Chemical Kinetics Theory

Chemical Kinetics
Introduction :
In the thermodynamics, we have studied whether a reaction will take place or not and if it does then
upto what extent. In this chapter (chemical kinetics) we will study about how fast a chemical reaction
takes place and what are the different factors affecting this rate of chemical reaction. How to optimise
the conditions as to maximise the output in optimum time. The last part of chapter will be dealing with
the mechanism of a chemical reaction and catalysis.
Section (A) : Rate of chemical reaction and Dependence of Rate : Basic

Rate/Velocity of chemical reaction :
The rate of change of concentration with time of different chemical species taking part in a chemical
reaction is known as rate of reaction of that species.
c mol / lit.
Rate = = = mol lit–1 time–1 = mol dm–3 time–1
t sec
For gaseous reactions, when concentration of gases is expressed in terms of their partial pressure,
then units of rate equation will be atms–1.
Rate is always defined in such a manner so that it is always a positive quantity.
Types of Rates of chemical reaction :
For a reaction R  P
Total change in concentration c  [R]  [P]
Average rate = = =– =
Total time taken t t t
Instantaneous rate : rate of reaction at a particular instant.
 c  dc d[R] d[P]
Rinstantaneous = lim   = =– =
t 0  t  dt dt dt
Instantaneous rate can be determined by drawing a tangent at time t on curve drawn for concentration
versus time.
Initial Rate : Instantaneous rate at ‘t = 0’ is called initial rate [slope of tangent at t = 0].
Relation between reaction rates of different species involved in a reaction :

For the reaction : N2 + 3H2  2NH3
d[N2 ] d[H2 ]
Rate of reaction of N2 = – ; Rate of reaction of H2 = –
dt dt
d[NH3 ]
Rate of reaction of NH3 =
dt
These rates are not all equal. Therefore by convention the rate of a reaction is defined as
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
Rate of reaction = – =– =
dt 3 dt 2 dt
Note : Rate of reaction value is dependent on the stoichiometric coefficients used in the reaction while
rate of any species will be fixed value under given conditions.
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Chemical Kinetics
Ex-1. From the concentrations of R at different times given below, calculate the average rate of the reaction:
RP during different intervals of time.
t/s 0 5 10 20 30
103 × [R]/mol L–1 160 80 40 10 2.5
Sol. We can determine the difference in concentration over different intervals of time and thus determine the
rate by dividing [R] by t.
[R]1  103 [R]2  103 t2 t1 rav  103 [R2  R1]  103
=
mol L1 mol L1 s s mol L1 s 1 [t 2  t1]
160 80 5 0 16
80 40 10 5 8
40 10 20 10 3
10 2.5 30 20 0.75
Factors affecting rate of chemical reaction :

1. Concentration 2. Temperature 3. Nature of reactants and products
4. Catalyst 5. pH of the solution 6. Dielectric constant of the medium.
7. Radiations/light 8. Pressure 9. Electrical and magnetic field.
The first four factors generally affect rate of almost all reactions while other factors are specific to some
reactions only.
1. Effect of concentration : We known from law of mass action that Rate is
proportional to concentration of reactants. “So rate of reaction decreases with
passage of time, since concentration of reactants decreases.
2. Effect of temperature : Most of the chemical reactions are accelerated by
increases in T. This will be discussed in detail further.
3. Effect of nature of reactants and Products :

(a) Physical state of reactants :
Gaseous state > Liquid state > Solid state
Decreasing order of rate of reaction.
Because collisions in homogeneous system are more effective than heterogenous system.
(b) Physical size of reactants : As we decreases the particle size rate of reaction increases since
surface area increases.
(c) Chemical nature of reactants :
 If more bonds are to be broken, the rate of reaction will be slow.
 Similarly bond strength is more, rate of reaction will be slow.
4. Effect of Catalyst :
 Presence of positive catalyst lower down the activation energy hence increases the rate of
reaction.
 Presence of negative catalyst increases activation energy hence decreases the rate of
reaction.
5. Effect of pH of solution : Few reactions take place only in a particular medium.
3
(Tl )
Ex. Fe(CN)64–   [Fe(CN)6]3–
This reaction takes place with appreciable rate in acidic medium, but does not take place in basic
medium.
6. Effect of dielectric constant of the medium : More is the dielectric constant of the medium greater
will be the rate of ionic reactions.
7. Effect of radiations/light : Radiation are useful for photochemical reaction.
8. Effect of pressure : Pressure is important factor for gaseous reaction.
9. Effect of electrical & Magnetic field : Electric and magnetic fields are rate determining factors if a
reaction involves polar species.
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Chemical Kinetics
Rate Law (Dependence of rate on concentration of reactants) :
The representation of rate of reaction in terms of the concentration of the reactants is called the rate
law.
It can only be established by experiments.
Generally rate law expressions are not simple and these may differ for the same reaction on conditions
under which the reaction is being carried out.
But for large number of reactions starting with pure reactants we can obtain simple rate laws. For these
reactions :
Rate  (conc.)order
Rate = K (conc.)order This is the differential rate equation or rate expression/Rate law.
Where K = Rate constant = specific reaction rate = rate of reaction when concentration is unity
unit of K = (conc)1– order time–1
K depend on temperature only and not on concentration.
Note : Value of K is a constant for a given reaction, depends only on temperature.
Order of reaction :
Let there be a reaction, m1A + m2B  products.
Now, if on the basis of experiment, we find that
R  [A]P [B]q where p may or may not be equal to m 1 and similarly q may or may not be equal to m 2.
p is order of reaction with respect to reactant A and q is order of reaction with respect to reactant B and
(p + q) is overall order of the reaction.
Note : Order of a reaction can be ‘zero’ or any whole number, it can be a fractional number and it can even be
negative with respect to a particular reactant. But overall order is not found to be negative for any
reaction till observed.
Examples showing different values of order of reactions :
Reaction Rate law Order
(i) 2N2O5 (g)  4NO2 (g) + O2 (g) R = K[N2O5]1 1
(ii) – – – – + 2
5Br (aq) + BrO3 (aq) + 6H (aq) 3Br2() + 3H2O() R= K[Br ] [BrO3 ] [H ]
+ 1+1+2=4
(iii) H2 (Para)  H2 (ortho) R = K[H2(Para)]3/2 3/2
(iv) NO2 (g) + CO(g)  NO (g) + CO2 (g) R = K[NO2]2[CO]0 2+0=2
(v) 2O3(g)  3O2 (g) R = K[O3]2 [O2]–1 2–1=1
h 0 0
(vi) H2 + Cl2   2 HCl R = K[H2] [Cl2] 0+0=0
The reaction (ii) does not take place in one single step. It is almost impossible for all the 12 molecules
of the reactants to be in a state of encounter simultaneously. Such a reaction is called complex
reaction and takes places in a sequence of a number of elementary reactions. For an elementary
reaction the sum of stoichiometric coefficients = order of the reactions. But for complex reactions order
is to be experimentally calculated.
 dC K1C
Ex-2. The rate of a certain reaction depends on concentration according to the equation : =
dt 1  K 2C
What will be the order of reaction, when concentration (C) is : (a) very-very high, (b) very-very low.
 dC K1C K1
Sol. (a) = =
dt 1  K 2C 1
 K2
C
1
if C is very-very high then being small may be neglected.
C
 dC K
 = 1 = constant, i.e., zero order reaction.
dt K2
(b) If C is very-very low 1 + K2C  K
 dC KC K 
  = 1 =  1  × concentration i.e.,  order reaction.
dt K  K 
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Chemical Kinetics
Section (B) : Integrated rate law : Zero and First Order Reaction
(a) Zero order reactions :
For a zero order reaction
General rate law is, Rate = k [conc.]0 = constant

If C0 is the initial concentration of a reactant and Ct is the concentration at time ‘t’ then
C0  C t
Rate = k = or kt = C0 – Ct or Ct = C0 – kt
't'
Unit of K is same as that of Rate = mol lit–1 sec–1.
C0
Time for completion =
k
C0 C C0
t1/2 (half life period) at t1/2 , Ct = , so kt1/2 = 0  t1/2 =
2 2 2k
 t1/2  C0
Examples of zero order reactions :
Generally decomposition of gases on metal surfaces at high concentrations follow zero order kinetics.
Ni
2PH3 (g)  2P + 3H2 Rate = K [PH3]º
2H (g) 
 H2 +  2
Au
Pt
2NH3(g)  N2 + 3H2
hv
H2 + Cl2   2HCl Rate = R [H2]º [Cl2]º
(b) First Order Reactions :
(i) Let a 1st order reaction is
A  Products
‘a’ 0 t =0
‘a–x’ ............ t = ‘t’
dx
Let be the rate of reaction at time ‘t’
dt
dx dx
 = k (a–x)1 or = kdt.
dt ax
2.303 a 2.303 C
On solving t = log or k= log 0
k ax t Ct
2.303 2C 2.303log2 ln2 0.693

Half life time (t1/2) k = log 0  t1/2 = = =
t1/ 2 C0 k k k
 Half life period for a 1st order reaction is a constant quantity.
Graphical representation :
2.303 2.303
t=– log Ct + log C0
k k
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Chemical Kinetics
First order growth reaction :

For bacteria multiplication or virus growth use following concept
Consider a growth reaction
Time Population (or colony)
0 a
t (a + x)
dx dx
= k (a + x) or = kdt
dt (a  x)
on integration
loge (a + x) = kt + C at t = 0 ; x = 0  C = loge a
a  a 
kt = – loge = – 2.303 log10 
(a  x)  (a  x) 
2.303 ax
k= log10 
t  a 
Generation time :
0.693
At t = generation time, x = a  t=
K
Examples of 1st order reactions :

1. Decomposition of azoisopropane

=N– (g)   N2(g) + C6H14 (g)
2. Conversion of N–chloro acetanilide into p–chloroacetanilide
HCl


1
3. H2O2  H2O + O2 (g)
2
4. NH4 NO2 2H2O + N2 (g)
5. Radioactive decay
All radioactive decays are always first order kinetics.
88 Ra  86 Ra + 2H
226 222 4
t0.75
Ex-3. Calculate for a 1st order reaction :
t0.50
2.303 C 2.303 C0 t3 / 4 log4 2log2
Sol. k= log 0 = log   = = =2
t3 / 4 1 t1/ 2 C0 t1/ 2 log2 log2
C0
4 2
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Chemical Kinetics
Ex-4. At least how many half-lives should elapse for a 1st order reaction A products so that the reaction is at
least 95% completed ? (log 2 = 0.3)
(A) 4 (B) 5 (C) 6 (D) 7
t1/ 2 t1/ 2 t1/ 2 t1/ 2 t1/ 2
Sol. (B) 100   50   25   12.5   6.25   3.125
0% 50% 75% 87.5% 93.75% 96.875%
Section (C) : Integrated Rate law : Second Order & Pseudo first order reaction
(a) Second Order reaction :
2nd order Reactions
Two types
A + A  products A + B  products.
a a a b 0
(a – x) (a –x) a–x b–x
dx Rate law
 = k (a–x)2
dt dx
= k (a – x) (b – x)
x dt
dx
  =  kdt  x t
2 dx
0 (a  x)  (a  x) =  kdt
x 0
(b  x) 0
 1 
  = kt
 (a  x)  0
1 1 1 1
 – = kt or – = kt
(a  x) a Ct C0
(b) Pseudo first order reaction :

A second order (or of higher order) reactions can be converted into a first order reaction if the other
reactant is taken in large excess. Such first order reactions are known as pseudo first order reactions.
 For A + B  Products [Rate = K [A]1 [B]1 ]
2.303 b(a  x)
k= log
t(a  b) a(b  x)
Now if ‘B’ is taken in large excess b > > a.
2.303 (a  x) 2.303 a
 k= log  k= log
bt a bt ax
2.303 a 2.303 a
 ‘b’ is very large can be taken as constant  kb = log  k = log
t ax t ax
  k is pseudo first order rate constant  K’ will have units of first order  K will have units of second
order.
 Examples of Pseudo 1st order reactions :
(a) Hydrolysis of canesugar :
C12H12O11 + H2O   C6H12O6 + C6H12O6
sucrose excess glucose fractose
(b) Hydrolysis of esters :
H
CH3COOCH3 + H2O 
 CH3COOH + CH3OH
excess
Ex-5. Hydrolysis of methyl acetate in aqueous solution has been studied by titrating the liberated acetic acid
against sodium hydroxide. The concentration of the ester at different times is given below :
t/min 0 30 60 90
c/M 0.8500 0.8004 0.7538 0.7096.
Show that it follows a pseudo first order reaction as the concentration of H 2O remains nearly constant
(51.2 M) during the course of the reaction. What is the value of k in the equation?
rate = k [CH3COOCH3] [H2O]
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Chemical Kinetics
Sol. For pseudo first order reaction, the reaction should be first order with respect to the ester when
[H2O] = constant. From the above data we note
t c k{H2O] = min–1
0 0.8500 –
30 0.8004 2.004 × 10–3
60 0.7538 2.002 × 10–3
90 0.7096 2.005 × 10–3
It can be seen that k [H2O] is constant and equal to 2.004 × 10–3 min–1 and hence it is pseudo first order
reaction. We can now determine k from
k [H2O] = 2.004 × 10–3 min–1
k [51.2 M] = 2.004 × 10–3 min–1
k = 3.914 × 10–5 M–1 min–1
It has the units of a second order reaction.
Table : Characteristics of Zero, First, Second and nth Order Reactions of the Type A  Products
Zero Order First-Order Second-Order nth order
d[A] d[A] d[A] d[A]
Differential Rate law = k[A]0 = k[A] = k[A]2 = k[A]n
dt dt dt dt
1 1
1 1 n 1
– =
(Integrated Rate law) [A]t = [A]0 – kt In [A]t = –kt + In [A]0 = kt + (A t ) (A 0 )n1
[A]t [A]0
(n – 1)kt
1 1
Linear graph [A]t v/s t In [A] v/s t v/s t v/s t
[A] (A t )n1
[A]0 0.693 1
t1/2 = t1/2 = t1/2 = 1
Half-life 2k k k[A]0 t1/2 
(A 0 )n1
(depends on [A]0) (independent of [A]0) (depends on [A]0)
(conc.)1–n
Unit mol L–1 s–1 s–1 mol–1 Ls–1
t
Graphical comparison of different orders
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Chemical Kinetics
Section (D) : Experimental method to calculate order and rate law of reaction and
methods to monitor the progress of reaction
Methods to determine order of a reaction :
(A) Initial rate method :
 By comparison of different initial rates of a reaction by varying the concentration
of one of the reactants while others are kept constant
r = k [A]a [B]b [C]c if [B] = constant
[C] = constant
then for two different initial concentrations of A we have
r01 = k [A0]1a r02 = k [A0]2a      
a
r01  [A ] 
    0 1
r02  [A 0 ]2 
Or in log form we have a=


log r01 r02 
log [A 0 ]1 [A 0 ]2 
(B) integrated rate law method :

 It is method of hit and trial. By checking where the kinetic data (experimental data) best fits into which
integrated rate law, we determine the order. It can also be done graphically.
Ex-6. The rate of decomposition of N2O5 in CCl4 solution has been studied at 318 K and the following results
have been obtained :
t/min 0 135 342 683 1693
c/M 2.08 1.91 1.67 1.35 0.57
Find the order of the reaction and calculate its rate constant. What is the half-life period?
Sol. It can be shown that these data will not satisfy the integrated rate law of zero order. We now try
ln(c 0 / c)
integrated first order equation i.e., k=
t
ln(c 0 / c)
t/min c/M k= min–1
t
0 2.08 6.32 × 10–4
135 1.91 6.30 × 10–4
342 1.67 6.32 × 10–4
683 1.35 6.32 × 10–4
1693 0.57 6.31 × 10–4
It can be seen that the value of k is almost constant for all the experimental results and hence it is first
order reaction with k = 6.31 × 10–4 min–1 .
0.693
t1/2 = = 1.094 × 103 min–1
6.31  104 min1
Graphical method: Alternatively, if we draw a graph between ln c against t, we obtain a straight line
with slope = – k.
(C) Method of half lives :


 The half lives of each order is unique so by comparing half lives we can determine order
1 t1/ 2 (C'0 )n1
for nth order reaction t1/2  n 1
 =
[C0 ] '
t1/ 2 (C0 )n1
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Chemical Kinetics
Ex-7. In the reduction of nitric gas with hydrogen, the reaction was found to be 50% complete in 210 seconds
when the initial pressure of the mixture was 200 mm. In a second experiment the time of half reaction
was 140 seconds when the initial pressure was 300 mm. Calculate the total order of the reaction.
1
Sol. For a nth order reaction (n  1), t1/2 
c n01
n 1
210  300 
=  n=2
140  200 
Methods to monitor the progress of the reaction :

(A) Pressure measurement :
Progress of gaseous reaction can be monitored by measuring total pressure at a fixed volume &
temperature.
This method can applied for those reaction also in which a gas is produced because of decomposition
of a solid or liquid. We can get an idea about the concentration of reacting species at a particular time
by measuring pressure.
 The pressure data can be given in terms of
(i) Partial pressure of the reactant (ii) Total pressure of the reaction system
Ex-8. Find the expression for K in terms of P0, Pt and n

Sol. Let there is a 1st order reaction
A(g)   nB(g)
Let initial pressure at time t P0 0 t=0
PA = (P0 – x) nx
 Pt (Total pressure at time ‘t’) = P0 – x + nx = P0 + (n – 1) x
Pt  P0
 x=
n 1
Pt  P0 P n  Pt
 PA = P0 – = 0
n 1 n 1
nP0  Pt
 a  p0 & a – x  PA =
n 1
2.303 P (n  1)
 k= log 0
t nP0  Pt
Final total pressure after infinite time = Pf = nP0
 Formula is not applicable when n = 1, the value of n can be fractional also.
 Do not remember the formula but derive it for each question.
(B) Volume measurement :
(i) By measuring the volume of product formed we can monitor the progress of reactions.
Ex-9. Study of a reaction whose progress is monitored by measuring the volume of a escaping gas.

NH4NO2 (s)   2H2O () + N2 (g)
Sol. Let, Vt be the volume of N2 collected at time ‘t’
V = be the volume of N2, collected at the end of the reaction.
a V and x Vt
(a – x)  V – Vt
2.303 V
 k= log
t V  Vt
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Chemical Kinetics
Section (E) : Method to monitor the progress of Reactions (Titration Method and
Optical Activity Method)
(ii) By titration method :
By measuring the volume of titrating agent we can monitor amount of reactant remaining or
amount of product formed at any time. It is the titre value. Here the milliequivalent or millimoles
are calculated using valence factors.
Ex-10. 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 permagnate required to react with a definite volume of
hydrogen peroxide solution.

Sol. The equation for a first order reaction is 2H2O2   2H2O () + O2 (g)
the volume of KMnO4 used, evidently corresponds to the undecomposed hydrogen peroxide.
Hence the volume of KMnO4 used, at zero time corresponds to the initial concentration a and the
volume used after time t, corresponds to (a – x) at that time. Inserting these values in the above
equation, we get
2.303 25
When t = 10 min. k1 = log = 0.022318 min–1 = 0.000372 s–1
10 20.0
2.303 25
when t = 20 min. k1 = log = 0.023265 min–1 = 0.000387 s–1
20 15.7
2.303 25
30 12.5
2.303 25
40 9.6
The constancy of k, shows that the decomposition of H 2O2 in aqueous solution is a first order reaction.
The average value of the rate constant is 0.0003879 s–1.
Ex-11. Conversion of N-chloro acetanilide into p-chloroacetanilide
HCl


The above reaction is first order reaction and its progress is monitored by iodometric titration in which
liberated iodine is titrated against a standard solution of Hypo using starch as indicator. Given that in
this reaction KI does not react with the product (p–chloro acetanilide). Calculate the rate constant of the
reaction. Given that volume of hypo consumed at t = 0 is V0 and at time ‘t’, Vt
Sol. Let, V0 = volume of hypo consumed at t = 0
Similarly Vt = volume of hypo consumed at t = ‘t’
 a  V0 { K reacts with the reactant only}
a – x  Vt
2.303 V
k= log 0
t Vt
Ex-12. Study of acid hydrolysis of an ester.


H
CH3COOCH3 + H2O (excess)  CH3COOH + CH3OH
(HCl)
The progress of this reaction is monitored or determined by titrating the reaction mixture at different
time intervals against a standard solution of NaOH using phenolphthalein as indicator. Find out rate
constant of the reaction in terms of volume of NaOH consumed at t = 0, V0, at t = , V & at time t, Vt.
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Chemical Kinetics
Sol. Let, V0 = vol. of NaOH used at t = 0 [this is exclusively for HCl.]
Vt = vol. of NaOH used at ‘t’
V = vol. of NaOH used at t = 
a  V – V0
a – x  V – Vt
x  Vt – V0
2.303 V V
a  V – V0 ; k= log  0
t V  Vt
(C) Optical rotation measurement :

It is used for optically active sample. It is applicable if there is at least one optically active species
involved in chemical reaction.
 The optically active species may be present in reactant or product.
It is found that (r  r0 )  a (a = initial concentration, x = amount consumed)
(r  rt )  (a  x)
where are r0, rt, r are angle of optical rotation at time t = 0, t = t and t = 
Ex-13. Study of hydrolysis of sucrose progress of this reaction is monitored with the help of polarimeter
because a solution of sucrose is dextrorotatory and on hydrolysis, the mixture of glucose as fructose
obtained becomes laevorotatory. That’s why this reaction is also known as inversion of cane sugar.

H
C12H22O11 + H2O   C6H12O6 + C6H12O6
excess glucose fructose
Sp. rotation +66.5º +52.7º –92.4º
Let the readings in the polarimeter are
t = 0, 0 ; t = ‘t’, t and at t =  
Then calculate rate constant ‘k’ in terms of these readings.
Sol. The principle of the experiment is that change in the rotation is directly proportional to the amount of
sugar hydrolysed.
 a  0 –  ; a – x  t – 
2.303   
k= log  0  
t   t   
Section (F) : Complication in 1st Order Reaction

PARALLEL 1st ORDER REACTION OR COMPETING FIRST-ORDER REACTIONS
At t=0 [A] = a [B] = [C] = 0

Calculate effective t1/2 for [A], [B], [C] & [B] / [C]
d[B] d[C]
= k1 [A] ; = k2 [A]
dt dt
 d[A] d[B] d[C]
= +
dt dt dt
 d[A]
= (k1 + k2 ) [A] = keff [A]
dt
keff = k1 + k2
n2 n2 n2
= + (where T represent half life)
Teff T1 T2
ADVCHK - 11
Chemical Kinetics
1 1 1
= + (remember)
Teff T1 T2
Now, [A]t = aekeff t = ae(k1 k2 )t

d[B]
= k1 [A]
dt
d[B]
= k1 ae(k1 k2 )t
dt
 ka 
[B] =  1  (1 – e(k1 k2 )t )
 k1  k 2 
k 2a
similarly [C] = (1 – e(k1 k2 )t )
k1  k 2
[B] k
= 1 (remember)
[C] k2
keff = k1 + k2
Aeff .e–Ea/RT = A1 e–Ea1/RT + A2e–Ea2/RT
on differentiating
E a  1 Ea  1 Ea  1
– Aeff.e–Ea/RT = – 1   A1 e–Ea1/RT – 2   A2e–Ea2/RT
R  T 2  R  T2  R  T2 
Ea Ea1 Ea2
× keff = k1 + k2
RT 2 RT 2 RT 2
Ea × keff = Ea1 k1 + Ea2 k2
Ea1k1  Ea2 k 2
Ea =
k1  k 2
Section (G) : Temperature dependence of rate

Effect of temperature on rate of reaction :
In early days the effect of temperature on reaction rate was expressed in terms of temperature
coefficient which was defined as the ratio of rate of reaction at two different temperature differing by
10ºC (usually these temperatures were taken as 25ºC and 35ºC)
K t  10
T.C. =  2 to 3 (for most of the reactions)
Kt
k 40ºC
Ex-14. For a reaction T.C. = 2, Calculate for this reaction.
k 25ºC
t 15 3
k2
Sol.  (T.C.)10  (2)10  (2) 2  8
k1
  But the method of temperature coefficient was not exact and to explain the effect of
temperature on reaction rate new theory was evolved
Arrhenius theory of reaction rate :

 It was developed by Max Trautz and William lewis.
It gives insight in to the energetics and mechanistic aspects of reactions.
It is based upon kinetic theory of gases. 
 Arrhenius proposed a theory of reaction rate which states as follows :
 A chemical reaction takes place due to the collision among reactant molecules. The number of
collisions taking place per second per unit volume of the reaction mixture is known as collision
frequency (Z).
 Every collision does not bring a chemical change. The collision that actually produce the
products are effective collision. For a collision to be effective the following two barriers are to be
cleared.
ADVCHK - 12
Chemical Kinetics
 Energy barrier : The minimum amount of energy which the colliding molecules must possess as to
make the chemical reaction to occur is known as threshold energy.
“The minimum amount of energy required by reactant molecules to participate in a reaction is called
activation energy (Ea)”
 Orientation barrier : Energy alone does not determine the effectiveness of the collision. The reacting
molecules must collide in proper direction to make collision effective. Following diagrams can explain
importance of suitable direction for collision.
head-on collision
Transition Product
Reactants state
approaching
A A
A A
A A
B B
B B B B
Reactants
Transition Product
state
 Collision to be effective the colliding molecules must possess some certain minimum
energy called threshold energy of the reaction.
 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.
 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 Active molecules, H = +ve
 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 energy 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.
 The essence of Arrhenius Theory of reaction rate is that there exists an energy barrier in the
reaction path between reactant(s) and product(s) and for reaction to occur the reactant
molecules must climb over the top of the barrier which they do by collision. The existence of
energy barrier and concept of Ea can be understood from the following diagram.
ADVCHK - 13
Chemical Kinetics
From the figure above it can be concluded that the minimum activation energy of any exothermic
reaction will be zero while minimum activation energy for any endothermic reaction will be equal to H.
Greater the height of energy barrier, greater will be the energy of activation and more slower will be the
reaction at a given temperature.
Activated
complex
Ea
 E C+D
Energy
Products
Reactants
A+B
Progress of the reaction
(Endothermic)
Rate of any chemical reaction = Collision frequency × fraction of the total number of effective collision
= Collision frequency × fraction of the total number of collision 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 10ºC rise in temperature, so it is the fraction of the total number
of effective collision that increases markedly resulting into marked increase in the reaction rate.
From maxwellian distribution it is found that fraction of molecules having excess energy greater than
threshold energy lead to the formation of product.
T2 > T1
Fraction of T2
molecule T1
Ea
eEa / RT  represents fraction of molecules having energy greater Ea
rate  eEa / RT
dependence of rate on temperature is due to dependence of k on temperature.
k  eEa / RT [Arrhenius equation]
k  AeEa / RT
A is pre exponential factor / frequency factor representing collisions taking place with proper orientation.
A and Ea are independent of temperature generally.
Ea = min K. E. that colliding molecules must have to reach transition state.
ADVCHK - 14
Chemical Kinetics
Ea
nk = n A – Ea  0
RT
 As T , K  A
REVERSIBLE REACTIONS
kf = Af eEaf / RT
kb = Ab eEab / RT
kf A e Eaf / RT A 
Keq = = f E / RT =  f  e(Eaf Eab ) / RT
kb A be ab  Ab 
H A 
n Keq = – + n  f 
RT  Ab 
At temperature T1, rate constant = k1

At temperature T2, rate constant = k2
Ea Ea k2 E 1 1
nk1 = nA –  nk2 = nA –  n = a    (remember)
RT1 RT2 k1 R  T1 T2 

Ex-15. Two st order reactions are initially having equal rate at a particular temprature. Temprature of both the
reaction is increased by same amount. Calculate rate of which reaction will increase by greater amount
(reaction with low Ea or high Ea)
 k2  E 1 1
Sol. n   = a    .....(i)
 k1  
R  T1 T2 
 k2 ' 
E ' 1 1 
n   = a    .....(ii)
 k1  R  T1 T2 ' 
Equation (i) – (ii).
 k2  T
n  = ( Ea – Ea,) if Ea > Ea, k2 > k2’
 k 2 '  R
dk  Ea  –1 
k = A eEa / RT A eEa / RT
R  T 2 
or or =
dT
1 dk E k
temprature coeff. of rate constant = a2 or = fractional change / unit temp. rise
K dT RT k.T
Ex-16. Explain on the basis of temprature coeff. of rate const. that equilibrium of endothermic reaction shifts in
forward direction on increasing temprature while equilibriums of exothermic shift back.
 K eq  H  1 1 
  
1
n   =
 K eq  R  T1 T2 

2
ADVCHK - 15
Chemical Kinetics
Sol. H = Eaf – Eab > 0 (for endothermic)
Eaf > Eab
on increasing temp. kf more than kb
equilibrium will shift in forward direction.
Section (H) : Catalyst dependence of rate and type of Reaction and Determination of
rate law and order with the help of given mechanism
Catalyst and catalysis :
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.
Catalyst are generally foreign substances but sometimes one of the product may act as a catalyst and
such catalyst is called “auto catalyst” and the phenomena is called auto catalysis.
Examples of catalysis
(a) Thermal decomposition of KCIO3 is found to be accelerated by the presence of MnO 2. Here MnO2
acts as a catalysts.
2KClO3 + [MnO2]  2KCl + 3O2 + [MnO2]
 MnO2 can be received in the same composition and mass at the end of the reaction.
(b) In the permanganate titration of oxalic acid initially there is slow discharge of the colour of
permanganate solution but afterwards 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, MnSO 4 is
an “auto catalyst” for this reaction. This is an example of auto catalyst.
2KMnO4 + 3H2SO4 + 5H2C2O4  K2SO4 + 8H2O + 10CO2 + 2MnSO4
General characteristics of catalyst :

 A catalyst does not initiate the reaction. It simply fastens it.
 Only a small amount of catalyst can catalyse the reaction.
 A catalyst does not alter the position of equilibrium i.e.
magnitude of equilibrium constant and hence Gº. It simply
lowers the time needed to attain equilibrium. This means if P.E. Ea
a reversible reaction in absence of catalyst completes to go E'a
to the extent of 75% till attainment of equilibrium, and this
state of equilibrium is attained in 20 minutes then in HR
Reactants
presence of a catalyst the reaction will go to 75% of
completion before the attainment of equilibrium but the time HP
Products
needed for this will be less than 20 minutes.
 A catalyst drives the reaction through a low energy path
and hence Ea is less. That is, the function of the catalyst is
to lower down the activation energy. Reaction Coordinate
Ea = Energy of activation in absence of catalyst.
E’a = Energy of activation in presence of catalyst.
Ea – E’a = lowering of activation energy by catalyst.
Comparison of rates of reaction in presence and absence of catalyst :
If k and kcat be the rate constant of a reaction at a given temperature T, E a and E’a are the activation
energies of the reaction in absence and presence of catalyst, respectively, the
k cat AeE ' a / RT
= = e(Ea E'a ) / RT
k AeEa / RT
ADVCHK - 16
Chemical Kinetics
k cat
Since Ea – E’a is positive so kcat > k. the ratio gives the number of times the rate of reaction will
k
increase by the use of catalyst at a given temperature.
The rate of reaction in the presence of catalyst at any temperature T 1 may be made equal to the rate of
reaction in absence of catalyst but for this sake we will have to raise the temperature. Let this
E 'a Ea
temperature be T2, eE'a/ RT1 = eEa / RT2 or =
T1 T2
Ex-17. For the reaction CO(g) + Cl2(g)  COCl2(g) under the same concentration conditions of the
reactants, the rate of the reaction at 250°C is 1500 times as fast as the same reaction at 150°C.
Calculate the activation energy of the reaction. If the frequency factor is 2.0 × 10 10 M–1 sec–1, calculate
the rate constant of the reaction at 150°C.
k2 E  T2  T1 
Sol. log =  
k1 2.303R  T1 T2 
E 100
log 1500 = ×
2.303  2 523  423
3.1761  2.303  2  523  423
E= = 32.36 kcal mol–1
100
E 32360
log k = log A – = log (2.0 × 1010) – = 10.301 – 16.609 = – 6.308
2.303 RT 2.303  2  423
k = 4.92 × 10–7 litres mol–1 sec–1
Ex-18. The pyrolysis of an organic ester follows a first order process and its rate constant can be expressed as
42075
ln k = 78.09 – where k is given in the min–1.
T
Calculate the time required for 25 percent reaction to complete at 227°C.
42075
Sol. ln k = 78.09 – = – 6.06
500
6.06
log k = – = – 2.63 ; k = 2.344 × 10–3 min–1
2.303
2.303 a
when x = 0.25 ; k = log
t1/ 4 0.75a
2.303
t1/4 = log 1.333 = 123.06 min
2.344  10 3
ADVCHK - 17
Chemical Kinetics
1
Ex-19. The slope of the plot of log k vs for a certain reaction was found to be – 5.4 × 103. Calculate the
T
energy of activation of the reaction. If the rate constant of the reaction is 1.155 × 10 –2 sec–1 at 373 K,
what is its frequency factor ?
E
Sol. (a) slope = = – 5.4 × 103
2.303R
E = 5.4 × 103 × 2.303 × 1.987 = 24.624 cal mol–1
24.624
(b) K = Ae– E/RT; log 1.155 × 10–2 = log A – or A = 1.764 × 103 sec–1
2.303  1.987  373
Molecularity and Order :

The number of molecules that react in an elementary step is the molecularity of the elementary
reaction. Molecularity is defined only for the elementary reactions and not for complex reactions. No
elementary reactions involving more than three molecules are known, because of very low probability of
near-simultaneous collision of more than three molecules.
The rate law for the elementary reaction
aA + bB  products rate = k[A]a[B]b, where a + b = 1, 2 or 3.
For an elementary reaction, the orders in the rate law equal the coefficients of the reactants.
While, the order is defined for complex as well as elementary reactions and is always experimentally
calculated by the mechanism of the reaction, usually by the slowest step of the mechanism known as
rate determining step (RDS) of the reaction.
Comparison B/W Molecularity and order of reaction
Molecularity of Reaction Order of Reaction
It is defined as the no. of molecules of reactart taking It is defined as the sum of the power of
1 part in a chemical reaction concnentraction terms that appear in rate law.
eq NH4NO2  N2 + 2H2O m = 1 NH4NO2  N2 + 2H2O. Rate = k[NH4NO2]
It is always a whole number. It can neither be zero
2 It may be zero, fractional or integer.
nor fractional.
3 It is derived from RDS in the mechanism of reaction. It is derived from rate expression.
4 It is theoretical value. It is experimental value.
5 Reactions with molecularity > 4 are rare. Reactions with order of reaction > 4 are also rare.
Molecularity is in independent of Pressure and Order of reaction depends upon pressure and
6
temperature. temperature.
Mechanism of a reaction :
Reactions can be divided into
 Elementary / simple / single step
 Complex / multi-step
 ELEMENTARY REACTION :
 These reaction take place in single step without formation of any intermediate
T.S.
P.E. Ep
Er
Reaction coordinates
 For elementary reaction we can define molecularity of the reaction which is equal to no of molecules
which make transition state or activated complex because of collisions in proper orientation and with
sufficient energy
 Molecularity will always be a natural number.
1 = unimolecular one molecule gets excited (like radioactivity)
2 = bimolecular
3 = trimolecular
ADVCHK - 18
Chemical Kinetics
 Molecularly  3 because the probability of simultaneous collision between 4 or more molecules in
proper orientation is very low
 For elementary reaction there is only single step and hence it is going to be rate determining step so
order of an elementary reaction is its molecularity
Order of elementary reaction w.r.t. reactant = stoichiometric co-efficient of the reactant
H2 +  2 2H (Simple reaction)
rate = k [H2] [2]
2H2 + 22 4H (not elementary)
reaction obtained by multiplying an elementary reaction with some number will not be of elementary
nature
H2 + Cl2 2HCl
order = 0

 COMPLEX REACTION :
 Reaction which proceed in more than two steps or having some T.S.
mechanism. (Sequence of elementary reaction in which any
complex reaction procceds)
 For complex reaction each step of mechanism will be having its
E intermediate
own molecularity but molecularity of net complex reaction will
not be defined.
Reaction coordinates
 Order of complex reaction can be zero fractions whole no, even negative w.r.t. some species.
 Order of reaction or rate law of reaction is calculated with the help of mechanism of the reaction
generally using Rate determine step (R.D.S) if given.
 Rate law of a reaction is always written in terms of conc. of reactant, products or catalysts but never in
terms of conc. of intermediates.
The mechanism of any complex reaction is always written in terms of elementary steps, so molecularity
of each of these steps will be defined but net molecularity of complex reaction has no meaning.
The mechanism of most of the reaction will be calculated or predicted by using mainly the following
approximations.
CALCULATION OF RATE LAW/ ORDER
(A) MECHANISM IN WHICH R.D.S. GIVEN
(i) If R.D.S. involves only reactant, product or catalyst on reactant side
rate law of R.D.S. = rate law of reaction
Ex-20. Calculate order and rate law of reaction

2NO2 + F2  2NO2F with help of mechanism
 K1
NO2 + F2 
 NO2F + F (slow )
molecularity = 2 for both
 K2
NO2 + F   NO2F (fast )
According to RDS
Rate = k1 [NO2] [F2]
Ex-21. Calculate rate law
3ClO–  ClO3– + 2Cl–
K1
2ClO–   ClO2– + Cl– (slow)
K2
ClO2– + ClO–   ClO3– + Cl– (fast)
Rate = k1[ClO–]2
ADVCHK - 19
Chemical Kinetics
(ii) RDS is having intermediate on reactant side
To calculate order, we have to specify [intermediate] in expression of rate law in terms of conc.
of [R], [P] or catalyst with the help of some equilibrium step given in mechanism.
Ex-22. 2O3  3O2

k1
O3 O2 + O (fast eq. step)
k2
(intermediate)
k3
O + O3  
 2O2 (slow)
From R.D.S., rate = k3 [O3] [O]
According to equilibrium step.
k1 [O ][O]
Keq. = = 2
k2 [O3 ]
 k [O ] 
[O] =  1 3 
 k 2 [O2 ] 
 k [O ] 
Rate = k3[O3] [O] = k3[O3]  1 3  .
 k 2 [O2 ] 
k1k 3 [O 3 ]2
Rate =
k 2 [O 2 ]
–
Br
Ex-23 H+ + HNO2 + C6H5NH2   C6H5N2+ + 2H2O
intermediate
k1
H+ + HNO2 H2 NO2+ (fast) equilibrium step
k2
intermediate
k
H2NO2+ + Br– 
3

 NOBr + H2O (slow)
k4
NOBr + C6H5NH2   C6H5N2+ + Br– + H2O (fast)
Sol. r = k3[Br–] [H2NO2+]
k1 [H NO  ]
Keq = = 2 2
k2 [H ][HNO2 ]
k 
[H2NO2+] =  1  [H+] [HNO2]
k2 
k1k 3
r= [H+] [HNO2] [Br–].
k2
Section (I) : Radio Activity

* All radioactive disintegration follow Ist order kinetics.
A  B + C
Int. nuclie N0
At time t. N
ADVCHK - 20
Chemical Kinetics
*  = Not dependent on temperature.

–dN –dN
dt
= N ;  N
=   dt
N  N0et
1 N  A 0 N0 n0 w 0
  ln  0  ;   
t  N A N n w
n0 = initial moles ; w0 = initial weight

1 w 
 = ln  0  (w = weight of A remaining after time t)
t  w 
1  w0 
  ln 
t  w 0  x 
Half life :
N0
t = t1/2 ; N=
2
1  N0 
= ln
t1/ 2  N0 / 2 
ln2
=
t1/ 2
ln 2 0.693
t1/ 2  
 
Average life :
1
Tavg.   1.44t1/ 2


 dN.t 1  dN
Tavg. = 0
= ( = N and N = N0e–t ,  dN = – N0e–t dt)
N0  dt
Unit of activity :
* Curie (Ci) = 3.7 × 1010 dps
Millicurie (mCi) = 3.7 × 107 dps
Microcurie (Ci) = 3.7 × 104 dps
* Rutherford (1 Rd) = 1 × 106dps
Application of radioactivity :
1. Carbon dating : (used for wooden object)
In living matter existing in nature : 14 12 1 : 1012
6C : 6C =
(radio active) (stable)
ADVCHK - 21
Chemical Kinetics
In upper atmosphere :
7N + 0n1  6C14 + 1p1
14
Ratio of radioactive carbon in dead animals / trees decreases with respect to time.
1  A0 
t= ln  
  A
Half life of 6C14 = 5770 yrs.
A = activity of old wood piece. ; A0 = activity of fresh wood piece.
2. Age of rocks or minerals

92U
238  82Pb
206
(radioactive) (stable)
Reaction :
92U
238  82Pb
206 + x2He4 + y–1e0
zX
A  z – 2X´
A–4 + 2He4
zY
A  z + 1Y´
A + –1e0
difference of mass no. 238  206

Number of -particles = = =8
4 4
238 = 206 + 4x + 0 .....(1)
92 = 82 + 2x – y .....(2)
On solving (1) and (2),
x=8 ; y=6
92U
238  82Pb
206 + 8(2He4) + 6(–1e0)
At time t wg yg
1  w0 
t= ln  
  w 
1  w0 
t= ln 
  w 0  x 
w = w0 – x
 w0 = w + x
1 mole or 238 g U provide 206 g of Pb
238 238
 g U provide 1 g Pb  × y g U provide y g Pb
206 206
238 238
x= ×y ; w0 = w + ×y
206 206
92U
238  82Pb
206 + 82He4 + 6–1e–
V(in mL) collected
PV
nHe = ........ (1)
RT
1  n0 
t= ln  
  n
w
n= ........ (2)
238
nHe
n0 = n +
8
ADVCHK - 22
Chemical Kinetics
___________________________________Summary
ADVCHK - 23
Chemical Kinetics
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
Ex-1. For each reaction below, express the rates of change of [product] and [reactant] in the correct
relationship to each other.
(a) 2O3(g)  3O2(g) (b) 2HOF(g)  2HF(g) + O2(g)
1 d[O 3 ] 1 d[O 2 ] 1 d[HOF] 1 d[HF] d[O 2 ]
Sol. (a) – =+ (b) – =+ =+
2 dt 3 dt 2 dt 2 dt dt
 d[O 3 ] 2 d  d[HOF] d[HF] 2d[O2 ]
= [O2] =+ =+
dt 3 dt dt dt dt
Ex-2. In a catalytic experiment involving the Haber's process, N 2 + 3H2  2NH3, the rate of reaction was
measured as rate = 2 × 104 M.s1. If there were no side reactions, express the rate of reaction in terms
of (a) N2 (b) H2?
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
Sol. Rate of Reaction = – = =+
dt 3 dt 2 dt
d[N2 ]
(a) 2 × 10–4 = –
dt
d[H2 ]
(b) 2 × 10–4 ×3=– = 6 × 10–4 MS–1.
dt
Ex-3. Write the units of the rate constants for a (i) Zeroth order, (ii) half order, (iii) first order, (iv) 3/2 order, (v)
second order, (vi) 5/2 order, (vii) third order reactions.
Sol. Unit of Rate Constant = (Mole)1–n (Litre)n–1 Sec–1 Where n is the order of Reaction
(i) For Zeroth order = Mole(1–0) (Litre)(0–1) Sec–1
Unit of K
n=0 Mole Litre(–1) Sec-1
Similarly For others
Ex-4. The reaction CO(g) + NO2(g)  CO2 + NO is second order in NO2 and zero order in CO at
temperatures less than 500K.
(a) Write the rate expression for the reaction.
(b) How will the reaction rate change if the NO2 concentration is halved?
d d
Sol. (a) [CO] = (NO2) = K[NO2]2 Order is zero w.r.t. CO but Conc will Still change
dt dt
(b) Rate of Rxn = K[NO2]2 of Conc of NO2 Half The Rate becomes One fourth
Ex-5. For a reaction A + 3B  Product, Rate = {– d[A] / dt} = k [A]2 [B] , the expression for the rate of reaction
in terms of change in the concentration of B; {– d[B] / dt} will be :
(A) k[A]2 [B] (B) k [A]2 [3B] (C) 3k [A2] [B] (D) (1/3) k [A2] [B]
Sol. (C) For the given reaction
 d[A] 1  d[B]
= = K[A]2[B]
dt 3 dt
 d[B]
then = 3K[A]2[B]
dt
Ex-6. Gaseous cyclobutane isomerizes to butadiene in a first order process which has k = 3.3 x 10 4 s1 at
153ºC. How many minutes would it take for the isomerization to proceed 40% completion at this
temperature.
Sol. For the First order Rxn
2.303 a 2.303  100 
t= log t= log 
K (a  x) 3.3  10 4  60 
t = 1.54 × 10+3 Second. = 25.80 Minute
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Chemical Kinetics
t0.5
Ex-7. Calculate for a 1st order reaction
t0.25
2.303 a
log
K a
(a  ) log 2
t0.5 2
Sol. = = = Ans.
t0.25 2.303 a 4
log (log )
K a 3
(a  )
4
Ex-8. For the reaction A + B  products

the following date were obtained :
Initial rate (mole/liter.sec) 0.030 0.059 0.060 0.090 0.089
[A] (mole/liter) 0.10 0.20 0.20 0.30 0.30
[B] (mole/liter) 0.20 0.20 0.30 0.30 0.50
Write the rate equation for this reaction. Be sure to evaluate k.
Sol. Rate = K[A]x [B]y
From data I. 0.030 = K [0.10]x [0.20]y (1)
From data II. 0.059 = K [0.20]x [0.20]y (2)
From III. 0.060 = K [0.20]x [0.30]y (3)
divide 1 equation by (2)
0.030 K[0.10]x [0.20]y
=  x=1
0.059 K[0.20]x [0.20]y
Then divide (2) equation by (3)
0.059 K[0.20] x [0.20] y
=  y=0
0.060 K[0.20] x [0.30] y
Put the value of x and y in (1) equation
0.030 = K[0.10]1 [0.20]0
0.030
K= = 0.3 sec–1
0.10
Ex-9. The following data is for the decomposition of ammonium nitrite in aqueous solution.
Volume of N2 in cc. Time (minutes)
6.25 10
9.00 15
11.40 20
13.65 25
35.05 infinity
The order of the reaction is
Sol. NH4NO2(s)  N2(g) + 2H2O(l)
Let Vt be the volume of N2 Collected at time ‘t’
V = be the volume of N2 Collected at the end of the Reaction
a V
 (a – x) V – Vt
Then from the given data we assume the Rxn is first order Then
2.303 a 2.303 V
K= log = log
t (a  x) t V – Vt
2.303 35.05
From Ist data K= log = 1.96 × 10–2 sec–1
10 (35.05  6.25)
2.303 35.05
IInd data K= log = 1.96 × 10–2 sec–1
15 (35.05  9)
2.303 35.05
IIIrd data K= log = 1.96 × 10–2 sec–1
20 (35.05  11.40)
From these relation the value of K are same the reaction will be First order
ADVCHK - 25
Chemical Kinetics
Ex-10. Decomposition of H2O2.
1
H2O2  H2O () + O2 (g)
2
The progress of this reaction is measured by titrating the reaction mixture with KMnO 4 at different time
intervals. Calculate rate constant of the reaction in terms of volume of KMnO 4 consumed at time t = 0,
V0 and at time t, Vt.
Sol. Assume the decomposition of H2O2 is a first order reaction
1
H2O2  H2O (l) + O2(g)
2
KMnO4 react only with the H2O2 them
2.303 a
For Ist order reaction K= log
t (a  x)
Then aVo and (a -x) Vt
2.303 V 
Then K = log  0 
t  Vt 
D
Ex-11. A  B+C
Time 0 t 
Volume of reagent V1 V2 V3
The reagent reacts with only B, C and D. Find k.
D
Sol. A   B+C

at t = 0 a 0 0
t=t (a – x) x x
t =   o a a
at t = 0 only D. React
after t = 0 reagent react with B.C.D.
2a  (V3 – V1)
(V3  V1)
A 
2
2x  (V2 – V1)
2(a – x)  (V3 – V1 – V2 + V1)
(V3  V2 )
(a – x) 
2
1 (V3  V1)
Then, K = ln
t (V3  V2 )
Ex-12. A  B + C
Time 0 t
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k.
Sol. A  B + C
t=0 a 0 0
t=t (a – x) x x
a V1
(a – x) + x + x  V2
(a + x)  V2
1 [A]o 1 V1
(a – x)  (2V1 – V2) ; K= ln = ln
t [A]t t (2V1  V2 )
Ex-13. A  B + C
Time T 
Volume of reagent V2 V3
Reagent reacts with all A, B and C and have ‘n’ factors in the ratio of 1 : 2 : 3 with the reagent. Find k.
ADVCHK - 26
Chemical Kinetics
Sol. A  B+C
t=0 a 0 0
t=t (a– x) x x
t= 0 a a
Reagent React with all A, B, C. and have ‘n’ factor in the Ratio 1 : 2 : 3
(2a + 3a)  V3
V3
a
5
(a – x) × 1 + 2x + 3x  V2
(a + 4x)  V2
V3
+ 4x  V2
5
1  V  V3 1  V 
x  V2  3   (a – x)  –  V2  3 
4  5 5 4  5
5(v 3  v 2 ) 1 4V3
(a-x)   K = ln
20 t 5(v 3  v 2 )
Ex-14. Now, let us assume that A, B and C are optically active compounds, which rotate the plane polarized
light in the clockwise or anticlockwise direction.
A(soln.)  B(soln.) + C(soln.)
Time 0 t 
Total rotation in degrees R0 rt r
Calculate the expression of rate constant.
Sol. The principle of the experiment is that change in the rotation is directly proportional to
concentration.
a  (ro – r)
(a - x)  (rt – r)
Then Expression For rate constant
2.303 r r
K= log o 
t rt  r
Ex-15. The hydrolysis of cane sugar was studied using an optical polarimeter and the following readings were
taken.
time (min.) : 0 84 min 
observed rotation (degrees) : 50 20 –10
When will the mixture optically inactive? (log 2 = 0.3, log 3 = 0.48)
Sol. From the hydrolysis
K=
2.303 r  r  2.303 log 50  10
log o  =
t rt  r 84 20  10
2.303
K= × 0.3010 = 8.252 × 10–3
84
The time taken when sample are optically Inactive is t
2.303  0.3010 2.303 50  10
K= = log
84 t 10
t = 217.14 minute
Ex-16. The optical rotation of sucrose in 0.5 M HCl at 350C at various time intervals are given below. Show that
the reaction is first order.
Time (minutes) 0 10 20 30 40  
Rotation (degrees) +32.4 +28.8 +25.5 +22.4 +19.6 –11.1
Sol. If reaction first order the value of K same in First-Order Expression
K=
2.303 r  r 
log o 
t rt  r
2.303 32.4  11.1 0.03751  2.303
K= log = = 8.63 × 10-3
10 28.8  11.1 10
ADVCHK - 27
Chemical Kinetics
2.303 32.4  11.1
K= log = 8.63 × 10-3
20 25.5  11.1
2.303 32.4  11.1
K= log = 8.63 × 10-3
30 22.4  11.1
2.303 32.4  11.1
K= log = 8.63 × 10-3
40 19.6  11.1
The reaction show 1st order kinetics
Ex-17. Temperature coefficient of the rate of a reaction is 3. How many times the rate of reaction would
increase if temperature is raised by 30 K :
(A) 3 (B) 9 (C) 27 (D) 81
30
R2 K
Sol. (C) For same concentration = 2 = 3 10 = 27.
R1 K1
Ex-18. The reaction A + B  products is first order with respect to both A and B has a rate constant of 6.0 L
mol–1 sec–1. at 27°C. Calculate the initial rate of the reaction at 47°C when equal volumes of A and B of
concentration 0.01 moles litre–1 in each are mixed. The activation energy of the energy of the reaction is
42 kJ mol–1 .
Sol. Reaction A + B  Product
 K2  E 1 1
We know log  =   
 K1  2.303R  T1 T2 
K  E  T2  T1 
log  2  =  
 K1  2.303R  T1T2 
 K2  42  103 [320  300] 840

log   = =
 6 2.303  8.3  300  320 1835.03
K2
log = .4577
6
K2
= anti log (.4577)
6
K2 = 2.863 × 6 = 17.178
Rate at 47oC will be
The Rate2 = 17.178 × [0.01] × [0.01]
Rate2 = 17.178 × 10-4 = 1.7178 × 10-3
Ex-19. An exothermic reaction A  B has an activation energy of 17 KJ per mole of A. The heat of reaction is
– 40 KJ/mole. The activation energy for the reverse reaction B  A is :
(A) 75 KJ per mole (B) 67 KJ per mole (C) 57 KJ per mole (D) 17 KJ per mole
Sol. (C)H = EA – EB
–40 = 17 – EB
EB = 57
Ex-20. The rate of decomposition for methyl nitrite and ethyl nitrite can be given in terms of rate constant (in
sec–1) K1 and K2 respectively. The energy of activations for the two reactions are 152.30 kJ mol –1 and
157.7 kJ mol–1 as well as frequency factors are 1013 and 1014 respectively for the decomposition of
methyl and ethyl nitrite. Calculate the temperature at which rate constant will be same for the two
reactions.
Sol. Rate constant will be same.
K1 = K2
 Ea1  Ea 2
A1 e RT = A2 e RT
Ea2  Ea1 157.7  152.3
T=  T=  T = 282K
A   104 
2.303 log  2   R 2.303  8  log  3 
 A1   10 
ADVCHK - 28
Chemical Kinetics
Ex-21. Use the diagram below to answer the following questions.
(a) Is the reaction exothermic or endothermic?
(b) What is the approximate value of  E for the forward reaction?
(c) What is activation energy in each direction?
(d) A catalyst is found that lowers the activation energy of the reaction by
about 10 kJ/mol. How will this catalyst affect the rate of the reverse
reaction?
Sol.
(a) Forward Rxn are endothermic (b) E = (Ea – Ea1) = (50 – 30) = 20 KJ / Mole.
(c) Eaf = 50 KJ/Mole, Eab = 30 KJ/Mole (d) Increases
Ex-22. The rate of a first order reaction is 0.05 mole/L/s at 10 minutes and 0.04 mole/L/s at 30 minutes after
initiation. Find the half-life of the reaction
Sol. Let the concentrations of the reactant after 10 min and 30 min be C1 and C2 respectively.
Rate after 10 min = KC1 = 0.05 × 60 and Rate after 30 min = KC2 = 0.04 × 60
c1 5
 = .
c2 4
Supposing the reaction starting after 10 minutes
2.303 c 2.303 5
k= log 1 = log = 0.011159
20 c2 20 4
0.6932 0.6932
 t1/2 = = = 62.12 min.
k 0.011159
Ex-23. For a chemical reaction A+B  Product, the order is 1 with respect to each of A and B Find x
and y from the given data.
Rate (moles/L/s) [A] [B]
0.10 0.1 M 0.1M
0.80 xM 0.1M
0.40 0.2 M yM
Sol. The rate law may be written as
rate = k [A] [B]
Substituting the first set of data in the rate law, we get,
0.10 = k × 0.1 × 0.1  k = 10
Now substituting the second and third sets of data, we get,
0.8 = 10 × x × 0.1  x = 0.80 M
and, 0.4 = 10 × 0.2 × y  y = 0.20 M.
Ex-24. In the decomposition of H2O2 at 300 K, the energy of activation was found to be 16 kcal/ mole, while it
decreased to 10 kcal/ mole when the decomposition was carried out in the presence of a catalyst at 300
K, How many times is the catalysed reaction faster than the uncatalysed one?
Sol. Suppose E1 and E2 are the energies of activation when the reaction is carried out in the absence and
presence of a catalyst respectively.
Thus, k1 = AeE1 / RT , k2 = AeE2 / RT
E1
Taking log, In k1 = In A –
RT
E
In k2 = In A – 2
RT
ADVCHK - 29
Chemical Kinetics
E2 E k2 1 6
 In k2 – In k1 = – + 1 or In = (16 –10) =
RT RT k1 0.002  300 0.002  300
k2
2.303 log = 10
k1
k2 10
log = = 4.342
k1 2.303
k2
Taking antilog = 2.190 × 104
k1
Ex-25. In Arrhenius`s equation for a certain Reaction, the value of A and E (activation energy) are 6 × 10 13 s-1
and 98.6 kJ mol-1 respectively. If the reaction is of first order, at what temperature will its half-life period
be 20 minutes ?
Sol. k = Ae-E/RT
E
In k = In A –
RT
E E
2.303 log k = 2.303 log A – or log k = log A – . .....(1)
RT 2.303RT
Given that A = 6 × 1013 s -1, E = 98.6 kJ mol-1
t1/2 = 20 × 60 s.
0.6932 0.6932 -1
For first-order reaction k = = s
t1/ 2 1200
Thus (1) becomes,
0.6932 98.6
log = log (6 × 1013) – [R = 8.314 × 10-3 kJ/K/mol]
1200 2.303  8.314  103  T
T = 302.26 K.
Ex-26. The decomposition of N2O5 according to the equation, 2N2O5(g)  4NO2(g) + O2(g)
is a first-order reaction. After 30 minutes from the 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 the reaction.
Sol. 2N2O5  4NO2 + O2
at t = 0 a
After 30 min: a–x 2x x/2
x 3x
 (a – x) + 2x + = 284.5 or a+ = 284.5 ....(1)
2 2
After complete decomposition of N2O5.
2N2O5  4NO2 + O2
0 2a a/2
a 5a
 2a + = 584.5 or = 584.5 ....(2)
2 2
From (1) and (2), we get,
a = 233.5, x = 34
Thus, for a first-order reaction of the type 2A  products
1 a
k= log
2t ax
2.303 233.5
k= log = 2.625 × 10-3 min-1
2  30 233.5  34
Ex-27. The complexation of Fe2+ with the chelating agent dipyridyl has been studied kinetically in both forward
and reverse directions.
Fe2+ + 3 dipy Fe(dipy)32+
Rate (forward) = (1.80 × 1013) [Fe2+] [dipy]3
and rate (reverse) = (1.20 × 10-4) [Fe (dipy)32+]
Find the stability constant for the complex.
ADVCHK - 30
Chemical Kinetics
Sol. At dynamic equilibrium,
rate of formation of complex = rate of its decomposition
(1.8 × 1013) [Fe2+] [dipy]3 = (1.20 × 10-4) [Fe(dipy)32+]
[Fe(dipy)3 2  ] 1.8  1013
Ks = = = 1.5 × 1017
[Fe2  ][dipy]3 12  10 4
Ex-28. The approach to the following equilibrium was observed kinetically from both directions.
PtCI42– + H2O Pt(H2O)CI–3 + CI– at 25oC It was found that
2
d[PtCI]
– = (4.8 × 10-5) [PtCI4]2– – (2.4 × 10–3) [Pt(H2O)CI-3] [CI-]
dt
Calculate the equilibrium constant for the complexation of CI– with Pt(II).
d[PtCl4 ]2
Sol. At equilibrium, =0
dt
Hence, 4.8 × 10–5 [PtCI2–4] = 2.4 × 10–3 [Pt(H2O)CI–3] [CI–]
[PtCl4 ]2  2.4  10 3
or K= = = 50.
[Pt(H2O)Cl3 ][CI ] 4.8  10 5
Ex-29. Some PH3(g) is introduced into a flask at 600oC containing an inert gas PH3 proceeds to decompose
into P4(g) and H2(g) and the reaction goes to completion. The total pressure is given below as a
function of time. Find the order of the reaction and calculate the rate constant for the reaction:
Time (s) 0 60 120 
p mm (Hg) 262.40 272.90 275.51 276.40
4PH3  P4 + 6H2
Sol. Let the initial Partial pressures of PH3 and the inert gas be p and p’ mm respectively and p’ mm of PH 3
decomposes at different time intervals.
Initial partial pressure (P)
4PH3  P4 + 6H2
Partial pressure at different times: p – p p/4 6p/4
As given, at t = 0 seconds.
p + p = 262.40 ...(1)
p' 6p '
and, t = 60 second p – p + + + p = 272.90 ...(2)
4 4
p 6p
At t = : + + p = 276.40. ...(3)
4 4
Solving, equations (1), (2) and (3), we get,
p = 18.67 and p = 14.
Similarly, at t = 120 seconds
p' 6p '
p – p + + + p = 275.51. ...(4)
4 4
Solving, equations (1), (4) and (3), we get
p = 18.67 and p’ = 17.48.
As the given reaction is of the type nA  products, where n = 4, we have the following equation for
first-order kinetics
2.303 a 2.303 p
k1 = log = log .
4t ax 4t p  p'
2.303 18.67
Thus, at t = 60s; k1 = log = 5.8 × 10–3 s–1
4  60 18.67  14
2.303 18.67
t = 120s; k1 = log = 5.8 × 10–3 s–1.
4  120 18.67  17.48
As the values of k1 are constant, the given reaction following the first order kinetics.
ADVCHK - 31

Chemical Kinetics Theory

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Chemical Kinetics

Section (A) : Rate of chemical reaction and Dependence of Rate : Basic

Relation between reaction rates of different species involved in a reaction :

Factors affecting rate of chemical reaction :

3. Effect of nature of reactants and Products :

General rate law is, Rate = k [conc.]0 = constant

2.303 2C 2.303log2 ln2 0.693

First order growth reaction :

Examples of 1st order reactions :

2. Conversion of N–chloro acetanilide into p–chloroacetanilide

(b) Pseudo first order reaction :

Graphical comparison of different orders

Or in log form we have a=

(B) integrated rate law method :

(C) Method of half lives :

Methods to monitor the progress of the reaction :

Ex-8. Find the expression for K in terms of P0, Pt and n

Ex-12. Study of acid hydrolysis of an ester.

(C) Optical rotation measurement :

Section (F) : Complication in 1st Order Reaction

At t=0 [A] = a [B] = [C] = 0

Now, [A]t = aekeff t = ae(k1 k2 )t

Section (G) : Temperature dependence of rate

Arrhenius theory of reaction rate :

At temperature T1, rate constant = k1

General characteristics of catalyst :

Molecularity and Order :

Ex-20. Calculate order and rate law of reaction

Ex-22. 2O3  3O2

Section (I) : Radio Activity

*  = Not dependent on temperature.

n0 = initial moles ; w0 = initial weight

2. Age of rocks or minerals

difference of mass no. 238  206

Ex-8. For the reaction A + B  products

 K2  42  103 [320  300] 840

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