Sri Chaitanya IIT- JEE Academy

CHEMISTRY ASSIGNMENT
[Chemical Kinetics]
***************************************************************************************
1. The rate of chemical reaction (ece!t "ero order#
1#decreases from moment to moment $# remains constant thro%&ho%t
'# de!ends %!on the order of reaction (# none
$. )adioacti*e decay follo+s ,,,,,, order -inetics
1# . $# I '# II (# III
'. The acid hydrolysis of ester is
1# I order reaction $# /imolec%lar reaction
'# 0se%do %nimolec%lar reaction (# none
(. The reaction C1
'
C22C
$
1
3
45a21

C1
'
C225a4C
$
1
3
21 is
1# /imolec%lar reaction $# II order reaction
'# III order reaction (# none
3. The rate constant of a II order reaction has %nits
1# mole l
-1
sec
-1
$# litre mole
-1
sec '# litre mole
-1
sec
-1
(# none of the a/o*e
6. 7or a reaction of II order -inetics its
1
T 2 is
1# a $# a
1
'# a
$
(# a
-1
8. The reaction $5a4Cl
$
9 $5aCl is fo%nd to follo+ III order -inetics. Its molec%larity is
1# 1 $# $ '# ' (# (
:. If ;a< is the initial conc. 2f a s%/stance +hich reacts accordin& to "ero order -inetic and
K is rate constant= the time for the reaction to &o to com!letion is
1# a K $# 2 Ka '# K a (# 2K a
>. In a reaction= the rate is K[A] [?]
$@'
the 2.). is
1# 1 $# $ '# 5 3 (# "ero
1.. Ahich one does not infl%ence the rate of reaction
1# nat%re of reactant $# conc. of reactant
'# tem!erat%re (# molec%larity
11. 7or the reaction A4?

!rod%cts= it is fo%nd that the order of A is $ and of ? is ' in

the rate e!ression +hen conc. of /oth is do%/led= the rate +ill increase /y
1# 1. $# 6 '# '$ (# 16
1$. 7or the reaction A

?= it is fo%nd that the rate of reaction increase /y : times +hen

the conc. of A is do%/led. The reaction is of BB.. 2.).
1# 1 $# $ '# ' (# (
1'. An increase in rate of reaction for a rise in tem!erat%re is d%e to
1# increase in collision freC%ency $# shortenin& of mean free !ath
'# increase in the n%m/er of acti*ated molec%les (# none
1(. The rate at +hich a s%/stance reacts is !ro!ortional to its
1# eC%i*alent +ei&hts $# molec%lar +ei&hts
'# n%m/er of moles (# n%m/er of moles !er litre
13. The rate constant of a reaction has same %nits as the rate of reaction. The rate is of
1# "ero order $# first order '# second order (# none of these
16. Increase in the concentration of the reactants leads to the chan&e in
1# heat of reaction $# acti*ation ener&y
'# collision freC%ency (# none of these
18. 7or a molec%lar collision to /e effecti*e= it sho%ld satisfy the follo+in& condition
1# it sho%ld in*ol*e the molec%les ha*in& a certain minim%m amo%nt of ener&y
$# it sho%ld in*ol*e only ionic com!o%nds
'# it sho%ld in*ol*e molec%les ha*in& a certain minim%m amo%nt of ener&y and a
!ro!er orientation
(# it sho%ld in*ol*e t+o or three molec%les
1:. An endothermic reaction A

? has an acti*ation ener&y as -J mole of A. If ener&y

chan&e of the reaction is y -J= the acti*ation ener&y of the re*erse reactions is
1# D $# D y '# 4y (# y D
1>. The reactions of hi&h molec%larity are rare /eca%se
1# many /ody collisions ha*e a lo+ !ro/a/ility
$# many /ody collisions are not fa*o%red ener&etical
'# acti*ation ener&y of many /ody collision is *ery hi&h
(# acti*ation ener&y of many /ody collision is *ery lo+
$.. The acti*ation ener&y of eothermic reaction A

? is $. -.cal. The heat of reaction
is 3. -.cal. The acti*ation ener&y for the reaction ?

A +ill /e
1# $. -.cals $# '. -.cals '# 8. -.cals (# 3. -.cals
$1. Increase in concentration of the reactants res%lts in
1# decrease in rate of the reaction $# increase in rate of the reaction
'# /oth increase or decrease in rate de!endin& %!on the nat%re of the reactants
(# none of the a/o*e
$$. 7or a chemical reaction $4y

" the rate of a!!earance of " is ...3 mol E

-1
!er min.
The rate of disa!!earance of +ill /e
1# ...3 mol E
-1
!er ho%r $# ...3 mol E
-1
!er min
'# ..1 mol E
-1
min
-1
(# ..$3 mol E
-1
!er min
$'. The acti*ation ener&y of a reaction is "ero. The rate constant of the reaction
1# increases +ith increase of tem!erat%re $# decreases +ith increase of
tem!erat%re
'# decreases +ith decrease of tem!erat%re (# is nearly inde!endent of tem!erat%re
$(. 2rder of reaction is
1# al+ays eC%al to its molec%larity $# al+ays a fraction
'# al+ays an inte&ral n%m/er (# the s%m of the e!onents in rate la+
$3. The s!ecific rate of a first order reaction de!ends on
1# the concentration of the reactants $# the concentration of the !rod%cts
'# tem!erat%re (# time
$6. The correct e!ression for Arrheni%s eC%ation sho+in& the effect of tem!erat%re on
the rate constant is
1#
a 2 2 1
1 1 2
E K T - T

K 2.303R T T

$#
a 2
1 1 2
E K 1 1
ln -
K R T T
_

,
'#
Ea RT
K = Ae
(#
a 2 1 2
1 2 1
E K T T
log =
K 2.303 T - T
$8. 7or the first order reaction half-life is 1(s. The time reC%ired for the initial
concentration to red%ce to
th
1 8 of its *al%e is
1# $: s $# ($ s '# (1(#
'
s (# (1(#
$
s
$:. The rate la+ for the reaction
)CI45a21(aC#

)2145aCl is &i*en /y= )ate 9 K[)Cl] the rate of the reaction +ill
/e
1# do%/led on do%/lin& the concentration of sodi%m hydroide
$# hal*ed on red%cin& the concentration of al-yl halide to one half
'# decreased on increasin& the tem!erat%re of the reaction
(# %naffected /y increasin& the tem!erat%re of the reaction
$>. The rate constant of a reaction de!ends on
1# tem!erat%re $# mass '# +ei&ht (# time
'.. 7or a &i*en rate la+ $A4?

C4F= the acti*e mass of ? is -e!t constant /%t that of
A is tri!led. The rate of reaction +ill
1# decrease /y ' times $# increase /y > times
'# increase /y ' times (# %n!redicta/le
'1. Ta-in& the reaction A4$?

!rod%cts to /e of second order +hich of the follo+in& is

the rate la+ e!ression for the reactionG
1#
dx
= K[A][B]
dt
$#
2
dx
= K[A][B]
dt
'#
2
dx
= K[A] [B]
dt
(#
2
dx
= K[A]+[B]
dt
'$. Consider a &aseo%s reaction= the rate of +hich is &i*en /y K[H][I]. The *ol%me of the
reaction *essel containin& these &ases is s%ddenly red%ced to 1@(
th
of the initial
*ol%me. The rate of the reaction as com!ared +ith ori&inal rate is
1# 1@16 times $# 16 times '# 1@: times (# : times
''. The rate of a reaction that does not in*ol*e &ases= does not de!end %!on
1# !ress%re $# tem!erat%re '# concentration (# datalyst
'(. 7or a reaction= a !lot of lo& (a D # *ers%s time (t# is a strai&ht line +ith slo!e eC%al to
K 2.303= the reaction is of
1# "ero order $# first order '# second order (# third order
'3. The rate constant of a reaction is 3.$1.
-1
min%tes
-1
the order of the reaction is
1# one $# "ero '# t+o (# three
'6. The first order rate constant for decom!osition of 5
$
2
3
is 6.>'1.
- (
sec
-1
. Ahat is half
chan&e time for decom!ositionG
1# 1.
$
sec $# 1.
'
sec '# 1.
(
sec (# 1. sec
'8. The half-life !eriod of a first order reaction is 13 min%tes. The amo%nt of s%/stance
left after one ho%r +ill /e
1# one half $# one fo%rth '# one ei&ht (# one siteenth
':. 7or a reaction A4$?

C4F= the follo+in& data= +ere o/tained

E!t. initial conc. initial conc. initial rate of
(mol. E
-1
# (mol E
-1
# formation of F
[A] [?] (mol E
-1
min
-1
#
1# ..1 ..1 6..1.
-'
$# ..' ..$ 8.$1.
-$
'# ..' ..( $.::1.
-1
(# ..( ..1 $.(1.
-$
The correct rate la+ e!ression +ill /e
1# )ate 9 K[A][?] $# )ate 9 K[A][?]
$
'# )ate 9 K[A]
$
[?]
$
(# )ate 9 0[A]
$
[?]
'>. The rate of the reaction A4?4C

!rod%cts is &i*en /y
1 2 1 3 1 4
- d[A]
r = = K[A] [B] []
dt

the order of reaction is
1# 1 $# $ '# 1 2 (# 13 12
(.. In a reaction the rate +as fo%nd to /e inde!endent of the concentration of the
reactants. The reaction is of
1# 1
st
order $# $
nd
order '# order 1.3 (# "ero
(1. Ahich one of the follo+in& factors does not infl%ence the reactions ratesG
1# concentrations $# tem!erat%re '# si"e of the *essel (# catalyst
($. In a m%ltiste! reaction= the o*erall rate of reaction is
1# eC%al to the rate of slo+est ste! $# eC%al to the rate of fastest ste!
'# eC%al to the a*era&e rate of *ario%s ste!s (# eC%al to the rate of the last ste!
('. Ahich of the follo+in& e!ression is correct for second order reactions (C
.
refers to
initial concentration of reactant#
1#
1 2 0
t !
$#
-1
1 2
t ! '#
-2
1 2 0
t ! (#
0
1 2 "
t !
((. The effect of tem!erat%re on reaction rate is &i*en /y
1# Cla%si%s cla!eron eC%ation $# Arrheni%s eC%ation
'# Ji//<s 1elmholt" eC%ation (# Jeneral &as eC%ation
(3. 7or a reaction !A4C?

!rod%cts= the rate la+ e!ression is r 9 K[A]

l
[?]
m
then
1# (!4C# (l4m# $# (!4C# 9 (l4m#
'# (!4C# may or not /e eC%al to (l4m# (# (!4C# K (l4m#
(6. The rate of reaction $524Cl
$

$52Cl /ecomes do%/led +hen the concentration of

Cl
$
is do%/led ho+e*er= +hen the concentration of /oth the reactants are do%/led the
rate /ecomes ei&ht times. Ahat is order of the reaction
1# first $# second '# third (# "ero
(8. The rate constant of a reaction is 1.$1.
-$
mol
-$
lit
$
sec
-1
. The order of reaction is
1# "ero $# 1 '# $ (# '
(:. 7or the reaction A4$?4C

F4$E the rate of formation of F is fo%nd to /e

(a# do%/led +hen [A] is do%/led -ee!in& [?] and [C] constant
(/# do%/led +hen [C] is do%/led -ee!in& [A] and [?] constant
(c# the same +hen [?] is do%/led -ee!in& [A] and [C] constant.
Ahich one is the rate eC%ation for the reactionG
1# rate 9 K[A][?][C] $# rate 9 K[A]
.
[?][C] '# rate 9 K[A][?]
.
[C] (# rate 9
K[A][?][C]
.
(>. The concentration of a reactant in a sol%tion falls (i# from ..$ to ..1L in $ hrs (ii# from
..$ to ...3L in ( hr. The order of the hydrolysis of the reactant is
1# "ero $# t+o '# one (# half
3.. T+o &ases A and ? are filled in a container= the e!erimental rate la+ for the reaction
/et+een them= has /een fo%nd to /e )ate 9 K[A][?] !redict the effect on the rate of
the reaction +hen !ress%re is do%/led
1# the rate is do%/led $# the rate /ecomes fo%r times
'# the rate /ecomes ei&ht times (# none of the a/o*e
31. The rate of the first order reaction H

!rod%cts is 8.31.
-(
mol lit
-1
s
-1
. Ahen the
concentration of is ..3 mole E
-1
. The rate constant in seconds is
1# '.831.
-(
S
-1
$# $.31.
-(
S
D1
'# 1.31.
-'
S
D1
(# '..1.
-(
S
-1
3$. 7or the reaction $A4?

F=
2
- d[A]
=K[A] [B]
dt
. The e!ression for
- d[B]
dt
+ill /e
1# K[A]
$
[?] $# $K[A]
$
[?] '# K[$A]
$
[?] (#
2
1
K[A] [B]
2
3'. A hy!othetical reaction A
$
4?
$
$A? follo+s the mechanism as &i*en /elo+.
2
A A+A #$a%t&

2
A+B AB+B #%lo'& A+B AB #$a%t&
The order of the o*er all reaction is
1# $ $# 1 '#
1
1
2
(# .
3(. 7or a chemical reaction $H4I

M the rate of a!!earance of M is ...3 mol E
-1
!er
min. The rate of disa!!earance of +ill /e
1# ...3 mol E
-1
!er ho%r $# ...3 mol E
-1
!er min.
'# ..1 mol E
-1
min
-1
(# ..$3 mol E
-1
!er min.
33. An endothermic reaction A

? has an acti*ation ener&y of 1. K.cals@mole and heat

of the reaction is 3 -.cals@mole. The acti*ation ener&y of the reaction ?

A is
1# $. -.cal@mole $# 3 -.cal@mole '# 1. -.cal@mole (# "ero
36. The decom!osition of a s%/stance ;)< ta-es !lace accordin& to first order -inetics. Its
initial concentration is red%ced to 1@:
th
in $(s. The rate constant of the reaction is
1#
-1
1 24 ( $#
-1
0.)* 1) ( '#
-1
ln 2 8 ( (#
-1
1 8 (
38. The half life !eriod of a first order reaction
2.303 a
K = log
t a - x
is
1# directly !ro!ortional to ;a< $# in*ersely !ro!ortional to ;a<
'# inde!endent of ;a< (# !ro!ortional to (a D #
3:. The incorrect order indicated a&ainst the rate of reaction A4?

C is
)ate 2rder )ate 2rder
1#
d[]
= K[A]
dt
1 $#
d[]
= K[A][B]
dt
$
'#
0
d[A]
= K[A][B]
dt
$ (#
d[A]
= K[A]
dt
1
3>. The minim%m ener&y necessary to !ermit a reaction to occ%r is
1# internal ener&y $# threshold ener&y
'# acti*ation ener&y (# free ener&y
6.. 7or a "ero order reaction
1#
1 2 0
t !
$#
1 2 0
T ! 1
'#
2
1 2 0
t ! (#
2
1 2 0
t ! 1
61. A first order reaction has s!ecific rate constant of $ min
-1
. The half-life of this reaction
+ill /e
1# 1.63' min $# ..'(8 min '# $ min (# ..3 min
6$. 7or a first order reaction +e ha*e -91.. sec
-1
. The time for com!letion of 3.N
reaction is
1# 1m sec $# (m sec '# 8m sec (# 1.m sec
6'. 7or the reaction A4$?

C= the rate of reaction at a &i*en instant can /e

re!resented /y
1#
d[A] 1 d[B] d[]
+
dt 2 dt dt
+ + $#
d[A] 1 d[B] d[]
dt 2 dt dt
+
'#
d[A] 1 d[B] d[]
dt 2 dt dt
+ (#
d[A] 1 d[B] d[]
dt 2 dt dt
+ + +
6(. In !hotochemical reactions
1# tem!erat%re has the same effect as on thermal reactions
$# tem!erat%re has o!!osite effect as on thermal reactions
'# tem!erat%re has no effect
(# tem!erat%re may ha*e a little effect in certain cases
63. In the reaction A4?

A? if the concentration of ;A< is do%/led= the rate of reaction

+ill
1# /e do%/led $# /e decreased to one half
'# increase fo%r times (# remain %naffected
66. The amo%nt of ( )
128
53 1 2
+ t - 25 ,-n.te% left after 3. min%tes +ill /e
1# 1 4 $# 1 2 '# 1 3 (# none of these
68. The first order rate constant for the decom!osition of 5
$
2
3
is 61.
-(
second
-1
. The half
life !eriod for the decom!osition in second is
1# 1133 $# 113.3 '# 11.33 (# 1.133
6:. If the half-time for a !artic%lar reaction is fo%nd to /e constant and inde!endent of the
initial concentration of the reactions then reaction is
1# first order $# "ero order '# second order (# none of these
6>. If initial concentration of reactants in certain reaction is do%/led= the half life !eriod of
the reaction do%/les= the order of a reaction is
1# "ero $# first '# second (# third
8.. The rate of reaction A4?

!rod%cts is &i*en /y the eC%ation r9K[A][?]. If ? is

ta-en in lar&e ecess= the order of the reaction +o%ld /e
1# $ $# 1 '# . (# %n!redicta/le
81. In the reaction= A4$?

C4$F= the initial rate

- d[A]
dt
at t 9 . +as fo%nd to /e
$.61.
-$
m sec
-1
. Ahat is the *al%e of
- d[B]
dt
at t 9 . in m sec
-1
G
1# $.61.
-$
$# 3.$1.
-$
'# 1..1.
-1
(# 6.31.
-'
8$. The %nit of the *elocity constant in case of "ero order reaction is
1# conc time
-1
$# conc
-1
time '# conc
-1
time
-1
(# conc (time#
$
8'. The con*ersion of molec%les A to ? follo+s second order -inetics. Fo%/lin& the
concentration of A +ill increase the rate of formation of ? /y
1# a factor $ $# a factor of ( '# factor of 1 2 (# a factor of 1 4
8(. 2f the concentration of a reactant A is do%/led and the rate of its reaction increases /y
a factor of $= the order of reaction +ith res!ect to A is
1# first $# "ero '# second (# third
83. If initial concentration is tri!led= the time for half reaction is also tri!led= the order of
reaction is
1# "ero $# first '# second (# third
86. )ate of chemical reaction can /e -e!t constant
1# /y startin& the com!onents $# /y -ee!in& the tem!erat%re
'# /oth of a/o*e (# none of a/o*e
88. Ahich of the follo+in& into la+s has an o*erall order of ..3 for reaction in*ol*in&
s%/stances and yG
1# ( ) ( )
x /
Rate = K $#
( ) ( )
0.5
0.5
x /
Rate = K
'#
( ) ( )
1
1.5
x /
Rate = K

(#
( ) ( )
1.5
x /
Rate = K
8:. The hydrolysis of methyl formate in acid sol%tion has rate e!ression
[ ]
+
3
rate = K 0""0 0 1
]
the /alanced eC%ation /ein& 1C22C1
'
41
$
2

1C2214C1
'
21. The rate la+ contains
+
0 1
]
tho%&h the /alanced eC%ation does not
contain
+
0 1
]
/eca%se
1# more for con*enience to e!ress the rate la+
$# 1
4
ion is a catalyst
'# 1
4
is an im!ortant constit%ent of any reaction
(# All acids contain 1
4
ions
8>. In a catalytic con*ersion of 5
$
to 51
'
/y 1a/er<s !rocess the rate of chan&e in the
concentration of 51
'
!er time is (.1.
-'
mol l
-1
. If there is no side reaction the rate of
the chan&e as e!ressed in terms of hydro&en is
1#
-3 -1 -1
)0 10 ,ol l %
$#
-1 -1
1200 ,ol l %
'#
-3 -1 -1
20110 ,ol l %
(#
-3 -1 -1
10.3110 ,ol l %
:.. In +hich of the follo+in& cases does the reaction &o to farthest to com!letionG
1# - 9 1. $# - 9 1 '# - 9 1.
'
(# - 9 1.
-$
:1. 7or an eothermic reaction the ener&y of acti*ation of the reactant is
1# eC%al to the ener&y of acti*ation of !rod%cts
$# less than the ener&y of acti*ation of !rod%cts
'# &reater than the ener&y of acti*ation of !rod%cts
(# sometimes &reater and sometimes less than that of the !rod%cts
:$. In a reaction 4y

!rod%cts= it +as fo%nd that (i# on do%/lin& the concentration of

= the rate do%/led (ii# on do%/lin& the concentration on y= the rate of the reaction
increased fo%r times= the o*er all order of the reactant is
1# ' $# $ '# 1 (# .
:'. The hydrolysis of ester in al-aline medi%m is a
1# 1
st
order reaction +ith molec%larity 1 $# $
nd
order reaction +ith molec%larity $
'# 1
st
order reaction +ith molec%larity $ (# $
nd
order reaction +ith molec%larity 1
:(. 7or the chemical chan&e A

?= it is fo%nd that the rate of reaction do%/les +hen

the concentration is increased fo%r times. The order A for this reaction is
1# t+o $# "ero '# one (# half
:3. 7or reaction (A4?

$C4$F +hich of the follo+in& statements is not correctG

1# the rate of disa!!earance of ? is one fo%rth of the rate of disa!!earance of A
$# the rate of a!!earance of C is one half the rate of disa!!earance of ?
'# the rate of formation of F is one half the rate of cons%m!tion of A
(# the rates of formation of C and F are eC%al
:6. The %nits for the rate constant to first order reaction is
1# S
-1
$# mol E
-1
S
-1
'# mol S
-1
(# E mol
-1
S
-1
:8. The rate of a certain reaction at different times are as follo+s
Time (min# . 1. $. '.
)ate $.:1.
-$
$.:1.
-$
$.:11.
-$
$.8>1.
-$
(moles litre
-1
min
-1
#
the order of the reaction is
1# one $# t+o '# three (# "ero
::. The reaction= $A4$?

!rod%cts= the follo+in& initial rates +ere o/tained at *ario%s

initial concentrations
[A] [?] )ate (mol l
-1
sec
-1
#
..1 L ..$ L ..(6
..$ L ..$ L 1.:(
..$ L ..1 L ..>$
The rate la+ for the reaction is
1# )ate 9 K[A]
$
[?]
.
$# )ate 9 K[A][?] '# )ate 9 K[A]
$
[?] (# )ate 9 K[A][?]
$
:>. The reaction $1
$
2
$

$1
$
242
$
is= [ ]
2 2
r = K 0 "
1# "ero order reaction $# first order reaction
'# second order reaction (# third order reaction
>.. A s%/stance A decom!oses in sol%tion follo+in& the first order -inetics. 7las- I
contains 1 E of 1 L sol%tion of A and flas- II contains 1..ml of ..6 L sol%tion. After :
hr. the concentration of A in flas- I /ecomes ..$3L= +hat +ill /e time for concentration
of A in flas- II to /ecome ..'L
1# ..( hr. $# $.( hr. '# (.. hr.
(# %n !redicta/le as rate constant is not &i*en
>1. The %nit of rate constant for a "ero order reaction is
1# litre sec
-1
$# litre mole
-1
sec
-1
'# mole litre
-1
sec
-1
(# mole sec
-1
>$. The rate constant for a first-order reaction +hose half-life is (:. sec. is
1# 1.((1.
-'
sec
-1
$# 1.(( sec
-1
'# ..8$1.
-'
sec
-1
(# $.::1.
-'
sec
-1
>'. The rate of a chemical reaction do%/les for e*ery 1.
.
C rise in tem!erat%re. If the rate
is increased /y 6.
.
C= the rate of reaction increases /y a/o%t
1# $. times $# '$ times '# 6( times (# 1$: times
>(. Ahich of the follo+in& statement a/o%t the order of reaction is tr%eG
1# the order of a reaction increases +ith increase in tem!erat%re
$# the order of a reaction can /e determined from the /alanced eC%ation
'# a second-order reaction is also /imolec%lar
(# the order of a reaction can only /e determined
>3. The rate of the reaction
2 2 3
2 #g&+30 #g& 220 #g& +as meas%red as
[ ]
4 -1 -1
3
1 d
20 2 10 ,ol 3 %e4
2 dt

+ . The rates of the reaction e!ressed in terms of 5
$
and
1
$
are rate in terms of 5
$
rate in terms of 1
$
.
( )
-1 -1
,ol 3 %e4
( )
-1 -1
,ol 3 %e4
( )
-1 -1
,ol 3 %e4
( )
-1 -1
,ol 3 %e4
1# 11.
-(
11.
-(
$# '1.
-(
11.
-(
'# 11.
-(
11.
-(
(# $1.
-(
61.
-(
>6. The %nit for s!ecific reaction rate of second order reaction is
1# sec
-1
$# mole litre
-1
sec
-1
'# litre
$
mole
-$
sec
-1
(# litre mole
-1
sec
-1
>8. The rate of a &aseo%s reaction is eC%al to K[A][?]. The *ol%me of the reaction *essel
containin& these &ases is s%ddenly red%ced to one-fo%rth the initial *ol%me. The rate
of the reaction +o%ld /e
1# 1 1) $# 1) 1 '# 1 8 (# 8 1
>:. Fia"oni%m salt decom!oses as
+ -
) 5 2 ) 5 2
0 2 l 0 l+2 . At .
.
C= the e*ol%tion of 5
$
/ecomes t+o times faster +hen the initial concentration of the salt is do%/led.
Therefore it is
1# a first order reaction $# a second order reaction
'# inde!endent of the initial concentration of the salt (# a "ero order
reaction
>>. Ahich one of the follo+in& rate la+s has an o*erall order of ..3 for the reaction
in*ol*in& s%/stances H= I= MG
1# ( ) ( ) ( )
x / 5
Rate = K $#
( ) ( ) ( )
0.5
0.5 0.5
x / 5
Rate = K
'#
( ) ( ) ( )
1
1.5 0
x / 5
Rate = K

(#
( ) ( )
0
x 5
Rate = K
( )
2
/

1... The con*ersion of A

? follo+s second order -inetics. Fo%/lin& the concentration

of A +ill increase the rate of reaction /y a factor of
1# $ $# 1 2 '# ( (# 1 4
1.1. In the re*ersi/le reaction
1
2
K
2 2 4
K
22" 2 "

the rate of disa!!earance of 52

$
is eC%al to
1# [ ]
2
1
2
2
2K
2"
K
$#
[ ] [ ]
2
1 2 2 2 4
2K 2" - 2K 2 "
'#
[ ]
2
1 2
2K 2" (# ( ) [ ]
1 2 2
2K - K 2"
1.$. The &i*en reaction $7eCl
'
4SnCl
$

$7eCl
$
4SnCl
(
is an eam!le of
1# first order reaction $# second order reaction '# third order reaction (# none of
these
1.'. 7or the reaction A4?

C= it is fo%nd that do%/lin& the concentration of A increase

the rate ( times and do%/lin& the concentration of ? do%/les the reaction rate. Ahat
is the o*erall order of the reaction
1# 3 2 $# ( '# 1 (# '
1.(. A first order is half com!leted in (3 min%tes. 1o+ lon& does it need for >>.>N of the
reaction to /e com!letedG
1# $. ho%rs $# 1. ho%rs '#
1
6
2
ho%rs (# 3 ho%rs
1.3. In a reactionO A

?= the rate of reaction increases t+o times on increasin& the

concentration of the reactants fo%r times= then the order of the reaction is
1# . $# $ '# 1 2 (# (
1.6. Lil- t%rns so%r at (.
.
C three times as faster at as .
.
C. 1ence E

(acti*ation ener&y# of
t%rnin& of mil- so%r is
1#
2.303 2 313 263
log 3 4al
40

$#
2.303 2 313 263
log #173& 4al
40

'#
2.303 2 40
log 3 4al
263 313

(#
2.303 2 40
log #173& 4al
263 313

1.8. A &ra!h /et+een lo&( )

50
T = and lo& (conc.# for n
th
order reaction is a
strai&ht line. )eaction of this nat%re is com!leted 3.N in 1.
min%tes +hen conc. is $ mol E
-1
. This is decom!osed 3.N in t
min%tes at ( mol E
-1
n and t are
1# ..$. min $# 1= 1. min '# 1= $. min (# .= 3 min
1.:. Jra!h /et+een lo& - and
1
T
(- is rate constant (s
-1
# and T the
tem!erat%re (K## is a strai&ht line +ith 2H93=
-1
1
8 = Tan
2.303
_

,
.
1ence E
a
+ill /e
1# $.'.'$ cal $#
2
4al
2.303
'# $ cal (# none
1.>. 1alf life ( )
1
T of the first order reaction and half life ( )
2
T of the second order reaction
are eC%al. 1ence ratio of the rate at the start of the reaction
2
1
T =
rate 4on%tant -n-t-al 4on%tant
_

,
1# 1 $# $ '# ..6>' (# 1.((
11.. )ate constant - of a reaction is ...6>' min
-1
. Startin& +ith $. mol E
-1
= rate of the
reaction after 1. min. +ill /e
1# ..6>' mol E
-1
min
-1
$# 1.':6 mol E
-1
min
-1
'# ...6>' mol E
-1
min
-1
(# 6.>' mol E
-1
min
-1
111. The rate of a chemical reaction &enerally increases ra!idly e*en for small tem!erat%re
increase /eca%se of a ra!id increase in the
1# collision freC%ency
$# fraction of molec%les +ith ener&ies in ecess of the acti*ation ener&y
'# acti*ation ener&y
(# a*era&e -inetic ener&y of molec%les
11$. 7or a reaction rate constant is eC%al to rate of the reaction of all concentrations= the
order is
1# . $# $ '# ' (# 1
11'. )ate constant of a reaction - is '..1.
-(
s
-1
= ener&y of acti*ation E
a
9 1.(.( -J mol
-1
and
Arrheni%s constant A is 6..1.
1(
s
-1
at $>: K. The *al%e of rate constant - as a T


is
1# $..1.
1:
s
-1
$# 6..1.
1(
s
-1
'# infinite (# '.61.
'.
s
-1
11(. A tan&ent dra+n on the c%r*e o/tained /y !lottin& concentration of !rod%ct (mole E
-1
#
of a first order reaction *s. time (min# at the !oint corres!ondin& to time $. min%te
ma-es an an&le to '.
.
+ith concentration ais. 1ence the rate of formations of
!rod%ct after $. min%tes +ill /e
1# ..3:. mole E
-1
min
-1
$# 1.8$' mole E
-1
min
-1
'# ..$>. mole E
-1
min
-1
(# ..:66 mole E
-1
min
-1
113. 7or reaction 'A

!rod%cts= it is fo%nd that the rate of reaction increases (-fold

+hen concentration of A is increased 16 times -ee!in& the tem!erat%re constant. The
order of reaction isG
1# $ $# 1 '# ' (# ..3
116. The reactionP $2
'

'2
$
= is assi&ned the follo+in& mechanism
I. 2
'


2
$
42
II. 2
'
42
2
%lo'
2"
The rate la+ of if the reaction +ill therefore /e
1#
[ ] [ ]
2
3 2
r ! " " $#
[ ] [ ]
2 1
3 2
r ! " "

'# [ ]
3
r ! " (#
[ ] [ ]
2
3 2
r ! " "

118. Fecom!osition of 5
$
2
3
occ%rs in the follo+in& manner $5
$
2
3

(52
$
42
$
its rate is
e!ressed in three +ays
(i#
[ ]
( )
2 5 11
2 5
d 2 "
9 2 "
dt
(ii#
( )
( )
2 1
2 5
d 2"
9 2 "
dt
(iii#
( )
( )
2 11
2 5
d "
9 2 "
dt

Ahat is the relation /et+een - Q
:
9
1# - 9
:
9
$# - 9 $
:
9
'#
:
9
9 $- (#
:
9
9 1 3 -
11:. All chemical reactions ta-e !lace at a definite rate de!endin& on the conditions= of
+hich the im!ortant are
1# concentration of reactants $# tem!erat%re
'# radiation (# !resence of a catalyst
11>. The rate constant of a reaction de!ends on
1# tem!erat%re $# mass '# density (# time
1$.. The rate at +hich a s%/stance reacts de!ends on its
1# atomic mass $# eC%i*alent mass '# molec%lar mass (# acti*e mass
1$1. The rate e!ression for a reaction is
3 2 -1
rate = 9[A] [B] = the order of reaction is
1# . $# 1 2 '# 3 2 (# 5 2
1$$. Ahich of the follo+in& rate la+ has an o*erall order of ..3 for the reactions in*ol*in&
s%/stances = y= "G
1# ( ) ( ) ( )
x / 5
Rate = 9 $#
( ) ( ) ( )
0.5
0.5 0.5
x / 5
Rate = 9
'#
( ) ( ) ( )
1
1.5 0
x / 5
Rate = 9

(#
( ) ( )
( )
0
x 5
2
/
R
Rate =

1$'. The reaction A(&#4$?(&#

C(&#4F(&# is an elementary !rocess. In an e!eriment

the initial !artial !ress%re of A Q ? are 0
A
9 ..6. and 0
?
9 ..:. atm. Ahen 0
C
9 ..$
atm the rate of reaction relati*e to the initial rate is
1# 1 48 $# 1 24 '# * 1) (# 1 )
1$(. If concentration are meas%red in mole@lit and time in min%tes= the %nit for the rate
constant of a '
rd
order reaction are
1# mol lit
-1
min
-1
$# lit
$
mol
-$
min
-1
'# lit. mol
-1
min
-1
(# min
-1
1$3. A radioacti*e element has a half life !eriod of 1(. days. 1o+ m%ch of it +ill remain
after 11$. days
1#
1
32
$#
1
25)
'#
1
512
(#
1
128
1$6. 7or a first order reaction the !lot of lo&
t
[A] Rs t is linear +ith a
1# !ositi*e slo!e and "ero interce!t $# !ositi*e slo!e and non "ero interce!t
'# ne&ati*e slo!e and "ero interce!t (# ne&ati*e slo!e and non "ero interce!t
1$8. The rate la+ for the reaction
)Cl45a21(aC#

)2145aCl
is &i*en /y )ate 9 -[)Cl]. The rate of the reaction +ill /e
1# %naffected /y increasin& tem!erat%re of the reaction
$# do%/led on do%/lin& the concentration of 5a21
'# hal*ed on red%cin& the concentration of 5a21 to one half
(# hal*ed on red%cin& the concentration of )Cl to one half
1$:. 7or a &i*en reaction of first order= it ta-es $. min%tes for the concentration to dro!
from 1.. mol litre
-1
to ..6 mol litre
-1
. The time reC%ired for the concentration to dro!
from ..6 mol litre
-1
to ..'6 mol litre
-1
+ill /e
1# more than $. min%tes $# less than $. min%tes
'# eC%al to $. min%tes (# infinity
1$>. The %nit of rate constant of a reaction ha*in& order 1.3 +o%ld /e
1#
( )
17 2
-1 -1
,ol 3 %

$#
( )
37 2
-1 -1
,ol 3 %

'# (conc#
- ..3
time
-1
(# (conc#
- ..83
time
-1
1'.. A catalyst lo+ers the acti*ation ener&y of the for+ard reaction /y $. -J mol
-1
. It also
chan&es the acti*ation ener&y of the /ac-+ard reaction /y an amo%nt
1# eC%al to that of for+ard reaction
$# eC%al to t+ice that of the for+ard reaction
'# +hich is determined only /y the a*era&e ener&y of !rod%cts
(# +hich is determined /y the a*era&e ener&y of !rod%cts relati*e to that of reactants
1'1. The half-life !eriod of a radioacti*e element is 1(. days. After 36. days= one &ram of
the element +ill red%ce to
1# ( ) 1 2 g $# ( ) 1 4 g '# ( ) 1 8 g (# ( ) 1 1) g
1'$. 7or a second order reaction of the ty!e rate 9 -[A]
$
= the !lot of 1@ [A]
t
*ers%s t is linear
+ith a
1# !ositi*e slo!e and "ero interce!t $# !ositi*e slo!e and non "ero interce!t
'# ne&ati*e slo!e and "ero interce!t (# ne&ati*e slo!e and non "ero interce!t
1''. The follo+in& statement(s# is (are# correct
1# A !lot of lo& K *ers%s 1@T is linear
$# A !lot of lo& (# *ers%s time is linear for a first order reaction H0
'# A !lot of lo& 0 *ers%s 1@T is linear at constant *ol%me
(# A !lot of 0 *ers%s 1@R is linear at constant tem!erat%re
1'(. The decom!osition of Cl
$
2
8
at (..- in the &as !hase to Cl
$
and 2
$
is a first order
reaction
(i# After 33 seconds at (..K the !ress%re of Cl
$
2
8
falls from ...6$ to ...(( atm. The
rate constant and !ress%re of Cl
$
2
8
after 1.. sec of decom!osition at this tem!erat%re
are
1# 3.$1.
-(
sec
-1
P ...3 atm $# 6.$1.
-'
sec
-1
P ...'' atm
'# 3.:1.
-'
sec
-1
P ..(( atm (# (.61.
-'
sec
-1
P ....3 atm
1'3. S%!!ose one does not ha*e an e!erimental !roced%re to follo+ the -inetics of a first
order reaction +ith a half life less than ..' nano seconds= then
1# The minim%m *al%e of rate constant that can still /e meas%red is $.'11.
1$
sec
-1
$# The maim%m *al%e of rate constant that can still /e meas%red is :.'161.
1$
hr
-1
'# The minim%m *al%e of rate constant that can still /e meas%red is more than
:.'161.
1$
hr
-1
(# The maim%m *al%e of rate constant= that can still /e meas%red is less than 31.
-1
hr
-1
.
1'6. 83N of a 1
st
order reaction +as com!leted in '$ min%tes. Ahen +as 3.N of the
reaction com!leted
1# $( min $# ( min '# 16 min (# : min
3# none of these
1'8. 7or a &eneral reaction=
aA4/?

cC4dF
the rate of reaction may /e &i*e as
1#
; A
A B
d 1
r = - 9
dt a
$#
a ; B
A B
d 1
r = - 9
dt ;

'#
a ;
A B
d 1
r = 9
dt 4
(#
a ; +
A B
d 1
r = - 9
dt d

1':. The half life of a second order reaction is
1#
172
t = 0.)*379 $#
172 0
t = 9[A] '#
172 0
t = [A] 7 9 (#
172
0
1
t =
9[A]
1'>. Accordin& to Arrheni%s the relationshi! /et+een rate constant= - and tem!erat%re can
/e &i*en /y
1#
- Ea RT
9 = Ae
$#
a 2 2 1
1 1 2
E 9 T - T
log = 1
9 2.303R TT
'#
a
E
log 9 = logA -
2.303RT
(# J
.
9 - $.'.' )T lo& K
1(.. Ahat +ill /e the amo%nt of ( )
n
, 172
< t 25 ,-n left after 3. min%tesG
1# 1@$ $# 1@( '# 1@' (# 1@1.
1(1. Ahat is the acti*ation ener&y for the decom!osition of 5
$
2
3
as
2 5 2 2
1
2 " 22" "
2
+


If the *al%es of the rate constants are '.(31.
-3
and 6.>1.
-'
at $8
.
C and 68
.
C
res!ecti*ely
1# 1.$1.
$
-J $# (::.3 -J '# 11$ -J (# 11$.3 -J
1($. 3.N of the amo%nt of a radioacti*e s%/stance decom!oses in 3 years. The time
reC%ired for the decom!osition of >>.>N of the s%/stance +ill /e
1# 1. years $# /et+een 1. and 3. years
'# less than 1. years (# /et+een (> and 3. years
1('. Ahich one of the follo+in& statements is +ron& re&ardin& molec%larity of the reactionG
1# It is calc%lated from the reaction mechanism
$# It may /e either a +hole n%m/er or fraction
'# It is the n%m/er of molec%les of the reactants ta-in& !art in a sin&le ste! chemical
reaction
(# It de!ends on the rate determinin& ste! of the reaction
1((. 1.':6 ho%rs are reC%ired for the disa!!earance of 83N of a reactant of first-order
reaction. Ahat is the rate constant of the reactionG
1# '.61.
-'
s
-1
$# 8.$1.
-'
s
-1
'# $.81.
-(
s
-1
(#
1.:1.
-'
s
-1
1(3. 7or a first order reaction= the ratio of time for the com!letion of >>.>N and half of the
reaction is
1# : $# 1. '# > (# 1$
1(6. A certain radioacti*e element A= has a half-life 9 t seconds. In (t@$# seconds the
fraction of the initial C%antity of the element so far decayed is nearly
1# $3N $# $>N '# $1N (# 18N
1(8. The terms rate of reaction and rate of a!!earance (or disa!!earance# of reactant (or
!rod%ct#
1# re!resent one and the same !hysical C%antity
$# differ /y constant factor
'# are !ositi*e !arameters and ha*e same *al%e
(# may or may not ha*e same *al%e de!endin& %!on the stoichiometric coefficient of
reactants (or !rod%cts# in the /alanced chemical eC%ation
1(:. 7or the first order reaction A(&#

$?(&#4C(&#= the initial !ress%re is 0

A
9 >.mm 1&=
the !ress%re after 1. min%tes is fo%nd to /e 1:.mm 1&. The rate constant of the
reaction is
1# 1.131.
-'
sec
-1
$# $.'1.
-'
sec
-1
'# '.(31.
-'
sec
-1
(# 61.
-'
sec
-1
I. Following facts is taken to expess ate of t!e eaction in te"s of
stoic!io"etic coefficients.
Answe t!e #$estions at t!e en% of it.
Fo t!e eaction aA&'(

cC&%)
dx 1 d[A] 1 d[B] 1 d[] 1 d[+]
= - -
dt a dt ; dt 4 dt d dt
+ +
1(>. 7or the reaction in al-aline aC%eo%s sol%tion=
- -
3
3Br" Br" 2Br

+
the *al%e of rate constant at :.
.
C in the rate la+ for
-
Br"
t
1
]

+as fo%nd to /e ...3(

E mol
-1
s
-1
. )ate constants +hen the rate la+ is +ritten for
- -
3
Br" Br
and
t t
1 1
] ]

are
-= interms of
-
3
Br"
t
1
]

in terms of
-
Br
t
1
]

1# ...1: E mol
-1
s
-1
...'6 E mol
-1
s
-1
$# ...1: E mol
-1
s
-1
...$8 E mol
-1
s
-1
'# ..16$ E mol
-1
s
-1
..1.: E mol
-1
s
-1
(# ..16$ E mol
-1
s
-1
...'6 E mol
-1
s
-1
13.. )ate of formation of S2
'
in the follo+in& reaction
$S2
$
42
$
$S2
'
is 1..& min
-1
. 1ence= rate of disa!!earance of 2
$
is
1# 3.& min
-1
$# 1..& min
-1
'# $..& min
-1
(# $.& min
-1
131. A reaction follo+s the &i*en concentration time &ra!h. The rate for this reaction at $.
seconds +ill /e
1# (1.
-'
L s
-1
$# :1.
-'
L s
-1
'# $1.
-$
L s
-1
(# 11.
-$
L s
-1
13$. In the follo+in& reactionO
xA /B
d[A] d[B]
log - log 0.3
dt dt
1 1
+
1 1
] ]
+here D *e si&n indicates rate of disa!!earance of the reactant. Th%s= O y is
1# 1 O $ $# $ O 1 '# ' O 1 (# ' O 1.
13'. 7or a &aseo%s reaction= the rate is often e!ressed in terms of
d=
dt
_

,
instead of
d
dt
_

,

or
dn
dt
_

,
= +here C is the concentration and n is the n%m/er of mole. 1ence= relation
/et+een three e!ressions is
1#
d 1 dn 1 d=
dt > dt RT dt
_ _


, ,
$#
d dn d=
dt dt dt
_ _


, ,
'#
d dn > d=
dt dt RT dt
_ _


, ,
(# none of these
13(. 7or the reaction $51
'

5
$
4'1
$
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
3 2 2
1 3 2 3 3 3
d 20 d 2 d 0
9 20 ? 9 20 ? 9 20
dt dt dt

Then relation /et+een
1 2 3
9 ? 9 and 9 is
1# 1.3
1
9 9 '
2
9 9
3
9 $# $-
1
9 -
$
9 '-
'
'# -
1
9 -
$
9 -
'
(# -
1
9 '-
$
9
$-
'
II. Consi%e t!e following state"ent an% answe t!e #$estions at t!e en% of it.
T!e ate at w!ic! a s$'stance eacts is popotional to its acti*e "ass an%
t!e ate at w!ic! a eaction pocee%s is popotional to t!e po%$ct of acti*e
"asses of t!e eacting s$'stances.
133. This is called BBB.
136. 7or the com!le reactionP
( )
+
+
3 3
2
Ag +220 Ag 20
1
]


[ ] ( )
2
6 2 -2 -1 + 2 -1
3 3
2
dx
2 10 3 ,ol % Ag 20 - 1 10 % ag 20
dt
+

_
1
1

]
]
,
1ence= ratio of rate constants of the for+ard and /ac-+ard reaction isO
1# $1.
8
E
$
mol
-$
$# $1.
>
E
$
mol
-$
'# 11.
-$
E
$
mol
-$
(# ..31.
->
E
-$
mol
$
138. In the reaction
2 2 3
2 +30 220


[ ] [ ] [ ]
3 2
2 -3 -3 -1
2 2 3
dx
=1110 @ 2 0 - 1 10 @ 20
dt
_

,
[ ] [ ]
[ ]
3
2 2 5 2
2
3
2 0
dx
10 @ -$
dt
20

_

,
is
1# . $# 11.
3
'# 11.
-3
(# 11.
-'
13:. In the follo+in& &ra!hical re!resentation for the reaction A

? there are t+o ty!es
of re&ionsO
1# I and II /oth re!resent -inetic re&ion at different time inter*al
$# I and II /oth re!resent eC%ili/ri%m re&ion at different time inter*al I re!resents
-inetic +hile II re!resents eC%ili/ri%m re&ion
'# I re!resents -inetic +hile II re!resents eC%ili/ri%m re&ion
(# I re!resents eC%ili/ri%m +hile II re!resents -inetic re&ion
13>. At a &i*en tem!erat%re= -
1
9 -
$
for the reaction
A+B ++


If
1 2
dx
= 9 [A][B] - 9 [][+]
dt
1
1
]
In +hich set of the concentration reaction ceasesG
[A] [?] [C] [F]
1# ..1 L ..$ L ..' L ..( L
$# ..( L ..$3 L ..$ L ..3 L
'# ..$ L ..$ L ..' L ..$ L
(# ..$ L ..$ L ..( L ..$ L
III. Fo t!e eaction A+2B Arod.4t
If ate law can 'e witten as
x /
dx
= 9[A] [B]
dt
_

,
t!en x is sai% to 'e o%e w..t. A an% + is sai% to 'e o%e w..t. (. If a
eaction in*ol*es "oe t!an one step, t!e o*eall eaction is o'taine% '+
a%%ing t!ese ele"enta+ steps. In s$c! cases, "olec$lait+ can-t 'e %eci%e%
'+ o*eall eaction on t!e 'asis of its stoic!io"etic an% ate e#$ation.
Howe*e, t!e o%e of an ele"enta+ step can 'e pe%icte% fo" its
"olec$lait+. In fact, t!e o%e of an ele"enta+ step is alwa+s e#$al to its
"olec$lait+. T!e slowest step is t!e o*eall ate %ete"ining step an% gi*es
o%e of t!e eaction.
T!e following eaction is fist.o%e in A an% fist.o%e in (
A&(

/o%$ct, Rate 0 k1A21(2

16.. )elati*e rate of this reaction in *essels I and II of eC%al *ol%me is
1# 1 O 1 $# 1 O $ '# $ O 1 (# 1 O (
161. The reaction of hydro&en and iodine monochloride is re!resented /y the eC%ation
2 2
0 #g&+2Bl#g& 20l#g&+B #g&
This reaction is first-order in 1
$
(&# and also first-order in ICl(&#. Ahich of these
!ro!osed mechanism can /e consistent +ith the &i*en information a/o%t this reactionG
Lechanism I O
2 2
0 #g&+2Bl#g& 20l#g&+B #g&
Lechanism II O
2
%lo'
0 #g&+Bl#g& 0l#g&+0B#g&
1# I only $# II only '# /oth I and II (# neither I nor II
16$. 7or the follo+in& reaction
( ) ( )
3 2 3
3 3
0 l+0 " 0 "0+0l
( )
3
3
dx
=9 0 l
dt
_
1

]
,
= hence= rate-determinin& ste! is
1# ( ) ( )
3 3
3 3
0 l 0 l

+ $# ( ) ( )
3 2 3
3 3
0 l+0 " 0 "0+0l
'# ( ) ( )
+
3 2 3
3 3
0 +0 " 0 "0+0

(#
0 l 0l

+
I3. Following popet+ is fo t!e gi*en o%e of a eaction. (ase% on t!is answe
t!e #$estions gi*en at t!e en% of it.
Ti"e of $n%egoing a %efinite faction of a eactant is in%epen%ent of t!e
concentation.
16'. 7or s%ch reactions (as a/o*e#= concentration of the reactant after t+o a*era&e life (also
called nat%ral life time# is red%ced to
1# ..$3 $# 1 e '#
2
1 e (# ..83
16(. Ahich re!resents a/o*e-ty!e reaction o%t of I= II and IIIG
1# I= II and III $# I and III '# II and III (# I and III
163. In the follo+in& reaction A

0rod%ct= I and II are t+o different sets of a/o*e ty!e

reactionO is eC%al to
1# 1. min $# 3 min '# $.3 min (# $ min
166. )ate constant of a reaction is ...6>' min
-1
. If +e start +ith $. mol E
-1
= it is red%ced to
$.3 mol E
-1
in
1# 1. min $# $. min '# '. min (# (. min
3. T!e ate constant fo t!e %eco"position of a cetain eaction is %esci'e% '+
t!e e#$ation4
( )
4
-1
10
1.25 10 K
log 9 % =14 -
T

168. 0re-e!onential factor for this reaction is

1# 1( s
-1
$# 1.
1(
s
-1
'# 1.
-1(
s
-1
(# 1.$31.
(
s
-1
16:. Ener&y of acti*ation (in -cal# is
1# 38.6 -cal $# 1.$31.
(
-cal '# 1(.. -cal (# 1( -cal
16>. At +hat tem!erat%re= rate constant is eC%al to !re-e!onential factorG
1#
4
1.25 10 K
T =
14

$# T 9 '# T 9 . (# ( )
4
14-1.25 10 K
18.. Ahat is effect on the rate of the reaction at 1$8
.
C= if in !resence of catalyst= ener&y of
acti*ation is lo+er /y 1. -J mol
-1
G
1# 3 times $# 1. times '# 8 times (# $. times
181. A t+o-ste! mechanism has /een s%&&ested for the reaction of nitric oide and
/romineO
1
9
2 2
2"#g&+Br #g& 2"Br #g&


2
9
2
2"Br #g&+2"#g& 22"Br#g&


2/ser*ed rate la+ is= rate 9 [ ]
2
2
9[2"] Br
1ence= rate-determinin& ste! is
1#
2 2
2"#g&+Br #g& 2"Br #g& $#
2
2"Br #g&+2"#g& 22"Br#g&
'#
2
22"#g&+Br #g& 22"Br#g& (# none of these
18$. A reaction ta-es !lace /y the follo+in& mechanism
A4?C

AC4?
AC4F

A4CF
The !otential ener&y !rofile for this is sho+n /elo+
Transition states are sho+n /y
1# I= R $# II= IR '# II= III= IR (# III only
3I. Consi%e t!e following eaction
+ 2+
2
Cn+20 Cn +0
Half.life peio% is in%epen%ent of concentation of 5n at constant pH. At
constant 5n concentation, !alf.life is 67 "in$tes at pH08 an% !alf.life is 677
"in$tes at pH09.
18'. 1ence rate la+ is
1#
+
9[Cn] 0 1
]
$#
2
+
9[Cn] 0 1
]
'#
0 +
9[Cn] 0 1
]
(#
2
0 +
9[Cn] 0 1
]
3II. Fo t!e eaction
A+B
1A2 1(2
d[A]
-
dt
6. 6.7 M 6.7 M 7.8: M "in
.6
8. 8.7 M 6.7 M 7.:7 M "in
.6
9. 6.7 M 8.7 M 7.8: M "in
.6
18(. 1ence= rate la+ is
1# -[A] [?] $# -[A] [?]
1@$
'# -[A] (# -[?]
3III. Following ae t!e *al$es of E
a
an% H fo t!ee eactions caie% o$t at t!e
sa"e te"peat$e
I 4 E
a
0 87 k; "ol
.6
, H 0 .<7 k; "ol
.6
II 4 E
a
0 67 k; "ol
.6
, H 0 .87 k; "ol
.6
III 4 E
a
0 =7 k; "ol
.6
, H 0 &6: k; "ol
.6
183. If all the three reactions ha*e same freC%ency factor then fastest and slo+est reactions
are
7astest Slo+est
1# I II
$# II III
'# I III
(# Can<t /e !redicted
I>. T!e A!eni$s e#$ations fo t!e ate constant of %eco"position of "et!+l
nitite an% et!+l nitite
( ) ( )
-1 -1
-1 13 -1 14
1 2
152300 D ,ol 156600 D ,ol
9 % =10 exA - and 9 % 10 exA -
RT RT
_ _

, ,
186. )ate constants -
1
and -
$
are eC%al at a tem!erat%re
1# 63. K $# $:. K '# '$3 K (# 63 K
>. Rea% t!e following expei"ents an% answe t!e #$estions at t!e en% of it.
/eox+acet+l nitate ?/AN@ is an ai poll$tant po%$ce% in p!otoc!e"ical
s"og '+ t!e eaction of !+%oca'ons, oxi%es of nitogen, an% s$nlig!t. It
%issociates as
A sa"ple of poll$te% ai is anal+se% fo its /AN content w!ic! is epote% as
"olec$les /AN pe lite of ai at 8:
7
C.
Ti"e ?"in@ Molec$les 67
.6=
A B ai
7.7 :.7
67.7 =.7
87.7 9.8
97.7 8.<
=7.7 8.6
:7.7 6.C
<7.7 6.9
188. Fetermine the order of the 0A5 decom!osition reaction
1# . $# 1 '# $ (# '
18:. )ate constant of the reaction is
1# ...$'1 min
-1
$# ....> min
-1
'# ...$'1 E mol
-1
min
-1
(# ....> E mol
-1
min
-1
18>. 1alf-life of the reaction is
1# 1. min $# $. min '# '. min (# 6. min
>I. St$%+ t!e following expei"ent an% answe t!e #$estions at t!e en% of it.
T!e following eaction was st$%ie% at 8:
7
C in 'enDene sol$tion containing
7.6M p+i%ine
( ) ( )
3 ) 5 ) 5 3
3 3
A
B
0 "0+ 0 l 0 ."0 0l +
T!e following sets of %ata wee o'se*e%
1:.. )ates
d[]
dt
in sets I= II and III are res!ecti*ely (in L min
-1
#
I II III
1# 1.'.1.
-(
$.61.
-(
1..$1.
-'
$# ...'' ....'> ....88
'# ...$1.
-(
...(1.
-(
...18
(# none of the a/o*e
1:1. )ate la+ of the a/o*e e!eriment is
1# -[A] [?] $# -[A]
$
[?] '# -[A] [?]
$
(# -[A]
$
[?]
.
1:$. )ate constant of the a/o*e e!eriment is ( )
2 -2 -1
-n 3 @ ,-n
1# 1.'1.
-1
$# $.61.
-$
'# $.61.
-1
(# 1.'1.
-$
>II. St$%+ t!e two p!otoc!e"ical eactions an% answe t!e #$estions at t!e en%.
Fo t!e o*eall eaction 'etween A an% ( to +iel% C an% ), two "ec!anis"s
ae popose%4
I.
E 5 -1 -1
1
A+B AB ++? 9 : 1 10 @ %

II.
E 4 -1
1
A A E? 9 1 10 %

10 -1 -1
2
E+B ++? 9 1 10 @ %
?species wit! E ae s!ot.li*e%@
1:'. )ate la+ for mechanism I +hen concentration of each is ..1 L= is
1# 11.
-8
L s
-1
$# 11.
-6
L s
-1
'# 11.
-3
L s
-1
(# 11.
-(
L s
-1
1:(. )ate la+ for mechanism II +hen concentration of each 1 L is
1# 11.
-(
L s
-1
$# 11.
1.
L s
-1
'# 11.
-6
L s
-1
(# 11.
-1.
L s
-1
1:3. At +hat concentration of ?= rates of t+o mechanism are eC%al
1# 1 L $# 3 L '# 8 L (# 1. L
>III. Rea% t!e following in%$stial "et!o%s of H
8
SF
=
an% answe t!e following
#$estions at t!e en%.
/ofesso Molina of t!e Massac!$setts Instit$te of Tec!nolog+ won t!e 6GG:
No'el /iDe in C!e"ist+ fo !is wok on at"osp!eic c!e"ist+. Fne
eaction t!at !e !as st$%ie% in %etail is t!e aci% ain eaction w!ic! po%$ces
H
8
SF
=
in t!e at"osp!ee. He !as popose% two possi'le stoic!io"etic
eactions4
/oposal A 4
2 3 2 4
0 "#g&+(" #g& 0 (" #g&
/oposal ( 4
2 3 2 4 2
20 "#g&+(" #g& 0 (" #g&+0 "#g&
1:6. Ssin& sim!le collision theory= +hat reaction orders +o%ld /e e!ected for !ro!osal ?G
0ro!osal ? is tho%&ht to !roceed /y the follo+in& t+o-ste! !rocess
1
- 1
9
3 2 3 2
9
(" +20 " (" .20 " #$a%t&


2
9
3 2 2 4 2
(" .20 " 0 (" +0 " #%lo'&
( )
3 2 2 1 - 1
(" .20 " -% a 4o,Alex 'h-4h -% %ta;-l-5ed ;/ h/drogen ;ond% and 9 F F 9 or 9
1# [ ] [ ]
2 3
9 0 " (" $#
[ ] [ ]
2
2 3
9 0 " (" '# [ ]
3
9 (" (# [ ]
2
9 0 "
/ART A
1. S%crose decom!oses in acid sol%tion into &l%cose and fr%ctose accordin& to first order
reaction= +ith half life of '.'''h at $3
.
C. Ahat fraction of a sam!le of s%crose remains
after > hrsG
[AnsO ..13'>8]
$. The rate constant for the decom!osition of 5
$
2
3
in CCl
(
is 6.$1.
-(
s
-1
at (3
.
C.
Calc%late the rate constant at 1..
.
C if the acti*ation ener&y is 1.' -J mole
-1
.
[AnsO ..1>'3 sec
-1
]
'. Calc%late the acti*ation ener&y of a reaction +hich do%/les in rate +hen the
tem!erat%re is raised from 1:
.
C to $:
.
C
[AnsO 1$.1(' -cal@mole]
(. The acti*ation ener&y of the reaction A4?

0rod%ct= is $(.6 -cal@mole
-1
at (.
.
C.
The !rod%cts are formed at the rate of ..1''L min
-1
. Ahat +ill /e the rate of !rod%ct
formation at :.
.
CG
[AnsO 11.8(> L min
-1
]
3. The tem!erat%re coefficient of the reaction rate is $.:. 1o+ many times +ill the
reaction rate increase +hen the tem!erat%re is raised from $. to 83
.
CG
[AnsO $:8.8 times]
6. T+o reactions !roceed at $3
.
C at the same rate= the tem!. coefficient of the rate of the
first reaction is $.. and of the second= $.3. 7ind the ratio of rates of these reactions at
>3
.
C.
[AnsO (.83 times]
8. In hydro&enation reaction at $3
.
C= it is o/ser*ed that hydro&en &as !ress%re falls from
$ atm to 1.$ atm in 3. min. Calc%late the rate of reaction in molarity !er sec. ()
9 ...:$ litre atm.#
[AnsO 1..>11.
-3
mol sec
-1
]
:. Fecom!osition of dia"o/en"ene chloride +as follo+ed at constant tem!erat%re /y
meas%rin& the *ol%me of nitro&en e*ol*ed at s%ita/le inter*als. 7ollo+in& readin&s
+ere o/ser*ed.
Time . $. 33 8.
Rol. of 5
$
. 1. $3 '' 16$
Calc%late order of the reaction.
[AnsO 7irst]
>. 7or a &aseo%s reaction= $A4?
$

$A?= the follo+in& rate data +as o/tained at

'..
.
C.
)ate of disa!!earance of ?
$
Conce. (mole@litre#
Lole litre
-1
time
-1
[A] [?
$
]
1.:1.
-'
...13 ..13
1..:1.
-$
...> ..13
3.(1.
-'
...13 ..(3
Calc%late the rate constant for the reaction and rate of formation of A? +hen A is
[...$] and [?
$
] is [...(] mole litre
-1
at '..
.
K
[AnsO ..: litre mole
-1
min
-1
= 1.$:1.
-'
mole litre
-1
min
-1
]
1.. Arsine decom!oses on heatin& to &i*e arsonic and hydro&en. The decom!osition +as
st%died at constant *ol%me and at constant tem!erat%re. The !ress%re at different
times are as follo+s.
t (ho%rs# . 3.3 6.3 :
0(atm# ..>63( 1..6 1..86 1.1
Calc%late the s!ecific reaction rate ass%min& the reaction to /e first order.
[Ans ...'> ho%r
-1
]
11. 7rom the follo+in& data sho+ that the decom!osition of 1
$
2
$
in aC%eo%s sol%tion is a
first order reaction. Ahat is the *al%e of the rate constantG
Time in mts. . 1. $. '. (.
5 $3 $. 13.8 1$.3 >.>
Ahere 5 is the n%m/er of ml of KLn2
(
reC%ired to decom!ose a definite *ol%me of
1
$
2
$
sol%tion.
[AnsO $.'1.
-$
min
-1
]
1$. The decom!osition of 5
$
2
3
accordin& to the eC%ation $5
$
2
3
(&#

(52
$
(&#42
$
(&#= is a
first order reaction. After '. min%tes from the start of the decom!osition in a closed
*essel= the total !ress%re de*elo!ed is fo%nd to /e $:(.3mm of 1& and on com!lete
decom!osition the total !ress%re is 3:(.3mm 1&. Calc%late the rate constant of the
reaction.
[AnsO 3.$.3:1.
-'
min
-1
]
1'. At $8
.
C it +as o/ser*ed= d%rin& a reaction of hydro&enation that the !ress%re of 1
$
&as
decreases from $atm to 1.1 atm in 83 min. Calc%late the rate of reaction
(molarity@sec#. Ji*en ()9...:$@litre atom K
-1
mole
-1
#
[AnsO :.1$1.
-6
molarity sec
-1
]
1(. T+o reactions of same order ha*e eC%al !re e!onential factors /%t their acti*ation
ener&ies differ /y $(.> -J mole
-1
. Calc%late the ratio /et+een rate constants of these
reaction at $8
.
C. ()9:.'1( J K
-1
#
[AnsO $.1>:1.
(
]
13. 7or a first order &aseo%s reaction H

I4M= the rate constant is &i*en /y.
K931.
1'
sec
-1
e
(- 3(...@)T#
Ahere ener&y of acti*ation is ta-en in %nit of cals. Fetermine the tem!erat%re at
+hich H +o%ld decom!ose at the rate of ...3N !er second.
[AnsO 6>(.$: K]
16. The *ariation of rate constant +ith tem!erat%re is &i*en /y the inte&rated form of
Arrhenio%s eC%ations.
a
10
- E
log K = + 4on%tant
2.303 RT
If for a certain reaction
10 a
31)3.0
log K = - + 11.8** 4al4.late E
T
[AnsO 1((8(..:1 cal@mole]
18. The rate of acid catalysed ester hydrolysis of ethyl acetate in hydrochloric acid sol%tion
o/eys.
)ate 9 -
d[e%ter]
=K[e%ter] [0l]
dt
If K9..1 L
-1
h
-1
at $3
.
C= calc%late the !se%do first order rate constant for 1Cl9...1
molar. 2n this /asis calc%late T
1@$
9 Time for half chan&e.
[AnsO 1.
-'
ho%r
-1
O 6>' ho%r]
1:. S%!!ose 3. /acteria are !laced in a flas- containin& n%trients for the /acteria so that
they m%lti!ly. A st%dy at '3
.
C &a*e follo+in& res%lts.
Time (min%tes# . 13 '. (3 6.
5o. of /acteria 3. 1.. $.. (.. :..
Sho+ that rate of !rod%ction of /acteria is first order.
1o+ many /acteria +ill /e after ' ho%rsG
[AnsO $..(1.
3
]
1>. The acti*ation ener&y of the reaction A4?

0rod%ct is $(.6 -cal@mole at (.
.
C. The
!rod%cts are formed at the rate of ..1''L !er min%te. Ahat +ill /e the rate of !rod%ct
formation at :.
.
CG
[AnsO )
$
9 ::.'((3..1''911.8(> L min
-1
]
$.. The decom!osition of hydro&en !eroide in an aC%eo%s sol%tion is a first order
reaction. Co%rse of reaction is st%died /y titratin& the 1.ml reaction mit%re after
*ario%s time inter*als. 7rom the follo+in& data calc%late the rate constant of the
reaction.
Time (seconds# . 6.. 1$..
KLn2
(
$$.: 1'.: :.$
[AnsO K9:.((61.
-(
sec
-1
]
$1. 7or the thermal decom!osition of $-nitro !ro!ane at '..
.
C= the acti*ation ener&y is
'>.' -cal and the *al%e of the constant A(freC%ency constant# is 1.111.
11
sec
-1
. Ahat
is the half life !eriod of the reaction at '..
.
CG ()9$ cal#
[AnsO (::'.> sec]
$$. T+o reactions (I#A

0rod%cts (II# ?

0rod%cts follo+ first order -inetics. The

rate of the reaction (I# is do%/led +hen tem!erat%re is raised from '..K to '1. K. The
half life for this reaction at '1. K is '. min%tes. At the same tem!erat%re ?
decom!oses t+ice as fast as A. If the ener&y of acti*ation for the reaction (II# is half
that of reaction (I#= calc%late the rate constant of reaction (II# at '..K.
[AnsO ...'$8 min
-1
]
$'. The &as has !hase decom!osition of dimethyl ether follo+s first order of -inetics.
C1
'
C2C1
'

C1
(
41
$
4C2. The reaction is carried at constant *ol%me container at
3..
.
C and has a half life of 1(.3 mins. Initially only diethyl ether is !resent at a
!ress%re of ..( atm. Ahat is the total !ress%re of the system after 1$ mins.
[AnsO ..8(:: atm]
$(. A"omethane decom!oses accordin& to the eC%ation ( )
3 2 2 ) 2
2
0 2 0 2 + . The
reaction +as st%died in a $..ml flas- at '..
.
C. The data o/tained +ere as follo+s.
T@min . 13 '. (: 83
0
total
@min '6.$ ($.( (6.3 3'.1 3>.'
Calc%late rate constant and half life
[AnsO K91.$61.
-$
m
-1
33 mts]
$3. The half time of first order decom!osition of nitramide is $.1 ho%r at 13
.
C.
51
$
52
$
(aC#

5
$
2(&#41
$
2(l#
If 6.$& of 51
$
52
$
is allo+ed to decom!ose= calc%late
(i# time ta-en for 51
$
52
$
to decom!ose >>N
(ii# *ol%me of dry 5
$
2 !rod%ced at this !oint meas%red at S.T.0.
$6. A dro! of sol%tion (*ol%me ...3 ml# contains '..1.
-6
mole 1
4
ions. If the rate of
disa!!earance of the 1
4
ions is 1...1.
8
L@sec= ho+ lon& +o%ld it ta-e for the 1
4
ions
in the dro! to disa!!ear.
[AnsO 6..1.
->
sec]
$8. The rate la+ for decom!osition of &aseo%s
5
$
2
3
O 5
$
2
3

$52
$
4
1
2
2
$
Is o/ser*ed to /e
[ ]
[ ]
2 5
2 5
- d 2 "
K 2 "
dt

A reaction mechanism +hich has /een s%&&ested to /e constant +ith this
e
K
2 5 2 3
2 " 2" +2"


(fast#
1
K
2 3 2 2
2" 2" 2" +2"+" + (slo+#
52452
'

2
K
2
22" (fast#
Sho+ that mechanism is consistent +ith the o/ser*ed rate la+
$:. Fimethyl ether &aseo%s !hase decom!osition is C1
'
2C1
'

C1
(
41
$
4C2 at 83. K
ha*in& rate constant 6.8$1.
-'
min
-1
. Calc%late the time in +hich initial !ress%re of
(..mm in closed container /ecomes 83.mm.
[AnsO :3.6( min]
$>. 7or the reaction $5241
$
5
$
241
$
2 the *al%e of D d!@dt +as fo%nd to /e 1.3
torr@sec for a !ress%re of '3> torr of 52 and ..$3 torr@sec for a !ress%re of 13$ torr.
The !ress%re of 1
$
/ein& constant. 2n the other hand= +hen the !ress%re of 52 is -e!t
constant. 2n the other hand= +hen the !ress%re of 52 is -e!t constant. Dd!@dt +as
1.6 torr@sec for a hydro&en !ress%re of $:> torr and ..8> torr sec
-1
for a !ress%re of
1(8 torr. Fetermine order of reaction.
[AnsO 2)9']
'.. A hydro&enation reaction is carried o%t at 3..K. If the same reaction is carried o%t in
the !resence of catalyst at the same rate. The tem!erat%re reC%ired is (..K.
Calc%late the acti*ation ener&y of the reaction if the catalyst lo+ers the acti*ation
/arier /y $. -J@mol.
[AnsO 1.. -J]
'1. A radioacti*e element A says to ? TI am half of +hat yo% +ere +hen yo% are one fo%rth
of +hat I +as. Loreo*er I +as 1.(1( times than +hat yo% +ere.U If the half life of A is
: days. Ahat is the half life of ?G
[AnsO : days]
'$. The first order reaction O S%crose

Jl%cose47r%ctose ta-es !lace at '.: K in ..35
1Cl. At time "ero the initial total rotation of the mit%re is '$.(
.
. After 1. min%tes the
total rotation is $:.:
.
. If the rotation of s%crose !er mol is :3
.
= that of a&l%cose is 8(
.
and fr%ctose is D:6..(
.
. Calc%late the half life of the reaction
[AnsO 68.$ mints]
''. The rate constant for the for+ard reaction A

0rod%cts is &i*en /y
( )
4
-1
1.25 10
log K %e4 =14.34 -
T

and the rate constant for the re*erse reaction is 1.$1.

-(
sec
-1
at 3.
.
C. Calc%late the
*al%e of maim%m rate constant !ossi/le for the /ac-+ard section.
Ji*en O Enthal!y of the reaction 9 -(8: -J@mol
[AnsO 1.
11$
sec
-1
]
'(. The decom!osition of a com!o%nd 0= at tem!. T accordin& to the eC%ation
$0(&#

(V(&#4)(&#4S(l# is a first order reaction. After '. min from the start of the
decom!osition in a closed *essel the total !ress%re de*elo!ed is fo%nd to /e '18mm
1& and after a lon& !eriod of time the total !ress%re o/ser*ed to /e 618mm 1&.
Calc%late the total !ress%re of the *essel after 83 min. Ji*en O Ra!o%r !ress%re of S( l#
at tem!. T9'$.3mm 1&
[AnsO '8>.8'mm 1&]
'3. The time reC%ired for 1.N com!letion of a first order reaction at '88
.
C is 33.$min and
the fraction of molec%les at (3.
.
C ha*e s%fficient ener&y to react is 1.>$1.
-16
.
Calc%late its rate constant at (..
.
C. Ass%min& the ener&y of acti*ation to /e constant
+ith in this tem!erat%re ran&e.
[AnsO K
68'
9 8.31$1.
-'
min
-1
]
'6. The hydrolysis of ethyl acetate C1
'
C22C
$
1
3
41
$
2

C1
'
C2214C
$
1
3
21 in aC%eo%s
sol%tion is first order +ith res!ect to ethyl acetate. S!on *aryin& the !1 of the sol%tion
the first order rate constant *aries as follo+O
!1 ' $ 1
- 4 -1
1
K 10 % 1.1 11 11.
Ahat is the order of the reaction +ith res!ect to 1
4
and the *al%e of the rate constantG
[AnsO 1.11.
-1
lit@mol@sec]
'8. 7or a first order reaction A

? the de!endence of rate constant - on tem!erat%re is
&i*en /y
10
log 9 = 23.02
3
8 10
T

= +here T is in Kel*in.
A $.N sol%tion of A /y mass decom!oses to the etent of $3N in $. min%tes at $>: K.
Ahat +o%ld /e the N dissociation of A in the same time at '(. K= if +e start +ith its
'.N sol%tion
[AnsO 1..N dissociated]
':. The rate of first order reaction is ...(mol lit
-1
sec
-1
at 1.mts and ...' mol lit
1
sec
-1
at $.
min%tes after initiation. 7ind half life of the reaction.
[AnsO $(..:>1 min%tes]
'>. The *a!o%r !ress%re of t+o misci/le liC%ids A and ? are '..mm and 3..mm of 1&
res!ecti*ely. In a flas- 1. moles of A is mied +ith 1$ moles of ?. 1o+e*er as soon as
sol%te is added A starts !olymeri"in& into a com!letely insol%/le solid. The
!olymerisation follo+s first order -inetics. After 1.. min%tes= ..3$3 moles of sol%te is
dissol*ed +hich arrests the !olymerisation com!letely. The final !ress%re of the
sol%tion is (..mm of 1&. Estimate the rate constant of the !olymerisation reaction.
Ass%me ne&li&i/le *ol%me chan&e on miin& and !olymerisation and ideal /eha*io%r of
final sol%tion.
[AnsO 1...31.
-(
min
-1
]
(.. Some 01
'
(&# is introd%ced in a flas- at 6..
.
C contains an inert &as. 01
'
!roceeds to
decom!ose into 0
(
(&# and 1
$
(&# and the reaction &oes to com!letion. The total
!ress%re is &i*en /elo+ as a f%nction of time. 7ind the order of the reaction and
calc%late the rate constant.
Time (sec# . 6. 1$.
0(mm 1&# $6$.( $8$.> $83.31 $86.(
[AnsO Ist order]
(1. 7or t+o reactions (i# 0

0rod%ct and (ii# V

0rod%ct the order of reaction (i# is

one +hile that of reaction (ii# is t+o. At '(8 K the ener&y of acti*ation of reaction (i# is
33 -J@mol /%t +hene*er this reaction is carried o%t in !resence of catalyst at the same
tem!erat%re= the ener&y of acti*ation is 3' -J@mol. Loreo*er for the reaction (ii# +hen
tem!erat%re is increased from $>:K to '.:K= the rate of reaction increases as many
times as for reaction (i# in !resence of catalyst. Calc%late the rate constant of reaction
(ii# at '1: K. If the !re-e!onential factor constant for reaction (ii# is '.361.
>
mol
-1
lit
sec
-1
.
[K98.'' mol
-1
lit sec
-1
]
($. The com!le
( )
2
3
5
" 20 G
+
1
]
reacts +ith +ater accordin& to the eC%ation
( ) ( ) ( )
2+ 3+
-
3 2 3 2
5 5
" 20 G +0 " " 20 0 " +G 1 1
] ]
and )ate9K[Com!le]
a
[1
4
]
/
The reaction is acid cataly"ed i.e.= [1
4
] does not chan&e d%rin& the reaction
Th%s rate 9 K
1
[Com!le]
a
= +here K
1
9K[1
4
]
/
Calc%late a and / from the follo+in& data (t9$3
.
C#
Com!le [1
4
]
172
T #hr&
374
T #hr&
..1 ..1 1 $
..$ ..$ ..3 1
[AnsO a91= /91]
/ART (
1. In the Arrhenio%s eC%ation for a certain reaction= the *al%e of A and E
a
(acti*ation
ener&y# are (1.
1'
sec
-1
and >:.6 -J mole
-1
res!ecti*ely. If the reaction is of first
order= at +hat tem!erat%re +ill its half life !eriod /e 1. min%tesG
[AnsO '11.'
.
K]
$. Consider t+o reaction I and II. The freC%ency factor of I is 1.. times of II. The
acti*ation ener&y of I is (.6 K cal hi&her than that of II. Calc%late the relation in
/et+een rate constant of I and II reactions at $$8
.
C.
[AnsO 1...6]
'. 7rom the follo+in& data for the decom!osition of 51
(
52
$
in aC%eo%s sol%tion= sho+
that the reaction is of the first order.
Time in mts. 1. 13 $3
Rol. of 5
$
in cc 6.$3 >... 1'.63 '3..3
(. 7rom the follo+in& data sho+ that the decom!osition of 1
$
2
$
in aC%eo%s sol%tion is a
first order reaction. Ahat is the *al%e of the rate constantG
Time in mts . 1. $. '. (.
5 $3 $. 13.8 1$.3 >.>
Ahere 5 is n%m/er of ml of KLn2
(
reC%ired to decom!ose a definite *ol. 1
$
2
$
sol%tion
3. Ethylene oide +as decom!osed in the closed *essel and fo%nd to ta-e !lace as /elo+
Aith the hel! of follo+in& data= find the *elocity constant of the reaction and sho+ that
the reaction follo+ed first order
Time . 3 > 1:
0ress%re 116.31 1$$.$6 1$:.8( 1(1.'8
6. The decom!osition of Cl
$
2
8
at (.. K in the &as !hase to Cl
$
and 2
$
is a first order
reaction
(i# After 33 seconds at (..K the !ress%re of Cl
$
2
8
falls from ...6$ to ...(( atm
calc%late that rate constant.
[AnsO 6.$'6(1.
-'
sec
-1
]
(ii# Calc%late the !ress%re of Cl
$
2
8
after 1.. sec of decom!osition at this
tem!erat%re.
[AnsO ...'' atm]
8. Thermal decom!osition of a com!o%nd is first order. If 3.N of a sam!le of the
com!o%nd is decom!osed in 1$. min%tes= ho+ lon& +ill it ta-e for >.N of the
com!o%nd to decom!oseG
[AnsO '>:.8: min]
:. 7or the reaction A4?

C= the follo+in& data +ere o/tained. In the first e!eriment

+hen the initial concentration of /oth A and ? is ..1. L= the o/ser*ed initial rate of
formation of C is 1..1.
-(
L !er min%te. In the second e!eriment +hen the initial
concentration of A and ? are ..1.L and ..'.L res!ecti*ely. The initial rate is >..1.
-(
L !er min%te. In the third e!eriment +ith the initial concentration of /oth A and ? is
..'. 5= the initial rate is $.81.
-'
!er min%te.
(i# Arite rate la+ e!ression for this reaction.
2
dx
An%H =K[A][B]
dt
1
1
]
(ii# Calc%late the *al%e of s!ecific rate constant for this reaction.
[AnsO 11.
-1
litre
4$
mole
-1
time
-1
>. 7or the reaction A4$?

$C=
The follo+in& data +ere o/tained
Initial concentration Initial reaction rate
(mole@litre# (mole litre
-1
min
-1
#
[A] [?]
(i# 1.. 1.. ..13
(ii# $.. 1.. ..'.
(iii# '.. 1.. ..(3
(i*# 1.. $.. ..13
(*# 1.. '.. ..13
Arite do+n the rate la+ e!ression for this reaction &i*in& yo%r e!lanation.
1.. )ate la+ for the follo+in& reaction.
Ester41
4


Acid4Alcohol= is
0
+
dx
K[e%ter] 0
dt
1
]
.
Ahat +o%ld /e the effect on the rate if
(i# Concentration of ester is do%/ledG
(ii# Concentration of 1
4
ion is do%/ledG
[AnsO (a# rate is do%/led (/# remain same]
11. 7or the reaction A

?4C= follo+in& data +ere o/tained

t in seconds . >.. 1:..
Concn. of A 3..>' 1>.8 8.6$
0ro*e reaction is first order.
1$. The reaction $A4?4C

F4$E= is fo%nd to /e first order in A= second order in ? and

"ero order in C.
(i# Ji*e the rate la+ for the a/o*e reaction in the form of a differential eC%ation
2 0
dx
An%H =K[A][B] []
dt
1
1
]
(ii# Ahat is the effect on the rate of increasin& the concentration of A= ? and C t+o
timesG
[AnsO : times]
1'. A first order reaction is 3.N com!lete in '. min%tes at $8
.
C and in 1. min%tes at (8
.
C.
Calc%late the reaction rate constant at $8
.
C and the ener&y of acti*ation of the
reaction in -J@mole.
[AnsO ...$'1 min
-1
= ('.:(: -J@mole]
1(. A first order &as reaction has K91.31.
-6
!er second at $..
.
C. If the reaction is
allo+ed to r%n for 1. ho%rs= +hat !ercenta&e of initial concentration +o%ld ha*e
chan&ed in the !rod%ctG Ahat is half-life of this reactionG
[AnsO 1$:.' ho%rs= 3.$3N]
13. Fecom!osition of 5
$
2
3
(&# into 52
$
(&# and 2
$
(&# is a first order reaction. If the initial
concentration of 5
$
2
3
(&#= i.e.= ( )
2 5
0
2 " is ...' mole litre
1
= +hat +ill /e concentration
after '. min%tesG )ate constant of the reaction is 1.'31.
-(
sec
-1
.
[AnsO ...$'3 mole@litre]
16. The *al%e of rate constant for decom!osition of nitro&en !entoide
2 5 2 4 2
1
2 " 2 " "
2
_
+

,
is '.(61.
-3
at $3
.
C and (.:81.
-'
at 63
.
C. Sho+ that ener&y
of acti*ation for the reaction is $(.: -cal@mole. ()91.>:8 cal@de&@mole#
[AnsO $(.: -cal@mole]
18. Startin& +ith 1 mole of a com!o%nd A= it is fo%nd that the reaction is '@(
th
com!leted in
one ho%r. Calc%late the rate constant if reaction follo+s first order -inetics.
[AnsO ...$'1 min
-1
]
1:. Startin& +ith one mole of a com!o%nd A= it is fo%nd that the reaction is '@( com!leted
in 1 ho%r. Calc%late the rate constant if the reaction is of
(a# I order (/# II order
[AnsO 7or I order-K91.':6 hr
-1
= 7or II order-K9' litre mole
-1
hr
-1
]
1>. A dro! of sol%tion (*ol%me ...3ml# contains '..1.
-6
mole 1
4
ions. If the rate of
disa!!earance of the 1
4
ions is 1...1.
8
L@sec= ho+ lon& +o%ld it ta-e for the 1
4
ions
in the dro! to disa!!ear.
[AnsO 6..1.
->
sec]
$.. 7or the reaction A

0rod%ct= it +as fo%nd that the order for the chan&e +ith res!ect
to A is $
(i# 1o+ does rate *ary if conc. of A is red%ced /y $@'G
(ii# 1o+ does rate *ary if *ol%me of container is red%ced /y $@'G
(iii# Calc%late rate +hen [A]9$ mole litre
-1
and
172
t =1 hr.
[AnsO (i# 1@> times (ii# > times (iii# $ mole litre
-1
hr
-1
]
$1. A Ist order reaction is 3.N com!lete in '. min%tes at $8
.
C and in 1. min%tes at (8
.
C.
Calc%late the
(a# )ate constant for reaction at $8
.
C and (8
.
C
(/# Ener&y of acti*ation for the reaction
[AnsO ('.:3 -J@ml]
$$. The rate constant for the first order decom!osition of a certain reaction is &i*en /y the
eC%ation En K(sec
-1
#91(.'( -
4
1.25 10
T

Calc%late O
(a# the ener&y of acti*ation (/# the rate constant at 3.. K
(c# At +hat tem!erat%re +ill its half life !eriod /e $36 min%tesG
[AnsO $(.:' Kl cal@ml 31' K]
$'. The &as has !hase decom!osition of dimethyl ether follo+s first order of -inetics.
Cl
'
C2C1
'

C1
(
41
$
4C2. The reaction is carried at constant *ol%me container at
3..
.
C and has a half life of 1(.3 mins. Initially only diethyl ether is !resent at a
!ress%re of ..( atm. Ahat is the total !ress%re of the system after 1$ mins.
[AnsO ..8(:: atoms]
$(. At ':.
.
C= the half life !eriod for the first order of decom!osition of 1
$
2
$
is '6. mts.
The ener&y of acti*ation of the reaction is $.. -J@mole. Calc%late the time reC%ired for
83N decom!osition at (3.
.
C.
[AnsO $..'6 mts.]
$3. 7or the reaction $52Cl

$524Cl
$
the rate constant is $.:1.
-3
mol
-1
dm
'
s
-1
at '..K
and 81.
-1
mol
-1
dm
'
s
-1
at (.. K. Calc%late the ener&y of acti*ation (/# the
!ree!onential factor (c# rate constant at '3.
.
K.
[AnsO 1.1 -J@mol 1..>11.
1'
mol
-1
dm
'
s
-1
161.
-'
]
$6. At a certain tem!erat%re= the half life !eriods for the catalytic decom!osition of
ammonia +ere fo%nd to /e as /elo+.
0ress%re in mm 1& 3. 1.. $..
1alf life in hrs. '.'$ 1.>$ 1...
7ind order of reaction
$8. The rate constant of a second order reaction is 3.81.
-3
dm
'
mol
-1
s
-1
at $3
.
C and
1.6(1.
-(
dm
'
mol
-1
s
-1
at (.
.
C. Calc%late acti*ation ener&y and Arrheni%s
freC%ency factor.
[AnsO 1'..$ -cal@mol]
$:. S%/stance A reacts accordin& to a first order rate la+ +ith K931.
-3
sec
-1
. (a# If the
initial concentration of A is 1 L. Ahat is the initial rate and rate after 1 ho%r.
$>. In the in*ersion of s%&ar in the !resence of an acid follo+in& readin&s are o/tained
Time in mts. . '. >. $'.
)otation in de&ree 4(6.83 4(1 4'..83 41$.83
-1:.83
Calc%late rate constant