CHEMICAL KINETICS

A brief review of the basic concepts

SECTION- A
1. Cheica! "inetics# The branch of chemistry which deals with the study of reaction rates and the
mechanism by which they occur is called chemical kinetics.
$. Fast, very slow and slow reactions: from the kinetic point of view, the chemical reactions can be
categorized as follows.
i% &ast or ionic reactions# these reactions take place almost instantaneously and get completed in
about
16 1
1! 1!

seconds. "uch reactions are very fast and take place between ions. For e#ample,
$ $
Ag No Na cl AgCl Na NO
+ +
+ + +
The rates of such reactions can not be measured conveniently by the commonly used techni%ues.
ii% &ery slow reactions: these reactions take place very slowly and may take very several months for
their completion. 'usting of iron is an e#ample of this type of reactions. These reactions are so slow
that their rates can not be measured easily.
iii% S!ow or o!ec'!ar reactions# between very fast and very slow reactions( we have a large number
of molecular reactions whose rates can be measured conveniently. For e#ample, reactions involved in
the formation of ammonia, etherification, hydrolysis of ester, decomposition of )*+, are the reactions
of this type. "uch reactions are termed as slow reactions or molecular reactions.
(. )ate of a cheica! reaction# the rate of a chemical reaction may be defined as the change in
concentration of any of the reactants or any of the products per unit time.
Following two types of rates of a chemical reaction are defined.
i- avera*e rate of a reaction# the change in concentration of any of the reactants or any of
the products per unit time over a specified interval of time is called the average rate of the
reaction i.e.
.verage rate of a reaction /
tan
int int
changeinconcentrationofareac toraproduct
time ervalinvolved hechange
For e#ample, for the reaction . 0 1, we have
.verage rate of reaction /
2 3 2 3 A B
t t

=

4here,
2 3 A
/decrease in the conc. +f . in mol 561,
2 3 B
/increase in the conc. +f 213 in mol 561, and
t / time interval involved in the change.
7t is to be noted that . is a negative %uantity because concentration of 2.3 decreases with time.
"ince the rate of a reaction is always e#pressed as a positive %uantity, a negative sign 86- is put
before . to make the rate positive.
The average rate of a reaction can be obtained by dividing the rate of disappearance of any of the
reactants or the rate of appearance of any of the products by its stoichiometric coefficient. For
e#ample,
a. 9 b1 0 c: 9 d;
the average rate of reaction /
1 2 3 1 2 3 1 2 3 1 2 3 A B C D
a t b t c t d t

= = =

ii- Instantaneo's rate of a reaction# the rate of change of concentration of any of the
reactants or products at a particular instant of time is called the instantaneous rate of the
given reaction at that instant.
For the determination of instantaneous rate, the time interval t is taken as small as possible.
Thus, the instantaneous rate can be e#pressed as
7nstantaneous rate /lim
x
x dx
t dt

4here d# represents an infinitesimally small change in concentration for any of the reactants
or products occurred in an infinitesimally small time dt.
For the reaction, a. 9 b1 0 c: 9 d; , the instantaneous rate can be e#pressed as
1
6
1 2 3 1 2 3 1 2 3 1 2 3 d A d B d C d D
a dt b dt c dt d dt
= = =
+nits of rate of reaction# The rate of a reaction is usually e#pressed in the units of mol 5
61
s
61
.
when the reactants and products are in the gaseous state and their concentrations are e#pressed in
terms of their partial pressures, the rate of reaction is e#pressed in the units of atm s
<1
,. )eaction !ife tie# the time taken by a reaction to got to completion is difficult to be measured
because most of the reactions become very slow at the verge of their completion. Therefore,
usually time take for =>? completion is measured. This time is referred to as reaction life time.
"horter the reaction life time, faster is the reaction. The time taken for ,!? completion of the
reaction is half life of the reaction. ;uring the half life of a reaction, the concentrations of reactants
are reduced to half of their original value.
-. &actors which affect the reaction rate#
Nat're of reactants# the reactions involving polar and ionic substances are %uite fast whereas
those involving covalent compounds are much slower.
Concentration of reactants# in general, the rate of a reaction increases on increasing the
concentration of reactants. This is due to an increase in the probability of molecular collisions.
Teperat're# the rate of a reaction usually increases on increasing the temperature. For most
of the homogeneous reactions, the rate becomes doubled to for each 1!
!
rise in temperature.
.resence of a cata!/st# a catalyst provides an alternate path with a lower energy barrier and
thus enables a larger number of reactant molecules to cross it and to take party in the reaction.
Therefore, a catalyst increases the rate of a reaction.
"urface area: if one of the reactants is a solid, the rate of reaction increases with an increase in
the surface area of the reactant. .n increase in surface area enhances the rate of encounters
between the reactant molecules and conse%uently the rate of reaction increases.
0. )ate !aw an1 rate constant# The law of mass action is unable to predict the observed
dependence of the rate of a chemical reaction on the molar concentrations of the reactants involved
in the reaction in several cases. 7n fact, the true rate e#pression for a reaction can not be written
@ust by seeing the balanced e%uation. 7t has to be derived on the basis of e#perimental facts.
The e#pression which describes the e#perimentally observed dependence of the reaction rate on
the molar concentrations of the reactants is called the rate law or rate e%uation.
The rate law describes the true dependence of the rate of reaction on the molar concentration of the
reactants. 7n the rate law, the rate of reaction is e#pressed in terms of the product of molar
concentrations of reactants, with each concentration term raise to the power describing the true
dependence of the rate on the concentration. This power may or may not be t he same as the
stoichiometric coefficient of the reactant in the balanced chemical e%uation. The rate laws of some
reactions are given below.
)ate constant 2specific reaction rate%# the constant k appearing in the e#pression for the rate law
of a reaction is called the rate constant or velocity constant or specific reaction rate of the reaction.
7t may be defined as e%ual to the rate of reaction when the concentration of each of the reactant is
unity.
The rate constant of a reaction has a definite value at a particular temperature. 7ts value increases
with increase in temperature. 7t does not depend upon the initial concentrations of reactants.
*
+nits of rate constant# The units of rate constant depend upon the overall sum of the powers to
which the concentration of the reactants is raise in the rate law. 7f for a general reaction
a. 9 b1 0 c: 0 products. The rate law is
'ate / 2 3 2 3 2 3
p q r
k A B C
.nd p9%9r / n then,
k/
1 1
1 1 1
8 . tan - 8 1-
n n
n n
rate molL s
molL L s
conc ofreac ts molL


=

Aere, in general, the units of rate constant are

1 1 1 n n
molL L s

, where n represents the sum of
powers appearing in the rate law. For a gaseous reaction, units of rate constant will be
1 1 n
atm s

Characteristics of rate constant#
i- 7t is a measure of the rate of reaction. Aigher the value of k, greater is the rate of reaction.
ii- . particular reaction has a definite value of k at a particular temperature.
iii- The value of rate constant increases with an increase in temperature.
iv- it does not depend upon the initial concentrations of reactants.
v- 7ts units depend upon the overall order of reaction.
3. Or1er of a reaction# the power to which the concentration term of a particular reactant in the rate
law is raised is called the order of reaction with respect to that reactant and the sum of all the powers
to which all the concentration terms in the rate law are raise to e#press the observed rate of reaction is
called the overall order of reaction.
For e#ample, if for the general reaction
a. 9 b1 0 c: 9 d; ,
'ate / k 2 3 2 3
p q
A B the e#perimentally observed then the reaction is said to be of order p with
respect to . and of order % with respect to 1. the overall order of the reaction is given by
+verall order of reaction / p 9 %
4hen the overall order of a reaction is 1, the reaction is said to be a first order reaction.
4hen the overall order is *, the reaction is said to be a second order reaction.
7n case the overall order is $, the reaction is referred to as a third order reaction.
7t is to be noted that the order of a reaction is purely an e#perimental %uantity and can not be known
@ust by seeing the e%uation. The stoichiometric coefficients present in the balanced chemical e%uation
have nothing to do with the order of the reaction.
The order of a reaction is usually a whole number. Aowever, it can be zero or fractional also.
4. )eactions of 1ifferent or1ers an1 the 'nits of their rate constants#
i% &irst or1er reactions# a reaction of a type . 0 products is said to be of first order, if its rate law
is given by
'ate / k 2.3
1
+bviously, in a first order reaction, the rate is directly proportional to the concentration of the
reactant. 7f the concentration of reactant . is doubled, the rate of reaction also gets double, some
e#amples of first order reactions are as follows:
, $ * ,
* * * *
* , * * * ,
* * * * * *
* * * * * *
( 2 3
* ( 2 3
1
* ( 2 3
*
1
( 2 3
*
( 2 3
PCl PCl Cl rate k PCl
NH NO N H O rate k NH NO
N O NO O rate k N O
H O H O O rate k H O
O Cl O Cl rate k O Cl
+ =
+ =
+ =
+ =
+ =
The units of rate constant for a first order reaction are time
61
i.e. s
61
, or min
61
, or hour
61
.
ii% Secon1 or1er reactions# a reaction of the type . 0 products is said to be of second order , if its
rate law is given by
'ate / k 2.3
*
$
+bviously, in a second order reaction, the rate depends upon the s%uare of the concentration of
reactants. 4hen the concentration of reactants is doubled, the rate increases by four times. "ome
e#amples of second order reactions are as follows.
*
* * *
* * ( 2 3 N O NO O rate k NO + =
* * * *
* ( 2 32 3 H ! H! rate k H ! + =
$ * * $
( 2 32 3 NO O NO O rate k NO O + + =
$ * , $ * , $ * ,
( 2 32 3 CH COOC H NaOH CH COONa C H OH rate k CH COOC H NaOH + + =
The units of rate constant for a second order reaction are conc
.61
. i.e. mol
61
ls
61
. For a gaseous reaction
the units of k will be atm
61
s
61
.
iii% Thir1 or1er reactions# when the rate of a reaction depends upon the cube of the concentration of
reactants, the reaction is said to be of third order. 7n such a case, when the concentration is doubled,
the rate of reaction increases by eight times.
The most common third order reactions are of the following type(
*. 9 1 0 Broducts : rate k 2.3
*
213
7n this case, the reaction is of order * with respect to .
+rder 1 with respect to 1.
The overall order is *91 / $.
"ome e#amples of third order reactions are as follows(
*
* * *
* * ( 2 3 2 3 NO O N O rate k NO O + =
*
* *
* * ( 2 3 2 3 NO Cl NOCl rate k NO Cl + =
*
* *
* * ( 2 3 2 3 NO Br NOBr rate k NO Br + =
The units of rate constant for a reaction of third order are conc
.6*
time
61
i.e. mol
6*
5
*
s
61
. for a gaseous
reaction the units will be atm
6*
s
61
.
iv% 5ero or1er reactions# a reaction . 0 products is said to be of zero order when its rate law is
given by
'ate /k 2.3! / k
+bviously, in a zero order reaction, the rate does not depend upon the concentration of reactants and
remains constant throughout the course of reaction when the concentration of a reactant is changed,
the rate does not change i.e. the reaction proceeds with a constant rate. "ome e#amples of zero order
reactions are as follows.
! !
* * * *
* ( 2 3 2 3 H Cl HCl rate k H Cl k + = =
!
$ * * $
* $ ( 2 3 NH N H rate k NH k + = =
The units of rate constant for a zero order reaction are conc. Time
61
ie.e. mol 5
61
s
61.
For a gaseous
reaction the units are atm s
61
.
v% )eaction of fractiona! or1er# some e#amples of reactions having fractional orders are as
follows.
$C *
$ $
( 2 3 $C * CH CHO CH CO rate k CH CHO order + = =
1C*
* * * *
* ( 2 32 3 $C * H Br HBr rate k H Br order + = =
$C *
* * *
( 2 3 $C * COCl CO Cl rate k COCl order + = =
* 1C *
* * *
( 2 3 2 3 , C * CO Cl COCl rate k CO Cl order + = =
6. &irst or1er reactions# some more details of the first order reactions are as follows(
a% )ate e7'ation for a first or1er reaction# a first order reaction is an e#ponential process and the
concentration of the reactant decreases e#ponentially with time. 5et us consider the following reaction
which is of first order.
. 0 products
7f, 2.3!

/ initial concentration of ., and 2.3 / concentration of . after a time interval of t , we have
2.3 /2.3! e
Dkt
EEEEE..8i-
4here, k is the rate constant of the reaction.
The above e%uation can also be written as
F /
!
2 3 *.$!$
log
2 3
A
t A
EEEEE8ii-

This e%uation represents the rate e%uation of a first order reaction.

7f the initial concentration of . is a mol 5
61
and # moles of it change into products during time interval
t, we have 2.3!/ a mol 5
61
and 2.3 / a D # mol 5
61
. Thus, the above e%uations can also be written as
1!
*.$!$
log
a
t a x
EE..8iii-
G%s. 8ii- and 8iii- are also referred to as integrated rate law or integrated rate e%uations for a first order
reaction.
b% 8raphica! representation of a first or1er reaction# following are the different graphical
representations of a first order reaction:
c% Ha!f !ife of a first or1er reaction# it is given by
t1C* /
!.6=$
k
4here, k is the rate constant of the reaction. The half life of a first order reaction is independent of the
initial concentration of the reactant.
1% Characteristics of a first or1er reaction# i- the rate of reaction is directly proportional to the
concentration of the reactant i.e. rate H 2.3
ii- The rate constant has the units of time
61
iii- . first order reaction obeys e%uations. 8i-, 8ii- and 8iii- given above.
iv- . plot of !o* 9A: against t is a straight line with slope e%ual to DkC*.$!$.
v- The half life of first order reaction is independent of the initial concentration.
vi- The time taken for the completion of any fraction of a first order reaction is independent of initial
:oncentration.
1;. <eterination of or1er of a reaction# following methods are used to determine the order of a
reaction.
i% 8raphica! etho1# this method is used when the reaction involves only one reactant. The method
is based on the fact that for a reaction of order n,
'ate H 2.3 n
For a first order reaction, n /1, Aence, rate H 2.3. Thus a plot of rate of reactions &s conc. 4ill be a
"traight line
For a second order reaction, n/*. Aence rate H 2.3
*
. Thus a plot of rate of reaction &s conc. will be a
"traight line.
ii% Initia! rate etho1# in this method, the rate law of the reaction is determined by determining the
orders of reaction with respect to all the reactants one by one. This is done by changing the initial
concentration of only one reactant keeping the concentrations of all other reactants constant and
measuring the rate of the reaction. The procedure is repeated with respect to each reactant and the
order determined. The overall order of the reaction can be obtained by summing up the indi>vidual
orders of reaction with respect to the reactants involved.
iii% Inte*rate1 rate !aw etho1# in this method, the data obtained from an e#periment is fed into the
rate e%uation of a particular order and the values of k are calculated for different sets of observations.
7f the values of k are found to be constant for all the sets, the reactions is supposed to obey that
particular rate law and follows the order suggested by that integrated rate law. 7n case, the values of k
are not constant, the data is used in the rate e%uation of other order. The rate e%uation for first and
second order reactions are as follows.
For first order reactions: k /
1!
*.$!$
log
a
t a x
For second order reactions: k /
1
8 -
x
"
t a x
,
iv% Ha!f !ife etho1# the half life 8t1C*- of a reaction is related to the initial concentration of the
reactant as
1C * 1
!
1
2 3
n
t
A

4here 2.3
!
is the initial concentration of the reactant and n is the order of reaction.
"uppose t1C* is the half life of a reaction when the initial conc. 7s 2.3
!
and t1=$ is the half life of the
same reaction when the initial conc. 7s 2.3
!
. Then we have
1 1C * !
1C * !
2 3
8 -
2 3
n
t A
t A

=
Thus, the order n of the reaction can be determined.
11. Effect of teperat're on reaction rate# the rate of a chemical reaction is significantly affected by
a change in temperature. For most of the chemical reactions, the rate increases with increase in
temperature. The rate usually becomes doubled for each 1!I rise in temperature.
a% Teperat're coefficient# it is defined as the ratio of the rate constant of a reaction at two different
temperatures separated by 1! :. the two temperatures generally taken are $, : and *, :. thus,
Temperature coefficient /
$,
*,
C
C
k
k
For most of the homogeneous reactions, the value of temperature coefficient lies between * and $.
b% Co!!ision theor/ of reaction rate# this theory was proposed to e#plain the effect of temperature on
reaction rates. The salient features of the theory are as follows.
i% . reaction occurs only when the reactant molecules undergo collisions with one another.
ii% .ll collisions between the reaction molecules are not effective in producing a chemical change.
+nly a fraction of total number of collisions is effective and leads to the formation f products.
iii% The collisions between the reaction molecules are effective only when they ac%uire a definite
amount of energy. The minimum amount of energy which must be possessed by the reacting molecules
to make effective collisions is called threshold energy.
Gffective collisions are those collisions which lead to the formation of products. The number of
effective collision is governed by the following two factors.
i- Gnergy barrier: the collisions are effective only when the molecules possess energy greater
than or e%ual to the threshold energy.
ii- +rientation barrier: the reactant molecules must collide with favorable orientation in order
to facilitate the breaking of old bond and formation of new bonds.
c% >'a!itative of increase in reaction rate with teperat're# the following figure shows the energy
distribution curves at temperature T1, T* and T$ such that T$ J T* J T1. .t temperature T1, the fraction
of molecules enclosed in the shaded are a b c d possesses kinetic energy greater than or e%ual to the
threshold energy and is capable of making effective collisions. .s the temperature increases from T1 to
T*. The fraction of molecules having kinetic energy greater than the threshold energy increase. Thus
effective collisions and hence the rate of reaction increases. The fraction of such molecules becomes
still larger as the temperature increases from T* to T$ resulting in a further increase in the rate of
reaction.
Thus, an increase in temperature increases the number of effective collisions resulting in an increase in
the rate of reaction.
The fraction of molecules having energy greater than or e%ual to the threshold energy increases
appreciably even with a small rise in temperature. Aence, the rate of a reaction increase appreciably
even with a small rise in temperature.
6
1$. Activation ener*/# the e#cess energy that the reactant molecules must ac%uire in order to cross the
energy barrier and to change into the products is called the activation energy of the reaction.
.ctivation energy / threshold energy6average energy possessed by reactant molecules.
Gach reaction has a definite value of activation energy. The value of activation energy decides the
fraction of collisions which are effective. "maller the activation energy of the reaction, higher is the
number of molecules capable of crossing the energy barrier and conse%uently the greater is the rate of
reaction.
The activation energies for forward and backward reactions in a reversible reaction are shown in the
following figures.
F/. e
6GaC'T
4here . is a constant known as fre%uency factor and gives the fre%uency of binary collisions of
reactant molecules per second per liter. Ga is the energy of activation, ' is gas constant and T
represents the temperature of the system. k is the rate constant of the reaction
.rrhenius e%uation can also be e#pressed as
1! 1!
log log
*.$!$
a
#
k A
$%
= + EEEE 8iv-
From this e%uation, it is clear that as the value of T increases, the value of k and hence the rate of
reaction increases.
Ca!c'!ation of activation ener*/# the .rrhenius e%uation enables us to calculate the value of
activation energy for a chemical reaction. Following two methods may be used.
K
i- Lraphical method: the .rrhenius e%uation 8iv- is the type, type / ? @ A c and represents a
straight line.
Therefore, if the values of !o* " are plotted against 1CT, a straight line is obtained. The slope of
this line is e%ual to the 6
*.$!$
a
#
$
. Aence, by measuring the slope of the line, the activation
energy Ga can be calculated.
ii- 'ate constant method: if k1 and k* are the rate constants measured at temperatures T1 and T*
respectively, then on the basis of .rrhenius e%uation, we can have
*
1!
1 1 *
1 1
log 8 -
*.$!$
a
# k
k $ % %
=
Thus, knowing the values of rate constant, k1 and k* of a reaction measured at two different
temperatures T1 and T* respectively. The energy of activation Ga of the reaction can be
calculated with the help of the above e%uation.
1(. Mo!ec'!arit/ of a reaction# the number of reacting species which must collide simultaneously in
+rder to bring about a chemical reaction is called the molecularity of that reaction.
The molecularity of a reaction is a whole number and may have values 1, *, $ etc.
The reactions with molecularity 1 are called unimolecular reactions.
"imilarly, we have bimolecular and trimolecular reactions when the values of molecularity are
* and $ respectively.
a% Mo!ec'!arit/ of e!eentar/ reactions# The simple chemical reactions which occur only
in one step are called elementary reactions. The molecularity of an elementary reaction is
e%ual to the number of reacting species as represented by the balanced chemical e%uation
of the reaction, for e#ample.
* * * *
* *
1
8 1, -
*
* * *8 *, -
* * 8 $, -
H O H O O molecularit& unimolecularreaction
H! H ! molecularit& bimolecularreaction
NO O NO molecularit& trimolecularreaction
+ =
+ =
+ =
b% Mo!ec'!arit/ of cop!e@ reactions# the reactions which occur in two or more steps are
called comple# reactions.
:omple# reactions proceed through a series of steps, each involving one, two, or at the most
three molecules. Gach step is an elementary reaction and has its own rate. The overall rate of a
comple# reaction is governed by the rate of the slowest elementary step called the rate
determining step.
The number of reacting species taking part in the slowest elementary step of a comple#
reaction is called the molecularity of the comple# reaction.
For e#ample, the reaction *)+ 9*A* 0 )*9A*+ is a comple# reaction and takes place in the
following two steps.
"tep1.
* * * *
* 8 - NO H N H O slo' + +
"tep*.
* * * *
* 8 - H O H H O fast +
>
+bviously, step 1 is the rate determining step and therefore the molecularity of the overall
comple# reaction is $.
Most of the chemical reactions involve the simultaneous collisions of one, two or at the most
three molecules. Therefore, the molecularity of most of the reactions is either 1 or *. Gven the
reactions with molecularity $ are only a few in number. The reactions with higher molecularity
are rare.
1,. .se'1o-'nio!ec'!ar reactions# for elementary reactions, the molecularity and order are
usually the same. Aowever, there are several first order reactions in which molecularity differs
from the order.
The first order reactions having molecularity greater than one are called pseudo6unimolecular
reactions.
. pseudo6unimolecular reaction is obtained when one of the reactants is present in large
e#cess. The reactant present in large e#cess does not contributes to the rate of reactions. 7ts
concentration remains almost constant during the course of reaction and therefore the rate of
the reaction does not depend upon its concentration. "ome e#amples of pseudo6unimolecular
reactions are as follows.
$ * , * $ * , $ * ,
1* ** 11 * 6 1* 6 6 1* 6 1* ** 11
( 2 3
( 2 3
CH COOC H H O CH COOH C H OH rate k CH COOC H
C H O H O C H O C H O rate k C H O
+ + =
+ + =
1-. +nits of rate constant#
=
10. 5ero or1er reaction#
1!
13. Ha!f !ife of Bero or1er reaction#
14. &irst or1er reaction#
11
1*
16. Ha!f !ife of first or1er reaction#
1$
CHEMICAL KINETICS
SECTION-C
>1.E@press the rate of fo!!owin* reactions in ters of concentrations of reactants an1
pro1'cts.
i% .C!- D .C!( A C!$
ii% $NO$ D $NO A O$
So!'tion#
i- rate of reaction / 6
, $ *
2 3 2 3 2 3 d PCl d PCl d Cl
dt dt dt
= =
ii- 'ate of reaction /
* *
2 3 2 3 1 1 2 3
* *
d NO d O d NO
dt dt dt
= =
>$. The concentration of reactant ) at 1ifferent ties are *iven be!ow#
Tie in secon1s 9): in o! L
-1
! 10; E 1;
-(
- 4; E 1;
-(
1; ,; E 1;
-(
$; 1; E 1;
-(
(; $.- E 1;
-(
Ca!c'!ate the avera*e rate of reaction ) D . 1'rin* the 1ifferent interva!s of tie.
So!'tion#
)ave ? -
* 1
2 3 2 3 $ $
t

V
9)1: 9)$: t1 t$ )ave
E1;
-(
E1;
-(
Sec Sec o!=!it=sec
16! >! ! , 6
$
$
8>! 16!- 1! -
16 1!
, !
x
x

>! ! , 1! 6
$
$
8! >!- 1! -
> 1!
1! ,
x
x

! 1! 1! *! 6
$
$
81! !- 1! -
$ 1!
*! 1!
x
x

1! *., *! $! 6
$
$
8*., 1!- 1!
!.K, 1!
$! *!
x
x

7t can be seen that the average rate decreases from 16 N 1!

6$
to !.K, N 1!
6$
molClitCsec
;uring time interval ! to $! sec.
>(. Aonia an1 O@/*en reacte1 at hi*h teperat're as shown be!ow.
,NH( A-O$ D ,NOA 0H$O
The rate of foration of NO is (.0 E 1;
-(
o!=!it=sec. ca!c'!ate rate of 1isappearance of
aonia an1 rate of foration of water.
So!'tion#
'ate /
$ * *
2 3 2 3 2 3 1 1 1 2 3 1
, 6
d NH d O d H O d NO
dt dt dt dt
= = =
i- 'ate of disappearance of )A$ / 'ate of appearance of )+ / $.6 N 1!
6$
molClitCsec
ii- 'ate of formation of A*+ /
* *
2 3 2 3 1 1 2 3
6
d H O d H O d NO
dt dt dt
= =
Therefore
*
2 3 d H O
dt
/
6

N $.6 N 1!
6$
molClitCsec

1
>,. The 1ecoposition of N$O- in CC!, so!'tion at (14 K has been st'1ie1 b/ onitorin* the
Concentration of N$O- in the so!'tion. Initia!!/F the concentration of N$O- is $.(( M an1
after 14, in'tesF it is re1'ce1 to $.;4 M. the reaction ta"es p!ace accor1in* to the
e7'ation#
$N$O- D ,NO$ A O$
Ca!c'!ate the avera*e rate of this reaction in ters of ho'rsF in'tes an1 secon1s. Ghat
is the rate of pro1'ction of NO$ 1'rin* this perio1.
So!'tion#
'ate of reaction
/ 6
1
*
* ,
2 3 N O
t
V
V
/ 6
1
*
1
8*.!> *.$$- -
1>min
molL

/ 6.K= N 1!
6
molClitCmin
7f time 1> / $.!6K hours
'ate / 6
1
*
1
8*.!> *.$$- -
$.!6K
molL
hr

/ .!KN1!
6*
molClitChr
7f time / 1> N 6! / 11!! sec
'ate / 6
1
*
1
8*.!> *.$$- -
11!!sec
molL

/ 1.1$ N 1!
6,
molClitCsec
'ate /
1

*
2 3 NO
t
V
V
*
2 3 NO
t
V
V
/ N rate
/ N 6.K= N 1!
6
molClitCmin
/ *.K* N 1!
6$
molClitCmin
>-. Ca!c'!ate the overa!! or1er of reaction which has the rate e@pression#
i% )ate ? "9A:
1=$
9C:
(=$
ii% )ate ? " 9A:
(=$
9C:
-1
iii% A A C D C is Bero or1erF write rate e7'ation.
So!'tion#
i- +rder of reaction /
1
*
9
$
*
/* "econd order.
ii- +rder of reaction /
$
*
9861- /
1
*
Aalf order.
iii- For zero order reaction
. 9 1 0 :
'ate / kO.3
!
213
!
+rder of the reaction / ! 9 ! / ! Pero order.
>0. i% If the concentration of A an1 C are e@presse1 in ters of o!e 1
-(
an1 tie in in'tesF
ca!c'!ate the 'nits for rate constant for the fo!!owin* reaction#
A A C D AC
ii% Ghat are the 'nits for 5ero or1er reactionH
So!'tion#
i- for the reaction . 9 1 0 .1
'ate / k2.3213
The rate is change in concentration with time. The time and concentration are e#pressed in
minutes and dm
6$
respectively.
$
$ $
8 -8 -
min
moldm
k moldm moldm

= or
F/ 8mol dm
6$
-
61
8min
61
- / mol
61
dm
$
min
61
ii- For zero order reaction, the rate is independent of the concentration:
'ate / k
Qnits of k are : k / 'ate /
1
mol
s

mol ClitCsec
1,
>3. Grite the rate constant for a nth or1er reaction. <e1'ce fro this the 'nits of rate constant
for a i% ha!f or1er reaction ii% (=$
th
or1er reaction iii% thir1 or1er reaction.
So!'tion#
The units of the rate constant for n
th
order reactions are:
'ate / k2.3
n
1
mol
s

/ k2mol 5
61
3
n
k/8mol 5
61
-
16n
s
61
i- n /
1
*
, units are : mol
1C*
5
61C*
s
61
ii- n /
$
*
units are : mol
61C*
5
1C*
s
61
iv- n / $ , units are: mol
6*
5
*
s
61
>4. The rate !aw of a reaction of AFC an1 C has been fo'n1 to be rate ? " 9A:9C:9C:
$
. How are
the rate of reaction chan*e when
i% concentration of C is 1o'b!e1
ii% concentration of A is ha!ve1
iii% concentration of both C an1 C are 1o'b!e1
iv% concentration of each of AF CF C an1 < are trip!e1H
So!'tion#
"uppose the initial concentrations are :
2.3 / a mol 5
61
,
213 / b mol 5
61
'ate / k abc
*
2:3/ c mol 5
61
i- )ew2:3 / *c
'ate / k ab8*c-
*
/ kabc
*

'ate of reaction is four folded 8 times-.
ii- )ew2.3 / aC*
'ate / k2
*
a
3bc /
1
*
kabc
'ate of reaction is halved.
iii- )ew213 / *b )ew2:3 / *c
'ate / ka8*b- 8*c-
*
/ >kabc
*
'ate of reaction increased to > times.
iv- )ew 2.3 / $a, 213 / $b, 2:3 / $c
'ate / k 8$a-8$b-8$c-
*
/ >1kabc
*
'ate increased to >1 times.
>6. The 1ecoposition of h/1ro*en pero@i1e in the presence of io1i1e ion has been fo'n1 to
be first or1er in H$O$#
$H$O$ D $H$O A O$
The rate constant has been fo'n1 to be 1.;1 E 1;
-$
in
-
F ca!c'!ate the rate of reaction
when i% 9H$O$: ? ;., o!=!it ii% 9H$O$: ? ;.1- o!=!it
iii% Ghat concentration of 9H$O$: wo'!1 *ive rate of 1.1$ E1;
-$
o!=!it =in
So!'tion#
The reaction is of first order in A*+* so that
'ate / k2A*+*3
i- k / 1.!1N1!
6*
min
61
, 2A*+*3 / !. molC5
61
'ate / 81.!1N1!
6*
min
61
-N8!. mol 5
61
-
ii- 4hen 2A*+*3 / !.1, mol 5
61
'ate /81.!1N1!
6*
min
61
N8!.1, mol 5
61
-
/1.,N1!
6$
mol 5
61
min
61
iii- To obtain concentration of A*+* when rate
/1.1*N1!
6*
mol 5
61
min
61
2A*+*3/
* 1 1
* 1
1.1* 1! min
1.!1 1! min
$ate " molL
k "


=
/ 1.11 mol 5
61
16
>1;. &or the reaction
$A A C A C D A$C A C
The rate !aw has been fo'n1 to be
)ate ? "9A:9C:
$
with " ? $.; E 1;
-0
o!
-$
L
$
s
-1
&or this reactionF 1eterine the initia! rate of reaction with9A:?;.1 o! L
-1
F9C:?;.$ o!
L
-1
F9C: ?;.4 o! L
-1
.<eterine the rate after ;.;, o! L
-1
of A has been reacte1.
So!'tion#
'ate law is :
'ate / k2.3213
*
4here k/ *.! N 1!
66
mol
6*
5
*
s
61
7nitial concentration,
2.3 / !.1 mol 5
61
,213/!.* mol 5
61
,2:3/!.> mol 5
61
'ate / 8*.!N1!
66
mol
6*
5
*
s61-8!.1 mol 5
6*
-8!.* mol 5
61
-
*
/>N1!
6=
mol 5
61
s
61
:onc. +f . after !.! mol 5
61
of . has been reacted
2.3 / !.16!.! / !.!6 mol 5
61
)ow , we know that when * moles of . are consumed then one mole of 1 gets consumed.
Therefore , moles of 1 consumed when !.! moles of . have been consumed/!.!N1C* / !.!*
mole
213 / !.* D !.!* / !.1> mol 5
61
'ate / 8*.!N1!
66
mol
6*
5
*
s6
*
-N8!.!6 mol 5
61
-N8!.1> mol 5
61
-
*
/$.>=N1!
6=
mol 5
61
s
61
>11. &o!!owin* reaction ta"es p!ace in one step#
$NO A O$ D $NO$
How wi!! the rate of the above reaction chan*e if the vo!'e of the reaction vesse! is
<iinishe1 to one thir1 of its ori*ina! vo!'eH Gi!! there be an/ chan*e in the or1er of
the reaction with re1'ce1 vo!'eH
So!'tion#
1efore the volume of the reaction vessel is changed, the rate of reaction is e#pressed as:
' /k2)+3
*
2+*3EEEEE8i-
4hen the volume is reduced to
1
$
,the concentration of each reactant is increased by $ times.
'
1
/ k2$)+3
*
2$+*3EEEE8ii-
/*K k2)+3
*
2+*3
1
$
$
= *K. 'ate became *K times.
7t is clear the order of reaction remained same.
>1$. How wi!! rate of a reaction chan*e when 9A:; is 1o'b!e1 an1 trip!e1 for
i% Bero or1er reaction
ii% secon1 or1er reaction
So!'tion#
4hen 2.3! is doubled
i- The rate of zero order reaction remains unchanged.
ii- The rate of second order reaction becomes four times.
4hen 2.3! is tripled
i- The rate of zero order reaction remains unchanged
ii- The rate of second order reaction becomes = times.
>1(. Gh/ is the 'se of instantaneo's rate of reaction preferre1 over avera*e rate of reactionH
So!'tion#
The rate of reaction continuously decreases with time 8e#cept for zero order reaction- and
Therefore, average rate has no significance for the reaction.
>1,. Ghat is the or1er of a reaction whose rate constant has sae 'nits as the rate of the
)eactionH
So!'tion#
Pero order reaction.
1K
>1-. A spontaneo's reaction is not necessari!/ a fast reaction. Gh/H
So!'tion#
. spontaneous reaction means that it has tendency to occur of its own. 1ut this reaction may
take very small time or e#tremely large time.
>10. A reaction is fo'n1 to be Bero or1er. Gi!! its o!ec'!arit/ be BeroH
So!'tion#
)o, molecularity of a reaction cannot be zero.
>13. Is there an/ reaction whose rate 1oes not fa!! with the pro*ress of the reactionH
So!'tion#
Pero order reaction.
>14. Gh/ 1oes the rate of reaction not reain constant thro'*ho'tH
So!'tion#
1ecause the rate of reaction depends upon concentration of reactants which keeps on
decreasing.
>16. How rate is constant re!ate1 to concentration of the reactantsH
So!'tion#
'ate constant does not depend upon the concentration of the reactants.
>$;. &or a reaction#
A A H$O D CF rate I 9A:
Ghat is its i% o!ec'!arit/ ii% or1er of reaction
So!'tion#
i- Bseudo unimolecular ii- +rder of reaction / 1.
>$1. &or the reaction# ( H$ A N$ D $NH( F how are the rate of reaction e@pressions
-
$ *
2 3 2 3 d NH d H
and
dt dt
interre!ate1H
So!'tion#
6
$ *
2 3 2 3 1 1
$ *
d NH d H
dt dt
=
>$$. I1entif/ the reaction or1er fro each of the fo!!owin* rate constants#
i% "? 0.$ E 1;
--
L o!
-1
s
-1
ii% "?,.;E1;
-,
s
-1
So!'tion#
+rder can be predicted by the inspection of units of rate constant
i- second order reaction
ii- first order reaction
>$(. &or the reaction# Ester A H
A
D Aci1 A A!coho!F rate?"9Easter:9H
A
:
;
. &in1 the or1er of
reaction.
So!'tion#
+rder/1
>$,. &or the ass'e1 reaction#E$A$J$ D $EJ$F write the rate e7'ation in ters of the rate
of 1isappearance of J$.
So!'tion#
*
2 3 1
*
d (
dt
/k 2N*32R*3
*
*
2 3 d (
dt
/*k2N*32R*3
*
>$-. A reaction is secon1 or1er with respect to a reactant. How is the rate of reaction affecte1
if the concentration of the reactant is
i% <o'b!e1 ii% re1'ce1 to K H
1>
So!'tion#
'ate/k2.3
*
i- 4hen concentration of reactant is doubled, the rate becomes times.
ii- 4hen concentration of reactant is reduced to S the rate becomes T times.
>$0. The 1ecoposition of N$O- at ($;K accor1in* to the fo!!owin* e7'ation fo!!ows first
or1er reaction#
N$O-2*% D $NO$2*% A
1
*
O$ 2*%
The initia! concentration of N$O- was 1.$,E1;
-$
o! L
-1
an1 that after 0; in'tes 'as
;.$;E1;
-$
o! L
-1
. Ca!c'!ate the rate constant of the reaction at ($;K.
So!'tion#
For a first order reaction
!
2 3 *.$!$
log
2 3
$
k
t $
=
T/6! min.2'3! /1.*N1!
6*
mol 5
61
,2'3
/!.*!N1!
6*
mol 5
61
* 1
* 1
*.$!$ 1.* 1!
log
6! !.*! 1!
" molL
k
" molL


=
/
*.$!$
log6.*
6!
/
1
*.$!$
!.K=* !.!$!min
6!
"

=
>$3. The rate of 1ecoposition of h/1ro*en pero@i1e at a partic'!ar teperat're was
eas're1 b/ titratin* its so!'tion with aci1ic KMnO, so!'tion. &o!!owin* res'!ts were
obtaine1#
TieF t 2in% ; 1; $;
Mo! 2KMnO,% $$.4 1(.4 4.(
Show that the reaction is of first or1er.
i% Ca!c'!ate the rate constant.
So!'tion#
&olume of FMn+ used is proportional to the amount of A*+* present. 7f the reaction is of first
order, it must obey the e%uation.
!
!
2 3 *.$!$
log
2 3
*.$!$
log
t
A
k
t A
or
)
k
t )
=
=
Aere &! / **.> and the value of k can be calculated by substituting the concentration of &t at
different temperatures.
T/1! min, &t /1$.>
1
1
*.$!$ **.>
log
1! 1$.>
!.!,!**min
*!min, >.$
*.$!$ **.>
log
*! >.$
!.!,!,$min
t
k
t )
k

=
=
= =
=
=
i% "ince the value of k comes out to be almost constant, the reaction therefore, is of First
order.
ii% The mean value of k/!.!,!$K min
61
1=
>$4. The fo!!owin* 1ata were obtaine1 1'rin* the first or1er thera! 1ecoposition of N$O-
2*% at constant vo!'eF
$N$O- 2*% D $N$O, 2*% A O$ 2*%
Tie 2s% ; 1;;
Tota! press're2at% ;.-;; ;.-1$
Ca!c'!ate the rate constant.
So!'tion#
5et the pressure of )*+, decreases by *# atm. "ince * moles of )*+, decompose to give *
moles of )*+ and 1 mole of +* , then the pressure of )*+ 8g- increases by *# atm and that of
+*8g- increases by # atm.
*)*+, 8g- 0 *)*+ 8g- 9 +* 8g-
.t time, t/! !., atm ! !
.t time t81!! s- 8!.,6*#-atm *# atm # atm
Total pressure, pt/!.,6*#9*#9#/!.,9#
.t/1!! s, pt/!.,1* atm
+r #/ pt6!.,/!.,1*6!.,/!.!1* atm
)ow p8)*+,-/!.,6*#/!.,6*N!.!1*/!.K6 atm
For a first order reaction,
* , !
* ,
1
8 - *.$!$
log
8 -
*.$!$ !.,
log
1!! !.K6
*.$!$
log1.,!
1!!
*.$!$
!.!*1
1!!
.=$ 1!
t
p N O
k
t p N O
atm
atm
"
" s

=
=
=
=
=
>$6. The fo!!owin* 1ata were obtaine1 for the reaction#
$NO2*% A Cr2*% D $NOCr2*%
E@perient initia! conc initia! rate
9NO: 9Cr$: 2o! L-
1
in
-1
%
I ;.1; ;.1; 1.(E1;
-0
II ;.$; ;.1; -.$E1;
-0
III ;.$; ;.(; 1.-0E1;
--
<eterine i% the or1ers with respect to NO an1 Cr$ ii% the rate !aw an1
iii% )ate constant.
So!'tion#
The rate law may be written as:
'ate/k2)+3
p
21r*3
%
The initial rate becomes
8'ate-! / k2)+3!
p
21r*3
%
:omparing e#periment 7 and 77, we get
8'ate-1/k8!.1-
p
8!.1-
%
/1.$N1!
66
8'ate-*/k8!.*-
p
8!.1-
%
/,.*N1!
66
;ividing G%. 8ii- by G%. 8i-
6
*
6
1
8 - 8!.*- 8!.1- ,.* 1!
8 - 8!.1- 8!.1- 1.$ 1!
p q
p q
$ate k "
$ate k "

= =
+r 8*-
p
/ or 8*-
p
/ *
*
B/*.
Th'sF or1er with respect to NO is $.
:omparing e#periments 77 and 777
8'ate-* k8!.*-
p
8!.1-
%
/ ,.*N1!
66
8'ate-$/k8!.*-
p
8!.$-
%
/1.,6N1!
6,
;ivding G%. 8iv- by G%.8iii-, we get:
*!
,
6
8!.*- 8!.$- 1.,6 1!
8!.*- 8!.1- ,.* 1!
p q
p q
k "
k "

=
+r 8$-
%
/ $
+r %/1
Thus, order with respect can be calculated by substituting the values of rate, 2)+3 and 21r*3 for
any e#periment
6
* *
*
1.$ 1!
2 3 2 3 8!.1- 8!.1-
$ate "
k
NO Br

= =
/1.$N1!
6$
mol
6*
5
*
s
61
>(;. The fo!!owin* 1ata were obtaine1 for the reaction
$NO$2*% A &$ D $NO$&
E@perient initia! conc initia! rate
9NO$:; 9&$:; 9Cr$: 2o! L-
1
in
-1
%
I ;.$; ;.;- 0.; E1;
-(
II ;.,; ;.;- 1.$E1;
-$
III ;.4; ;.1; ,.4E1;
-$
<eterine i% Or1er of reaction ii% rate !aw iii% rate of reaction when 9NO$:?;.-; o!=!it
an1 9&$:?;.0; o!=!it
>(1. A reaction that is of first or1er with respect to reactant A has a rate constant 0 in
-1
. if
we start with 9A:?-.; o! L
-1
F when wo'!1 9A: reach the va!'e of ;.;- o! L
-1
H
So!'tion#
For the first order reaction,
!
2 3 *.$!$
log
2 3
A
t
k A
=
2.3! / ,.! mol 5
61
,2.3/!.!, mol 5
61
, k /6 min
61
,
*.$!$ ,.!
log
6 !.!,
*.$!$
log1!! !.K6>min
6
t =
= =
>($. The initia! rate of a reaction is
A A -C A 0C D (L A (M
Has been 1eterine1 b/ eas'rin* the rate of appearance of A 'n1er the fo!!owin*
con1itions.
E@pt. 9A:; 9CL; 9C:; Initia! rate
No. M M M M=in-
1
1. ;.;$ ;.;$ ;.;$ $.;4E1;
-(
$. ;.;1 ;.;$ ;.;$ 1.;,E1;
-(
(. ;.;$ ;.;, ;.;$ ,.10E1;
-(
,. ;.;$ ;.;$ ;.;, 4.($E1;
-(
<eterine the or1er of reaction with respect to each reactant an1 overa!! or1er of
reaction.
Ghat is the rate constantH Ca!c'!ate the initia! rate of reaction when the concentration of
a!! the reactions is ;.;1M. Ca!c'!ate the initia! rate of chan*e in concentration of C an1 L.

>((. The rate constant for the first or1er reaction is 0; sec. how 'ch tie wi!! it ta"e to
re1'ce the concentration to 1=10
th
va!'eH
So!'tion#
5et the initial conc.2.3! / a Final concentration /
1
16
a
'ate constant /6! s
61
!
2 3
*.$!$
log
2 3
A
t
k A
= /
*.$!$
log
6! C 16
a
a
=
*.$!$
log16
6!
= /
*.$!$
1.*! !.!6sec
6!
" = =
*1
>(,. Ca!c'!ate the ha!f !ife perio1 of a first or1er reaction where the specific rate constant is
i% $;;s
-1
ii% $ in
-1
iii% , /ears
-1
So!'tion#
For the first order reaction,
1C*
1
$
1C*
1
1C*
1
1C*
!.6=$
- *!!
!.6=$
$.6, 1!
*!!
- *min
!.6=$
!.$6,min
*
-
!.6=$
!.1K$*
*
t
k
i k s
t " s
ii k
t
iii k &ear
t &ear

=
=
= =
=
= =
=
= =
>(-. A first or1er reaction is fo'n1 to have rate constant "?-.-E1;
-1,
S
-1
. &in1 ha!f !ife perio1
of the reactionH
So!'tion#
1C*
1 1
1$
!.6=$
!.6=$
,., 1!
1.*6 1!
t
k
" s
" s

=
=
=
>(0. The ha!f !ife for ra1ioactive 1eca/ of
1,
C is -3(; /ears. An archaeo!o*ica! artifact
containe1 woo1 ha1 on!/ 4;M of
1,
C fo'n1 in a !ivin* tree. Estiate the a*e of sap!e.
So!'tion#
1C *
1C*
1
1
!
!

!.6=$
tan ,
,K$!
!.6=$
1.*!= 1!
,K$!
sin ,
1!!, >!
*.$!$
, log
*.$!$ 1!!
log
1.*!= 1! >!
*.$!$
1.*!=
Deca&cons t k
t
t &ear
k " &ear
&
incetherateofcountsisproportionaltothenumberof Catom thesample
N N
N
No' t
k N
"
"

=
=
= =
= =
=
=
=

!.!=6=
1!
1>6 .
"
&ears

=
>(3. &or a first or1er reactionF ca!c'!ate the ratio between the tie ta"en to cop!ete three-
&o'rth of the reaction an1 the tie ta"en to cop!ete ha!f of the reaction.
So!'tion#
!
2 3 *.$!$
log
2 3
A
t
k A
=
For U of a reaction to take place, t /t$C,2.3/2.3!6
$

2.3!
1

2.3!
**
Thus, t$C/
!
!
2 3 *.$!$ *.$!$
log log
1C 2 3
A
k A k
=
)ow, for half of a reaction
T/t1C*(2.3/1C*2.3!
!
1C*
!
2 3 *.$!$ *.$!$
log log *
2 3 C *
A
t
k A k
= =
$C
1C *
log !.6!*!
*
log* !.$!1!
t
t
= = =
Aence time re%uired for $C
th
of reaction to occur is two times that re%uired for half of the
reaction.
>(4. Show that in case of first or1er reaction the tie ta"en for the cop!etion of 66.6M
reaction is 1;ties tie re7'ire1 for ha!f chan*e of a reaction.
So!'tion#
! !
==.=
2 3 2 3 2 3
1!!
$ $ $ =
!
!.!!12 3 $ =
!
!
2 3 *.$!$
log
!.!!12 3
$
k $
=
$
*.$!$
log1!
*.$!$ $
k
"
k
=
=
4hen half of the reaction is completed
!
1C*
!
2 3 *.$!$
log
!.,2 3
*.$!$
log *
*.$!$ !.$!1!
$
t
k $
k
"
k
=
=
=
;ividing t==.=? by t1C*
8==.=?-
1C*
$
1!
!.$!1!
t
times
t
= =
> (6. The specific rate constant for the cobination of H$ an1 I$ to for HI is $.(, E 1;-(
o!=!it=sec. at 03( K an1 3.-; E1;-$ o!=!it=sec at 33(K. Ca!c'!ate the activation ener*/
for the reaction.
So!'tion#
The .rrhenius e%uation is:
*
1 1 *
1 1
log 2 3
*.$!$
a
# k
k $ % %
=
*
$

K.,! 1! 1 1
log 2 3
*.$ 1! *.$!$ 6K$ KK$
KK$ 6K$
log$*.!, 8 -
*.$!$ >.$1 6K$ KK$
1!!
1.,!6
*.$!$ >.$1 6K$ KK$
1.,!6 *.$!$ 6K$ KK$ >.$1
1!!
1.,1 1! C 1,.1 C
a
a
a
# "
" $
#
" "
#
"
" "
" " " "
#a
" * mol k+ mol

=
=
=
= =
*$
>,;. The rate constant s of a reaction at 3;;K an1 30;K are ;.;11Ms
-1
an1 ;.1;-Ms
-1

respective!/. Ca!c'!ate Arrheni's paraeters.
So!'tion#
*
1 1 *
1 1
log 2 3
*.$!$
a
# k
k $ % %
=
$
!.1!, 1 1
log 2 3
!.!11 *.$!$ K!! K6!
K6! K!!
log=.,=, 8 -
*.$!$ >.$1 K6! K!!
6!
!.=K=>
*.$!$ >.$1 K!! K6!
!.=K=> *.$!$ >.$1 K!! K6!
6!
166.$* 1! C 166.! C
a
a
a
#
$
#
" "
#
"
" "
" " " "
#a
" * mol k+ mol
=

=
=
=
= =
5og k / log .6
*.$!$
a
#
$%
5og ./log k 9
*.$!$
a
#
$%
5og . / log !.!119
$
166.$* 1!
*.$!$ >.$1 K!!
"
" "
/ 6 16=,>6 9 1*.11
/ 1!.,*
./ *.>$N1!
1!
M
61
s
61
>,1. The first or1er rate constant for the 1ecoposition of eth/! io1i1e b/ the reaction#
C$H-I D C$H, A HI
At 0;; K is 1.0;E 1;
--
s
-1
. its ener*/ of activation is $;6 "N o!
-1
. ca!c'!ate the rate
constant of the reaction at 3;;K.
So!'tion#
$
*
,
*
,
*
,
,
*
$ 1
*!= 1! K!! 6!!
log 2 3
1.6! 1! *.$!$ >.$1 K!! 6!!
log *.,==
1.6! 1!
$=K.1=
1.6! 1!
$=K.1= 1.6! 1!
6.$6 1!
k "
" " "
k
"
k
"
k " "
" s

=
=
=
=
=
>,$. Can activation ener*/ for reactions be BeroH
So!'tion#
7n the .rrhenius e%uation,
F/.e
DGaC'T
7f Ga is zero then k/.
i.e, every collision between molecules leads to chemical reaction. 4hich is not possible hence
Ga can not be zero.
>,(. Ghat va!'e of " is pre1icte1 for the rate constant b/ Arrheni's e7'ation if T D I H Is
this va!'e ph/sica!!/ reasonab!eH
So!'tion#
From the e%uation, k/.e
DGaC'T
,if T 0 H( k 0 . so that Ga/!. This is not feasible.
>,,. Gh/ O8 is positive for photocheica! reactionsH
So!'tion#
This is because a part of light energy absorbed by the reactants gets converted into free energy.
>,-. Ghat is the ain 1ifference between a photo sensitiBer an1 a cata!/stH
So!'tion#
. catalyst only changes the speed of the reaction, while a photo sensitizer only initiates the
reaction.
*
>,0. 8ive the 1aa*in* effect of photocheistr/.
So!'tion#
The color of fabrics fades away on e#posure to sunlight.
>,3. The ha!f !ife perio1 of a first or1er reaction is @ an1 three-fo'rth of the sae reaction is
/. how are @ an1 / re!ate1 to each otherH
So!'tion#
R is twice of # because the time re%uired for $C
th
of a reaction to occur is two times that
re%uired for half of the reaction.
>,4. After five ha!f !ife perio1s for a first or1er reaction what fraction of reactant reainsH
So!'tion#
1
$*
>,6. A s'bstance with initia! concentration Co fo!!ows Bero or1er "inetics. How !on* wi!! this
reaction ta"e to *ot to cop!etionH
So!'tion#
For zero order reaction,
:o / : 9kt
For the reaction to be completed : / !
:o/kt or t/
!
C
k
>-;. The rate !aw for a reaction is )ate ? "9A: 9C:
(=$
Can the reaction be an e!eentar/ processH E@p!ain.
So!'tion#
)o. .n elementary process would have a rate law with orders e%ual to its molecular ties and,
Therefore, must be integers.
>-1. A reaction is first or1er in A an1 secon1 or1er in C.
i% Grite 1ifferentia! rate e7'ation.
ii% How is the rate affecte1 when concentration of C is trip!e1H
iii% How is the rate affecte1 when concentration of both A an1 C is 1o'b!e1H
So!'tion#
i- 'ate D k2.3213
*
ii- 'ate becomes 8$-
*
/ = times
iii- 'ate becomes 8*-8*-
*
/> times
>-$. )eaction between NO$ an1 &$ to *ive NO$& ta"es p!ace b/ the fo!!owin* echanis#
NO$ A &$ D NO$& A &
NO$ A & D NO$&
Grite the rate e@pression for the reaction.
So!'tion#
"ince the slow step is the rate determining: 'ate/k 2)+*32F*3
>-(. It has been fo'n1 that for a reaction a !ar*e n'ber of co!!i1in* o!ec'!es has ener*/
ore than thresho!1 va!'eF /et the reaction is s!ow. Gh/H
So!'tion#
This is because the colliding molecules may not have proper orientation at the time of
collision, which is also a necessary condition for effective collisions.
>-,. Ghat are Bero or1er reactionsH 8ive an e@ap!e. Ghat are 'nits of " for Bero
or1er reactionH
So!'tion#
. zero order reaction is one in which rate of reaction remains unchanged by change in
concentration of reactants. The rate of reaction remains constant throughout the course of
reaction. e.g.
*,
'ate / order / !
'ate /
Qnit of k / mol 5
D1
s
D1
>--. Ca!c'!ate the or1er of reaction fro fo!!owin* 1ata -
)ate 9A: 9C: ? ;.1; ;.1; ? ;.$; ;.$; ? ;.1; ;.$;
"olution:
5et rate /
+rder of reaction /
+rder of reaction /
>-0. The activation ener*/ of reaction was fo'n1 to be 1$.,6 " ca! o!
P1
. If teperat're is
Increase1 fro $6-K to (;-K. &in1 the increase in rate of reaction.
So!'tion#
Liven ' / !.!!* F cal F
D1
mol
D1

/
/
/ !.$!1
/ *.!!

7ncrease in rate /
7ncrease in rate /
>-3. 3-M of first or1er reaction is cop!ete1 in (0 in'tes. How !on* wi!! it ta"e to cop!ete
-;M of reactionH
So!'tion#
F /
F /
*6
F / !.!6$= log
F /
/ !.!$>
F /
!.!$> /
!.!$> /
!.!$> /
+r / !.6=$*
t /
/ 1>.* minutes
>-4. Grite 1ifferences between o!ec'!arit/ an1 or1er of reaction.
So!'tion#

Mo!ec'!arit/ Or1er
1. 7t is the total number of
molecules as present in balanced
chemical reaction leading to
formation of products.
7t is the total number of molecule whose
concentration changes.
*. Molecularity of reaction can
never be in fractions.
+rder of reaction can be in fractions.
$. Molecularity of reaction cannot
be zero.
+rder of reaction can be zero.
>-6. &in1 the activation ener*/ of reaction *iven that Q
So!'tion#
/
or /
or log /
or !.6!* /
/
/ *=$>1.>1 VCmol.
*K
>0;. The ha!f-!ife perio1 of reaction is 1; in'tes. How !on* it wi!! ta"e for concentration of
reactant to be re1'ce1 to 1;M of ori*ina!.
So!'tion#
t ?
t /
t /
t /
>01. The s!ope of a !ine in the *raph of verses for a reaction is
P-0,$". Ca!c'!ate the activation ener*/ for this reaction.
So!'tion#
"lope /
/
?
?
?
>0$. The reaction .ro1'ctF is fo'n1 to be first or1er with respect to AF secon1
or1er with respect to C an1 Bero or1er with respect to C.
2i% Grite rate !aw for above reaction.
2ii% Ghat wi!! happen to rate of reaction when concentration of AF C an1 C are 1o'b!e1.
So!'tion#
8i- 'ate /
or /
8iii- 5et the rate of reaction
/
4hen concentration of ., 1 and : are doubled, let the rate /
/
/
/
*>
>0,. )ate of foration of pro1'ct for certain reaction is . The initia!
concentration of reactant was fo'n1 to ;.;1 o!=L. Ca!c'!ate the rate constant for the
*iven secon1 or1er reaction.
So!'tion#
For second order reaction6
'ate /
/
k /
/
>0-. In a first or1er reactionF 3-M of reactants 1isappeare1 in 1.(40 hrs. Ca!c'!ate the rate
constant of the reaction.
So!'tion#
F /
/
/
/
/
>00. $E ,JA5 &or the above chan*e if concentration of / increases b/ in 1;
sec. Ca!c'!ate the rate of appearance of / an1 rate of 1isappearance of @.
So!'tion#
'ate of reaction /
'ate of appearance of y /
/
'ate of disappearance of # /
/
*=
>03. Grite the e@pression for avera*e an1 instantaneo's rates for the fo!!owin* reaction-
So!'tion#
.verage rate /
7nstantaneous rate /
>04. A reaction .ro1'ct is fo'n1 to be thir1 or1er reaction. Ghat wi!! happen to rate of
reaction when concentration of A is 1o'b!e1H
So!'tion#
8Liven-
:onc. of . is doubled.
7t becomes *..
'ate of reaction will increase by factor of >.
>06. &in1 the 'nit of " for n
th
or1er reaction.
So!'tion#
For nth order reaction6
'ate /
k /
Qnits of k /
>3;. &or a reaction .ro1'cts. The rate of reaction 1o'b!es when concentration of A is
increase1 b/ ,. Ghat is the or1er of reactionH
So!'tion#
5et order of reaction / n
<<<<<<<<<< 81-
* <<<<<<<<<< 8*-
;ivide e%. 8*- by e%. 81-
>.31 <efine 2i% Activation ener*/ 2ii% Co!!ision fre7'enc/
So!'tion#
2i% Activation ener*/# .ctivation energy is the e#cess energy that the reactant molecule must
ac%uire in order to cross energy barrier and change into products.
.ctivation energy / Threshold energy D.verage energy of reactant molecule
2ii% Co!!ision fre7'enc/: The number of collisions per second per unit volume of reaction
mi#ture is known as collision fre%uency.
/
$!
>.3$
This reaction is of first or1er an1 rate constant of reaction is .
So!'tion#
'ate /
?
?
>.3( The rate constant of a reaction is o!
P1
in
P1
. Ghat is the or1er of reactionH
So!'tion#
The units of reaction are 8mol 5
D1
-
D1
min
D1
i.e. conc.
D1
time
D1
. These are the units of k for second
order reaction.
The order of reaction is *.
>3,.The rate constant for first or1er reaction has the va!'e . &in1 va!'e of
So!'tion#
/
/
/ 1*1., s
>.3- Ghat is
2i%)ate!awe@pressionH
2ii% )ate 1eterinin* stepH
So!'tion#
8i- 'ate law e#pression is the e#pression in which rate is given in terms of molar concentration
of reactants with each term raised to power which is e#perimentally determined.
8ii- 'ate determining step 6 The slowest step in a multiple step reaction which determines the
overall rate of reaction is called rate6determining step.
>.3- How 1oes chan*e in teperat're effects rate constantH Grite the re!ationshipF which
e@p!ains the teperat're 1epen1ence of a reaction.
So!'tion#
For a chemical reaction, every 1!W rise in temperature, nearly doubles the rate constant.
.rrhenius established the relationship between rate constant and temperature of reaction.
4here, . / .rrhenius factor C fre%uency factor
/ .ctivation energy in V mol
D1
>30. <<T on e@pos're to water 1ecoposes. Ha!f-!ife ? 1; /ears. How 'ch tie wi!! it ta"e
for its 6;M 1ecopositionH
So!'tion#
K! years
>33. In the reaction $A A C D a$CF if the concentration of A is 1o'b!e1 an1 that of C is ha!ve1
then the rate of reaction wi!!#
So!'tion#
7ncrease by * times
7nitially rate / k2.3
*
213 / a
*
b, new rate / k8*a-
*
8bC*-*ka
*
b
$1
>34. The cheica! reaction was carrie1 o't at (;;K an1 $4;". The rate constants were fo'n1
to be K1R K$ respective!/. Then
So!'tion#
F* / !.*,F1
For every 1!
!
rise in temperature, rate constant is doubled. Aence for *!
!
rises in the
temperature rate constant will become times.
>36. In Arrheni's p!otF intercept ?
So!'tion#
ln .
ln k / 68GaC'T- 9 ln .. Aence intercept / ln .
>4;. If I is the intensit/ of absorbe1 !i*ht an1 C is the concentration of AC for the
.hotocheica! reaction AC A h

D ACS the rate of foration of ACS is 1irect!/

proportiona! to#
So!'tion#
'ate of photochemical reaction is directly proportional to the 7ntensity of light.
>41. Ghen a biocheica! reaction is carrie1 o't in !aborator/ fro o'tsi1e of h'an bo1/ in
absence of enB/e then the rate of reaction obtaine1 is 1;
-0
ties then activation ener*/
of reaction in presence of enB/e is#
So!'tion#
;ifferent from Ga obtained in the laboratory
'ates are different due different activation energies.
>4$. 3-M of the first or1er reaction was cop!ete1 in ($ in'tes. -;M was
So!'tion#
16
K,? of the reaction is completed in two half lives.
>4$. The rate of *aseo's reaction is *iven b/ the e@pression "9A:9C:. If the vo!'e of reaction
vesse! is s'11en!/ re1'ce1 to 1=, of the initia! vo!'e the reaction rate re!atin* to the
ori*ina! rate wi!! be#
So!'tion#
16
rate/Fab when volume is reduced to 1C concentrations will become / times. )ew rate /k
8a- 8b- /16kab/16 times.
$*
SECTION-C 2CHEMICAL KINETICS%
>1. 8ive an e@ap!e of pse'1o or1er reaction.
So!'tion#
.n e#ample of pseudo order reaction is the hydrolysis of cane6sugar in the presence of mineral
acid A*"+ or A:l .
:1*A**+11 9 A*+ 0 :6A1*+6 9 :6A1*+6
.n e#ample of pseudo order reaction is the hydrolysis of easter in the presence
of mineral acid A*"+ or A:l .
:A$:++:*A, 9 A*+ 0 :A$:++A 9 :*A,+A
>$. A reaction is first or1er in A an1 secon1 or1er in C.
i% Grite 1ifferentia! rate e7'ation.
ii% How is the rate affecte1 if the concentration is trip!e1.
iii% How is the rate affecte1 when the concentration of both A an1 C are 1o'b!e1H
iv% Ghat is the si*nificance of rate constant in the rate e@pressionH
So!'tion#
i- ;ifferential rate e%uation is:
'ate / k2.3213
*
ii- 7f the concentration of 1 is tripled the rate becomes = times
'ate / k2.32$13
*
/ =k2.3213
$

iii- 7f the concentration of both . and 1 are doubled the rate becomes > times.
'ate / k2*.32*13
*
/ >k2.3213
$
iv- "ignificance: a- The value of rate constant 8k- is independent of concentration but
depends on temperature T
b- .t fi#ed temperature, k is constant and characteristic of the reaction.
c- k is proportionality constant ,7f both 2.3 and 213 are 1M each then rate of reaction is
e%ual to k.
>( E@press the re!ation between the ha!f !ife perio1 of a reactant an1 its initia! concentration
for a reaction of n
th
or1er.
So!'tion#
1C* 1
!
1
2 3
n
t
k A

=
>,. Is there an/ reaction for which reaction rate 1oes not 1ecrease with tieH
So!'tion#
For a zero order reaction, the reaction rate does not decrease with time because it is
independent of concentration of the reactants.
>-. E@press the re!ation between the ha!f !ife of a reaction an1 its initia! concentration if the
reaction invo!ve1 is of secon1 or1er.
So!'tion#
For second order reaction t1C* H
1
a
, a is initial concentration.
>0. A first or1er reaction ta"es 06.( in for -;M cop!etion. Set'p an e7'ation for
1eterinin* the tie nee1 for 4;M cop!etion of this reaction.
So!'tion#
First order reaction: 7n first case
*.$!$
log
*.$!$ 1!!
log
1!! ,!
*.$!$
log *
6=.$
a
k
t a x
k
t
k
=

=
7n second case
$$
*.$!$
log
*.$!$ 1!!
log
1!! >!
*.$!$
log,
a
k
t a x
k
t
k
t
=

=
*.$!$
log,
t
/
*.$!$
log *
6=.$
*.$!$log,
*.$!$
log *
6=.$
6=.$log,
16!.=$min
log *
t =
= =
>3. A certain reaction is -;M cop!ete in $; in'tes at (;;Kan1 the sae reaction is a*ain
-;M cop!ete in five in'tes at (-;K.Ca!c'!ate the activation ener*/ if it is a first or1er
reaction.2 )? 4.(1,T="=o!. An1 !o* , ? ;.0;$%
So!'tion#
1
1
1
*
!.6=$
!.!$6,min
*!min
!.6=$
!.1$>6min
,min
k
k

= =
= =
T1 / $!!F T* / $,!F
* * 1
1 1 *
log 2 3
*.$!$
$,! $!! !.1$>6
log 2 3
!.!$6, *.$!$ >.$1 $,! $!!
,!
2 3
1=.1K $,! $!!
log 1=.1K $,! $!!
,!
!.6!* 1=.1K $,! $!!
,!
1*1!*>1.>K
,!
**!,.6 C
*.*!, C
a
a
a
a
# k % %
k $ %%
#
" "
#
log
x
x x x
#
x x x
+ mol
k* mol

=
=
=
=
=
=
=
>4. &or the reaction A D CF the rate of reaction becoes $; ties when the concentration is
increase1 ( ties. Ghat is the or1er of the reactionH
So!'tion#
' / k2.3
n
EE.G% 8i-
*K' / k 2$.3
n
EEG%8ii-
;ividing the above 8ii- by 8i-
*K / $
n
n / $
Aence the order of reaction is $.
$
>6. The rate of a partic'!ar reaction trip!es when the teperat're chan*es fro -;
;
C to
1;;
;
C. Ca!c'!ate the activation ener*/ of reaction.2!o* ( ?;.,331.) ? 4.(1,N=K=o!.
So!'tion#

* * 1
1 1 *
* 1 *
1 * 1
1
log 2 3
*.$!$
*.$!$ 2 3log
$*$ $K$
*.$!$ >.$1 2 3log$
8$K$ $*$-
$*$ $K$
*.$!$ >.$1 2 3 !.KK1 C
,!
**!1.K6 C
**.!1* C
a
a
a
a
a
# k % %
k $ %%
% "% k
# "$"
% % k
," ,
# " +, "
,
"
# " " " + mol
# + mol
k+ mol

=
=

=
=
=
>.1; C!$ A $NO D $NOF the rate !aw is e@presse1 as rate ?"9C!$:9NO:
$
Ghat is
the over a!! or1er of this reactionH
So!'tion# $
>11. The 1ecoposition of NH( of p!atin' s'rface $NH( D N$ A (H$ is Bero
or1er reaction with " ? $.- E1;
-,
o!=sec.Ghat are the rates of pro1'ction of N$ an1 H$H
So!'tion#
*)A$ 0 )* 9 $A*
For a zero order reaction, 'ate of the reaction / k
* *

1 $
*., 1! C sec.
*., 1!
$ $
!.>$ 1! C sec.
rateofreactionofN $ateofproductionofH
$ateofproductionofN , " mol
, "
$ateofproductionofH
" mol

= =
= =
= =
=
>1$. Ghat is eant b/ e!eentar/ reactionH
So!'tion#
Glementary reaction is the reaction which takes place in one step. For e#ample
A* 9 7* 0 *A7
>1(. &o!!owin* reaction ta"es p!ace in one step. How wi!! the rate of this reaction chan*e if
vo!'e of the reaction vesse! is 1iinishe1 to one-thir1 of its ori*ina! vo!'eH
$NO A O$ U $NO
$
So!'tion#
The rate of the reaction *)+ 9 +* X *)+* is given by
'ate 8r- / k 2)+3
*
2+*3
7f the volume of the vessel is reduced to one6third of its original volume the rate of the reaction
will be raised to *K times.

1 * *
* *
8$2 3- 8$2 3- *K 2 3 2 3 *K r k NO O k NO O r = = =
>1,. 8ive the e@ap!es of pse'1o first or1er reaction.
So!'tion#
Aydrolysis of cane sugar in the presence of mineral acids like A:l or A*"+
:1*A**+11 9 A*+ 0 :6A1*+6 9 :6A1*+6
.n e#ample of pseudo order reaction is the hydrolysis of ester in the presence
of mineral acid A*"+ or A:l .
:A$:++:*A, 9 A*+ 0 :A$:++A 9 :*A,+A
$,
>1-. E@press the re!ation between ha!f !ife perio1 of reactant an1 its initia! concentration for a
reaction of n
th
or1er.
So!'tion#
t 1C* H
1
1
n
a

4here n is the order of reaction.
>10. The activation ener*/ of a reaction is 3- .$"N=o! in the absence of cata!/st an1
-;.1,"T=o! with a cata!/stF how an/ ties the rate of reaction *rows in the presence of
the cata!/st if the reaction procee1s in the presence of cata!/st at $-
;
CH
So!'tion#
1
*
1 *
* 1
*
1 *
1
*
1 1
1
*
1 1
1
*
1
*
1
n
n
1
8 -
1
*.$!* og 8K,.* C ,!.1 C -
*=> >.$1
*,.!6 1!!! C
*.$!$ *=> >.$1
*,!6!
log .!
,K!,.>
a
a
a a
a a
#
l k lnA
$%
#
l k lnA
$%
# #
lnk lnk
$% $%
k
ln # #
k $%
k
l k+ mol k+ mol
k ," +, mol
k " + mol
log
k " ," +, mol
k
k
k
k


=
=
=
=
=
=
= =
= log.! Anti
/ *., N 1!

Aence rate of reaction raised by *,!!! times in the presence of the catalyst.
>13. A reaction is -;M cop!ete in $ho'rs an1 3-M cop!ete in , ho'rs. Ghat is the or1er of
reaction.
So!'tion# First order
>14. E@press the rate of fo!!owin* reaction in ters of 1isappearance of h/1ro*en in the
reaction. (H$ A N$ D $NH(
So!'tion#
*
2 3 1
$
d H
$ate
dt
=
>16. The rate constant for a first or1er reaction is 0;s
-1
.How 'ch tie wi!! it ta"es to re1'ce
the concentration of the reactant to
1
1!
th
of its initia! va!'eH
So!'tion#
!
*
2 3 *.$!$
log
2 3
21 3 *.$!$
log
1
6!
2 3
1
!.!$>
$.> 1! .
$
t
k $
s
" s

=
=
=
=

>$;. State the con1ition at which a bio!ec'!ar reaction a/ becoe "inetica!!/ of first or1er
reaction.
So!'tion#
. bimolecular reaction may become kinetically of first order reaction if any one of the reactant
is taken in e#cess and the other is taken significantly low.
$6
"G:T7+)6 ; 8:AGM7:.5 F7)GT7:"-
1. )itric o#ide, )+, reacts with o#ygen to produce nitrogen dio#ide:
* )+8g- 9 +*8g- 0 *)+*8g-
The rate law for this reaction is
'ate/k 2)+3* 2+*3.
Bropose a mechanism for the above reaction.

$. The decomposition of a compound is found to follow a first6order rate law. 7f it takes 1,
minutes for *! percent of original material to react, calculate i- the specific rate constant, ii- the
time at which 1! percent of the original material remains un reacted, iii- the time it takes for
the ne#t *! percent of the reactant left to react first 1, minutes.
(. Find the two6third life, t*C$ , of a first order reaction in which k/,. # 1! 61 s 61
,. First order reaction is 1,? complete in *! minutes. Aow long will it take to be 6!? completeW
-. The catalyst decomposition of hydrogen pero#ide was studied by titrating it at different
intervals with FMn+. calculate the rate constant from the following data, assuming the
reaction to be of first order:
t8sec- ! 6!! 1,*!!
FMn+ 8ml- **.> 1$.> >.*3
0. The decomposition of phosphene, BA$ 8g- 0 B 9 6A* 8g- has rate law, rate F 2 BA$3. The
rate constant is 6.!# 1!
6
at $!!F and activation energy is $.!,# 1!
,
@Cmol. 4hat is the value
of rate constant at $!!F 8'/>.$1@CkCmol-.
3. . first order reaction is *!? complete in1! mints. :alculate time forK,?completion of the
reaction.
4. 7n general it is observed that the rate of a chemical reaction doubles for every 1!
!
. 7f this
generalization holds good for the reaction in the temperature range *=, D $!,F, what would be
the value of activation energy for this reaction.
6. 4hat are photochemical reactionsW Live an e#ample to illustrate the course of a photo
chemical reaction.
1;. For a first order reaction, show that time re%uire for the completion of ==.=? of reaction is $
times time re%uired for completion of =!? of the reaction.
11. . certain reaction is ,!? complete in *! mnts at $!!F and the same reaction is again ,!?
complete in , minutes in $,!F. :alculate the energy of activation if it is the reaction of first
order.
1$. The rate constant F of a reaction varies with temperature according to the e%uation: 5og
k / constant D Ga C *.$!$ ' T where Ga is activation energy for the reaction. 4hen a graph is
plotted for log k versus 1CT a straight line with a slope 666K! k is obtained. :alculate the
activation energy for this reaction. "tate the units 8'/>.$1@CkCmol-.
1(. "tate the role of activated comple# in a reaction and state its relation with activation energy.
1,. For a certain reaction, it takes , minutes for the initial concentration of !., moles per litre to
become !.*, mole per litre and another , minutes to become !.1*, made per liter. 4hat is the
order of this reaction and why it is soW :alculate the rate constant for the reaction.
1-. The reaction is "+*:l* 9 "+* 9 :l* is first order reaction with k / *.*N1!
6,
at $*!
!
:. what
? of "+*:l* is decomposed on heating this gas for =! minutes.
10. . certain reaction N 9 R 0 products, is first order with respect to each reactant with k /
, # 1!
6$
5C molC s. :alculate the concentration of N remaining after 1!! sec. 7f initial
concentration of N was !.1!!M and that of R was 1!M. "tate any appro#imation that you will
make in obtaining the result.
$K
13. 4rite stoichiometric e%uation whose mechanism is detailed bellow .* X *. kf / 1!
1!
sec
61
,kb/1!
1!
M
61
sec
61
. 4rite i- value of e%uilibrium constant for the first step ii- The rate law
e%uation for the overall reaction in terms of initial concentrations.
14. The rate constant for the decomposition of )*+, at various temperatures are given bellow
Blot log k against 1C T and calculate the energy of activation. Bredict the reaction rate at $!$F
and $$F.

Teperat're in centi*ra1e )ate constant "
! K.>K # 1!
6K
*! 1.K! #1!
6,
! *.,K # 1!
6
6! 1.K> # 1!
6$
>! *.1 # 1!
6*
16. The reaction *)+ 8g- 9 :l* 8g- X *)+:l was studied at 6 1!
!
:, and the following data
were obtained: 7nitial concentrations 8mol 5
61
- 7nitial rate of formation of )+:l mol 5
61
min
61
-

'un 2)+3 2:l*3
1 !.1! !.1! !.1>
* !.1! !.*! !.$6
$ !.*! !.*! 1.
i- 4hat is the order of reaction with respect to )+ and with respect to :l*W
ii- 4hat is the numerical value of the rate constant at 1!
!
:W

$;. The inversion of sucrose was studied in 1M A:l at *=> F. The following data were
obtained for optical rotation at different time intervals.
Time 8Min.- !.! 1!.! *!.! $!.! 6
'otation 8degrees- *., **.$ *!.$ 1>. 61!.K
:alculate i- rate constant of the reaction, and ii- half6life period. .lso show that the reaction
follows the first order kinetics.
$1. The decomposition of :l*+K at !! F in the gas phase to :l* and +* is 1
st
order reaction.
i- .fter ,, seconds at !!F, the pressure of :l*oK falls from !.!6* to !.!atm. :alculate the
rate constant. ii- :alculate the pressure of :l*+K after 1!! sec of decomposition at this
temperature.
$$. The rate of decomposition of )*+, is 1.$ # 1!
6
mol 5
61
s
61
when 2)*+,3 concentration is !.**M.
4hat is the value of k for this first order reactionW
$(. . gas phase decomposition of dimethyl either follows the first order kinetics
:A$ 6 + 6 :A$8g- 9 A*8g- 9 :+8g-
The reaction is carried out in a constant volume container at ,!!
!
: and has a half life period of
1., min. 7nitially only dimethyl either is present at a pressure of !.! atmosphere. 4hat is the
total pressure of the system after 1* minW .ssume ideal behavior.
$,. . first order reaction . 0 1 re%uires activation energy of K! k@ mol
61
. 4hen *!? solution of
. was kept at *,
!
: for *! minutes, *,? of decomposition took place what will be the
percentage decomposition of $!? solution at !
!
: in the same time.. .ssume activation energy
remains constant in this range of temperature.
$-. The half6time for the decomposition of nitramide is *.1 hour at 1,
!
:.
)A*)+*8a%- 0 )*+8g- 9 A*+8l- 7f 6.* g of )A*)+* is allowed to decompose, calculate:
i- time taken for )A*)+* to decompose ==? ii- volume of dry )*+ produced at this point
measured at ).T.B.
$>
$0. :onsider the data for the reaction between . and 1
9A: 9C: Initia! rate
2o! L
-1
% 2o! L
-1
% 2o! L
-1
s
-1
%
VVVVVVVVVVVVVVVVVVVVVV
T (;; K At ($; K
<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
*., # 1!
6
$.! # 1!
6,
, # 1!
6
* # 1!
6$
,.! # 1!
6
6.! # 1!
6,
# 1!
6$
66666666666
1.! # 1!
6$
6.! # 1!
6,
1.6 # 1!
6*
666666666666
<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<

:alculate i- +rder w.r.t. . and 1 ii- rate constant at $!! F iii- the energy of activation iv- the
pre6e#ponential factor
$3. The rate constant of a first order reaction is 6 times when the temperature is increased from
$,!F to 1!F. :alculate the energy of activation for the reaction.8 '/ >.$1 @k
61
mil
61
-.
$4. :onsider the following data for the reaction . 9 1 0 products
:onc.of . :onc.of 1 7nitial rate
8mol 5
61
- 8mol 5
61
- 8mol 5
61
s
61
-
!.1 !.1 .! # 1!
6
!.* !.* 1.6 # 1!
6$
!., !.1 1.! # 1!
6*
!., !., 1.! # 1!
6*
:alculate: i- the order w.r.t. . and 1 ii- the rate constant iii- reaction rate when the
concentration of . and 1 are !.* M and !.$, M respectively.
$6. .t $>!
!
:, the half6life period for the first order decomposition of A*+* is $6! min. The energy
of activation is *!! k@ C mol. :alculate the time re%uired for K,? decomposition at ,!
!
:.
(;. The ionization constant of )A
9
ion in water is ,.6 # 1!
1!
at *,
!
:. The rate constant for the
reaction between +A
6
and )A
9
to form )A$ and A*+ at *,
!
: is $. # 1!
1!
5C molC s. calculate
the rate constant for proton transfer from A*+ to )A$.
(1. The rate constant for the first order decomposition of certain reaction is described by the
e%uation
5og k8 s
61
-/ 1.$ D 81.*, # 1!

F- C T
i- 4hat is the energy of activation for this reactionW
ii- .t what temperature will the half life period be *,6 minW
($. :onsider the following data for the reaction: . 9 1 0 products. ;etermine the overall order
w.r.t.. and 1.
Conc.of A Conc.of C Initia! rate
2o! L
-1
% 2o! L
-1
% 2o! L
-1
s
-1
%
!.1 M 1.!! M *.1 # 1!
6$
!.* M 1.!! M >. # 1!
6$
!.* M *.!! M >. # 1!
6$
((. The time re%uired for 1!? completion of a first order reaction at *=> F is e%ual to that
re%uired for it *,? completion at $!>F if pre6e#ponential factor of reaction is $.,6# 1!
=
s
61
.
:alculate the rate constant at $1>F and also energy of activation.
(,. The rate constant of a reaction is 1., # 1!
K
at ,!
!
: and ., # 1!
K
s
61
at 1!!
!
:. Gvaluate the
.rrhenius parameters . and Ga.
(-. For the reaction )*+, 0 *)+* 9 !., +* . :alculate the mole fraction of )*+, decomposed at
constant volume and temperature if initial pressure is 6!! mm of Ag and the pressure at any
time is =6!mm of Ag. .ssuming the gas to be ideal.
(0. The rate constant for an iso6merization reaction is . 0 1 ., # 1!
6$
min.
61
. 7f initial
concentration of . is 1M. :alculate the rate of reaction after one hour.
$=
(3. The vapour pressure of two miscible li%uids . and 1 are $!! and ,!! mm of Ag respectively.
7n a flask 1! moles of . is mi#ed with 1* moles of 1. Aowever, as soon as 1 is added, . starts
polymerizing into a insoluble solid. The polymerization follows first order kinetics. .fter 1!!
minutes, !.,*, mole of a solute is dissolved which arrests the polymerization completely. The
final vapour pressure of the solution is !! mm of Ag. Gstimate the rate constant of the
polymerization reaction. .ssume negligible volume changes on mi#ing and polymerization and
ideal behaviour for the final solution.
(4. For the reaction, . 9 1 0 products, the following initial rates were obtained at various given
initial concentrations
S.No. 9A: o! L
-1
9C: o! L
-1
)ate
2o! L
-1
s
-1
%
1 !.1 !.1 !.!,
* !.* !.1 !.1!
$ !.1 !.* !.!,
4rite the rate law and find the rate constant of the above reaction.


!