Chemical Kinetics

CHEMICAL KINETICS
CHEMICAL KINETICS
1. INTRODUCTION :
The branch of physical chemistry which deals with the rate and mechanism of chemical reaction as
well as the factors which influences the rate of chemical reaction is called Chemical Kinetics.
2. TYES O! REACTIONS :
On the basis of their rates, the chemical reactions may be classified into the following three types:
2.1 "ERY !AST OR INSTANTANEOUS REACTIONS:
These reactions occur as soon as the reactants are brought together.
These are mostly ionic reaction and do not involve any type of bond fission and formation
between atoms. Examples:
AgNO
!a"# $ %&l!a"#
Ag&l!s# $ %NO
!a"#
NaO% !a"# $ %&l !a"#
Na&l!a"# $ %
'
O!l#
As these types of reactions are very first, it is very difficult to determine the rate of such
reactions.
2.2 "ERY SLO# REACTIONS:
These are very slow reactions and ta(es very long time for any measurable changes.
As these reactions are very slow, it is also very difficult to determine the rate of such reactions.
Examples:
)oom temperature
'
&O '% &% O% +
)usting of iron
*ermentation reactions, etc
These reactions are molecular in nature and generally involve a large number of bond cleavage
and formation.
2.$ MODERATE REACTIONS:
These are neither two fast are two slow reactions. They ta(e place at moderate speed.
+ost of these reactions are molecular in nature. Examples:
'%
'
O
'

'%
'
O $ O
'
'N
'
O
,

'N
'
O
-
$ O
'
'NO
'
$ &O
NO $ &O
'
The rate of such reactions can be determined easily. .e study mainly the (inetics of such
reactions.
$. RATE O! TEACTION :
)ate of a reaction is defined as the change in concentration of reactant or product per unit time.
)ate of reaction /
&
t
/
0
change in concentration of reactant or product !in mol 1 #
time!insecond#
*or most of the reactions, the rate of reaction changes with time and hence it is expressed as
instantaneous rate as, r /
d&
dt
. The expression
&
t
represents the average rate of reaction.

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CHEMICAL KINETICS
The charge in concentration of different reaction components per unit time depends on the
balanced chemical reaction and hence the rate is normally expressed as change in concentration
per unit time per mol of that substance. *or example: for the reaction: m
0
A $ m
'
7
n
0
8 $ n
'
9,
rate of reaction /
0 ' 0 '
0 d:A; 0 d:7; 0 d:8; 0 d:9;
m dt m dt n dt n dt

%ere, <ve sign represent the decrease in concentration with time and $ve sign, increase in
concentration with time.
Normally, the rate of reaction is expressed in mol l
<0
sec
<0
.
%. RATE LA# AND RATE CONSTANT :
At a &i'en tem(e)at*)e+ the )ate ,- a )eacti,n at a (a)tic*la) instant is (),(,)ti,nal t, the
(),.*ct ,- the acti'e masses ,- the )eactants )aise. t, the e/(e)imentall0 .ete)mine.
(,1e)s.
&onsider a general reaction a8 $ b9
8roducts
rate :8;
=
:9;
>

or, rate / 5:8;
=
:9;
>
%ere 5 is 'el,cit0 c,nstant or )ate c,nstant or s(eci-ic )eacti,n )ate and x and y are
experimentally determined values.
?f :A; / :7; / 0 or rate / 5. @o rate constant is defined as rate of reaction when concentration of
all reactants is ta(en unity.
Aalue of rate constant of a reaction depends only on temperature and catalytic condition.
Bnit of rate constant / !conc.#
0< n
time
<0
, where n is the order of reaction.
2. MOLECULARITY O! REACTION :
*or elementary or single step reactions the molecularity is defined as the number of molecules of
reactants involved in the balanced chemical reaction. Examples:
8&l
,

8&l
$ &l
'
!Bnimolecular#
'%?
%
'
$ ?
'
!7imolecular#
*or multi step reactions, the molecularity is defined as the minimum number of reacting particles
!molecules, atoms or ions# ta(ing part in slowest step or rate determining step !)C@# of chemical
reaction. %owever, the molecularity of such reactions has no significance.
!a# %
'
O
'

%
'
O $ O!@low#
O $ O
O
'
!*ast#
'%
'
O
'

'%
'
O $ O
'
!Bnimolecular#
!b# NO
'
$ *
'

NO
'
* $ * !@low#
NO
'
$ *
NO
'
*!*ast#
'NO
'
$ *
'

'NO
'
* !7imolecular#
+olecularity of any reaction can not be Dero, negative or fractional. ?ts maximum value will be .

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CHEMICAL KINETICS
3. ORDER O! REACTION :
It is the s*m ,- (,1e)s ,n the acti'e masses ,- )eacti,n c,m(,nents in the )ate la1
e/()essi,n ,- the )eacti,n. *or example, if for the reaction: aA $ b7
products, the rate law

expression is
r / 5:A;
x
:7;
y
, then !x $ y# is order of reaction.
?f x / a, y / b, then the order and molecularity of reaction are same. *or single step or elementary
reactions, such condition is always true. *or multi step reactions, order and molecularity may or
may not be same.
Order is an experimentally determined "uantity. ?t can not be determined from stoichiometric
coefficient of reaction components.
?t may be Dero, positive, negative, fractional and even, in rare cases, greater that three.
4. SEUDO5UNIMOLECULAR REACTION :
?n second order reaction, when one reactant is present in large excess, the second order reaction
confirms to be first order. @uch reactions are called 8seudo unimolecular reaction. *or example,
molecularity for the acidic hydrolysis of ester is ' but order is 0.

%
' , ' ' ,
&% &OO& % % O &% &OO% & % O%
+
+ +
+olecularity / 'E order / 0 !%
'
O in excess#
6. INTERATED RATE LA#S :
Cifferential e"uation !rate laws# obtained from experimental data or mechanism of reaction represents
only the rate of change in concentration of reaction components with time. ?t can be integrated for
certain time period to get the concentrations of reaction components at time, t.
6.1 7ERO ORDER REACTIONS
)eactions whose rate is proportional to the Deroth power of concentration of the reactants are Dero
order reactions. )ate of such reactions do not changes with time. *or a Dero order reaction,
A
8roducts
)ate, r /
d:A;
(:A; (
dt

@ome photochemical reactions, heterogeneous reactions and enDyme catalyDed reactions are Dero
order reactions. Examples:
!i#
' '
h
% &l '%&l
+
!ii#
gold
' ' surface
'%l % $l
!iii#
+o
' '
'N% N $%
?ntegrated rate law:
o
:A ; :A;
5
t
%alf life 0
'
! # t
:
2
0F'
:A ;
t /
'5
6.2 !IRST ORDER REACTIONS:
A reaction is called first order if its rate is proportional to concentration of reactant. *or a first order
reaction,

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CHEMICAL KINETICS
A
8roducts
)ate, r / <
[ ]
[ ] [ ]
0
d A
5 A 5 A
dt

Examples:
!i# %
'
O
'

%
'
O $ 0F'O
'
!ii# N%
-
NO
'

N
'
$ '%
'
O
!iii# N
'
O
,

'NO
'
$ 0F'O
'
!iv# )adioactive decays, virus or bacteria generation or inactivation.
?ntegrated rate law:
2
2
(t
:A ; '.2
(/ log or :A; / :A; e
t :A;

%alf life, 0
'
! # t
:
0F '
2.GH
5
t
6.$. SECOND ORDER REACTION:
A reaction is called second order reaction if is depend on two concentration terms.
Examples:
!i# &%
&OO&
'
%
,
$ NaO%
&%
&OONa $ &
'
%
,
O% !@aponification#
!ii# ' NO
'

' NO $ O
'
!iii# '&%
&%O
'&%
-
$ '&O
6.%.2 Sec,n. ,).e) 8inetics can 9e a((lie. ,n t1, t0(es ,- )eacti,ns:
!a# 'A
product, the integrated rate law is ( /

2
0 0 0
: ; : ;
1
1
]
t A A
!b# &onsider another reaction,
A $ 7

product
t / 2 a b 2
t / t a < x b < x x
dx
/ (!a x#!b x#
dt

On integrating, ( /
02
'.2 b!a x#
log
t!a b# a!b x#

%alf life 0
'
! # t
: *or second order reactions of type 'A
product,
0F'
2
0
t /
5:A ;
*or second order reaction of type !b#, the half life of reaction is given as the half life of limiting
reagent.
:. SOME SECIAL CASES :
:.1 ARALLEL REACTIONS:
&onsider following first order reaction proceeding through two parallel paths,
one leading to product 7 and other leading to product &.
The overall rate constant , 5 / 5
0
$ 5
'

A
7
&
(
0
(
'

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CHEMICAL KINETICS
*ractional yield of 7 /
0
0 '
(
( $(
and, fractional yield of & /
'
0 '
(
( $(
At any time t 2,
0
'
:7; (
/
:&; (
?f the concentration of A, 7 and & at any time, t, are :A;, :7; and :&;, then
:A; / :A
2
;
5 t
e

:7; /
0 2
5 :A ;
5
!
0
5 t
e
3 0#
:&; /
' 2
5 :A ;
5
!
'
5 t
e
3 0#
SUCCESSI"E REACTIONS:
&onsider A is converted into 7 and simultaneously 7 is converted into &, following first order
(inetics.
0 '
( (
A 7 &

1et after time, t, concentrations of A, 7 and & are :A;, :7; and :&; respectively. Then
:A; / :A
2
;
0
3 ( t
e
:7; /
0 '
( t ( t 0 2
' 0
( :A ;
:e e ;
!( ( #

:&; / :A
2
; < !:A; $ :7;#
*rom the above e"uations, the following cases of e"uilibrium may exist:
!i# T)ansient e;*ili9)i*m: ?f 5
0
I 5
'
, then
' 0
0
:A; 5 35
:7; 5
!ii# Sec*la) e;*ili9)i*m: ?f 5

0
II 5
'
, then
'
0
:A; 5
/
:7; 5
Time for maximum concentration of 7,
0
0 ' '
5 0
.ln
5 5 5
_
,
t
and the maximum concentration of 7 is, :7;
max
/ :A
2
;.
'
' 0
5
5 5
0
'
5
5

_

,
OOSIN< OR RE"ERSI=LE REACTIONS:
*or the first order reaction opposed by first order reaction of type A
0
0
5
5

7
:7; /
0 2
0 30
5 :A ;
5 $ 5
!0 3
0 30
!5 $ 5 # t
e
# and :A; / :A
2
; < :7;
1>. COLLISION THEORY :
This theory was given by Arrhenius and AonJt %off.
This theory is mainly applicable for the bimolecular gaseous reactions.

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CHEMICAL KINETICS
A chemical reaction ta(es place due to the collisions between the reactant molecules. 7ond
cleavage as well as bond formation ta(es place at the time of collision between the molecules.
The number of molecular collisions ta(ing place per second unit volume of the reaction mixture is
(nown as collision fre"uency !K
00
or K
0'
#.
*or binary collisions between similar molecules, K
00
/
'
'
0
& N
'

, where
is collision
diameter, & is average speed, and N is number of molecules per unit volume.
*or binary collisions between different molecules, K
0'
/
'
av 0 '
& N N

, where
av
/
0 '
'
+ _

,
is the average collision diameter, & /
L )T

is average speed !
is reduced molar
mass /
0 '
0 '
+ +
+ + +
# and N
0
and N
'
are the number of molecules of the gases per unit volume.
Bnder normal conditions, the value of K
00
or K
0'
is about 02
G
mol l
30
s
30
. Normally, the reactions
are not so fast. ?t represents that all molecular collisions do not response reaction. )eaction occurs
due to a very small fraction of collisions.
The collisions that actually produce products are called e--ecti'e c,llisi,n. *or a collision to be
effective, the following two barriers should be crossed by the molecules:
1>.1 ENER<Y =ARRIER:
According to the (inetic theory of gases, in any gaseous system, different gas molecules may
travel with different speeds. The molecular collision with low energy can never cause bond
cleavage and hence can not result the product formation. Only those molecular collision result the
formation of product in which the molecules collides with a certain minimum energy.
The minimum amount of energy, which the colliding molecules must posses in order to ma(e the
chemical reaction to occur, is (nown as Th)esh,l. Ene)&0+ E
T
.
The minimum amount of energy re"uired to ma(e active participation of almost all molecules in a
reaction is called Acti'ati,n Ene)&0+ E
a
. The activation energy is e"ual to E
T
< E
)
, where E
)
is
the average energy level of reactant molecules.
The activation energy of reaction depends on the nature of reactant and temperature. ?t decreases
with increase in temperature but the decrease is so small that it is normally considered
temperature independent.
The fraction of molecules having energy e"ual to threshold energy or more is given by the
7erthelotJs expression,
a
E F )T
e
.
1>.2 ORIENTATION =ARRIER:
The reacting molecules must collide in proper direction to ma(e the collision effective. The
colliding molecules must be in the direction of maximum overlapping.
The orientation factor is not much significant in all reactions. 7ut, is become important when
different products may form at molecular collisions at different places.
The fraction of molecular collision at right place is given by ,)ientati,n or (),9a9ilit0 -act,)+ 8.
1>.$ On considering these barriers for reaction, the rate of reaction may be given by the collision theory as
)ate / collision fre"uency M fraction of effective collision
/ &ollision fre"uency M fraction of collisions with M fraction of molecules in
sufficient energy proper orientation
or, r / !K
00
or K
0'
# M
a
E F )T
e
M 8

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CHEMICAL KINETICS
7ut, for bimolecular elementary reaction of type, 'A
products, the experimental rate of reaction

should be r / 5 :A;
'
. Therefore,
5 :A;
'
/ K
00
.
a
E F )T
e
.8
or, K ? A.
a
E F )T
e
.
A /
00
'
K
:A;
/
' '
A
0
& N
'

is called pre3exponential factor. *or any reaction, its value will depend
on temperature but due to very small change in its value, it is also considered temperature
independent.
The e"uation is called A))heni*s e;*ati,n and is used to represent temperature dependence of
reaction rate. %owever, in actual Arrhenius e"uation, the term 8 was not present. Actually, the
orientation factor was not given by Arrhenius. This is why, the e"uation is simply represented as
5 / A.
a
E F )T
e
11. ACTI"ATED COMLE@ THEORY ,) TRANSITION STATE THEORY

This theory was given by E0)in& and ,l0ani.
A reaction occurs due to interaction between reactant molecules. The reactant molecules come closer
to each other to form an acti'ate. c,m(le/, whose energy is greater than that of reactant molecules.
The configuration of atoms in the activated complex at its maximum potential energy is called
t)ansiti,n state.
The activated complex is supposed to be in e"uilibrium with the reactant molecules and it has all the
attributes of a normal molecule except that one of the vibrational degree of freedom is converted into
translational degree of freedom along the reaction coordinate.
The experimental existence of transition state has been shown by Ahme. H. 7e1ail.
A reaction occurs when the activated complex decomposes to give product. Therefore, a simple
bimolecular reaction may be represented as A A =
5

A=
5
),.*cts, where A7 is the

activated complex and 5 is the e"uilibrium constant for the e"uilibrium between reactants and
activated complex.
The rate of reaction will be e"ual to the rate of conversion of activated complex into the products.
%ence,
r / :A7; fre"uency of conversion of activated complex into products
As, 5 /
:A7N;
:A; :7;

:A7; / 5 :A; :7; /

2
O F )T
e
:A; :7;
The decomposition of activated complex will occur due to conversion of its one of the vibrational
degree of freedom into translational degree of freedom. *rom classical mechanics, the vibrational
energy is 5
b
T, where 5
b
is the 7oltDmann constant !)FN
A
#. 7ut from "uantum mechanics, it is h,
where h is the 8lanc(Js constant and is the fre"uency of vibration. Oreater the fre"uency of
vibration, greater will be the possibility of decomposition of activated complex into products. %ence,
the fre"uency of conversion of activated complex into products may be given as . / .5
b
TFh, where
is called the t)ansmissi,n c,e--icient.
%ence, finally, according to the activated complex theory,
rate of reaction, r / :A7; fre"uency of conversion of activated complex into products
/ !
2
O F )T
e
:A; :7;#.!.5
b
TFh#
/ !.5
b
TFh#.
2
@ F )
e
.
2
% F )T
e
.:A; :7;
and the rate constant of reaction, 5 / !.5
b
TFh#.
2
@ F )
e
.
2
% F )T
e
. This is called E0)in& e;*ati,n for

the rate constant of simple bimolecular reactions. %ere, %
2
and @
2
are enthalpy and entropy of
activation, respectively. Enthalpy of activation is normally very close to the activation energy, which
was used in collision theory.

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CHEMICAL KINETICS
The following relation may be found on comparing collision theory and activated complex theory:
Activation energy, Ea / %
2

8re3exponential factor, A / !.5
b
TFh#.
2
@ F )
e
12. !ACTORS A!!ECTIN< RATE O! REACTION :

12.1 NATURE O! REACTANTS:
h0sical state ,- )eactants:
gaseous state Q li"uid state Qsolid state
Cecreasing order of rate of reaction
Chemical nat*)e ,- )eactants: Number of bonds to be bro(en and bond strength of reacting
molecules affects the rate of reaction.
!i# ?f more bonds are to be bro(en, the reaction will be slow.
!ii# ?f bond strength is more, the reaction will be slow.
12.2 CONCENTRATION O! REACTANTS:
*or most of the reactions, rate of reaction depends on concentration of reactants. %ence, normally
rate of reactions decrease with decease in concentration of reactants.
12.$ E!!ECT O! TEMERATURE:
)ate of reaction increases with increase in temperature. Normally, for every 02& rise in temperature,
the rate of reaction increases ' to times.
The temperature coefficient !# of a chemical reaction is defined as the ratio of the specific rates of a
reaction at ,& and at ',&.
2 2
2 2
, c , c
', c ', c
r 5
R / /
r 5
Arrhenious suggested an e"uation which describes 5 as a function of temperature.
?f 5
0
and 5
'
are the rate constants at T
0
5 and T
'
5
,
then
a '
0 0 '
E ( 0 0
log
( '.2) T T
_ _

, ,
12.% RESENCE O! CATALYST:
8resence of positive catalyst increases the rate of reaction by decreasing the activation energy.
8resence of negative catalyst decreases the rate of reaction by increasing the activation energy.
A catalyst mainly affects the activation energy of reaction and hence the rate constant and rate of
reaction changes.
12.2 SUR!ACE AREA:
The rate of reaction having solid reactant increases with the increase in surface area of the solid
reactant. *or example, when Dinc is reacted with %&l solution, the rate will be greater by adding Dinc
powder in the acid solution than immersing Dinc rod in it.

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CHEMICAL KINETICS
12.3 INTENSITY O! RADIATION:
The rate of photochemical reactions normally increases with increase in intensity of radiation.
#ORKED OUT E@AMLES
E/am(le 1: The )eacti,n 2NO A =)
2

2NO=)+ ,9e0s the -,ll,1in& mechanism:

Ste( I: NO A =)
2

*ast

NO=)
2
Ste( II: NO=)
2
A NO
@low
2NO=)
S*&&est the )ate e/()essi,n.
@olution: @tep ?? is the rate determining step of the reaction and hence,
r / 5 :NO7r
'
; :NO; S !0#
%owever, NO7r
'
is an intermediate and thus its concentration should be determined from the
e"uilibrium of step ?.
*or step ?, e"uilibrium constant, K
&
/
[ ]
[ ] [ ]
'
'
NO7r
NO 7r
:NO7r
'
; / K
C
:NO;:7r
'
; S !'#
Thus, by e"uations !0# and !'#, r / K K
&
:NO;
'
:7r
'
;
or, ) ? K BNOC
2
B=)
2
C+ where 5J / 5.5c
E/am(le 2: The )ate c,nstant -,) the )eacti,n:
CO
2
A OH
D
HCO
in the a;*e,*s s,l*ti,n is % E 1>

D$
lit)e m,l
D1
sec
D1
. Calc*late the n*m9e) ,- m,le ,- CO
2
an. OH
D
*se. *( (e) sec,n. 1hen BCO
2
C an. BOH
D
C a)e 1>
D3
an. 1>
D1
m,l lit)e
D1
. Als,
()e.ict the m,le ,- HCO
-,)me. (e) sec,n..

@olution:
[ ] [ ]
'
d O%
d &O d %&O
)ate of reaction
dt dt dt
1
]
+
The unit of 5 suggests that it is a ?? order reaction. Thus, the rate of reaction,
r / 5 :&O
'
; :O%
<
; / - M 02
<
M 02
<G
M 02
<0
/ - M 02
<02
mol litre
<0
sec
<0
%ence, mole of &O
'
and O%
<
consumed and mole of %&O
formed per sec / % E 1>

D1>
E/am(le $: The .ata &i'en 9el,1 a)e -,) the )eacti,n ,- NO an. Cl
2
t, -,)m NOCl at 2:2K.
BCl
2
C BNOC Initial )ate Fm,l lit)e
D1
sec
D1
G
>.>2 >.>2 1 E 1>
D$
>.12 >.>2 $ E 1>
D$
>.>2 >.12 : E 1>
D$
FaG #hat is the ,).e) ,- )eacti,n 1ith )es(ect t, NO an. Cl
2
.
F9G #)ite the )ate e/()essi,n.
FcG Calc*late the )ate c,nstant.
F.G Dete)mine the )eacti,n )ate 1hen c,nc. ,- Cl
2
an. NO a)e >.2 M an. >.% M
)es(ecti'el0.

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CHEMICAL KINETICS
@olution: *or the reaction 'NO $ &l
'
'NO&l
)ate, r / 5 :&l
'
;
x
:NO;
y
S..!0#
where, x and y are order of reaction with respect to &l
'
and NO respectively
*rom the given data:
0 M 02
<
/ 5 :2.2,;
x
:2.2,;
y
S..!'#
M 02
<
/ 5 :2.0,;
x
:2.2,;
y
S..!#
H M 02
<
/ 5 :2.2,;
x
:2.2,;
y
S..!-#
*rom e"uations !'# and !#, / ? 1
and from e"uations !'# and !-#, 0 ? 2
!a# Order with respect to NO is ' and with respect to &l
'
is 0.
!b# )ate expression, r ? KBCl
2
C
1
BNOC
2
!c# )ate constant, 5 /
[ ] [ ] [ ] [ ]
0 ' 0 '
'
r 0
&l NO 2.2, 2.2,
? 6 lit)e
2
m,l
D2
sec
D1
!d# r / 5:&l
'
;
0
:NO;
'
/ L:2.';
0
:2.-;
'
? >.223 m,l lit)e
D1
sec
D1
E/am(le %: The )ate e/()essi,n -,) a )eacti,n is
d& .&
dt 0 &

+
+ 1he)e + H >. Calc*late the t
1I2
-,)
this )eacti,n.
@olution:
d& &
dt 0 &

+
or,
( ) d& 0 &
.dt
&
+
or,
d&
.d& .dt
&

?ntegrating both sides
2
c
c
dc
c
<
2
c
c
dc
/
c
o
dt
or, ln ( )
2
2
&
& &
&
+ / .t S.. !0#
.hen t / t
0F'
, & /
2
&
'
*rom e"uation !0#, ln
2 2
2 0F '
2
& &
& t
& F ' '
1
+
1
]
or, t
1I2
?
2
.& 0
ln '
'
+

E/am(le 2: A)sine .ec,m(,ses ,n heatin& t, &i'e As an. H
2
. The .ec,m(,siti,n st*.ie. at c,nstant
',l*me an. tem(e)at*)e &i'es the -,ll,1in& .ata:
Time in h,*) > 2.2 3.2 6
)ess*)e in atm >.:32% 1.>3 1.>43 1.1
Calc*late 'el,cit0 c,nstant+ ass*min& -i)st ,).e) )eacti,n.
@olution: As%
!g# As!s# $ F'%

'
!g#
+ole at t / 2 a 2 2
+ole at t / t a < x x
x
'
Q +ole pressure !at constant A and T#
a 2.HG,- at t / 2 hr
and !a < x $
x
'
# 0.2G at t / ,., hr
%ence, x 2.0LH'

CHEMICAL KINETICS
5 /
( )
'.2 a
log
t a x
/
'.2 2.HG,-
log
,., 2.HG,- 2.0LH'
? $.:3 E 1>
D2
h)
D1
@imilarly, a 2.HG,- at t / 2 hr.
and, !a < x $
x
'
# 0.2PG at t / G., hr
%ence, x 2.''0'
5
'
/
'.2 2.HG,-
log
G., 2.HG,- 2.''0'
? %.>> E 1>
D2
h)
D1
@imilarly, a 2.HG,- at t / 2 hr
and, !a < x $
x
'
# 0.0 at t / L hr
%ence, x 2.'GH'
02
'.2 2.HG,-
5 log
L 2.HG,- 2.'GH'
? %.>6 E 1>
D2
h)
D1
5 /
( )
'
0 '
.HG -.22 -.2L 02 5 5 5

+ + + +
? %.>1 E 1>
D2
h)
D1
E/am(le 3: H0.),&enati,n ,- 'e&eta9le &hee at 22C )e.*ces the ()ess*)e ,- H
2
-),m 2 atm t, 1.2 atm
in 2> min*te. Calc*late the )ate ,- )eacti,n in te)ms ,- FaG ()ess*)e (e) min*te F9G
m,la)it0 (e) sec,n..
@olution: !a# )ate of reaction /
&hange in pressure ' 0.'
Time in min ,2
/
2.L
,2
1.3 E 1>
D2
atm min
D1
!b# &hange in molarity may be derived by 8A / n)TE
n 8
A )T
/
2.L
2.2L'0 'HL
/ 2.2'P +
Now, )ate of reaction /
&hange in molarity
Time in second
/
2.2'P
,2 G2
? 1.>: E 1>
D2
m,l lit)e
D1
sec
D1
E/am(le 4: A ce)tain )eacti,n =
nA
is &ettin& c,n'e)te. t, =
FnA%GA
in s,l*ti,n. The )ate c,nstant ,- this
)eacti,n is meas*)e. 90 tit)atin& a ',l*me ,- the s,l*ti,n 1ith a )e.*cin& a&ent 1hich
)eacts ,nl0 1ith =
nA
an. =
Fn A %GA
. In the (),cess it c,n'e)ts =
nA
t, =
Fn A 2GA
an. =
Fn A %GA
t,
=
Fn D 1GA
. At t ? >+ the ',l*me ,- )ea&ent c,ns*me. is 22 ml an. at t ? 1> min*te+ the ',l*me
*se. is $2 ml. Calc*late the )ate c,nstant -,) the c,n'e)si,n ,- =
nA
,-
=
Fn A %GA
ass*min& it t, 9e a -i)st ,).e) )eacti,n.
@olution: 7
n$
7
!n $ -#$
+illimole at t / 2 a 2 'e $ 7
n$
7
!n $ '#$

t / t !a < x# x ,e $ 7
!n $ -# $
7
!n < 0#$
1et normality be N for reducing agent.
Thus, at t / 2, A
0
N
0
/ A
'
N
'
or, a M ' / N M ',
a /
',
'
N
and at t / t, !a < x# M ' $ x M , / N M '

CHEMICAL KINETICS
x /
P
N
Now,
'.2 ',F 'N '.2 ', G
5 log log
', P 02 02 ' G0
N
'

,
? 2.>4 E 1>
D2

min
D1
E/am(le 6: The )ate c,nstant -,) the .ec,m(,siti,n ,- N
2
O
2
as N
2
O
2
N
2
O
%
A 1I2O
2
+ a)e $.%3 E 1>
D2
an. %.64 E 1>
D$
at 22C an. 32C )es(ecti'el0. Sh,1 that the ene)&0 ,- acti'ati,n is 2%.6
8cal (e) m,l. FR ? 1.:64 calI85m,lG
@olution: Oiven: K
'
/ -.LP M 02
<
, T
'
/ G, $ 'P / L 5
K
1
/ .-G M 02
<,
, T
0
/ ', $ 'P / 'HL 5
Q '.2 log
a '
0 0 '
E 5 0 0
5 ) T T
1

1
]
or,
a
,
E -.LP 02 0 0
'.2 log
0.HLP 'HL L .-G 02
1

1
]
Ea ? 2%.6 8cal m,l
D1

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0'
CHEMICAL KINETICS
RATE LA#+ ORDER J MOLECULARITY
HASEEN SHURUAT FD D IG
0. *or the reactionE '%? %
'
$ ?
'
, the
0
'
d:%?;
dt
expression represents
!A# the rate of formation of %? !7# the rate of disappearance of %?
!&# the instantaneous rate of the reaction !C# the average rate of the reaction
'. *or reaction -A $ 7 '& $ 'C, the incorrect statement is
!A# The rate of disappearance of 7 is one fourth the rate of disappearance of A
!7# The rate of appearance of & is half the rate of disappearance of 7
!&# The rate of formation of C is half the rate of consumption of A
!C# The rates of formation of & and C are e"ual
. *or the reaction ' N
'
O
,
!g# - NO
'
!g# $ O
'
!g#, the concentration of NO
'
increases by '.-M02
'
+
in G seconds. .hat will be the rate of appearance of NO
'
and the rate of disappearance of N
'
O
,
T
!A# ' M 02
+s
0
, - M 02
+s
0
!7# ' M 02
+s
0
, 0 M 02
+s
0

!&# ' M 02 +s
0
, ' M 02
+s
0
!C# - M 02
+s
0
, ' M 02
+s
0
-. The reaction: '*e&l
$ @n&l
'
'*e&l
'
$ @n&l
-
is a reaction of
!A# Dero order !7# first order !&# second order !C# third order
,. .hich one of the following statement is wrong regarding molecularly of a reactionT
!A# ?t is calculated from the reaction mechanism.
!7# ?t may be either a whole number or fraction.
!&# ?t is the number of molecules of the reactants ta(ing part in a single step chemical reaction.
!C# ?t depends on the rate determining step reaction in the reaction.
G. The reaction 'Na $ &l
'
'Na&l is found to follow ??? order (inetics. ?ts molecularity is
!A# 0 !7# ' !&# !C# -
P. A Dero order reaction is one
!A# in which reactants to not react
!7# in which one of the reactants is in large excess
!&# whose rate does not change with time
!C# whose rate increase with time
L. .hen the concentration of reactants in the reaction A 7 is increased by L times, the rate increases
only by ' times. The order of reaction is

CHEMICAL KINETICS
!A# !7# 0F !&# ' !C# 0F'
H. .hat is the order of a chemical reaction A $ '7 &, if the rate formation of & increases by a factor
of '.L' on doubling the concentration of A and increases by a factor of H on tripling the concentration
of 7
!A# PF' !7# PF- !&# ,F' !C# ,F-
02. ?n the reaction: A
0
5
7
'
5
&
5
C, where 5
Q 5
'
Q 5
0
E the rate of formation of C is
determined by
!A# the rate of reaction A 7
!7# the rate of reaction 7 &
!&# the rate reaction & C
!C# the rate of reaction A 7 with rate constant 5
0
. 5
'
. 5
00. The condition at which average rate can be e"ual to instantaneous rate of the reaction is
!A# n / 2 !7# t 2
!&# reaction is elementary !C# reaction is complex
0'. *or the reaction N%
-
$
$ O&NU N%
'
&ON%
'
.. The probable mechanism is
N%
-
$
$ O&NU N%
'
O&N !fast#
N%
-
O&N N%
'
&ON%
'
!slow#
The rate law will be
!A# rate / 5 :N%
'
&ON%
'
; !7# rate / 5 :N%
-
$
; :O&N;U
!&# rate / 5 :N%
-
O&N; !C# None of these
0. The rate constant for the reaction, N
'
O
,
-NO
'
$ O
'
, is .2M02
,
s
0
. ?f the rate is '.-M02
3,
mol l
1
s
0
,
then the concentration of N
'
O
,
!in mole litre
0
# is
!A# 0.- !7# 0.' !&# 2.2- !C# 2.L
0-. ?n the gas phase, two butadiene molecules can dimerise to give larger molecules according to the
reaction '&
-
%
G
!g# &
L
%
0'
!g#. The rate law for this reaction is rate / 5 :&
-
%
G
;
'
with 5 / G.0-M02
'
1
mol
0
s
0
at the temperature of reaction. *ind the rate of formation of &
L
%
0'
when the concentration of
&
-
%
G
is 2.2'+.
0,. .hich of the following e"uations, as written, could describe elementary reactionsT
!a# &l
'
$ &O &O&l
'
E r / 5 :&l
'
;
F'
:&O;
!b# 8&l
$ &l
'
8&l
,
E r / 5 :8&l
; :&l
'
;
!c# 'NO $ %
'
N
'
O $ %
'
OE r / 5 :NO; :%
'
;
!d# 'NO $ O
'
'NO
'
E r / 5 :NO;
'
:O
'
;
!e# NO $ O
NO
'
$ O
'
E r / 5 :NO; :O
;

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0-
CHEMICAL KINETICS
ATHRILA RASTA FD D IIG
0. *or a chemical reaction = >, the rate of reaction increases by a factor of 0.LP when the
concentration of = is increased by 0., times. The order of the reaction with respect to = is
!A# 0 !7# 0., !&# ' !C# 0
'. 8oint out the incorrect statement.
!A# )ate law is an experimental fact whereas law of mass action is a theoretical proposal.
!7# )ate law is always different from the expression of law of mass action.
!&# )ate law is more informative than law of mass action for the development of mechanism.
!C# Order of a reaction is e"ual to the sum of powers of concentration terms in the rate law.
. The rate constant is numerically the same for three reactions of first, second and third order,
respectively. .hich one is true for rate of three reactions, if concentration of reactant is greater than
0+T
!A# r
0
/ r
'
/ r
!7# r
0
Q r
'
Q r
!&# r
0
I r
'
I r
!C# none
-. The rate expression for the reaction A !g# $ 7 !g# & !g# is rate / (&
A
'
&
7
V
. .hat changes in the
initial concentration of A and 7 will cause the rate of reaction increase by a factor of eightT
!A# &
A
M ' E &
7
M ' !7# &
A
M 'E &
7
M - !&# &
A
M 0, &
7
M - !C# &
A
M - , &
7
M 0
,. The hydrolysis of an ester was carried out separately with 2.2, + %&l and 2.2, + %
'
@O
-
. .hich of
the following will be trueT
!A# 5
%&?
Q
' -
% @O
5
!7#
' -
%&? % @O
5 % <
!&#
' -
%&? % @O
5 5
!C# ( )
' -
'
% @O %&?
5 5
G. The rate constant of a second order reaction is 02
'
lit mole
0
sec
0
. The rate constant, when expressed
as ml molecule
0
min
0
, is
!A# 0.22 x 02
21
!7# 0.22 x 02
20
!&# H.HG x 02
0L
!C# H.HG x 02
<''
P. The rate constant !(# for the reaction 'A $ 7 8roducts, was found to be '.,L x 02
,
l mol
0
s
0
after
0, sec, '.G2 M 02
,
l mol
0
s
0
after 2 sec and '.,, x 02
,
l mol
0
s
0
after ,2 sec. %ence the order of
the reaction is
!A# 2 !7# 0 !&# ' !C#
L. )ate of a reaction A $ '7 8 is ' x 02
'
molFlit3sec, when concentrations of A and 7 are 0 molFlit
and rate, r / 5 :A;
'
:7;. The rate when half of the 7 has reacted will be
!A# ,.G x 02
!7# .P, x 02
'
!&# '., x 02
'
!C# '., x 02
H. A
'
!g# 7 !g# $ 0F' & !g#, the increases in pressure from 022 mm to 0'2 mm is , min. The rate of
disappearance of A
'
in mmFmin is
!A# - !7# L !&# ' !C# 0G

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0,
CHEMICAL KINETICS
02. The overall rate,
[ ]
dt
P d
, for the reaction 'A
5

7E 7 $ &
f
5
8 !where, 5 / e"uilibrium
constant and 5
f
/ forward rate3constant# is given by
!A#
[ ]
[ ] [ ] C A K K
dt
P d
f
'
!7#
[ ]
[ ][ ] B A K
dt
P d
!&#
[ ]
[ ][ ] C B K
dt
P d
f
!C#
[ ]
[ ] [ ][ ] C B A K K
dt
P d
f
'
00. *or a two step reaction, A $ & 7 $ 8, the reaction mechanism is

A ) $ 7
k0
) $ &
k

8

k'
where, ) is a reactive intermediate whose concentration is maintained at some low steady state
throughout the reaction. The rate law expression will be
!A#
[ ]
[ ]
[ ] C k
B k
A k
dt
dx
'
0
0+
!7# [ ] A k
dt
dx
0
!&# [ ]
'
0
A k
dt
dx
!C#
[ ][ ][ ] R B A k
dt
dx
0
0'. *or the reaction:
7rO 7rO '7r

+ in al(aline a"ueous solution, the value of the second order
rate constant !in 7rO
<
# in rate law for <
d:7rO ;
dt
was found to be 2.2,G mol

<0
s
<0
. &alculate the rate
constant when the rate law is written as below: !a# $
d:7rO ;
dt
!b# $
d:7r ;
dt
.
0. *or the reactions of ?, ?? and ??? orders, 5
0
/ 5
'
/ 5
, where concentrations are expressed in mol l

<0
.
.hat will be the relation in 5
0
, 5
'
and 5
, if concentrations are expressed is mol ml

<0
.
0-. The rate constant for the decomposition of oDone following second order (inetics is , M 02
<
l mol
<0
s
<0
at a certain temperature. .hat is the rate of reaction if concentration of oDone is ' M 02
<L
mol lit
<0
.
Also calculate the rate in terms of number of molecules decomposed per ml per minute.
0,. The following mechanism are proposed for the reaction &O $ NO
'
&O
'
$ NO at low temperature:
!a# 'NO
'

N
'
O
-
!fast#
N
'
O
-
$ '&O '&O
'
$ NO !slow#
!b# 'NO
'
NO
$ NO !slow#
NO
$ &O NO
'
$ &O
'
!fast#
.hich of the above mechanism are consistent with the observed rate law: $
'
d:&O ;
dt
/ 5 :NO
'
;
'
T
0G. *or the formation of phosgene gas from &O and chlorine: &O $ &l
'
&O&l
'
, the following
mechanism is suggested
&l
'

'&l !fast#
&O $ &l

&O&l !fast#

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0G
CHEMICAL KINETICS
&O&l $ &l
'
&O&l
'
$ &l !slow#
@uggest the rate law e"uation for it from !a# e"uilibrium approach and !b# steady state approximation.
0P. The reaction of the reactive fragment O% with %
'
@: -O%!g# $ %
'
@!g# @O
'
!g# $ '%
'
O!g#, was
studied at a particular temperature.
[OH]
mol/litre
[H
2
S]
mol/litre
1.3 x 10
-8
2.1 x 10
-8
3.9 x 10
-8
2.1 x 10
-8
3.9 x 10
-8
4.2 x 10
-8
8.4 x 10
-6
Rate of disappearaes
of H
2
S mol l
-1
s
-1
1.4 x 10
-6
4.2 x 10
-6
!a# .rite the rate law expression for the reaction.
!b# .hat is the rate constant of the reaction at the given temperatureT
!c# &alculate the rate, mol l
<0
s
<0
, at the instant when :O%; / 0.P M 02
<L
+ and :%
'
@; / 0.2 M 02
<L
+
!d# &alculate the rate, mol sec
<0
, at the instant when :O%; / 0.P M 02
<L
+ and :%
'
@; / 0.2 M 02
<L
+
and the volume of the reacting system is 2.0 litre.
0L. *or a chemical reaction A $ 7 8roducts, the order is one with respect to each A and 7. *ind x and
y from the following data.
rate
mol l
-1
s
-1
[!]
mol l
-1
s
-1
["]
mol l
-1
s
-1
0.10 0.20 0.0#
0.40 x 0.0#
0.80 0.40 $
0H. *or the chemical reaction between mercuric chloride and potassium oxalate, the mass of %g
'
&l
'

precipitated in different time intervals, at 022W&, is given below:
.hat is the rate law expression of this reactionT
'2. *or the reaction, 'NO!g# $ %
'
!g#
N
'
O!g# $ %
'
O!g#, the value of 3
d8
dt
was found to be 0., 8a s
30
for
a pressure of ,H 8a for NO and 2.', 8a s
30
for a pressure of 0,' 8a for NO. The pressure of %
'
being
constant. ?f pressure of NO was (ept constant, the value of 3
d8
dt
was found 0.G2 8a s
30
for a pressure
of 'LH 8a for %
'
and 2.PH 8a s
30
for a pressure of 0-P 8a for %
'
. .hat is the order of reaction with
respect to NO and %
'
T

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0P
%xp. &o.
[H'(l
2
]
0
mol l
-1
[)
2
(
2
O
4
mol l
-1
*ime
mi+
-1
H'
2
(l
2
formed 'm
1 0.0836 0.404 6# 0.0068
2 0.0836 0.202 120 0.0031
3 0.0418 0.404 60 0.0032
]
0
CHEMICAL KINETICS
INTE<RATED RATE LA#
HASEEN SHURUAT FD D IIIG
0. The time ta(en in P,X completion of a Dero order reaction is 02 hours. ?n what time, the reaction will
be H2X completedT
!A# 0'.2 hr !7# 0G.G hr !&# 02.2 hr !C# '2.2 hr
'. A Dero order reaction A 7. At the end of 0 hr, A is P,X reacted. %ow much of it will be left
unreacted at the end of ' hrs.
!A# 0'.,X !7# G.',X !&# .0' X !C# 2X
. The two3third life !t
'F
# of a first order reaction in which ( / ,.-L M 02
0-
sec
0
is
!A# '.2 x 02
02
s !7# '.2 M 02
00
s !&# '.20 M 02
0
s !C# '.2 M 02
0,
s
-. *or the first order reaction t
HHX
/ x M t
H2X
. The value of YxJ will be
!A# 02 !7# G !&# !C# '
,. *or the second order reaction ' A 7, time ta(en for the :A; to fall to one fourth value is how many
times the time it ta(es for :A; to fall to half of its initial valueT
!A# two !7# three !&# four !C# indefinite
G. The half life for a given reaction is doubled if the initial concentration of the reactant is doubled. The
order of the reaction is
!A# 2 !7# 0 !&# ' !C#
P. A (inetic study of the reaction A products provides the data: t / 2 sec, :A; / '.22 +E ,22 s, 0.22
+E 0,22 s, 2.,2 +E ,22 s, 2.', +. ?n the simplest possible way determine, whether this reaction is of
!A# Dero order !7# first order !&# second order !C# Dero or first
order
L. *or a given reaction the concentration of the reactant plotted against time gave a straight line with
negative slope. The order of the reaction is
!A# !7# ' !&# 0 !C# 2
H. *or a certain reaction involving a single reactant, it is found that &
2 T
is constant where &
2
is the
initial concentration of the reactant and T is the half3life. .hat is the order of the reactionT
!A# 0 !7# Dero !&# ' !C#
02. *or the first order reaction, A !g# ' 7 !g# $ & !g#, the total pressure, after time t from start of
reaction with A is 8 and after infinite time, it is 8
. Then the rate constant of the reaction is

!A#
8 0
ln
t 8
!7#
0
t
ln
( )
'8
8 8

!&#
0
t
ln
'8
8 8

!C#
'8 0
ln
t 8 8

00. As the initial concentration increases from 2.P, to 0.,, mole F lit in a reaction, t
0F'
decreases from G2
sec to 'H sec., order of reaction is
!A# Dero !7# first !&# second !C# third

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0L
CHEMICAL KINETICS
0'. ?f t
0F'
of a second order reaction is 0 hour. After what time the amount will be ',X of the initial
amount
!A# 0., hour !7# ' hour !&# '., hour !C# hour
0. The decomposition of a substance follows first order (inetics. ?ts concentration is reduced to 0FL
th
of
its initial value in '- minutes. The rate constant of the decomposition process is
!A# 0F'- min
30
!7# 2.GHF'- min
30
!&# 2.GHFL min
30
!C# 2.GHFP' min
30
0-. A substance is reduced to one third of its original concentration in 022 minutes. &alculate the time in
which it will be reduced to one ninth of its original value. Assume it as a first order reaction.
0,. The decomposition of &l
'
O
P
at -22 5 in the gaseous phase into &l
'
and O
'
is a first order reaction.
After ,, second, at -22 5, the pressure of &l
'
O
P
falls from 2.2G' to 2.2-- atm. &alculate the rate
constant. &alculate the pressure of &l
'
O
P
after 022 second of decomposition at -22 5.
ATHRILA RASTA FD D I"G
0. *or a Dero order reaction,
!A# the reaction rate is double when the initial concentration is doubled.
!7# the time for half change is half the time ta(en for completion of the reaction.
!&# the time for half change is independent of the initial concentration.
!C# the time for completion of the reaction is independent of the initial concentration.
'. A substance A decomposes in solution following first order (inetics. *las( 0 contains 01 of 0+
solution of A and flas( ' contains 022 ml of 2.G+ solution. After L hrs the concentration of A in flas(
0 becomes 2.',+, what will be the time for concentration A in flas( ' to become 2.+T
!A# 2.- hr !7# '.- hr !&# -.2 hr !C# unpredictable
. After '2X completion, the rate of reaction A products, is 02 unit and after L2X completion, the
rate is 2.G', unit. The order of the reaction is
!A# Dero !7# first !&# second !C# third
-. At the point of intersection of the two curves shown, the concentration of 7 is given as
!A n 7#
!A#
2
A
n
!7#
2
A
n 0
!&#
2
nA
n 0 +
!C#
2
n 0
A
n 0
+
"
!
,. .hich of the graph is correct representation for the reaction of type A $ '7 &.
!A# !7# !&# !C#
G. The decomposition of N%
on tungsten surface follows Dero order (inetics. The half life is 'H2
seconds for an initial pressure of G, mm of N%
. ?f the initial pressure had been 0,2 mm, what would

be the total pressure after one half3lifeT .hat is the half lifeT
!A# HG2 s, '', mm !7# HG2 s, 0,2 mm !&# GHG s, 0,2 mm !C# GGH s, '', mm
P. A certain reaction obeys the following rate law: <
d:&;
dt
/ 5 :&;
F'
!a# ?ntegrate the rate e"uation if the initial concentration of & is :&
2
;.
!b# Obtain the expression of t
0F'
.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 0H
CHEMICAL KINETICS
L. A drop of solution !volume / 2.2, ml# contains M 02
<G
moles of %
$
. ?f the rate constant of
disappearance of %
$
is 0.2 M 02
<P
mol l
<0
s
<0
, how long would it ta(e for %
$
in drop to disappearT
H. A viral preparation was inactivated in a chemical bath. The inactivation process was found to be first
order in virus concentration and at the beginning of the experiment, '.2X of the virus was found to be
inactivated per minute. &alculate the rate constant for the inactivation process.
02. ?n the biological processes, the time ta(en by certain virus or bacteria to double its population, is
called generation time. ?n mil(, at PZ&, lactobacillus acidophilus has a generation time of about P,
min. &alculate the population relative to the initial value at G2 min.
00. ?n an experiment, a &&l
-
solution containing L.LG M 02
<,
mole of N
'
O
,
per gm of solution was
observed while decomposition of N
'
O
,
occurred at -.'Z &. After PP.' min, .GP M 02
<,
mole of N
'
O
,
per gm of solution had decomposed. *ind the rate constant of this first order decomposition.
0'. At ',Z&, the second order rate constant for the reaction ?
3
$ &lO
3
?O
3
$ &l
3
is 2.2G +
0
s
0
. ?f is a
solution is initially 2.2, + with respect to each reactant, what will be the concentration of each
species present after 22 secT
0. A certain reaction, A $ 7 &, the first order with respect to each reactant 5 / 02
+
0
s
0
.
Cetermine the final concentration of A after 022s, if the initial concentration of A was 2.0+ and that
of 7 was 2.' +.
0-. The inversion of cane sugar proceeds with constant half life of ,22 min. at p
%
/ ,, for any
concentration of sugar. %owever, if p
%
/ -, the half life changes to ,2 min. Cerive the rate law for
inversion of cane sugar.
0,. ?f for a reaction A products, the concentration of A are &o , a
'
&o a
&o, .............. after time

interval 2, t, 't, t .............where a is constant and 2 I a I 0, show that reaction follows first order
(inetics.
0G. *rom the following data for the decomposition of ammonium nitrite in a"ueous solution, show that
the reaction is first order.
Time !min# 02 0, '2 ',
Aolume of N
'
!ml# G.', H.22 00.-2 0.G, ,.2,
0P. @how that the ratio t
F-
Ft
0F'
for an nth order reaction is a function of n alone. .hat is the value of this
ratio.
0L. The acid catalysed reaction of acetic acid with ethanol, &%
&OO% $ &
'
%
,
O%
&%
&OO&
'
%
,
$
%
'
O follows the rate law : <d :&%
&OO%; F dt / ( :%
$
; :&%
&OO%; :&
'
%
,
O%;
?f :&%
&OO%;
2
/ :&
'
%
,
O%;
2
/ 2.'+ and 8
%
/ and t
0F'
/ ,2 min, calculate the apparent and true rate
constants.
0H. @ome 8%
!g# is introduced into a flas( at G22

2
& containing an inert gas. 8%
proceeds to decompose
into 8
-
!g# and %
'
!g# and the reaction goes to completion. The total pressure is given below as a
function of time. *ind the order of reaction and calculate the rate constant.
Time !sec# 2 G2 0'2
8 !mm %g# 'G'.-2 'P'.H2 'P,.,0 'PG.-2
'2. The reaction &%
&O* $ %
'
O &%
&OO% $ %* has been studied under the following initial

conditions:
&ase ? &ase ??
:%
'
O;
2
/ 0.2+ :%
'
O;
2
/ 2.2'+

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. '2
CHEMICAL KINETICS
:&%
&O*;
2
/ 2.20+ :&%
&O*;
2
/ 2.L2+
The variation of concentration with time were noted as
&ase ? time !min# 2 02 '2 -2
:&%
&O*; 2.2022+ 2.22L,P+ 2.22P,+ 2.22,-2+

&ase ?? time !min# 2 02 '2 -2
:%
'
O; 2.2'22+ 2.20PG+ 2.20,G+ 2.20''+
Cetermine the order of reaction and the rate constant of reaction.
SECIAL KIND O! REACTIONS
HASEEN SHURUAT FD D "G
0. *or a first order homogeneous reaction of the type = > K !consecutive
reaction#, which of the following curves respectively show the variation of the
concentration of =, > and K with timeT
!A# ?, ?? , ??? !7# ??? , ?? , ?
!&# ???, ?, ?? !C# ??, ???, ?
?
? ?
? ? ?
(
o
+
e
+
t
r
a
t
i
o
+
'. *or irreversible elementary reactions in parallel A

,
1

)E A
,
2

@. The rate of disappearance
of reactant A is given by
!A# !(
0
(
'
# &
A
!7# !(
0
$ (
'
# &
A
!&# V !(
0
$ (
'
# &
A
!C# (
0
&
A
. A substance undergoes first order decomposition. The decomposition follows two parallel first order
reaction as 5
0
/ 0.'G M 02
-
sec
0
for the formation of 7 and (
'
/ .L M 02
,
sec
0
for the formation of
&. The percentage distribution of 7 and & are
!A# L2X 7 [ '2X & !7# PG.LX 7 [ '.'X& !&# H2X 7 [ 02X & !C# G2X 7 [ -2X
-. *or the consecutive unimolecular3type first order reaction A
0
(
)
'
(
@, the concentration of
component ), &
)
at any time t is given by
&
)
/ &
A
O 5
0
0 '
( t ( t
' 0 0 '
e e
!( ( # !( ( #

+

1
1
]
?f &
A
/ &
A
O, &
)
/ 2 at t / 2, the time at which the maximum concentration of ) occurs is
!A# t
max
/
( )
' 0
' 0
ln ( (
( F (
!7# t
max
/
' 0
' 0
n!( F ( #
( (
l
!&# t
max
/
' 0
( F (
' 0
e
( (
!C# t
max
/
' 0
( (
' 0
e
( (
,. The net rate of reaction :&u!N%
#
-
;
'$
$ %
'
O
:&u!N%
!%
'
O#;
'$
$ N%
is:
dx
dt
/ !'.2 02
3-
# :&u!N%
#
-
'$
;: %
'
O; 3 !.2 02
,
# :&u!N%
!%
'
O#
'$
;: N%
;.
&alculate the e"uilibrium constant for the reaction. Also predict the direction in which the above
reaction will be more dominant.
G. *or the series of parallel reactions

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. '0
CHEMICAL KINETICS
% $ %O
'
0
5
%
'
$ O
'

% $ %O
'
'
5
'O%
% $ %O
'

%
'
O $ O
it has been found that 5
0
: 5
'
: 5
/ 2.G' : 2.'P : 2.00. *ind the ratio of products at time, t.

P. *or the parallel first order reactions: A
0
5
7, 'A
'
5
&, find
!a# the overall rate constant for the disappearance of A
!b# the ratio of concentrations of 7 and & at time, t.
L. *or the consecutive first order reactions A
0
5
7
'
5
&, the concentrations of A and 7 are 2.'+

and 2.20+, respectively at steady state. ?f 5
0
is '.,M02
3-
min
30
, what is the value of 5
'
T
H. *or the consecutive first order reactions A
0
5
7
'
5
&, the concentrations of A and 7 are 2.'+

and 2.20+, respectively at transient e"uilibrium. ?f 5
0
is '.,M02
3-
min
30
, what is the value of 5
'
T
02. &onsider the following first order consecutive reactions: A
0
5
7
'
5
&. The initial

concentration of A is 022+ and 5
0
: 5
'
/ 0.2 : 2.0,. &alculate the concentrations of each species after
02 min. Oiven that 5
0
/ -.2M02
3'
min
30
. ?n what time, the concentration of 7 will become maximumT
Also calculate the maximum concentration of 7.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. ''
CHEMICAL KINETICS
ATHRILA RASTA FD D "IG
0. ?n the 1indemann theory of unimolecular reactions, it is shown that the apparent rate constant for such
a reaction is (
app
/
0
( &
0 & +
where & is the concentration of the reactant, (
0
and are constants. The
value of & for which (
app
has H2X of its limiting value at & tending to infinitely large is ( / H x 02
,
#.
!A# 02
G
moleFlitre !7# 02
-
moleFlitre !&# 02
,
moleFlitre !C# , M 02
,
moleFlitre
'. The rate e"uation for an autocatalytic reaction
( A
A A )
d&
A ) ) ) is r (& &
dt
+ +
The rate of disappearance of reactant A is maximum when
!A# &
A
/ '&
)
!7# &
A
/ &
)
!&# &
A
/ &
)
F ' !C# &
A
/ !&
)
#
0F'
. ?n the following first order competing reaction:
A $ )eagent 8roduct
7 $ )eagent 8roduct
The ratio of (
0
F (
'
if only ,2X of 7 will have been reacted when H-X of A has been reacted is
!A# -.2G !7# .2G !&# '.2G !C# 2.2G
-. ?n L2X ethanol at ,,&, isopropyl bromide reacts with hydroxide ion according to the following
(inetics:
[ ]
dt
RX d
/ !-.P M 02
<,
+
<0
s
<0
# :)=; :O%
<
; $ '.- M 02
<G
s
<0
:)=;
.hat percentage of isopropyl bromide reacts by the @
N
' mechanism when :O%
<0
; / 2.20 +T
!A# 0G.L X !7# L.G' X !&# H,.0- X !C# -.LG X
,. @urface catalysed reactions that are incorporated by the product obey the differential rate expression
for desorption:
dy
dt
/
2
(:& y;
0 by
+
, where &
2
/ initial amount of gases adsorbed at the surface, y is the
amount of gases adsorbed at time t and 5 and b are constants.
@how that t
0F'
/ :!0 $ &
2
b# ln' 3
2
& b
'
;.

CHEMICAL KINETICS
G. *or overall reaction: A $ '7 $ &

C, the reaction rate is given as
r / ' x 02
G
1
'
mol
3'
min
30
:A;
'
-
[ ]
[ ] [ ]
'
G
0.' 02 C
7 &
mol 1
30
min
30
?f initially each of the reactant has concentration 0 moleFlitre, calculate the rate of reaction when
concentration of & becomes 2.P + assuming no C is present at the start of the reaction.
P. Trans30, '3dideuterocyclopropane !A# undergoes a first order decomposition. The observed rate
constant at a certain temperature, measured in terms of the disappearance of A, was 0.,' M 02
<-
s
<0
.
Analysis of the reaction products showed that the reaction follows two parallel paths, one leading to
dideuteropropene !7# and the other to cis30, '3dideuterocyclopropane !&#. 7 was found to constitute
00.'X of the reaction product, independent of the extent of reaction. .hat is the order of the reaction
for each of the paths and what is the value of rate constant for the formation of each of the productsT
L. A mixture of two substances A and 7 gives the same product & by two parallel first order reactions:
A
A
T
& and 7
7
T
&
?f the initial concentration of A and 7 are 02 + and L + and their half lives, T
A
and T
7
, are 02 min
and 0, min, respectively, what will be the concentration of & after 2 minT
H. The gas3phase decomposition of acetic acid at 00LH 5 proceeds by way of two parallel reactions :
0. &%
&OO%
&%
-
$ &O
'
, 5
0
/ .P- s
<0
'. &%
&OO%
%
'
& / & / O $ %
'
O, 5
'
/ -.G, s
<0
.hat is the maximum percentage yield of the (etene, &%
'
&O, obtainable at this temperature
02. An organic compound A decomposes following two parallel first order reactions: A
0
5
7 and A
'
5
&. ?f 5
0
is 0. 02
3,
sec
30
and 5
0
F5
'
is 0FH, determine :&;F:A; after one hour of start of reaction
by ta(ing only A.
00. A substance A decomposes into 7 and & as: A
0
5
7 !first order#, 'A

'
5
& !second order#.

Cerive the expression for the concentration of A at time, t.
0'. *or the consecutive first order reactions: A
0
5
7
'
5
&, 7 is in steady state. .hat will be the

concentration of & at this stageT At t / 2, :A; / :A;
2
and :7; / :&; / 2.
0. *or the given reaction: A
f
b
5
5

7, :A;
2
/ 2.0,+, :A;
e
/ 2.2LG+, :A;
02
/ 2.0-' and :A;
022
/ 2.02'+,
where times are given in min. &alculate 5
f
, 5
b
and 5
e"
.
0-. .hen excess toluene3
3d !&
G
%
,
&%
'
C# was photochemically monochlorinated at L2
2
& with 2.0 mole
of chlorine, there was obtained 2.2'0' mole C&l and 2.2LGL mole %&l. .hat is the value of the
isotope effect 5
%
F5
C
T
0,. *or the reaction A
0
0
5
5

7, the percentage of A varies with time as follows:
Time !hr# 2 0 ' -
X A 022 P'., ,G.L -,.G H., 2.2
&alculate 5
0
, 5
30
and 5
e"
.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. '-
CHEMICAL KINETICS
TEMERATURE DEENDANCE
HASEEN SHURUAT FD D"IIG
0. The activation energy for a chemical reaction is primarily dependent on
!A# temperature !7# nature of the reacting species
!&# collision fre"uency !C# concentration of reactants
'. The activation energy of a reaction is Dero. The rate constant of the reaction
!A# increases with increase of temperature !7# decreases with increase of temperature
!&# decreases with decrease of temperature !C# is nearly independent of temperature
. At a certain temperature, the reaction between NO and O
'
to form NO
'
is fast, while that between &O
and O
'
is slow. ?t is due to the fact that
!A# NO is more reactive than &O
!7# &O is smaller in siDe than NO
!&# activation energy for the reaction 'NO $ O
'

'NO
'
is less
!C# intrinsic energy for the reaction 'NO $ O
'

' NO
'
is less
-. )ate of which type of reaction increases with increase in temperatureT
!A# any !7# exothermic !&# endothermic !C# none
,. ?n gaseous reactions important for the understanding of the upper atmosphere, %
'
O and O react
bimolecularly to form two O% radicals. % for this reaction is P' 54 at ,225 and E
a
is PP 54Fmol,
then E
a
for the bimolecular recombination of two O% radicals to form %
'
O and O is
!A# 54Fmol !7# - 54Fmol !&# , 54Fmol !C# P 54Fmol
G. Activation energy of a chemical reaction can be determined by
!A# evaluating rate constant at standard temperature
!7# evaluating velocities of reaction at two different temperatures
!&# evaluating rate constants at two different temperatures
!C# changing concentration of reactants
P. &ombustion of carbon is exothermic, but coal stored in coal depots does not burn automatically
because of
!A# high threshold energy barrier !7# (inetic stability of coal
!&# higher energy of activation needed for burning !C# all

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. ',
CHEMICAL KINETICS
L. According to the Arrhenious e"uation straight line is to be obtained by plotting the logarithm of the
rate constant of a chemical reaction !log (# against
!A# T !7# log T !&# 0FT !C# log 0FT
H. The velocity of a reaction is doubled for every 02Z& rise in temperature. ?f the temperature is raised by
,2Z&, the reaction velocity increases by about
!A# 0' times !7# 0G times
!&# ' times !C# ,2 times
02. The rate of chemical reactions increases with the increase in temperature. ?t is due to
!A# increase in number of collisions between reactant molecules
!7# increase in effective collisions between reactant
!&# increase in activation energy of reaction
!C# decrease in threshold energy of reaction
00. ?n general, the rate of a reaction can be increased by all the factors except
!A# increasing the temperature !7# increasing the concentration of reactants
!&# increasing the activation energy !C# using a catalyst
0'. The rate of chemical reactions is independent of
!A# molecularity !7# nature of reactants
!&# concentration of reactants !C# temperature of reaction
0. .hich of the following is correctT
!A# Total collision rate mean speed absolute temperature
!7# Total collision rate
0
mean speed

0
absolute temperature
!&# Total collision rate mean speed !absolute temperature#
V
!C# Total collision rate !mean speed#
'
!absolute temperature#
0-. The mechanism of the reaction: A $ ' 7 C $ EE % / 3 ve is

@tep: ? A $ ' 7 & !slow#
@tep: ?? & C $ E !fast#
The energy profile of the reaction should be:
!A#
t
%
! - 2 "
(
. - % !7#
t
%
! - 2 "
(
. - %
!&#
t
%
! - 2 "
(
. - %
!C#
t
%
! - 2 "
(
. - %
0,. &onsider the following consecutive reactions:
A
0
5
7 !slow#
7
'
5
& !fast#
The activation energy of reaction is given as
!A#
0
a
E
!7#
'
a
E
!&#
0
a
E
$
'
a
E
!C#
0
a
E
$
0
a
E

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 'G
CHEMICAL KINETICS
ATHRILA RASTA FD D "IIIG
0. &ollision theory of chemical reactions explains
!A# rate of reactions !7# order of reactions
!&# molecularity of reactions !C# all of these
'. The distribution of molecular (inetic energy at two temperatures is as shown in
the following graph. .hich of the following conclusions are correct
!A# The number of molecules with energy E
a
or greater is proportional to the
shaded area for each temperature
!7# The number of molecules with energy E
a
or less is proportional to the
shaded area for each temperature
!&# The number of molecules with energy E
a
is the mean of all temperature
!C# The graph is not according to the +axwell 7oltDmann energy distribution
1aw
3 0 0 )
# 0 0 )
R
e
l
a
t
i
/
e

+
0
m
1
e
r

o
f

m
o
l
e
0
l
e
s

2
i
t
3

a

p
a
r
t
i
0
l
a
r

e
+
e
r
'
$
% e + e r ' $
a
. The radioactive decay is first order reaction. ?ts rate, on increasing 02Z& temperature
!A# increases '3 times !7# decreases '3 times !&# does not change !C# increases 02
times
-. On increasing the temperature, half life of reactions
!A# remain unchanged !7# increases !&# decreases !C#increases or
decreases
,. The reaction, NO $ 0 F ' O
'
NO
'
exhibits
!A# small negative temperature coefficient !7# decrease in value of ( with temperature
!&# increase in value of rate with temperature !C# all
G. *or a certain reaction it is observed that log 5 / $ log T <
T
where 5 is the rate constant, T is

the temperature !5elvin# and , and are constants. .hat is the Arrhenius activation energyT
!A# )T $ '.2 ) !7# '.2 ) !&# $ '.2 ) !C# )T $ )
P. .hich step in the following reaction se"uence is the rate determining stepT

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 'P
CHEMICAL KINETICS

)eactant
8roduct
!A# 0
st
!7# '
nd
!&#
rd
!C# cannot be
predicted
L. Arrhenius e"uation gives the change in rate constant !i.e. reaction3rate# with temperature. ?f the
activation energy of the reaction is found to be e"ual to )T, then
!A# the rate of reaction does not depend upon initial concentration.
!7# the rate constant becomes about PX of the Arrhenius constant A.
!&# the rate constant becomes e"ual to PX of the Arrhenius constant A.
!C# the rate of the reaction becomes infinite or Dero.
H. At ',Z &, a reaction is complete in - hrs. Approximately what temperature must be used to cause the
reaction to be completed in 0F' hrsT Assume temperature coefficient / '.
02. &onsider two first order reactions ? and ??. The fre"uency factor of ? is 022 times that of ??, the
activation energy of ? is -.G 5cal higher than that of ??. @how that the rate constants for the reactions
have nearly the same value at ''PZ &.
00. The rate of decomposition for &%
NO
'
and &
'
%
,
NO
'
can be given in terms of rate constant !in sec
<0
#
5
0
and 5
'
, respectively. The energy of activation for these reactions are 0,'.2 and 0,P.P 54Fmol and
the fre"uency factors are 02
0
and 02
0-
sec
<0
respectively. &alculate the temperature at which rate
constant will be same for both decomposition.
0'. The activation energy of a first order reaction is 02-., 54Fmol and pre3exponential factor is , M 02
0

sec
<0
. At what temperature will the reaction have half life of one minuteT
0. ?f activation energy of a reaction is L2.H 54 per mole, calculate the fraction of molecules at -22Z &
which have enough energy to form products.
0-. A given sample of mil( turns sour at room temperature !'2Z &# in G- hours. ?n a refrigerator at Z &,
mil( can be stored three times as long before it sours. Estimate
!a# the activation energy for souring of mil(
!b# how long it ta(e mil( to sour at -2Z &T
0,. *or a reaction, if the effective rate constant 5 is given by 5 / '
'
5
5
0F '
0
-
5
5
_

,
. &alculate the effective
activation energy and effective fre"uency factor. ?n the above expression, 5
0
, 5
'
, 5
and 5
-
stand for
the rate constants for the different steps of the reaction.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 'L
CHEMICAL KINETICS
CHEMISTRY ARENA FLE"EL K IG
O=LECTI"E MUESTIONS HA"IN< ONLY ONE CORRECT OTION
0. *or the reaction aA $ b7 8, dxFdt / 5 :A;
a
. :7;
b
. ?f concentration of A is doubled, the rate is
doubled. ?f 7 is doubled, the rate becomes four times. .hich is correctT
!A#
[ ] [ ] d A d 7
dt dt
!7#
[ ] [ ] d A d 7
'
dt dt

!&#
[ ] [ ] d A d 7
'
dt dt
!C#
[ ] [ ] d A d 7
dt dt
+
'. *or a reaction ' N%
N
'
$ %
'
, it is observed that
( )
( )
0
d N%
5 N%
dt
,
( )
( )
'
'
d N
5 N%
dt
+
,
( )
( )
'
'
d %
5 N%
dt
+
. .hat is the relation between 5
0
, 5
'
and 5
T
!A# 5
0
/ 5
'
/ 5
!7# ' 5
0
/ 5
'
/ G 5
!&# 5
0
/ G 5
'
/ ' 5
!C# G 5
0
/ 5
'
/ ' 5
. The rate of a reaction is expressed in different ways as follows

$
0
'
d:&;
dt
/
0
d:C;
dt
/ $
0
-
d:A;
dt
/ 3
d:7;
dt
. The reaction is
!A# - A $ 7 ' & $ C !7# 7 $ C - A $ ' &
!&# - A $ ' & 7 $ C !C# 7 $ 0F' C - A $ ' &
-. )ate constant of a reaction depends upon
!A# &oncentration !7# 8ressure !&# Temperature !C# %
,. @ometimes reaction rates can be estimated by (nowing
!A# the atmospheric pressure !7# the number of bond changes
!&# the number of apparatus used in the experiment !C# the net ionic e"uation

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. 'H
CHEMICAL KINETICS
G. The hydrolysis of methyl formate in acid solution has rate expressionE rate / (:%&OO&%
;:%
$
;. The
balanced e"uation is %&OO&%
$%
'
O %&OO% $ &%
O%. The rate law contains :%

$
; though the
balanced e"uation does not contain %
$
, because
!A# more for convenience to express the rate law
!7# %
$
ion is a catalyst
!&# %
$
ion is an important constituent of any reaction
!C# all acids contain %
$
ions
P. *or a reversible reaction ' NO
'

N
'
O
-
, the rate of disappearance of NO
'
is e"ual to
!A#
0
'
'(
(
:NO
'
;
'
!7# '(
0
:NO
'
;
'
'(
'
:N
'
O
-
;
!&# '(
0
:NO
'
;
'
(
'
:N
'
O
-
; !C# !'(
0
3 (
'
# :NO
'
;
L. The reaction A!g# $ '7!g# &!g# $ C!g# is an elementary process. ?n an experiment, the initial
partial pressure of A and 7 are 8
A
/ 2.G2atm and 8
7
/ 2.L2atm. .hen 8
7
/ 2.'2atm, the rate of
reaction, relative to the initial rate is
!A# 0 F -L !7# 0 F '- !&# 0 F ' !C# 0 F 0G
H. *or a gas reaction at T !5# the rate is given by
A
d8
dt
/ (J8
A
'
atmFhr. ?f the rate e"uation is expressed
as: r
A
/
0
A
A
dn
dt
/ (&
A
'
, molF!litre3hr#, the rate constant ( is given by
!A# ( / ( !7# ( / ()T !&# ( / (F)T !C# ( / (!)T#
'
02. *or the chemical reaction A products, the rate of disappearance of A is a given by
r
A
/
A
d&
dt
/ (
0
&
A
F !0 $ (
'
&
A
#
At low &
A
the reaction is of the first 3 order with rate constant
!A# (
0
F (
'
!7# (
0
!&# (
0
F (
'
!C# (
0
F !(
0
$ (
'
#
00. &onsider the following statements:
The law for the acid catalysed hydrolysis of an ester being given as rate / 5 :%
$
; :ester; / 5Y:ester;.
?f the acid concentration is doubled at constant ester concentration,
0. The second order rate constant, 5, is doubled.
'. The pseudo first order rate constant, 5J is doubled.
. The rate of reaction is doubled.
.hich of the above statements are correctT
!A# 0 and ' !7# ' and !&# 0 and !C# 0, ' and
0'. The order of a reaction is Dero. ?t will be definitely
!A# exothermic !7# endothermic !&# elementary !C# complex
0. The inversion of cane sugar proceeds with half life of ,22 minute at 8
%
/ , for any concentration of
sugar. %owever, if 8
%
/ G, the half life changes to ,2 minute. The rate law expression for the sugar
inversion can be written as
!A# r / 5 :sugar;
'
:%
$
;
2
!7# r / 5 :sugar;
0
:%
$
;
2

CHEMICAL KINETICS
!&# r / 5 :sugar;
0
:%
$
;
0
!C# r / 5 :sugar;
2
:%
$
;
0
0-. The rate law for a reaction between the substances A and 7 is given by rate / 5:A;
n
:7;
m
. On doubling
the concentration of A and halving the concentration of 7, the ratio of the new rate to the earlier rate
of the reaction will be as
!A# 0F'
m$n
!7# !m$n# !&# !n<m# !C# '
!n<m#
0,. The order of the reaction A products is 2.,. The time for complete reaction, T and time for ,2X
reaction, t
0F'
will be related as
!A# T / ' M t
0F'
!7# T / - M t
0F'
!&# t
0F'
/ 2. T !C# t
0F'
/ 2.P T
0G. Two radioactive substance A and 7 are present such that :A; / L :7; and t
0F'
of A / 02 min. and t
0F'
of
7 / '2 min. ?f they start decaying at the same time, after how much time concentration of both of
them would be same
!A# '2 min !7# -2 min !&# G2 min !C# '22 min
0P. A solution of N
'
O
,
in &&l
-
yields by decomposition at -,&, ,ml of O
'
, '2 minutes after the start of
the experiment and H.G ml of O
'
after a very long time. The decomposition obeys ? order (inetics.
.hat volume of O
'
would have evolved, -2 minutes after the startT
!A# P.HG ml !7# P.HG ml !&# G.PH ml !C# G.HP ml
0L. The decomposition of %
'
O
'
can be followed by titration with 5+nO
-
and is found to be a first order
reaction. The rate constant is -., M 02
'
. ?n an experiment the initial titre value was ', ml. The titre
will be , ml after
!A# -., M 02
'
M , min. !7#
'
ln,
-.,x02
min
!&#
'
ln!,F -#
-.,x02
min !C# -., M 02

'
M ', M , min.
0H. The half life of a first order reaction is 02 min. ?n what time, the rate of reaction will decrease from
G x 02
'0
molecules ml
0
sec
0
to -., x 02
',
molecules litre
0
min
0
T
!A# 02 min !7# '2 min !&# 2 min !C# infinite
'2. *or the irreversible unimolecular type reaction A products in a batch reactor, L2X reactant
!:A
2
; / 0 +# is converted in a L min. run and conversion is H2X after 0L min. The order of this
reaction is
!A# 0 !7# ' !&# 0F' !C# F'
'0. *or a certain reaction of order n, the time for half change, t
0F'
, is given by t
0F'
/
' '
(
1
] M &
2
0F'
where ( is the rate constant and &
2
is the initial concentration. .hat is nT
!A# 0 !7# ' !&# 2 !C# 2.,
''. The reaction %&
&%
'
NO
'
$ O%U &%
&%U NO
'
$ %
'
O obeys the rate law for pseudo
first order (inetics in the presence of a large excess of hydroxide ion. ?f 0X of nitro ethane undergoes
reaction in half a minute when the reactant concentration is 2.22'+, what is the pseudo first order rate
constantT
!A# ' x 02
'
min
0
!7# G x 02
min
0
!&# - x 02
'
min
0
!C# 0 x 02
'
min
0

CHEMICAL KINETICS
'. %ydrolysis of ethyl acetate is catalysed by %&l. The rate is proportional to the concentration of both
the ester and %&l. The rate constant is 2.0+
0
hr
0
. .hat is the half3life if the initial concentrations are
2.2'+ for the ester and 2.20+ for the catalyDing acidT
!A# -P hours !7# ,0H hours !&# LG hours !C# GH hours
'-. The rate of change of concentration of !7# for reaction, A
7 !product# is given by
[ ]
[ ]
0
A k
dt
A d
, the half3life period of the reaction will be
!A#
[ ] ( )
( ) k
A
,
'
'
'
2
'
0 '
1
]
1
!7#
[ ] ( )
k
A
1
]
1
0 '
'
'
'
2
!&#
[ ] ( )
( ) k
A
'
'
2
'
0 '
1
]
1
!C#
[ ] ( )
k
A
1
]
1
0 '
'
'
'
2
',. Cecomposition of N%
on heated tungsten yields the following data:

?nitial pressure !mm# G, 02, > 0L,
%alf life !sec.# 'H2 = GP2 L'2
.hat are the values of = and > in that orderT
!A# -'2 s, 002 mm !7# ,22 s, 0G2 mm !&# ,'2 s, 0P2 mm !C# -G2 s, 0,2 mm
'G. Oiven that for a reaction of order n, the integrated form of the rate e"uation is ( /
0 n 0 n
2
& &
t!0 n#

where
&
2
and & are the values of the reactant concentration of the start and after time t. .hat is the
relationship between t
\
and t
V
where t
\
is the time re"uired for & to become ] &
2

!A# t
\
/ t
V
:'
n0
$ 0; !7# t
\
/ t
V
:'
n0
0; !&# t
\
/ t
V
:'
n0
0; !C# t
\
/ t
V
:'
n$0
0;
'P. The activation energies of two reactions are E
0
and E
'
with E
0
QE
'
. ?f the temperature of the reacting
system is increased from T
0
to T
'
predict which of the following alternative is correctT
!A#
^
0
0
5
5
/
^
'
'
5
5
!7#
^
0
0
5
5
Q
^
'
'
5
5
!&#
^
0
0
5
5
I
^
'
'
5
5
!C#
^
0
0
5
5
I '
^
'
'
5
5
'L. .hich graph shows Dero activation energyT
!A# !7# !&# !C#
'H. *or ' @O
' @O
'
$ O
'
energy of activation is E
0
, then the value of activation energy for the reaction
@O
@O
'
$ 0F'O
'
will be
!A#
0
E
'
!7# ' E
0
!&# E
0
!C# None of these
2. The order of reaction A product cannot be given by the expression

CHEMICAL KINETICS
!A#
[ ] [ ]
' 0
' 0
nr nr
n A n A
l l
l l
!7#
[ ] [ ]
( ) ( )
2
' 0
0F ' 0F '
' 0
n Ao n A
n t n t
l l
l l
!&#<
[ ]
[ ]
d A
5 A dt
!d#
[ ]
n r F (
n A
l
l
MULTILE CHOICE MUESTIONS MAY HA"E ONE OR MORE THAN ONE CORRECT OTION.
0. .hich of the following are true about rate of a reactionT
!A# )ate of a reaction cannot be negative
!7# )ate of a reaction is change in concentration of the reactant per unit time per mole
!&# Average rate and instantaneous rate can never be e"ual
!C# )ate depends upon surface area of the reactants
'. *or a complex reaction,
!A# the overall rate is the rate of slowest step
!7# the overall molecularity has no significance
!&# molecularity and order may or may not be same
!C# the overall order is always the order of slowest step
. ?n a consecutive reaction system A
0
E
7
'
E
& when E
0
is much greater than E
'
, the yield of
7 increase with
!A# increase in temperature !7# decreases in temperature
!&# increase in initial concentration of A !C# decrease in initial concentration of A
-. .hich of the following statements are correctT
!A# *or endothermic reactions, energy of activation is always greater than heat of reaction.
!7# *or exothermic reactions, energy of activation is always smaller than heat of reaction.
!&# )ate of reaction always increases with increase in temperature.
!C# Temperature coefficient of a reaction is given by 5
t $02
F 5
t
,. &hoose the incorrect statement!s#.
!A# ?t is possible to change the specific rate constant for a reaction by changing the temperature.
!7# The specific rate constant for a reaction is independent of reactant concentrations.
!&# The rate of a catalysed reaction is always independent of the concentration of the catalyst.
!C# ?n stepwise reactions, the rate3determining step is the slowest one.
G. .hich of the following isFare correct statement!s#T
!A# @toichiometry of a reaction tells about the order of the elementary reactions.
!7# *or a Dero order reaction, rate and the rate constant are identical.
!&# A Dero order reaction is controlled by factors other than concentration of reactants.
!C# A Dero order reaction is always elementary reaction.
P. .hich of the following statement isFare incorrectT
!A# The order of reaction is the sum of powers of all the concentration terms in the rate e"uation.
!7# The order of reaction with respect to one reactant is the ratio of the change of logarithm of the
rate of the reaction to the change in the logarithm of the concentration of the particular reactant,
(eeping the concentrations of all other reactants constant.
!&# Orders of reactions can be whole numbers or fractional numbers.
!C# The order of a reaction can only be determined from the stoichiometric e"uation for the reaction.
L. .hich of the following statement is trueT

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#.
CHEMICAL KINETICS
!A# The rate law for a reaction depends on the concentrations of all reactants that appear in the
stoichiometric e"uation
!7# The rate of a catalysed reaction is independent of the concentration of catalyst
!&# The specific rate constant for the reaction is independent of the concentrations of the reacting
species
!C# There is a single rate determining step in any reaction mechanism.
H. .hich of the following is an incorrect statement about first order reactionT
!A# The time for H.P,X completion of reaction is two times the time for P,X completion of
reaction.
!7# %alf life is the half of the time of complete reaction.
!&# About GX reaction completes in time, e"ual to 0F5.
!C# The time for H2X reaction will be e"ual to '.2F5, irrespective of initial concentration of the
reactant.
-2. .hich of the following "uantities isFare temperature independentT
!A# A !7# E
a
!&# ) !C# 5
COMREHENSION =ASED MUESTIONS HA"IN< ONLY ONE CORRECT OTION
COMREHENSION 5 I
The A))heni*s )elati,nshi( ,- t1, .i--e)ent )eacti,ns is sh,1n 9el,1:

7
l
o
g

5

0 F T
A
-0. .hich reaction is faster at a lower temperatureT
!A# A !7# 7 !&# e"ual !C# nothing can be predicted
-'. .hich is more sensitive to changes of temperatureT
!A# A !7# 7 !&# e"ual !C# nothing can be predicted
COMREHENSION 5 II
!,) the )eacti,n se;*ence

A 7
k
0
k30
&
k
'
k3'
C
k

k3
D is m,)e sta9le than A 90 %2.6 KcalIm,l+ = is m,)e sta9le than C 90 1$.2 KcalIm,l an. A is
m,)e sta9le than C 90 2>.6 KcalIm,l. The t)ansiti,n state &,in& -),m A t, = is m,)e sta9le than
the t)ansiti,n state &,in& -),m = t, C 90 1>.2 KcalIm,l 9*t it is less sta9le than the t)ansiti,n
state &,in& -),m C t, D 90 2.% KcalIm,l. The ene)&0 ,- acti'ati,n ,- C -,) t)ansiti,n state C t,
D is %.$ KcalIm,l.
-. .hich is the faster step in the forward directionT
!A# A 7 !7# 7

& !&# &

C !C# &an not be predicted
--. .hich is the faster step in the bac(ward directionT
!A# C

& !7# & 7 !&# 7 A !C# &an not be predicted

CHEMICAL KINETICS
-,. .hich is fastest step among these six stepsT
!A# & C !7# & 7 !&# 7 A !C# 7 &
-G. .hich is rate determining step in forward directionT
!A# A 7 !7# 7 & !&# & C !C# &an not be predicted
-P. .hich is rate determining step in bac(ward directionT
!A# C & !7# & 7 !&# 7 A !C# &an not be predicted
COMREHENSION 5 III
Chain )eacti,ns a)e a s(eci-ic class ,- )eacti,ns in 1hich hi&hl0 )eacti'e s(ecies a)e (),.*ce. as
inte)me.iates 1hich ca))0 the )eacti,n at a )a(i. )ate -,) a l,n& time. These )eacti,ns 1e)e -i)st
st*.ie. in 1:$% 90 !)an8 O. Rice an. Ka)l !. He)N-el. an. a)e )e-e))e. t, as Rice5He)N-el.
chain )eacti,ns. The stea.0 state a((),/imati,n has (),'e. hi&hl0 *se-*l in acc,*ntin& -,) thei)
)ate la1s. A t0(ical chain )eacti,n is that 9et1een H
2
an. =)
2
t, -,)m H=): H
2
F&G A =)
2
F&G
H=)F&G+ -,) 1hich a -i'e ste( mechanism has 9een (),(,se.:

Ste( I: =)
2

0
5
2=) FChain initiati,nG

Ste( II: =) A H
2

'
5
H=) A H FChain (),(a&ati,nG

Ste( III: H A =)
2

H=) A =) FChain (),(a&ati,nG

Ste( I": H A H=)
-
5
H
2
A =) FChain )eta).ati,nG
Ste( ": 2=)
,
5
=)
2
FChain te)minati,nG
-L. The concentration of bromine radical is
!A# 5
0
:7r
'
;
'
!7#
' 0
'
,
5
:7r ;
5
!&#
0
'
,
5
:7r ;
5
!C#
0F '
0
'
,
5
:7r ;
5
_

,
-H. The concentration of hydrogen radical is
!A#
' 0 ' '
, ' -
5 5 :7r ;:% ;
5 !5 :7r ; 5 :%7r;# +
!7#
0F '
' 0 ' '
, ' -
5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
!&#
0F ' 0F '
' 0 ' '
0F '
, ' -
5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
!C#
0F ' 0F ' '
' 0 ' '
0F ' 0F '
, ' -
5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
,2. The rate of formation of %7r, $
d :%7r;
dt
is
!A#
0F ' F '
' 0 ' '
0F '
, ' -
'5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
!7#
0F ' 0F '
' 0 ' '
0F '
, ' -
5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
!&#
0F ' 0F '
' 0 ' '
0F '
, ' -
5 5 :7r ; :% ;
5 !5 :7r ; 5 :%7r;# +
!C#
0F ' 0F '
' 0 ' '
0F '
,
'5 5 :7r ; :% ;
5
,0. .hat is the initial rate of formation of %7r, $
d :%7r;
dt
T
!A#
0F ' 0F '
' 0 ' '
0F '
,
'5 5 :7r ; :% ;
5 5
!7#
0F ' F '
' 0 ' '
0F '
,
'5 5 :7r ; :% ;
5 5
!&#
' 0F '
' 0 ' '
'
,
5 5 :7r ; :% ;
5 5
!C# Dero

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. ,
CHEMICAL KINETICS
COMREHENSION D I" :
A .e-inite ',l*me ,- H
2
O
2
*n.e)&,in& .ec,m(,siti,n )e;*i)e. 22.6 ml ,- stan.a). KMnO
%
s,l*ti,n -,) tit)ati,n. A-te) 1> an. 2> min+ the ',l*mes ,- (e)man&anate )e;*i)e. 1e)e 1$.6 an.
6.22 ml+ )es(ecti'el0.
,'. *ind order of reaction.
!A# 0 !7# ' !&# !C# F'
,. &alculate the time !in. min# re"uired for the decomposition to be half completed.
!A# 0.L !7# P.G !&# 0.P !C# '2.-
,-. &alculate the fraction of %
'
O
'
decomposed after ', minute.
!A# 2.0', !7# 2.,', !&# 2.G-L !C# 2.0P,
,,. The reaction is an example of
!A# pseudo unimolecular !7# pseudo bimolecular
!&# complex reaction !C# photosensitive reaction
COMREHENSION D " :
The -i)st ,).e) .ec,m(,siti,n ,- .i5te)t59*t0l(e),/i.e FDT=G t, acet,ne is &i'en 90 the
e;*ati,n:
C
6
H
16
O
2
F&G 2CH
$
CO CH
$
F&G A C
2
H
3
F&G.
The )eacti,n has a hal- li-e ,- 6> min at 1%4O C. Sta)tin& 1ith (*)e DT= in a -las8 ,- c,nstant
',l*me at a ()ess*)e ,- 6>> t,))+
,G. At what time !in min# the partial pressure of CT78 be 022 torr
!A# G2 !7# 0'2 !&# 0L2 !C#'-2
,P. At what time !in min# will the partial pressure of CT78 be P22 torr and
!A# P.'G !7# 0,.-' !&# -.'L !C# H.-G
,L. .hat will be the total gas pressure !in torr# when the partial pressure of CT78 is P22 torrT
!A# 0222 !7# '222 !&# 222 !C# -222
MATCH THE COLUMN MAY HA"E MORE THAN ONE MATCH
,H. +atch the following columns :
C,l*mn 5 I C,l*mn D II
FE/()essi,n ,- )ateG FT0(e ,- Reacti,nG
!A# ( )
dx
'( a x
dt
!8# 'A 8 !0
st
order#
!7# ( )
' dx
( a x
dt
!9# A $ '7 8 !0
st
order w.r.t. each reactant#
!&# ( ) ( )
dx
( a x b x
dt
!)# A $
0
7 8
'
!0
st
order w.r.t each reactant#
!C# ( ) ( )
dx
( a x b x F '
dt
!@# A 8 !'
nd
order#
G2. +atch the following columns :
C,l*mn D I C,l*mn D II

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. G
CHEMICAL KINETICS
F<)a(hs )eacti,n A ),.*ctsG FC,5,).inatesG
!A#

!8# n:A; !y < axis#, t!x < axis# !order / 0#
!7#

!9# t
0F'
!y < axis#, :A
2
; !x < axis# !order / 0#
!&#

!)# r!y < axis#, t!x < axis#!order Q 2#
!C#

!@# r!y < axis#, t!x < axis#!order / 2#
!T# t
0F'
!y < axis#, :A
2
; !x < axis# !order Q 0#
!B#
[ ]
( ) ( ) ( )
0
y axis , t x axis order '
A

!A# r!y < axis#, :A; !x < axis#!order / 0#
REASONIN< ASSERTION TYE
FAG I- 9,th Asse)ti,n an. Reas,n a)e t)*e an. the Reas,n is c,))ect e/(lanati,n ,- the
Asse)ti,n.
F=G I- 9,th Asse)ti,n an. Reas,n a)e t)*e+ 9*t Reas,n is n,t c,))ect e/(lanati,n ,- the
Asse)ti,n
FCG I- Asse)ti,n is t)*e+ 9*t the Reas,n is -alse
FDG I- Asse)ti,n is -alse+ 9*t the Reas,n is t)*e.
G0. Asse)ti,n: The rate of reaction some times does not depend on concentration.
Reas,n: The order of reaction can be negative
!A# A !7# 7 !&# & !C# C
G'. Asse)ti,n: ?n a reversible endothermic reaction, E
act
of forward reaction is higher than that of
bac(ward reaction.
Reas,n: The threshold energy of forward reaction is more than that of bac(ward reaction.
!A# A !7# 7 !&# & !C# C
G. Asse)ti,n: ?f the activation energy of a reaction is Dero, temperature will have no effect on the rate
constant.
Reas,n: 1ower the activation energy, faster is the reaction.
!A# A !7# 7 !&# & !C# C
G-. Asse)ti,n: According to steady state hypothesis, in a multi step reaction, the change in
concentration with time for reactive intermediates is Dero.
Reas,n: The intermediates are so reactive that after a brief initial period their concentrations rise
from Dero to a small value and remains constant for most of the duration of the reaction.
!A# A !7# 7 !&# & !C# C
G,. Asse)ti,n: The active mass of pure solid and pure li"uid is ta(en unity.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. P
CHEMICAL KINETICS
Reas,n: The active mass of pure solid and li"uids depends on density and molecular mass. The
density and molecular mass of pure li"uids and solids are constant.
!A# A !7# 7 !&# & !C# C
A<NI ARICHHA FLE"EL K IIG
0. ?n thermal decomposition of &
'
%
,
7r to &
'
%
-
and %7r, the initial pressure changes from '22 to H2
mm of %g at the end of reaction. .hat fraction remains unchanged when pressure of mixture was
22mm of %gT
'. ?n a certain polluted atmosphere containing O
at a steady state concentration of 'M02

<L
mol l
<0
, the
hourly production of O
by all sources was estimated as P.'M02

<0,
mol l
30
. ?f only mechanism for the
destruction of O
is second order reaction, calculate the rate constant for the destruction reaction.
. &onsider the following proposed mechanism A
0
'
5
5

7 and 7 $ A
5

& for the overall
chemical e"uation 'A

&. Bsing steady state approximation, show that <
[ ] [ ]
[ ]
'
0
'
d A '5 5 A
dt 5 5 A
+
.
-. *or a reaction A $ 7 $ & C, it was found that the rate of reaction doubled when the concentration
of 7 was doubled, the rate remain constant when the concentrations of both A and 7 are doubled and
the rate "uadruples when concentration of A and & are doubled. .hat should be the unit of rate
constant, if concentrations are expressed in molFlitre and time in minT
,. ?n the acid hydrolysis reaction A $ %
'
O $ %
$
8roducts where :%
$
; / 2.0 + and %
'
O is present in
large excess, the apparent rate constant is 0., M 02
<,
s
<0
. &alculate the true rate constant.
G. The decomposition of a compound A at temperature T, according to the e"uation:
'8 !g# -9 !g# $ ) !g# $ @ !#
is a first order reaction. After 2 min, from the start of the decomposition in a closed vessel, the total
pressure developed is found to be 0P mm and after a long time, total pressure is G0P mm. &alculate
the total pressure of the vessel after P, min. The vapour pressure of @!# at this temperature is '.,
mm.
P. A first order reaction A!g# n 7 !g# is started with A. The reaction ta(es place at constant
temperature and pressure. ?f the initial pressure was 8
2
, show that at any time, t, the total pressure of
the reaction system will be 8 / 8
2
:n $ !0 < n# e
<
( t
;, where 5 is the rate constant of the reaction.

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. L
CHEMICAL KINETICS
L. The half life for the first order decomposition of nitramide:
N%
'
NO
'
!a"# N
'
O !g# $ %
'
O !#
is 0' min at 0,Z&. ?f 0G, ml of 2.20,+3N%
'
NO
'
solution is allowed to decompose, how long must
the reaction proceed to produce ,2 ml of YwetJ N
'
O!g# measured at 0,Z& and P,G mm %gT The vapour
pressure of water at 0,Z& is 0'.L mm %g.
H. %ydrogen peroxide in a"ueous solution decomposes by a first order reaction to water and oxygen. The
rate constant for this decomposition is P.-2M02
<-
@
<0
. .hat "uantity of heat energy is initially liberated
per second from '1 of solution that is 0.,+3%
'
O
'
T Oiven % of %
'
O
'
!# / < 0LP.22 54Fmol and %
%
'
O !# / < 'L,.L- 54Fmol.
02. Thermal decomposition of dibromosuccinic acid !C7@A# ta(ing place according to the following
e"uation, obeys first order (inetics
&% !7r# &OO% &%&OO%
_ __ $ %7r
&% !7r# &OO% &7r&OO%
The progress of reaction may be followed by means of al(ali titration of the solution !reaction
mixture# at various time intervals. ?f T
2
and T
t
be the litres at Dero time and at any time t, respectively,
a and a3x be the concentrations of C7@A at Dero time and at any time t, respectively, show that
a
a x
/
2
2 t
T
T 'T
.
00. An optically active drug has one chiral centre and only dextrorotatory isomer is effective. +oreover, it
becomes ineffective when its optical activity is reduced to 2X of original. ?t was found that
mutarotation of this drug was first order reaction with rate constant 0 x 02
3L
sec
30
. *ind the expiration
time of the drug in years.
0'. The reaction 'A $ 7 & $ C goes to completion and follows the rate law <
d:A;
dt
/ 5 :A;
'
:7;
&alculate the values of x and y in the following data:
@et :A
2
; M 02
G
molF :7
2
; M 02
G
molF half life !s#
0. 22 -2 G'.G
'. 22 G2 x
. , 22 G',
-. 02 22 y
0. The acidic hydrolysis of ethyl acetate in a"ueous solution is first order with respect to ethyl acetate.
Bpon varying the p
%
of solution, the first order rate constant varies as follows:
p
%
' 0
5
0
!M 02
3 -
s
<0
# 0.0 00 002
.hat is the order of reaction with respect to %
$
and the value of the rate constantT
0-. The complex :&o!N%
#
,
*;
'$
reacts with water as:
:&o !N%
#
,
*;
'$
$ %
'
O :&o !N%
#
,
!%
'
O#;
$
$ *
<
.
The rate of reaction may be given as, r / 5 :complex;
a
:%
$
;
b
. The reaction is acid catalysed and hence
:%
$
; does not change during the reaction. Thus, the rate may be given as r / 5^ :complex;
a
where 5^ /
5:%
$
;
b
. &alculate a and b from the following data:
:&omplex; :%
$
; t
0F'
!hr# t
F-
!hr#
2.0 + 2.20 + 0.2 '.2

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. H
CHEMICAL KINETICS
2.' + 2.2' + 2., 0.2
0,. The decomposition of benDenediaDonium chloride in a"ueous solution is a reaction of first order
which proceeds as: &
G
%
,
N
'
&l &
G
%
,
&l $ N
'
!g#. A certain solution of benDenediaDonium chloride
contains initially an amount of this compound which gives L2 cm
of nitrogen on complete
decomposition. ?t is found that at 2Z &, -2 cm
of nitrogen are evolved in -2 minute. %ow long after

the start of the decomposition, will P2 cm
of nitrogen have been evolvedT

0G. &atalytic decomposition of nitrous oxide by gold at H22Z& at an initial pressure of '22 mm was ,2X
in , min and P X in 022 min.
!a# .hat is the order of the reactionT
!b# .hat is the velocity constant of the reactionT
!c# %ow much will it decompose in 022 min at the same temperature but an initial pressure of
G22 mmT
0P. The rate of decomposition of a gas A was P.', in some units when ,X had reacted and it was ,.0- in
the same unit when '2X had undergone decomposition. &alculate the order of the reaction.
0L. The gaseous reaction
0
A!g#
'
7!g# is first order with respect to A. ?t is studied at a constant
pressure with a2 as the initial amount of A. @how that the volume of the system at time t is given by
the expressions A / A
2
0
( t ' '
0 0
0 e
1
_ _

1

1 , ,
]
.
0H. &alculate the rate constant and the time re"uired for the solution to become optically inactive from the
following data for the inversion of cane sugar obeying first order (inetics.
Time !min# 2 P.'
Optical rotation !in degree# '-.0 '0.- 302.P
'2. The rate of an uncatalysed first order reaction at T5 is half of the rate of catalysed reaction at TF' 5.
?f the catalyst lowers the threshold energy by '2 5cal, what is the activation energy of uncatalysed
reactionT !T / 22 5#

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. -2
CHEMICAL KINETICS
ENLOY THE "ICTORY FLE"EL K IIIG
0. The decomposition of N
'
O
,
according to the e"uation 'N
'
O
,
!g# -NO
'
!g# $ O
'
!g# is a first order
reaction. After 2 min from the start of the decomposition in a closed vessel, the total pressure
developed is found to be 'L-., mm of %g and on complete decomposition, the total pressure is ,L-.,
mm %g. &alculate the rate constant of the reaction. F1::1+ Ma)8s ? 3G
'. Two reactions !?# A 8roducts !??# 7 8roducts follow first order (inetics. The rate of reaction !?#
is doubled when temperature is raised from 225 to 025. The half life for this reaction at 02 5 is
2 min. At the same temperature, 7 decomposes twice as fast as A. ?f the energy of activation for the
reaction !??# is half that of reaction !?#, what is the rate constant of reaction !??# at 225T F1::2+
Ma)8s ? $G
. A first order reaction A 7 re"uires activation energy of P2 54Fmol. .hen a '2X solution of A was
(ept at ',Z& for '2 minute, ',X decomposition too( place. .hat will be the percent decomposition in
the same time in a 2X solution maintained at -2Z&T Assume that activation energy remains constant
in this range of temperature. F1::$+ Ma)8s ? %G
-. The gas phase decomposition of dimethyl ether follows first order (inetics:
&%
3O3&%
&%
-
!g# $ %
'
!g# $ &O !g#
The reaction is carried out in a constant volume container at ,22
2
& and has a half life of 0-., minutes.
?nitially only dimethyl ether is present at a pressure of 2.-2 atmosphere. .hat is the total pressure of
the system after 0' minutesT Assume ideal gas behaviour. F1::$+ Ma)8s ? %G
,. *or the reaction, N
'
!g# $ %
'
!g# ' N%
!g# under certain conditions of temperature and partial

pressure of the reactions, the rate of formation of N%
is 2.220 (g.%r
30
. The rate of conversion of %
'
under the same conditions is ``` (g. hr
30
. a F1::%+ Ma)8 ? 1G
G. *rom the following data for the reaction between A and 7E calculate F1::%+ Ma)8s ? 2G
:A;Fmol.1
30
:7;Fmol. 1
30
?nitial rateFmol.1
30
s
30
, at
22 5 '2 5
'., x 02
3-
.2 x 02
3,
,.2 x 02
3-
'.2 x 02
3

,.2 x 02
3-
G.2 x 02
3,
-.2 x 02
3
333
0.2 x 02
3
G.2 x 02
3,
0.G x 02
3'
333

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. -0
CHEMICAL KINETICS
!i# the order of the reaction with respect to A and with respect to 7,
!ii# the rate constant at 22 5,
!iii# the energy of activation, and
!iv# the pre3 exponential factor.
P. At L2
2
&, the half life period for the first order decomposition of %
'
O
'
is G2 min. The energy of
activation of the reaction is '22 54Fmol. &alculate the time re"uired for P,X decomposition at -,2
2
&.
F1::2+ Ma)8s ? %G
L. The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction at ',
2
&
are .2 x 02
3-
s
30
, 02-.-54Fmol and G.2 x 02
0-
s
30
, respectively. The value of the rate constant as T, is
F1::3+ Ma)8 ? 1G
!A# '.2 x 02
0L
s
30
!7# G.2 x 02
0-
s
30
!&# infinity !C# .G x 02
2
s
3
0
H. The time re"uired for 02X completion of a first order reaction at 'HL 5 is e"ual to that re"uired for its
',X completion at 2L 5. ?f the pre3exponential for the reaction is .,G x 02
H
s
30
, calculate its rate
constant at 0L 5 and also the energy of activation. F1::4 cancelle.+ Ma)8s ? $G
02. ?n the Arrhenius e"uation, 5 / A exp!3EF)T#, A may be termed as the rate constant at ````.
F1::4 )e5e/am+ Ma)8 ? 1G
00. The rate constant for the first order decomposition of a certain reaction is described by the e"uation
log !5Fs
30
# / 0-.- 3
-
0.',x02 5
T
!i# .hat is the energy of activation for this reactionT
!ii# At what temperature will its half 3 life period be ',G minutesT F1::4 )e5e/am+ Ma)8s ? 2G
0'. *or a first order reaction, F1::6+ Ma)8s ? 2G
!A# the degree of dissociation is e"ual to !0 3 e
3( t
#
!7# a plot of reciprocal concentration of the reactant vs. time gives a straight line
!&# the time ta(en for the completion of P,X reaction is thrice the t
0F'
of the reaction
!C# the pre3exponential factor in the Arrhenius e"uation has the dimension of time, T
30
.
0. The rate constant of a reaction is 0., x 02
P
s
30
at ,2
2
& and -., x 02
P
s
30
at 022
2
&. Evaluate the
Arrhenius parameters A and E
a
. F1::6+ Ma)8s ? 2G
0-. The following statement!s# is !are# correct F1:::+ Ma)8s ? $G
!A# A plot of log 5p versus 0FT is linear
!7# A plot of log:=; versus time is linear for a first order reaction, = 8
!&# A plot of log 8 versus 0FT is linear at constant volume
!C# A plot of 8 versus 0FA is linear at constant temperature
0,. The rate constant for an isomerisation reaction A 7 is -., x 02
3
min
30
. ?f the initial concentration
of A is 0 +, calculate the rate of the reaction after 0 hour. F1:::+ Ma)8s ? %G
0G. The rate constant for the reaction, N
'
O
,
-NO
'
$ O
'
, is .2 x 02
,
sec
0
. ?f the rate is '.-2 x 023, mol
litre
1
sec
0
, then the concentration of N
'
O
,
!in mole litre
0
# is F2>>> S+ Ma)8s ? $G
!A# 0.- !7# 0.' !&# 2.2- !C# 2.L

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. -'
CHEMICAL KINETICS
0P. A hydrogenation reaction is carried out at ,22 5. ?f the same reaction is carried out in the presence of
a catalyst at the same rate, the temperature re"uired is -22 5. &alculate the activation energy of the
reaction if the catalyst lowers the activation energy by '2 54Fmol. F2>>> M+ Ma)8s ? $G
0L. ?f Y?J is the intensity of absorbed light and Y&J is the concentration of A7 for the photochemical
process A7 $ hv A7 , the rate of formation of A7 is directly proportional to F2>>1 S+ Ma)8s ? $G
!A# & !7# ? !&# ?
'
!C# &.?
0H. The rate of a first order reaction is 2.2- litre
0
s
0
at 02 minutes and 2.2 mol litre
0
s
0
at '2 minutes
after initiation. *ind the half life of the reaction. F2>>1 M+ Ma)8s ? 2G
'2. &onsider the chemical reaction, N
'
!g# $ %
'
!g# ' N%
!g#. The rate of this reaction can be

expressed in terms of time derivative of concentration of N
'
!g#, %
'
!g# or N%
!g#. ?dentify the correct

relationship amongst the rate expressions F2>>2 S+ Ma)8s ? $G
!A#
[ ] [ ] [ ]
' '
d N% d N d %
0 0
rate
dt dt ' dt
+ !7#
[ ] [ ] [ ]
' '
d N% d N d %
rate '
dt dt dt
+
!&#
[ ] [ ] [ ]
' '
d N% d N d %
0 0
rate
dt dt ' dt
+ !C#
[ ] [ ] [ ]
' '
d N% d N d %
rate
dt dt dt
+
'0. ?n a first order reaction, the activity of reactant drops from L22 molFdm
to ,2 mol dm
in time ' x 02
-
sec. The rate constant of the reaction in sec
30
is F2>>$ S+ Ma)8s ? $G
!A# 0.L x 02
-
!7# 0.L x 02
!&# 0.L x 02
0
!C# , x 02
,
''. *or a first order reaction A 8roduct the initial concentration of A is 2.0+ and after time -2 min it
becomes 2.2', +. &alculate the rate of reaction at reactant concentration 2.20+. F2>>% S+ Ma)8s ?
$G
!A# .-P x 02
4
mol lit
0
min
0
!7# .-P x 02
5
mol lit
0
min
0
!&# 0.P, x 02
6
mol lit
0
min
0
!C# 0.P, x 02
4
mol lit
0
min
0
'. *or the given reaction, A $ 7 8roducts, the following data were given F2>>% M+ Ma)8s ? 2G
?nitial conc. !mF1# ?nitial conc. !mF1# ?nitial rate :m1
0
s
0
;
:A; :7;
2.0 2.0 2.2,
2.' 2.0 2.0
2.0 2.' 2.2,
!i# .rite the rate e"uation.
!ii# &alculate the rate constant.
'-. .hich one of the following statement for order of reaction is not correctT F2>>2 S+ Ma)8s ? $G
!A# Order can be determined experimentally
!7# Order of reaction is e"ual to sum of the powers of concentration terms in differential rate law
!&# ?t is not affected with the stoichiometric coefficient of the reactants
!C# Order cannot be fractional.
',. At constant temperature and volume, = decomposes as F2>>2 M+ Ma)8s ? %G
'=!g# >!g# $ 'K!g#
8
x
is the partial pressure of =.
Observation No. Time !in minute# 8
x
!in mm of %g#

CHEMICAL KINETICS
0 2 L22
' 022 -22
'22 '22
!i# .hat is the order of reaction with respect to =T
!ii# *ind the rate constant
!iii# *ind the time for P,X completion of the reaction.
!iv# *ind the total pressure when pressure of = is P22 mm of %g.
ANS#ERS
RATE LA#+ ORDER J MOLECULARITY
HASEEN SHURUAT FD D IG
1. & 2. & $. C %. C 2. 7 3. &
4. & 6. 7 :. A 1>. A 11. 7 12. 7
1$. C 1%. '.-,G M 02
<,
+@
<0
12. b, d and e
ATHRILA RASTA FD D IIG
1. 7 2. 7 $. & %. 7 2. 7 3. C
4. A 6. C :. 7 1>. A 11. A
12. !a# 2.20LP +
<0
@
<0
!b# 2.2P +
<0
@
<0
1$. 5
0
/ 5
'
M 02
<'
/ 5
M 02
<G
1%. ' M 02
30L
+@
<0
, P''PG molecules ml
<0
min
<0
12. 7
13. !a# r / 5:&O;:&l
'
;
F'
; !b# r /
0F ' F '
, 0 '
0F '
' - , '
5 5 5 :&l ; :&O;
5 !5 5 :&l ;# +
14. 7
14. !a# r / 5:O%;:%
'
@; !b# ,.0 M 02
H
+
<0
@
<0
!c# L.P M 02
3P
!d# L.P M 02
3L
16. x / 2.L, y / 2.' 1:. r / 5:%g&l
'
;:5
'
&
'
O
-
;
'
2>. ' and 0
INTE<RATED RATE LA#
HASEEN SHURUAT FD D IIIG
1. A 2. C $. & %. C 2. 7 3. A
4. & 6. C :. C 1>. 7 11. & 12. C
1%. '22 min 12. G.' M 02
<
s
<0
, 2.2 atm
ATHRILA RASTA FD D I"G
1. 7 2. & $. & %. & 2. C

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. --
CHEMICAL KINETICS
4. !a#
2
0 (t 0
' c c
+
!b#
2
2.L'H
( c
6. G M 02
<H
sec :. 2.2' min
<0
1>. 0.P- 11. G.H M 02
<
min
<0
12. 2.2'0 +, 2.20- + 1$. 2.2HL +
1%. r / 5:sugar;:%
$
;
'
14. '
n30
$ 0 16. 5
app
/ 2.0+
30
min
30
, ( / 022+
3'
min
30
1:. 0st order, '. x 02
3'
sec
30
; 2>. :0 $ 0 / ', 0.,- x 02
3'
l mol
30
min
30
;
SECIAL KIND O! REACTIONS
HASEEN SHURUAT FD D "G
1. 7 2. 7 $. 7 %. 7
2. G.GP 02
302
, bac(ward 3. !%
'
/ O
'
# : O% : !%
'
O / O# / 2.G' : 2.,- : 2.00
4. !a# 5 / 5
0
$ 5
'
!b# '(
0
: (
'
6. ,.2M02
3
min
30
:. '.,M02
3
min
30
1>. :A; / GP.2P+, :7; / 0.PG, :&; / 0.0P+, :7;
max
/ P0.,,+, t
max
/ ,,.L2 min
ATHRILA RASTA FD D "IG
1. & 2. 7 $. A %. A 3. 0.G M 02
<G
+ min
<0
4. *irst order : 5
7
/ 0.P M 02
<,
@
<0
E 5
&
/ 0., M 02
<-
@
<0
6. 0-.P, +
:. ,,.-X 1>. 2.,P 11. ln
2 0 '
0 ' 2
:A; !5 '5 :A;#
:A; !5 '5 :A; #
+
+
/ 5
0
t
12. :A
2
; !03
0
5 t
e
# 1$. 5
f
/ ,.L 02
3
min
30
, 5
b
/ P.PH 02
3
min
30
, 5
e"
/ 2.P--
1%. -.2H : 0.22 12. H.P- 02
3,
s
30
, -.0L 02
3,
s
30
, '.
TEMERATURE DEENDANCE
HASEEN SHURUAT FD D"IIG
1. 7 2. C $. & %. A 2. & 3. &
4. C 6. & :. & 1>. 7 11. & 12. A
1$. & 1%. C 12. A
ATHRILA RASTA FD D "IIIG
1. A 2. A $. & %. & 2. & 3. A
4. 7 6. 7 :. ,,& 11. 'L'5 12. -H5 1$. ,.'G M 02
<P
1%. !a# 02.-, (calFmol , !b# '2., hr 12. E
a
/
' -
0F '
' 0
a a a a
-
A A 0 0
E E E E E A '
' ' A A
_
+

,
CHEMISTRY ARENA FLE"EL K IG
1. & 2. & $. 7 %. & 2. 7 3. 7 4. &
6. & :. 7 1>. 7 11. 7 12. C 1$. 7 1%.C
12. 7 13. & 14. A 16. 7 1:. & 2>. 7 21.C
22. A 2$. C 2%. & 22. C 23. A 24. 7 26.&
2:.& $>. & $1. A,7,C $2. A7& $$. A& $%. A& $2.&
$3. A7& $4. C $6. & $:. 7 %>. & %1. A %2.7
%$. & %%. = %2. A %3. 7 %4. A %6. C %:.&
2>. A 21. A 22. A 2$. & 2%. C 22. A 23.C
24. 7 26. A 2:. A 8 E 7 @ E & 9 E C )
3>. A 8, B E 7 9, @ E & ), T EC A 31. 7 32. & 3$.7
3%. A 32. 7

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. -,
CHEMICAL KINETICS
A<NI ARICHHA FLE"EL K IIG
1. 2.-P 2. , M 02
<
+
<0
@
<0
%. +
<'
min
<0
2. '.P M 02
<G
+
<'
@
<0
3. PH.P min 6. ' min
:. '0P.G 4@
<0
11. 0.P yr 12. x / G'.G, y / 0'.,
1$. 0, 2.00 +@
<0
1%. a / b / 0 12. 0'2 min
13. !a# 0, !b# 2.20 min
<0
, !c# PX 14. '
1:. 0.0' 02
3'
min
30
, 02,.- min 2>. H.,L (calFml
ENLOY THE "ICTORY FLE"EL K IIIG
1. ,.' x 02
3
min
30
2. 2.2'P min
30
$. GP.'0X %. 2.P-LL atm
2. 2.2220PG 3. !i# ', 0 !ii# '.GPx02
L
+
3'
s
30
!iii# ,,.54Fmol !iv# 0.0-,x02
0L
+s
30
4. '2.G min 6. 7 :. H.- x 02
3-
s
30
, PG.,P 54Fmol
1>. infinite temperature 11. !i# 'H. 54Fmol !ii# -.,0 x 02
3,
s
30
12. A, C
1$. ,.-' x 02
02
s
30
, '' 54Fmol1%. A, 7,C 12. .-, x 02
3
+ min
30
13. C 14. 022 54Fmol 16. C 1:. '-.'P sec
2>. A 21. A 22. A
2$. !a# r / 5 :A; :7;
2
!b# 2., s
30
2%. C
22. !i# 0, !ii# G.H M 02
<
min
<0
, !iii# '22 min, !iv# H,2 mm %g

Sri Chaitanya IIT-JEE Academy, 023A, Talwandi, 4halawar )oad, 5ota3 '-22,, !)a6#. -G

Chemical Kinetics

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Chemical Kinetics

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CHEMICAL KINETICS

represents the average rate of reaction.

products, the rate law

product, the integrated rate law is ( /

!ii# Sec*la) e;*ili9)i*m: ?f 5

products, the experimental rate of reaction

11. ACTI"ATED COMLE@ THEORY ,) TRANSITION STATE THEORY

),.*cts, where A7 is the

:A7; / 5 :A; :7; /

. This is called E0)in& e;*ati,n for

12. !ACTORS A!!ECTIN< RATE O! REACTION :

2NO=)+ ,9e0s the -,ll,1in& mechanism:

in the a;*e,*s s,l*ti,n is % E 1>

-,)me. (e) sec,n..

formed per sec / % E 1>

!g# As!s# $ F'%

00. *or a two step reaction, A $ & 7 $ 8, the reaction mechanism is

0'. *or the reaction:

7rO 7rO '7r

was found to be 2.2,G mol

, where concentrations are expressed in mol l

, if concentrations are expressed is mol ml

. Then the rate constant of the reaction is

. ?f the initial pressure had been 0,2 mm, what would

&o, .............. after time

!g# is introduced into a flas( at G22

&OO% $ %* has been studied under the following initial

&O*; 2.2022+ 2.22L,P+ 2.22P,+ 2.22,-2+

'. *or irreversible elementary reactions in parallel A

,. The net rate of reaction :&u!N%

/ 2.G' : 2.'P : 2.00. *ind the ratio of products at time, t.

&, the concentrations of A and 7 are 2.'+

&, the concentrations of A and 7 are 2.'+

&. The initial

7 !first order#, 'A

& !second order#.

&, 7 is in steady state. .hat will be the

0-. The mechanism of the reaction: A $ ' 7 C $ EE % / 3 ve is

where 5 is the rate constant, T is

. The rate of a reaction is expressed in different ways as follows

O%. The rate law contains :%

min !C# -., M 02

on heated tungsten yields the following data:

H=)F&G+ -,) 1hich a -i'e ste( mechanism has 9een (),(,se.:

2=) FChain initiati,nG

H=) A H FChain (),(a&ati,nG

H=) A =) FChain (),(a&ati,nG

at a steady state concentration of 'M02

by all sources was estimated as P.'M02

of nitrogen are evolved in -2 minute. %ow long after

of nitrogen have been evolvedT

!g# under certain conditions of temperature and partial

!g#. The rate of this reaction can be

!g#. ?dentify the correct

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in the a;e,s s,l*ti,n is % E 1>