'a / RT1 = e
E 'a E a
or = …(6)
T1 T2

2.13 Radioactivity
All radioactive decay follow 1st order kinetics and this is where the similarity ends. This will be
explained in a short while.
We measured the rate of reaction in chemical kinetics based on the rate of change of
concentration of reactant or products. But this procedure will not work for calculating the rate of
radioactive reaction. This is because most of the time the radioactive substance is a solid.
Therefore its concentration would be a constant with time (assuming it to be pure and that the
product does not remain with the reactants). Therefore the rate of radioactive reactions are
measured by calculating the rate of change of nuclei of the radioactive substance. For a
radioactive decay A → B, the rate of reaction is calculated as
−dN A
=  NA
dt
Integrating the differential rate law we get
Nt t
d NA
− =   dt
No
Na o

N0
log = t Where No = number of nuclei of A at t = 0
Nt

Nt = number of nuclei of A at t = t
 = decay constant
The expression can be rearranged to give
Nt = N0e–t …(1)
This suggests that the number of nuclei of radioactive substance A at any instant of time can be
calculated, by knowing the number of nuclei at t = 0, its decay constant and the time.

Half-Life
Just like a 1st order reaction the half life of radioactive decay is given by
0.693
t1/ 2 =


82
Note: Let us start with 10 nuclei. If the half life is 5 minutes, then at the end of first 5 minutes,
number of nuclei would be 5. Now what would be the number of nuclei after next minutes? Will
it be 2.5 or 2 or 3? We can clearly see that it cannot be called as half life. This dilemma can be
overcome by understanding that all formula relating to kinetics are only valid when the sample
size is very large and in such a large sample size, a small difference of 0.5 will be insignificant.

The fact that radioactive decay follows the exponential law implies that this phenomenon is
statistical in nature. Every nucleus in a sample of a radionuclide has a certain probability of
decaying, but there is no way to know in advance which nuclei will actually decay in a particular
time span. If the sample is large enough – that is, if many nuclei are present – the actual fraction
of it that decays in a certain time span will be very close to the probability for any individual
nucleus to decay. To say that, a certain radioisotope has a half–life of 5 hr., then, signifies that
every nucleus of this isotope has a 50 percent chance of decaying in every 5 hr. period. This
does not mean a 100 percent probability of decaying in 10 hr. A nucleus does not have a
memory, and its decay probability per unit time is constant unit it actually does decay. A half
life of 5 hr. implies a 75% probability of decay in 10 hr., which increases to 87.5% in 15 hr, to
93.75% in 20 hr, and so on, because in every 5 hr. interval the probability of decay is 50 percent.

Average–Life Time
Average life time is defined as the life time of a single isolated nucleus. Let us imagine a single
nucleus which decays in 1 second. Assuming 1 second time interval to be very small the rate of
change of nuclei would be 1/1 (because –dN = 1 and dt = 1). We can also see that since
−dN −dN
=N , for a single isolated nucleus N = 1, =  . Therefore in this present case  = 1.
dt dt
−dN
Now let us assume the same nucleus decays in 2 seconds, we can see that i.e.,  is
dt
equal to 1/2. You will also notice that in the 1st case the nucleus survived for 1 second and in the
1
second case it survived for 2 second. Therefore the life time of a single isolated nucleus is .

1
 t av = .


2.14 Activity
Activity by definition is the rate of decay of a radioactive element. It is represented as ‘A’ and is
equal to N. By no means should be confused with rate of change of radioactive nuclei
−dN −dN
represented by . This is because talks about the overall change in the number of nuclei
dt dt
in a given instant of time while activity only talks about that change which is decay. For
example if you go out to a market with Rs. 50 in your pocket and you spend Rs. 20 in 5 minutes

83
then your rate of change of money in the wallet is Rs. 4/ min and in fact the rate of spending the
money is also Rs. 4/min. Here you can see both are same. But if while spending Rs. 20 in 5
mintues, somebody keeps Rs. 10 in your wallet, then the rate of change of money in you wallet
would become Rs. 2.5/min, while the rate of spending the money is Rs. 4/min. This implies that
as long as the radioactive substance is only decaying the rate of change of nuclei and activity are
same and equation (1) in terms activity of a radioactive substance can be written as At = a0 e–t.
dN
But if the radioactive substance is also being produce this = rate of production – activity,
dt
(Of course it’s a different matter, rate of production may or may not be a constant).

2.15 Specific Activity

This is activity per unit mass of the sample. Let radioactive sample weighting w gms have a
w
decay constant . The number of nuclei in the w gms would be  Av , where M = molecular
M
weight of the radioactive substance and Av = Avogadro’s number.
 w 
    Av    Av
 Specific activity =  M =
w M
It should be remembered that if a radioactive sample is pure and the product does not
remain with reactant then specific activity is a constant.

Unit of Activity
The unit of radioactivity of a substance is measured as the rate at which it changes into daughter
nucleus. It has been derived on the scale of disintegration of Radium.
Let us consider 1 g of radius (atomic mass = 226 and t1/2 = 1600 yrs) undergoes decay, then
Rate of decay of radius =   Number of nuclei of Ra in 1 g
0.693 1 6.023 1023
=  = 3.7  1010 dps = 3.7  1010 Becquerrel.
1600  365  24  60  60 226
= 1 curie (Q 1 Ci = 3.7  1010 dps)
= 3.7  104 Rutherford (Q 1 rd = 106dps)
The Si unit of activity is dps of Becquerrel.

*****

84
 MISCELLANEOUS PROBLEMS
OBJECTIVE TYPE
Example 1
Consider a gaseous reaction, the rate of which is given by K[A] [B], the volume of the reaction
vessel containing these gases is suddenly reduced to 1/4th of the initial volume. The rate of
reaction relative to the original rate would be
(a) 16/1 (b) 1/16 (c) 8/1 (d) 1/8
Solution
1
By reducing volume to th the concentration will become 4 times hence rate 16 times.
4
(a)
Example 2
The rate of a reaction increases 4-fold when concentration of reactant is increased 16 times. If
the rate of reaction is 4  10–6 mole L–1 S–1 mole L–1 when concentration of the reactant is 4 
10–4, the rate constant of the reaction will be
(a) 2  10–4 mole1/2 L–1/2 S–1 (b)1  10–2 S–1
(c) 2  10–4 mole–1/2, L1/2 S–1 (d) 25 mole–1 L min–1
Solution
Rate  concen , Rate = k concen
Rate 4  10−6 4  10−6
k= = = = 2  10–4 mole1/2 L–1/2 S–1
(concen)1/ 2 (4  10−4 )1/ 2 2  10−2
(a)
Example 3
A catalyst lowers the activation energy of a reaction from 20 kJ mole–1 to 10 kJ mole–1. The
temperature at which the uncatalysed reaction will have the same rate as that of the catalysed at
27°C is
(a) –123 °C (b) 327 °C (c) 227 °C (d) + 23 °C
Solution
E 'a Ea 10 20
= = =
T1 T2 300 T2
 T2 = 600 K = 327°C
(b)
Example 4
A first order reaction is 87.5% complete in an hour. The rate constant of the reaction is
(a) 0.0346 min–1 (b) 0.0693 h–1 (c) 0.0693 min–1 (d) 0.0346 h–1

Solution

85
 1
For 87.5% change there will be three half-changes. Hence half-time of the reaction will be h=
3
60
= 20 min, since half-time of a first order reaction is a constant independent of initial
3
concentration.
100% ⎯⎯⎯ 20 min
→ 50% ⎯⎯⎯
20 min
→ 25% ⎯⎯⎯
20 min
→ 12.5%
(un reacted)

0.693 0.693
k= = = 0.0346 min–1
t1/ 2 20
(a)
Example 5
The half-life a first order reaction is 24 hours. If we start with 10 M initial concentration of the
reactant then conc. After 96 hours will be
(a) 6.25 M (b) 1.25 M (c) 0.125 M (d) 0.625 M
Solution
96
Number of half-lives = =4
24
10
Concentration remaining after 96 hrs = = 0.625 M
(2) 4
(d)
Example 6
During the particular reaction 10% of the reactant decompose in one hour 20% in two hours
30% in three hours and so on. The unit of the rate constant is
(a) Hour–1 (b) L mol–1 hour–1 (c) mol L–1 hour–1 (d) mol hour–1
Solution
This reaction is a zero order reaction.
(c)
Example 7
The temperature coefficient of a reaction is 2, by what factor the rate of reaction increases when
temperature is increased from 30°C to 80°C.
(a) 16 (b) 32 (c) 64 (d) 128
Solution
k 80
= 25 = 32
k 30
(b)
Example 8
The rate constant, the activation and Arrhenius parameter of a chemical reaction at 25°C are 3 
10–4 s–1, 104.4 kJ mol–1 and 6  1014 s–1 respectively. The value of the rate constant at T →  is
(a) 2  1018 s–1 (b) 6  1014 (c)  (d) 3.6  1030 s–1
Solution
K = Ae–Ea/RT when T ⎯⎯ → 
 value is 6  10 s
14 –1

86
 (b)
Example 9
If t1/2 does not change with initial concentration, then order of the reaction is
(a) zero (b) second (c) first (d) third
Solution
1
t1/ 2  n −1
→ 
K = Ae–Ea/RT when T ⎯⎯
a
(c)

Example 10
A substance undergoes a first order decomposition. The B
K1
decomposition follows two parallel first order reaction as
given A
The percentage distribution of B and C are K2 C
(a) 80% B and 20% C (b) 75% B and 25% C
(c) 90% B and 10% C (d) 60% B and 40% C

Solution
K1 [B]
For parallel reaction =
K 2 [C]
[B] 1.14  10−4 3
= =
[C] 3.8  10−5 1
 % of B = 75  and percentage of C = 25
(b)
Example 11
A tangent drawn on the curve obtained by plotting concentration of product (mole L–1) of a first
order reaction vs. time (min) at the point corresponding to time 20 minute makes an angle to 30°
with concentration axis. Hence the rate of formations of product after 20 minutes will be
(a) 0.580 mole L–1 min–1 (b) 1.723 mole L–1 min–1
(c)0.290 mole L–1 min–1 (d) 0.866 mole L–1 min–1
Solution
Tangent makes an angle of 30° with concentration axis so it must make an angle of 60° with the
time axis
(–ve direction). The slope of the tangent will be tan 60° i.e., 1.723.
(b)

87
Example 12
For reaction 3A ⎯⎯ → products, if is found that the rate of reaction increases 4–fold when
concentration of A is increased 16 times keeping the temperature constant. The order of reaction
is?
(a) 2 (b) 1 (c) 1 (d) 0.5
Solution
The rate data suggests the rate law as follows
Rate  A i.e., r  A1/2
 order = 0.5
(d)
Example 13
The thermal decomposition of acetaldehyde: CH3CHO ⎯⎯
→ CH4 + CO, has rate constant of 1.8
d[CH3CHO]
 10–3 mole–1/2 L1/2 min–1 at a given temperature. How would − will change if
dt
concentration of acetaldehyde is doubled keeping the temperature constant?
(a) will increase by 2828 times (b) will increase by
11.313 times
(c) will not change (d) will increase by 4 times
Solution
Unit of the rate constant mole –1/2L1/2 . min1/2 suggests that the reaction obeys kinetics of 1.5
order.
Rate = k [CH3CHO]3/2
Rate mole L−1 min −1
Or k = = = Mole–1/2, L1/2 . min–1
[CH3CHO]3/ 2 (mole L−1 )3/ 2
So, by doubling the concentration of acetaldehyde the rate will increase 21/5 i.e., 2.828 times.
 (a)
Example 14
The reaction ; 2O3 ⎯⎯ → 3O2, is assigned the following mechanism.
(I) O3 ‡ˆ ˆˆ †ˆ O2 + O
(II) O3 + O ⎯⎯⎯ slow
→ 2O2
The rate law of if the reaction will, therefore be
(a) r  [O3]2 [O2] (b) r  [O3]2 [O2]–1 (c) r  [O3] (d) r  [O3] [O2]–2
Solution
Step II, being r.d.s.
Rate of overall reaction = rate of Step II = KII [O3] [O]
Putting the value of [O] from the equilibrium of Step I,
K II K C [O3 ]2
Rate =
[O 2 ]
 (b)

88
Example 15
For an endothermic reaction where H represents the enthalpy of the reaction, the minimum
value for the energy of activation will be
(a) Less than H (b) zero (c) more than H (d) equal to H
Solution

EP
E H
ER

Reaction coordinate
 (c)
Example 16
The rate law for a reaction between the substances A and B is given by
Rate k [A]n [B]m
On doubling the concentration of A and halving the concentration of B, the ratio of the new rate
to the earlier rate of the reaction will be
1
(a) m + n (b) (n – m) (c) 2(n – m) (d)
2(m + n )
Solution
Earlier rate = k an bm
New rate – k (2 a)n (b)m
New rae 2n a n b m 2− m
= = 2n . 2–m = 2n–m.
Earlier rate a n bm
 (c)

Example 17
The half-life of a reaction is halved as the initial concentration of the reactant is doubled. The
order of reaction is
(a) 0.5 (b) 1 (c) 2 (d) 0
Solution
n −1
1 (t1/ 2 )1 [A 0 ]2n −1 [A 0 ]2 
T1/2  , = = 
[A 0 ]n −1 (t1/ 2 ) 2 [A 0 ]1n −1  [A 0 ]1 
n −1
t  2a 
=  or 2 = (2)n–1
t/2  a 
or n – 1 = 1 or n = 2.
 (c)

89
Example 18
The rate constant of the reaction at temperature 200 K is 10 times less than the rate constant at
400 K. What is the activation energy of the reaction?
(a) 1842.4 R (b) 921.2 R (c) 460.6 R (d) 230.3 R

Solution
At T1 = 200 K, if k1 = k, then
at T2 = 400 K, k2 = 10 k
10k E a  400 − 200 
log =  
k 2.303 R  400  200 
or Ea = 921.2 R
 (b)
Example 19
In the reaction 2A + B ⎯⎯ → A2B, if the concentration of A is doubled and that of B is halved,
then the rate of reaction will
(a) increase by 4 times (b) decrease by 2 times (c) increase by 2 times (d) remain the
same
Solution
Initially rate = k [A]2 [B] = k a2b.
New rate = k (2a)2   = 2 k a2b i.e. increased 2 times.
b
2  
 (c)
Example 20
The rate constant k, for the reaction
1
N 2 O5 (g) ⎯⎯
→ 2NO2 (g) + O2 (g)
2
Is 2.3  10–2 s–1. Which equation given below describes the change of [N2O5] with time? [N2O5]0
and [N2O5]t correspond to the concentration of N2O5 initially and at time t.
(a) [N2O5]t = [N2O5]0 + kt (b) [N2O5]0 = [N2O5]tekt
[N2 O5 ]0
(c) log [N2O5]t = log [N2O5]0 + kt (d) In = kt
[N2 O5 ]t

Solution
1 a 1 C 1 [N O ]
k = In = In 0 = In 2 5 0
t a − x t Ct t [N2O5 ]t
 (d)

90
 SUBJECTIVE TYPE
Example 1
A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the
presence of a catalyst at the rate, the temperature required is 400 K. Calculate the activation
energy of the reaction if the catalyst lowers the activation energy by 20 kJ mol–1.
Solution
Suppose activation energy in the absence of catalyst is Ea and that in the presence of catalyst it is
Eb. Then
K = Ae−Ea / 500R = Ae−Eb / 400R
(as k is same in both the cases).
Ea Eb 4
Hence, = or E b = E a
500 R 400 R 5
4
But Ea – Eb = 20 kJ or E a − E a = 20
5
1
or Ea = 20 or Ea = 100 kJ mol–1.
5
Example 2
At constant temperature and volume, X decomposes as
2X(g) → 3 Y(g) + 2 Z (g)
Px is the partial pressure of X.
Observation Time (in Px (in mm of
No. minutes) Hg)
1 0 800
2 100 400
3 200 200
(i) What is the order of reaction with respect to X?
(ii) Find the time for 75% completion of the reaction
(iii) Find the total pressure when pressure of X is 700 mm of Hg.
Solution
(i) as pressure of X is changing with time, it cannot be a zero order reaction. Let us now check
it for 1st order.
At t = 100 min,
2.303 P 2.303 800
log o = log = 6.932  10–3 min–1
100 Pt 100 400
At t = 200 min,
2.303 800 2.303
k= log = log 4
200 200 800
= 6.932  10–3 min–1
As k comes out to be constant, hence it is a reaction of 1st order.

91
 2.303 100
(ii) t 75% = log
k 100 − 75
2.303
= log 4
6.932  10−3 min −1
= 200 min.
(iii) 2X (g) ⎯⎯
→ 3Y(g) + 2 Z(g)
Initial 800 mm 0 0
aftr time t 800 − 2p 3p 2p
When pressure of X is 700 mm,
800 – 2p = 700 or p = 50 mm
Total pressure = (800 – 2 p) + 3p + 2p
= 800 + 3p = 800 + 3  50 = 950 mm.
Example 3
Show that for a first order reaction time required for 99% completion is twice for the time
required for the completion of 90% of the reaction.
Solution
2.303 100
T99% = log10 …(1)
k 100 − 99
2.303 100
T90% = log10 …(2)
k 100 − 90
By Eq. (1) & (2)
t 99% log10 100
= =2
t 90% log10 10
t99% = 2 t90%.
Example 4
The decomposition of Cl2O7 at 400 K in the gas phase to Cl2 and O2 is of 1st order. After 55 sec
at 400 K the pressure of Cl2O7 falls from 0.062 to 0.044 atm. Calculate.
(1) The rate constant (2) Pressure of Cl2O7 after 100 sec.

Solution
7
Cl2 O7 ⎯⎯→ Cl2 + O 2
2
Mole at t = 0, a 0 0
7x
Mole at t = 55 sec, (a − x) x
2
(a) Since pressure of Cl2O7 is given
a  0.062
(a – x)  0.044
2.303 a
k= log
t a−x
2.303 0.062
= log k = 6.023  10–3 sec–1.
55 0.044

92
(b) Let t = 100 sec, (a – x)  P
2.303 0.062
6.023  10−3 = log10
100 P
P = 0.033 atm.
Example 5
A 22.4 litre flask contains 0.76 mm of ozone at 25°C. Calculate
(i) The concentration of oxygen atoms needed so that the elementary reaction O + O3 → 2O3
having rate
constant equal to 1.5  107 litre mol–1 sec–1 can proceed with a rate of 0.15 mol litre–1 sec–1
(ii) The rate of formation of oxygen under this condition.
Solution
The unit of rate constant suggests the second order for reaction. Thus,
Rate of reaction = K[O3] [O] or 0.15 = 1.5  107  
0.76
 [O]
 0.0821 298  760 
 n P 0.76 
 for O3 = = 
 V RT 0.0821 298  760 
[O] = 2.45  10–4
n/V for O = 2.45  10–4
P
for O = 2.45  10–4
RT
P0 = 2.45  10–4  0.0821  298
= 5.99  10–3 atm
= 5.99  10–3  760 mm = 4.5 mm
1 d[O 2 ] 1
Also, rate of reaction = = rate of formation of O2
2 dt 2
 Rate of formation of O2 = 2  0.15 = 0.30 mol L–1 t–1.
Example 6
(a) In a reaction with initially 0.12 M, the concentration of reaction is reduced to 0.06 M in 10
hour and to
0.03 M in 20 hour.
(i) What is order of reaction? (ii) What is rate constant?
(b) The rate of a first order reaction is 0.04 mol litre–1 s–1 at 10 minute and 0.03 mol litre–1 at
20 minute
after initiation. Find the half life of the reaction.

Solution
2.303 a
(a) Assuming Ist order, i.e., K = log10 a = 0.12 M
t (a − x)

2.303 0.12
(a – x) = 0.06 M For case I : K = log10 = 0.069 hr–1 t = 10 hr
10 0.06

93
 a = 0.12 M
2.303 0.12
(a – x) = 0.03 M For Case II: K = log10 = 0.069 hr −1 t = 20 hr
20 0.03
Reaction is of 1 order and rate constant k = 0.069 hr–1
(b) Rate = K  [A]
0.04 = K[A[10 and 0.03 = K[A]20
[A]10 0.04 4
= =
[A]20 0.03 3

2.303 [A]10
Also t = log when t = 10 min
K [A]20
2.303 4
10 = log
K 3
2.303 4
K= log = 0.288 min–1
10 3
2.693 0.693
t1/ 2 = = = 24.06 min.
K 0.0288

Example 7
The following data represent for the decomposition of NH4NO2 in aqueous solution.
Time in minute 10 15 20 25 
Volume of N2(in 6.25 9.0 11.40 13.65 33.05
mL)
(a)Show that reaction is of 1st order (b)Calculate velocity constant.

Solution
NH 4 NO2(s) → N 2(g) + 2H 2 O( l )
Mole at t = 0 a 0 0
Mole at t = t (a − x) x 2x

the volume of N2 formed at any time is proportional to the amount of NH4NO2 decomposed in
that time.
At t =  VN2 = 33.05 mL  a  33.05
I At t = 10 VN2 = 6.25  x  6.25
II At t = 15 VN2 = 9.0 mL  x  9.0
III At t = 20 VN2 = 11.40 mL  x  11.40
IV At t = 25 VN2 = 13.65 mL  x  13.65

94
 2.303 a
Now use, k = log10
t a−x
Case I
2.303 33.05
k= log10
10 33.05 − 6.25
k = 2.0  10–2 min–1
Similarly, calculate k for each case. The values of k come almost constant and thus showing that
reaction is 1 order. Average of all k value gives rate constant.

*****

95
Exercise - I
OBJECTIVE TYPE QUESTIONS
Multiple choice questions with ONE option correct
1. At 250°C, the half life for the decomposition of N2O5 is 5.7 hour and is independent of
initial pressure of N2O5. The specific rate constant is
0.693 5.7
(a) (b) 0.693  5.7 (c) (d) None
5.7 0.693
a
2. In a first order reaction the was found to be 8 after 10 min. The rate constant is
a−x
(2.303  3log 2) (2.303  2log3)
(a) (b)
10 10
(c) 10  2.303  2 log 3 (d)10  2.303  3 log 2
3. For a reaction A ⎯⎯ → products, initial conc. of A is 2M. After 10 minutes reaction is 10%
completed. If r = k[A] then half life is approximately.
(a) 0.693 (b) 69.3 min (c) 66 min (d) 0.0693 min
4. The rate of formation of C is the following reaction 2A + B ⎯⎯ → 2C is 10 Kg min–1. Hence
the rate of disappearance of A will be (kg/min)
(a) 10 (b) 8 (c) 6.4 (d) 3.2
5. In the presence of catalyst Ea is lowered by 2Kcal at 27°C. Hence rate will be
(a) 20 times (b) 14 times (c) 28 times (d) 2 times
6. For reaction A2 + 2B ⎯⎯ → 2AB. Then order w.r.t. A2 and B are respectively
[A2] [B] Rate (M sec–
1
)
0.1 0.2 1  10–2
0.2 0.2 2  10–2
0.2 0.4 8  10–2
(a) 1, 2 (b) 2, 1 (c) 1, 1 (d) 2, 2
1
7. The plot of log K versus is linear with a slope of
T
Ea Ea
(a) Ea/R (b) – Ea/R (c) (d) −
2.303 R 2.303R
8. The rate of a reaction gets doubled when the temperature changes from 7°C to 17°C. By
what factor will it change when the temperature change from 17°C to 27°C?
(a) 2 (b) 2.1 (c) 1.91 (d) 2.3
9. Two first order reactions have half lives in the ratio of 3 : 2. Calculate the ratio of time
intervals t1 : t2, the time t1 and t2 are the time period for 25% and 75% completion for the
first and second reaction respectively.
(a) 0.311 : 1 (b) 0.420 : 1 (c) 0.273 : 1 (d) 0.119 : 1

96
 → 2NOBr obey’s following mechanism,
10. The reaction, 2NO + Br2 ⎯⎯
NO + Br2 ‡ˆ ˆˆ ˆˆ †ˆ NOBr2
fast

NOBr2 + NO ⎯⎯⎯
slow
→ 2NOBr
The rate expression of the above reaction can be written as
(a) r = k[NO]2 [Br2] (b) r = k[NO] [Br2] (c) r = k[NO] [Br2] (d) r = k[NOBr2]
11. A substance (initial concentration, a) reacts according to zero-order kinetics. The time it
takes for the completion of the reaction is
(a) a/k (b) a/2k (c) k/a (d) 2k/a
12. The order of a reaction and rate constant
for a chemical change having log t50% vs
log t50%
log [A]0 curve as would be

(a) 0, ½ 45°
(b) 1, 1 Log [A] 0
(c) 2, 2
(d) 0, 1

13. Half life (t1) of the first-order reaction and half life (t2) of the second-order reaction are
equal. Hence, assuming [A]0 to be same, the ratio of the rate at the start of the reaction
(assuming same initial concentration of the reactant in both the reactions) would be
(a) 1 (b) 2 (c) 0.693 (d) 1.44
14. The chemical reaction, 2O3 ⎯⎯ → 3O2 proceeds as follows
O3 ‡ˆ ˆˆ †ˆ O2 + O …..(fast)
O + O3 ⎯⎯ → 2O2 ….(slow)
The rate law expression should be
(a) r = k[O3]2 (b) r = k[O3]2 [O2]–1 (c) r = k[O3] [O2] (d) unpredictable
15. The concentration of the reactant A in the reaction A ⎯⎯ → B at different times are given
below
Concentration Time (Minutes)
(M)
0.069 0
0.052 17
0.035 34
0.018 51
The rate constant of the reaction according to the correct order of reaction is
(a) 0.001 M/minute (b) 0.001 minute–1 (c)0.001 minute/M (d)0.001M–1 minute–1

97
Multiple choice questions with MORE THAN ONE option correct
1. The half-period T for the decomposition of ammonia on tungsten wire, was measured for
different initial pressures P of ammonia at 25°C. Then
P (mm 11 21 48 73 120
Hg)
T (sec) 48 92 210 320 525
(a) zero order reaction (b) First order reaction
(c) rate constant for reaction is 0.114 seconds
(d) rate constant for reaction is 1.14 seconds.
2. For an isomerisation reaction A ⎯⎯⎯⎯⎯⎯⎯ → B in gaseous phase, the equilibrium constant at
Catalyst
⎯
60°C is 3.60. Both forward and backward reactions are of first order. Starting with an initial
pressure of P atm, of A, the pressure became 0.25 P atm in 40 minutes. The values of
individual rate constants for the forward (kf) and backward (kb) reactions are
(a) kf = 3.466  10–2 min–1 (b)kf = 9.628  10–3 min–1
(c) kb = 9.628  10–3 min–1 (d)kb = 3.466  10–2 min–1
3. The substance undergoes first order decomposition. The decomposition follows two parallel
first order reaction as
B
K1

A
K2 C
K1 = 1.26  10–4 sec–1 and K2 = 3.8  10–5 sec–1
The percentage distribution of B and C
(a) 76.83% (b) 23.17% C (c) 90% B (d) 40% C
4. A certain reaction obeys the rate equation (in the integrated form) [C – C0(1 – n)] = (n – 1)
(1–n)

kt where C00 is the initial concentration and C is the concentration after time, t.
(a) the unit of k for n = 1 is sec–1 (b)the unit of k for n = 2 is litre mol–1 sec–1
(c) the unit of k for n = 3 is mol litre–1 sec–1(d) the unit of k for n = 3 is litre2 mol–2 sec–1
5. Consider the following case of COMPETING 1ST ORDER REACTIONS
C
K1

A
K2
B
After the start of the reaction at t = 0 with ony a, the [C] is equal to the [D] at all times. The
time in which all three concentrations will be equal is given by
1 1 1 1
(a) t = ln 3 (b) t = l n3 (c) t = ln2 (d) t = ln2
2k1 2k 2 3k1 3k 2

98
6. In acidic medium, the rate of reaction between BrO3– and Br– is given by the expression
d [BrO3− ]
− = k[BrO3− ] [Br − ] [H + ]2
dt
It means
(a) Rate constant of the reaction depends upon the concentration of H+ ions
(b) Rate of reaction is independent of the concentration of the acid added
(c) The change in pH of the solution will affect the rate of reaction
(d) Doubling the concentration of H+ ions will increase the reaction rate by 4 times
7. The rate constant of a reaction is given by
K = 2.1  1010 exp (– 2700/RT)
It means that
2700
(a) log k vs. 1/T wll be a straight line with slope = −
2.303R
(b) log k vs. 1/T will be a straight line with intercept on log k axis = 2.1  1010
(c) The number of effective collisions are 2.1  1010 cm–3 sec–1
(d) Half life of the reaction increases with increase of temperature
8. A catalyst
(a) increases the average kinetic energy of the reacting molecules
(b) decreases the activation energy
(c) alters the reaction mechanism
(d) increases the frequency of collisions of the reacting species
9. The rate law for the reaction
RCl + NaOH ⎯⎯ → ROH + NaCl
Is given by: rate = k [RCl]. The rate of this reaction
(a) is doubled by doubling the concentration of NaOH
(b) is halved by reducing the concentration of RCl by one half
(c) is increased by increasing the temperature of the reaction
(d) is unaffected by change in temperature
10. According to Arrhenius the relationship between rate constant, k and temperature can be
given by
k2 Ea T −T
(1) k = Ae− Ea / RT (2) log =  2 1
k1 2.303R T1T2
Ea
(3) log k = log A − (4) Go = −2.303RTlog K
2.303RT
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99
Exercise – II

ASSERTION & REASON , COMPREHENSION & MATCHING TYPE

Assertion and Reason
In the following question, a statement of Assertion (A) is given which is followed by a
corresponding statement of reason (R). Mark the correct answer out of the following
options/codes.
(a) If both (A) and (R) are true and (R) is the correct explanation of (A).
(b) If both (A) and (R) are true but (R) is not correct explanation of (A).
(c) If (A) is true but (R) is false.
(d) If both (A) and (R) are false.
1. A : Half life of a certain radioactive element is 100 days. After 200 days, fraction left
undecayed will be 50%.
n
N 1
R: =   , where symbols have standard meaning
N0  2 

2. A : Catalysts do not change the heat effect of the reaction i.e., exothermic or endothermic
nature of the reaction.
R : Catalysts do not shift chemical equilibrium in reversible processes, but only help in
attainment of the equilibrium

3. A: Temperature coefficients of most of the reactions lies between 2 and 3.

R: Increase in temperature increases the number of collisions.

4. A: The molecularity of the reaction H2 + Br2 → 2 HBr is 2.

R: The order of the reaction is 3/2.

5. A: For the reaction RCl + NaOH(aq) → ROH + NaCl, the rate of reaction is reduced to half
on reducing the concentration of RCl to half.
R: The rate of the reaction is represented by k [RCl], i.e., it is a first order reaction

Passage Based Questions

Passage – I
Read the following paragraph and answer the following questions numbered
The reaction S2O82− + 3I− ⎯⎯
→ 2SO42− + I3− is of first order both with respect to the persulphate and
iodide ions. Taking the initial concentration as ‘a’ and ‘b’ respectively and taking x as the
concentration of the triodide at time t a differential rate equation can be written.

100
 Two suggested mechanisms for the reaction are
(I) S2O82− + I− ‡ˆ ˆˆ †ˆ SO4 I− + SO42− (fast) (II) S2O82− + I− ⎯⎯
k1
→ S2O8 I3− (slow)
I− + SO4 I− ⎯⎯
k1
→ I2 + SO42− (slow) S2O8I3− ⎯⎯
k2
→ 2 SO42− + I+ (fast)
I− + I2 ⎯⎯
k2
→ I3− (fast) I+ + I− ⎯⎯
k3
→ I2 (fast)
I2 + I− ⎯⎯
k4
→ I3− (fast)
1. The general differential equation for the above reaction is
dx dx
(a) = k [a – x] [b – 3x] (k > 0) (b) = – k [a – x] [ b – 3x] (k > 0)
dt dt
dx dx
(c) = k [a – x] [b – x] (k > 0) (d) = – k [a – x] [b – x] (k > 0)
dt dt
2. How could the progress of this reaction be best monitored?
(a) by monitoring the color of the reaction mixture (b)by titration of I3− with hypo
(c) by precipitation of I– with Ag+ (d) by monitoring the change in pressure
3. Which mechanism is consistent with the facts given about the reaction rate equation?
(a) mechanism (I) (b) mechanism (II) (c) both (I) and (II) (d) neither (I) nor (II)
4. For the reaction I2 + 2S2O32− ⎯⎯
→ S4O62− + 2I−
d[I2 ] 1 d[S2O32− ] d[I2 ] d[S O2− ]
(i) − =− (ii) − = −2 2 3
dt 2 dt dt dt
d[I2 ] d[I ] d[S2O32− ] d[S2O62− ] 1 d[I− ]
(iii) − = −2 2  (iv) =
dt dt dt dt 2 dt
Correct option is
(a) only (i) (b) (i) & (iv) (c) (ii) & (iv) (d) only (iii)
5. Statement (A): In the reaction, I2 + 2S2O32− → S4O62− + 2I− , the rate of disappearance
thiosulphate ions is twice the rate of disappearance of I2.
Statement (B): The rate of disappearance of I2 is one half the rate of disappearance of
S2O32– ions.
(a) Statement (A) & Statement (B) are true
(b)Statement (A) is false & Statement (B) is true
(c) Statement (B) is false & Statement (A) is true
(d)Statement (A) & (B) are False

Passage – II
Arrhenius studied the effect of temperature on the rate of a reaction and postulated that rate
constant varies with temperature exponentially as k = Ae−Ea / RT . For most of the reactions, it was
found that t he temperature coefficient of the reaction lies between 2 to 3. The
method is generally used for finding the activation energy of a reaction. Keeping temperature
constant, the effect of catalyst on the activation energy has also been studied by studying how

101
much the rate of reaction changes in the presence of catalyst. In most of the cases, it is observed
that catalyst lowers the activation energy barrier and increases the rate of reaction.
1. The pre-exponential factor in the Arrhenius equation of a second order reaction has the units
(a) mol L–1 s–1 (b) L mol–1 s–1 (c) s–1 (d) dimensionless
2. Which of the following plot will be linear?
(a) In k versus T with –ve slope (b)k versus 1/T with –ve slope
(c) In k versus 1/T with –ve slope (d) In k versus 1/T with + ve slope
3. If the rate of reaction grows 15.6 times on increasing the temperature by 30 K the
temperature coefficient of the reaction will be nearly
(a) 2 (b) 2.5 (c) 3.0 (d) 3.5
4. If the rate of reaction doubles for 10° rise of temperature from 290 K to 300 K, the activation
energy of the reaction will be approximately
(a) 40 kJ mol–1 (b) 50 kJ mol–1 (c) 60 kJ mol–1 (d) 70 kJ mol–1
5. If x is the fraction of molecules having energy greater than Ea, it will be given by
Ea Ea
(a) x = − (b) In x = (c) x = eEa / RT (d) Any of these
RT RT

Matching Type Questions

1. Match the following
Column I Column II
(a) Decomposition of H2O2 (p) 10t1/2
t 308 K
(b) (q) 1st order
k 298 K
(c) Arrhenius equation (r) Temperature coefficient
k2 Ea  T2 − T1 
(d) t99.9% (s) log =  
k1 2.303 R  T1 T2 
(t) 2 to 3
(a) (a-q), (b-r,t), (c-s), (d-p) (b)(a-r), (b-s), (c-q), (d-p)
(c) (a-s), (b-r), (c-p), (d-q) (d)(a-q), (b-r), (c-p), (d-s)
2. Column I Column II
(a) H2 + I2 → 2HI (p) Order of reaction = 1.5
(b) C6H5N2Cl + H2O → C6H5OH + N2 + HCl (q)Order of reaction = 3
(c) 2FeCl3 + SnCl2 → SnCl4 + 2FeCl2 (r) Order of reaction = 1
(d) H2 + Br2 → 2HBr (s) Order of reaction = 2
(a) (a-q), (b-r,t), (c-s), (d-p) (b) (a-r), (b-s), (c-q), (d-p)
(c) (a-s), (b-r), (c-p), (d-q) (d) (a-s), (b-r), (c-q), (d-p)

*****

102
Exercise - III
SUBJECTIVE TYPE
1. The progress of the reaction with time is presented in the figure. Determine
A ‡ˆ ˆˆ †ˆ nB
(i) the value of n
(ii) the initial rate of conservation of A.

Conc. Mol/l
0.5

0.3

1 3 5 7

Time/Hour
2. The following data are for the reaction A + B products:
Concn A (M) Concn B (M) Initial Rate (mole L–1 s–1)
0.1 0.1 4.0 ×10–4
0.2 0.2 1.6 ×10–3
0.5 0.1 1.0 ×10–2
0.5 0.5 1.0 ×10–2
(a) What is the order with respect to A and B for the reaction?
(b) Calculate the rate constant.
(c) Determine the reaction rate when the concentrations of A and B are 0.2 M and 0.35
M, respectively.
3. At 100°C gaseous reaction is observed to be a first order reaction. One starting with pure
A, at the end of 14 minutes, the total pressure was found to be 264 mm of Hg. After a long
time the total pressure of the system was found to be 450 mm of hg. From the data
calculate;
(i) the initial pressure of A
(ii) the pressure at the end of 14 min.
(iii) the rate constant of the reaction.
(iv) the half-life period of the reaction.
4. The solvolysis of cinnamyl chloride can be studied spectrophotometrically by observing
the decrease in absorbance of the absorption maximum at 260 nm. The following
observations were made in ethanolic sodium hydroxide at 298 K.
Time in minutes 0 10 31 74
Absorbance at 260 nm 4.41 0.38 0.34 0.18 0
What are the order and rate constant of this reaction?

103
5. 1 g 226Ra is placed in an evacuated tube whose volume is 5 c.c. Assuming that each Ra
nucleus yields four He atoms which are retained in the tube, what will be the pressure at
27°C of He produced at the end of a year? t½ for 226Ra is 1590 years.

6. The gas phase decomposition of dimethyl ether follows first order kinetics:
The reaction is carried out in a constant volume container at 500°C and has a half life of
14.5 minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere.
What is the total pressure of the system after 12 minutes? Assume ideal gas behavious.

7. The rate constant for the forward reaction is 1.2 × 10–3 min–1 at 30°C. The enthalpies of
activation and reaction are 85.48 kJ mole–1 and –107.1 kJ mol–1, respectively. The rate
constant for the reverse reaction is 1.2 × 10–4 min–1 at 50°C. what is its value at 40°C.
8. The time required for 10% completion of a first order reaction at 298 K is equal to that
required for its 255 completion at 308 K. If the pre exponential factor for the reaction is
3.56 × 109 s–1, calculate its rate constant at 318 K and also the energy of activation.
9. A sample of uraninite, a uranium containing mineral, was found on analysis to contain
0.214 g of Pb206 for every gram of uranium. Assuming that the lead all resulted from the
radioactive disintegration of the uranium since the geological formation of the uraninite
and that all isotopes of uranium other than 238U can be neglected, estimate the date when
the mineral was formed in the earth’s crust. The half life of 238U is 4.5 × 109 y.
10. In nature a decay chain series starts with 90Th232 and finally terminates at 82Pb208. A
thorium ore sample was found to contain 8 × 10–5 ml of helium at STP and 5 × 10–7 g of
Th232. Find the age of the ore sample assuming the source of helium to be only due to the
decay of Th232. Also assume complete retention of helium within the ore. (Half life of
Th232 = 1.39 × 1010 Y).

*****

104
Exercise – IV
IIT – JEE PROBLEMS

A Subjective Problems
1. The gas phase decomposition of dimethyl ether follows first order kinetics
CH3 – O – CH3 (g) → CH4 (g) + H2(g) + CO(g)
The reaction is carried out in a constant volume container at 500°C and has a half-life of
14.5 minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere.
What is the total pressure of the system after 12 minutes ? Assume ideal gas behaviour.
2. At 380°C, the half-life period for the first order decomposition of H2O2 is 360 min. The
energy of activation of the reaction is 200 kJ mol–1. Calculate the time required for 75%
decomposition at 450°C.
3. The rate constant for the first order decomposition of a certain reaction is described by the
equation
1.25  104 K
log k (s–1) = 14.34 –
T
(i) What is the energy of a activation of this reaction?
(ii) At what temp. will its half-life period be 256 minutes ?
4. The time required for 10% completion of a first order reaction alt 298 K is equal to the
required for its 25% completion at 308 K. If the pre-exponential factor for the reaction is
3.56  109 s–1, calculate its rate constant at 318 K and also the energy of activation.
5. The rate constant of a reaction is 1.5  107 s–1 at 50°C and 4.5  107 s–1 at 100°C. Evaluate
the Arrhenius parameters A and Ea.
6. For the reaction N2O5(g) = 2 NO2 (g) + 0.5 O2(g), calculate the mole fraction of N2O5(g)
decomposed at a constant volume and temperature, if the initial pressure is 600 mm Hg and
the pressure at any time is 960 mm Hg. Assume ideal gas behaviour.
7. The rate constant for an isomerisation reaction. A → B is 4.5  10–3 min–1. If the initial
concentration of A is 1 M, calculate the rate of reaction after 1 h.
8. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the
presence of a catalyst at the same rate, the temperature required is 400 K. Calculate the
activation energy of the reaction if the catalyst lowers the activation energy by 20 kJ mol–1.

105
9. For the reaction, A + B → Products, the following initial rates were obtained at various
given initial concentrations
S. No. [A] [B] Rate (mol L–1
sec–1)
1. 0.1 0.1 0.05
2. 0.2 0.1 0.10
3. 0.1 0.2 0.05

Write rate law and find the rate constant of the above reaction.
10. At constant temperature and volume, X decomposes as
2X (g) → 3Y(g) + 2 Z (g)
Px is the partial pressure of X.

Observation Time (in Px (in mm of

No. minutes) Hg)
1. 0 800
2. 100 400
3. 200 200
(i) What is the order of reaction with respect to X ?
(ii) Find the time for 75% completion of the reaction.
(iii) Find the total pressure when pressure of X is 700 mm of Hg

*****

106
 Answers

Exercise – I
Only One Option is correct
1. (a) 2. (a) 3. (c) 4. (b) 5. (c)
6. (a) 7. (d) 8. (c) 9. (a) 10. (a)
11. (a) 12. (a) 13. (c) 14. (b) 15. (a)

More Than One Option is correct

1. (a, c) 2. (a, c) 3. (a, b) 4. (a, b, d) 5. (a, b)
6. (c, d) 7. (a, b) 8. (b, c) 9. (b, c) 10. (a,b,c)

Exercise – II
Assertion and Reason
1. (a) 2. (c) 3. (b) 4. (b) 5. (c)
Passage – I
1. (a) 2. (b) 3. (b) 4. (b) 5. (a)
Passage – II
1. (b) 2. (c) 3. (a) 4. (b) 5. (b)

Matching Type Questions

1. (a ) 2. (d)
Exercise - III
Subjective Type
1. (i) 2, (ii) 0.1 mol L–1 hr–1
2. (a) a = 2, b = 0, (b) 4 ×10–2 mol L–1 sec–1, (c) 1.6 ×10–3 mol L–1 sec–1
3. (i) 150 mm/Hg, (ii) 93 mm/Hg (iii) 3.415 ×10–2 min–1, (iv) 20.3 min
4. First order; 1.01 +10–4 sec–1 5. 37.96 ×10–3
6. 0.7488 atm 7. 1.21 × 10–5 min–1
8. 9.22 × 10–4 sec–1, 18.33 Kcal mol–1 9. 1.4 × 109 yrs.
10. 4.89 × 109 yrs.

Exercise - IV
IIT-JEE Level Problem
Section - A
1. 0.749 atm 2. 20.36 min 3. (i) 239.34 kJ mol–1 (ii) 669 K
4. k = 9.3  10–4 s–1 5. (i) 22.01 kJ mol–1 (ii) 5.433  1010 s–1
6. 0.4 7. 3.44  10 mol L–1 min–1
–3

8. 100 kJ mol–1 9. 0.5 s–1 10. (i) 6.932  10–3 min–1 (ii) 200 min. (iii) 950 mm

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107