05 Chemical Kinetics F

Chemical Kinetics Sri Vyshnavi
Chapter 5
Chemical Kinetics
Introduction
Chemca Knetcs s the branch of scence that deas wth rate of reacton, factors affectng
the rate of reacton and reacton mechansm.
Dfferent reactons occur at dfferent rate. In fact a chemca reacton nvoves
redstrbuton of bonds breakng n the reactant moecue(s) and makng of bonds n the
product moecue(s). The rate of a chemca reacton actuay depends upon the strength
of the bond(s) and number of bonds to be broken durng the reacton. It takes onger tme
for the reactant moecues to acqure hgher amount of energy whch they do by coson.
Hence reactons nvovng strong bond breakng occur at reatvey sower rate whe
those nvovng weak bond breakng occur at reatvey faster rate. On the bass of rate,
reactons are cassfed as.
(i) Instantaneous or extremey fast reacton .e. reactons wth haf-fe of the order of
fracton of second.
(ii) Extremey sow reactons .e. reactons wth haf-fe of the order of years.
(iii) Reactons of moderate or measurabe rate.
Ionc reactons are nstantaneous. If a drop of sver ntrate souton s added to a
souton of the chorde sat of any meta or souton of HC, a whte precptate of sver
chorde appears wthn twnkng of eye. Ths s because of the fact that n aqueous
souton an onc compound exsts as ts consttuent ons. No bond needs to be broken
durng the reacton. Hence reacton takes no tme to compete. The haf fe perod of an
onc reacton s of the order of 10
10
s.
3 3
Na Cl Ag NO AgCl Na NO
+ + +
+ + + + +
Free radcas beng very unstabe (reactve) due to the presence of unpared eectron,
reactons nvovng free radcas aso occur nstantaneousy. Thus, the reactons, are
nstantaneous.
3 2 3
CH Cl CH Cl Cl

+ +
3 3 3 3
CH CH H C CH

+
5.1 Rate of Reaction
Wth the progress of reacton the concentraton of reactants decreases whe that
(those) of product(s) ncreases. If the reacton occurs fasty, the concentraton (moe L
1
) of
reactant w decrease rapdy whe that of product w ncrease rapdy. Thus, the rate
of reacton s defned as the rate at whch the concentraton of reactant decreases or
Sri Vyshnavi SIIT CHEMISTRY -1-
Sri Vyshnavi Chemical Kinetics
aternatvey, the rate at whch concentraton of product ncreases. That s the change n
concentraton of any of the substance (reactant/product) per unt tme durng the reacton
s caed rate of reacton. If C be the change n concentraton of any reactant or any
product durng the tme nterva t then the rate may gven as
Rate =
C
t
( ve sgn appes n the case of reactant whose concentraton goes on decreasng wth
tme and + ve sgn appes n the case of product whose concentraton goes on ncreasng
wth tme).
However, the rate of reacton s not unform. Wth the passage
of tme the concentraton(s) of reactant(s) goes on decreasng
and hence accordng to Law of Mass Acton, the rate of
reacton goes on decreasng. Infact, the rate of reacton
decreases moment to moment. Ths s shown n the graph of
rate vs tme curve of a reacton.
Rate vares from moment to moment so rate of reacton has to
be specfed at a gven nstant of tme caed nstantaneous
rate or rate at any tme t. Ths s as defned beow.
T im e
Rate
r
nst
or
t
dc
r
dt
t
Where dc s the nfntesma change n concentraton durng nfntesma tme
nterva dt after tme t ..e. between t and t + dt. The tme nterva dt beng nfntesma
sma, the rate of reacton may be assumed to be constant durng the nterva.
The rate of reacton expressed as C/t s actuay the average rate wth tme nterva
consdered.
For the reacton; 2N
2
O
5
4NO
2
+ O
2
The rate of reacton at any tme t may be expressed by one of the foowng
2 5 2 2
d[N O ] d[NO ] [O ]
, or d
dt dt dt
+ +
Where square bracket terms denote moar concentraton of the speces encosed.
The above three rates are not equa to one another as s evdent from the
stochometry of the reacton. For every moe of N
2
O
5
decomposed, 2 moes NO
2
and 1/2
moe of O
2
w be formed. Obvousy, the rate of formaton of NO
2
w be four tmes that of
O
2
and t s twce the rate of consumpton of N
2
O
5
. Thus, ther three rates are nterreated
as,
2 5 2 2
d[N O ] d[NO ] d[O ]
2 4
dt dt dt

+
' ; ' ;

Dvdng through out by 4,
-2-
SIIT CHEMISTRY Sri
Vyshnavi
2 5 2 2
d[N O ] d[NO ] d[O ] 1 1
2 dt 4 dt dt

+ +
' ; ' ;

Thus, rate of reacton expressed n terms of the varous speces nvoved n a
reacton w be equa to one another f each of there s dvded by the stochometrc
consttuent of the speces concerned. Rate dvded by stochometrc coeffcent may be
caed as rate per moe.
The knetc experment has shown that the rate of reacton mentoned above
ncreases same number of tmes as the number of tmes the concentraton of N
2
O
5
s
ncreased. That s, rate s doubed by doubng the concentraton of N
2
O
5
. Ths may be
mathematcay expressed as
Rate |N
2
O
5
|
or Rate = k |N
2
O
5
| .(1)
Where k s the proportonaty constant caed rate constant, veocty coeffcent or
specfc reacton rate of the reacton, and s a constant for a gven reacton at a gven
temperature. Equaton 1 showng the concentraton dependence of rate s caed rate aw
of the reacton. Expressng rate n terms of change of concentraton of varous speces,
equaton may be put as
2 5
d[N O ]
dt
= k |N
2
O
5
|
5
d[NO ]
dt
+ = k |NO
2
|
2
d[O ]
dt
+ = k |O
2
|
when k, k and k are the rate constants of the reacton. These three rate constants are
nter-reated
k' k''
k'''
2 4

Thus, for a reacton represented by the genera equaton
aA + bB
cC + dD
c A B D
dC dC dC dC 1 1 1 1
a dt b dt c dt d dt

+ +
' ; ' ; ' ; ' ;

We have,
!
k k k k
a b c d

where
k
I
, k
II
, k
III
and k
IV
are the rate constants of the reacton when ts rate s expressed n terms A, B, C and D,
respectvey.
The rate of reacton at any tme t s determned n the foowng way,
(i) Concentraton of any of the reactants or products whch ever may be convenent s
determned at varous tme ntervas.
(ii) Then concentraton vs tme curve s drawn.
(iii) A tangent s drawn at the pont p of the curve whch corresponds to the tme t at
whch rate s to be determned.
(iv) The sope of the tangent gves the rate of reacton at the requred tme as shown
beow.
1"# %

&
C
R
A
Time
R ' ta( ' % ta()1"# % * ' %
t

OA
OB
t
r ' t a( '
t

OA
OB
C
&
A
t im e
B
1
O
B
t
(C
R
and C
P
denote concentraton of reactant and product respectvey)
Unt of rate =
+(it o, co(ce(tratio(
+(it o, time
= Concentraton tme
1
.e. moe L
1
S
1
5.2 Molecularity
A chemca reacton that takes pace n one and ony one step .e., a that occurs n a
snge step s caed eementary reacton whe a chemca reacton occurrng n the
sequence of two or more steps s caed compcated reacton. The sequence of steps
through whch a compcated reacton takes pace s caed reacton mechansm. Each
step n a mechansm s an eementary step reacton.
The moecuarty of an eementary reacton s defned as the mnmum number of
moecues, atoms or ons of the reactants(s) requred for the reacton to occur and s equa
to the sum of the stochometrc coeffcent of the reactants n the chemca equaton of
the reacton. Thus, the moecuarty of some eementary reactons are as mentoned
beow.
Eementary reacton Moecuarty
PC
5
` `
` `
PC
3
+ C
2
1
H
2
+ I
2
` `
` `
2HI 1 + 1 = 2
Reactons wth moecuarty equa to one, two, three etc., are caed unmoecuar,
bmoecuar, termoecuar, etc., respectvey.
A compcated reacton has no moecuarty of ts own but moecuarty of each of the
steps (eementary reactons) nvoved n ts mechansm.
-4-
SIIT CHEMISTRY Sri
Vyshnavi
For exampe, consder the reacton: 2NO + 2H
2
N
2
+ 2H
2
O, whch s compcated
reacton and takes pace n the sequence of foowng three steps.
(i) NO + NO ` `
` `
N
2
O
2
(fast and reversbe)
(ii) N
2
O
2
+ H
2

r-d-.-
N
2
O + H
2
O(sow)
(iii) N
2
O + H
2

N
2
+ H
2
O (fast)
The moecuarty of each step n the mechansm s two, so what we say s that the
reacton takes n the sequence of three steps each of whch s bmoecuar. There s
another vew aso. Accordng to whch moecuarty of a compcated reacton s taken to
be equa to the moecuarty of the sowest step .e. rate determnng step (r.d.s.) n the
mechansm.
For exampe, the reacton
2
/(Cl
2
ROH HCl RCl H O + +
s sad to be unmoecuar nuceophc substtuton (S
N
1) snce the reacton occurs n the
sequence of the foowng three steps and the sowest step .e. r.d.s. s unmoecuar.
()
2
ROH HCl ROH Cl ),a.t*

+ +
` `
` `
()
2 2
ROH R H O ).lo0*
+
` `
` `
()
R Cl RCl ),a.t*
+
Reactons of hgher moecuarty (moecuarty > 3) are rare. Ths s because a
reacton takes pace by coson between reactant moecues and as number of reactant
moecues .e. moecuarty ncreases the chance of ther comng together and codng
smutaneousy decreases.
6.3 Order of a Reaction
The speed of a chemca reacton, n genera depends on the concentraton of reactng
speces of the reacton. An eary generazaton n ths regard s due to Guberg and
Waage. Ths generazaton s known as aw of mass acton and s stated as foows.
The rate of a chemca reacton s proportona to the product of effectve
concentraton (actng masses) of the reactng speces, each rased to a power that s equa
to the correspondng stochometrc number of the substance appearng n the chemca
reacton.
Thus, for a genera reacton aA + bB
cC + dD .(2a)
We have
R |A}|
a
|B|
b
or r = k|A|
a
|B|
b
.(2b)
where k s the constant of proportonaty.
Sri Vyshnavi SIIT CHEMISTRY --
If the rate of a reacton s determned expermentay, t s found that equaton (2b) s
not aways appcabe. However, the expermenta resuts can be ftted to satsfy a reaton
of the type of equaton (2b) where the exponents may or may not be equa to the
respectve stochometrc coeffcents. In genera, we may wrte the rate as
R = k |A|
a
|B|
b
.(2c)
where the dmensoness exponents a & b may or may not be equa to a & b respectvey.
The constants a & b may have postve, negatve ntegra or fractona vaues or zero
vaue. The constant a s k known as the order of the reacton wth respect to A, b as the
order of the reacton wth respect to B and so on. The sum (a + b) s known as the overa
order of the reacton (whch does not have much of sgnfcance).
If (a + b) = 1, the reacton s sad to be of frst-order; f (a + b) = 2, the reacton s sad
to be second-order and so on. The dependence of reacton rate on concentraton s of
great use as t heps n proposng the mechansm of a reacton.
The constant k, whch appears n equaton (2c) s known as rate constant or more
formay, the specfc reacton rate constant, snce t s numercay equa to the rate of the
reacton provded a concentraton were set equa to unty. Each reacton s characterzed
by ts own reacton rate constant. From equaton (2c), we fnd that unts of k s (mo )
n
s
1
where n = 1 (a + b).
The expresson of equaton (2c), whch reates the rate of reacton, wth the
concentraton of reactng speces s known as the dfferenta rate aw.
It may be emphaszed once agan here that the rate equaton wth ts rate constant
and order of varous reactng speces s an expermenta fndng and cannot be predcted
from the stochometry of the baanced reacton.
Athough many reactons obey equaton (2c), there are numerous others whose rate
expressons are not of such smpe form. A few such reactons are sted n Tabe.
Exampes of reactons obeyng compcated Rate Laws
Overa reacton Expermentay determned rate
aws
2 2
H 2H +
` `
` `
1 d[H]
2 dt
= k
1
|H
2
| |I
2
| k
1
|HI|
2
2 2
H Br 2HBr +
11 2
2 2
2
k[H ] [Br ] 1 d[HBr]
[HBr]
2 dt
1 k'
[Br ]
+
OH
OCl O Cl

+ +
d[Cl ] [OCl ] [ ]
k
dt [OH ]

H
3 3 2 3 2
CH COCH CH COCH H
+
+ +
2
3 3
d[ ]
k[CH COCH ] [H ]
dt
+

Tabe reveas the foowng facts.
1. The rate aw may not bear a smpe reatonshp to the stochometrc equaton.
2. The rate aw may not depend on the concentraton of every reactant of the reacton.
3. The rate aw may depend on the concentraton of speces (e.g., cataysts) whch do
not appear n the equaton for the overa reacton.
-!-
SIIT CHEMISTRY Sri
Vyshnavi
These facts ceary ndcate that the rate equaton cannot be predcted from the form of
the stochometrc equaton for the overa reacton. Hence, the rate equaton must be
determned expermentay. In some cases, the order of the reacton s meanngess. For
exampe, for the hydrogen-bromne reacton, the reacton s of frst-order wth respect to
hydrogen gas but t woud be mpossbe to assgn the order wth respect to bromne and
to hydrogen bromde. Thus, the concept of order of reacton has no meanng f a rate aw
does not have the form as gven n equaton (2c).
In the reacton between hypochorte and odde ons, though OH
does not appear n the

overa reacton, yet t appears n the denomnator of the rate aw. Ths ndcates that OH

acts as an nhbtor. Smary, the reacton between acetone and odne does not nvove
H
+
n the overa reacton, but t appears n the numerator of the rate aw. Ths shows that
H
+
acts as an acceerator or a catayst.
5.4 Difference Between Order and Molecularity
(i) Order s an expermentay property whe moecuarty s the theoretca property.
(ii) Order concerns wth knetcs (rate-aw) whe moecuarty concerns wth mechansm.
(iii) Order may be any number, fractona, ntegra or even zero whereas moecuarty s
aways an nteger exceptng zero.
Example
Reactons Rate Law Order
3 4
CH CHO CH CO +
Rate |CH
3
CHO|
3/2
1.5
3 2 2
1 3
NH N H
2 2
+
Rate |NH
3
|
0
0
2 2
2H H +
Rate |HI|
0
.e. Rate = k
0
Note that a zero order reacton s one n whch concentraton of reactant remans
throughout constant and as such rate of reacton remans throughout constant equa
to the rate constant.
(iv) Order may change wth change n expermenta condton whe moecuarty cant.
Example
i.omeri2atio(
H
2
C
CH
3
The reacton foows 1
st
order knetcs at hgh gas pressure and 2
nd
order knetcs at
ow gas pressure of cycopropane.
5.5 Kinetics of First Order Reaction
A frst order reacton s one whose rate vares as 1
st
power of the concentraton of the
reactant .e. the rate ncreases as number of tmes as the number of tmes the
concentraton of reactant s ncreased.
Sri Vyshnavi SIIT CHEMISTRY -"-
Let us consder a unmoecuar frst order reacton represented by the genera equaton.
A ___________ Product
A x = 0 . t = 0
A x x = x . t = 0
The nta concentraton of A s a moe L
1
and ts concentraton after any tme t s (a
x) moe L
1
. Ths means durng the tme nterva t, x moe L
1
of A has reacted.
The rate of reacton at any tme t s gven by the foowng frst order knetcs.
d)a 3*
)a 3*
dt
or
d)3*
dt
(a x)
or
d3
dt
= k (a x)
(
da
#
dt
O a has a gven vaue for a gven expt.)
where k s the rate constant of the reacton.
d3
kdt
a 3

Ths s dfferenta rate equaton and can be soved by ntegraton.

d3
k dt
a 3

or ln (a x) = k.t + C .(1)
The constant C can be evauated by appyng the nta condton of the reacton .e. when
t = 0, x = 0. Puttng these n equaton 1, we get
C = lna
Puttng the vaue of C n equaton 1, we get
ln (a x) = k.t. lna or
1 a 2-3#3 a
k ( log
t a 3 t a 3

l .(2)
If |A
0
| and |A| be the concentratons of reactant at zero tme and tme t, respectvey then
Eq. 2 may be put as
#
[A ] 1
k (
t [A]
l
Ths s the ntegrated rate expresson for frst order reacton. Unt of the rate constant
1 a
k (
t a 3
l
kt = lna ln(a x)
a x = ae
kt
x = a(1 e
kt
)
The dfferenta rate expresson for nth order reacton s as foows.
-#-
SIIT CHEMISTRY Sri
Vyshnavi
(
d3
k)a 3*
dt
or
( (
d3 co(ce(tratio(
k
)a 3* dt )co(ce(tratio(* time

= conc.
1n
. tme
1
If concentraton be expressed n moe L
1
and tme n mnute, then
k = (moe L
1
)
1n
mn
1
For zero order reacton: n = 0 and hence k = moe L
1
mn
1
For 1
st
order reacton: n = 1 and hence
k = (moe L
1
)
0
mn
1
= mn
1
For 2
nd
order reacton: n = 2 and hence
K = (moe L
1
)
1
mn
1
= moe
1
1 mn
1
The rate constant of a frst reacton has ony tme unt. It has no concentraton unt. Ths
means the numerca vaue of k for a frst order reacton s ndependent of the unt n
whch concentraton s expressed. If concentraton unt s changed the numerca vaue of
k for a frst order reacton w not change. However, t woud change wth change n tme
unt. Say, k s 6.0 10
3
mn then t may aso be wrtten as 1 10
4
s
1
.e. numerca
decrease 60 tmes f tme unt s changed from however to mnute or from mnute to
second.
Haf-tme or haf-fe perod of a frst order reacton
The haf-tme of a reacton s defned as the tme requred to reduce the concentraton of
the reactant to haf of ts nta vaue. It s denoted by the symbo t
1/2
. Thus,
When
a
3 ,
2
t = t
1/2
Puttng these n equaton 2 mentoned above, we get
11 2 11 2 11 2
2-3#3 a 2-3#3 2-3#3
k log log2 #-3#1#3
a
t t t
a
2

(O og 2 = 0.30103)
t
1/2
=
#-453
k
.(3)
Snce k s a constant for a gven reacton at a gven temperature and the expresson
acks any concentraton term so from equaton 3 t s evdent that haf-tme of a 1
st
order
reacton s a constant ndependent of nta concentraton of reactant. Ths means f we
start wth 4 moe L
1
of a reactant reactng by frst-order knetcs and after 20 mnute t s
reduced to 2 moe L
1
w aso be 20 mnute. That s, after 20 mnutes from the start of
reacton the concentraton of the reactant w be 2 moe L
1
, after 40 mnutes from the
start of reacton of concentraton s 1 moe L
1
. After 60 mnutes from the start of reacton
the concentraton of the reactant w be reduced to 0.5 moe L
1
. In order words, f durng
20 mnutes 50% of the reacton competes, then n 40 mnute 75%, n 60 mnute 85.5% of
the reacton and on w compete as shown wth foowng pot.
Sri Vyshnavi SIIT CHEMISTRY -$-
Fracton eft after n haf-ves =
(
1
2
_

,
Concentraton eft after n ves
(
( #
1
a a
2
_

,
It s aso to be noted that equaton 3 heps to cacuate
t
1/2
or k wth the knowedge of k or t
1/2
. A genera
expresson for t
1/2
s as foows
11 2
( 1
1
t
a

1##
65
5#
25
#
2# 4# 4# "#
C)7*
t )mi(*
Where n = order of reacton.
5.6 ra!"ical Re!resentation
Snce for nth order reacton
(
d3
k)a 3* ,
dt
or
(
d3
k-c
dt

So, from ths t s evdent that a pot of
d3
dt
vs(a x)
n
w be straght ne passng
through the orgn and w have ts sope equa to k, the rate constant of reacton.
Thus, for a frst order reacton one w get
straght ne passng through the orgn of
d3
dt
.e.
rate of reacton be potted aganst a x as show
beow.
Takng ogarthm of the above equaton

8 ' t a(
d3
dt
)a % 3*
d3
log
dt
= n og (a x) + og k
Ths equaton demands that a pot of
d3
log
dt
vs og (a
x) w be straght ne of the sope equa to n, order of
reacton and ntercept equa to og k. For frst order reacton
ths sope w be 1 as shown.

B
1
d 3
dt
l o g
B O
l o g )a % 3 *
(
# ' 45 9 i , ( ' 1 ,
i -e- OA ' OB
Equaton 2 may be rearranged as
og (a x) =
k
t loga
2-3#3
_
+

,
Thus, a pot of (a x) vs. t w be straght ne wth sope equa to
k
2-3#3
and
ntercept equa to og a, f the reacton s of frst order.

Ill ustrati ons
Illustration 1
In a reacton wth ntay 0.12 M, the concentraton of reactant s reduced to 0.06 M n 10
hour and to 0.03 M n 20 hour.
(a) What s the order of reacton?
(b) What s rate constant ?
-1%-
SIIT CHEMISTRY Sri
Vyshnavi
Solution
Assumng 1
st
order,
2-3#3 a
8 log
)a 3*

For case 1
2-3#3 #-12
8 log
1# #-#4
= 0.069 hr
1
.
Reacton s of 1
st
order and rate constant = 0.069 hr
1
.
Illustration 2
For a reacton 3A Products, t s found that the rate of reacton doubes f
concentraton of A s ncreased four tmes, cacuate order of reacton.
Solution
Rate = K |Reactant|
n
f |Reactant| = q
rate = r
1
r
1
= K|a|
n
.(1) f |Reactant| = 4 q
2r
1
= K|4a|
n
.(2) rate = 2r
1
Dvdng
(
1 1
2 4
_ _

, ,
,
1
(
2
Practice Exercise
1. The rate constant for the reacton
2 3
CO OH HCO

+
In the aqueous souton s 4 10
3
tre mo
1
sec
1
. Cacuate the n umber of moe of
CO
2
and OH
used up per second when |CO

2
| and |OH
| are 10
6
and 10
1

mo tre
1
.
Aso predct the moe of HCO
3
formed per second.

2. For a reacton 3A Products, t s found that the rate of reacton doubes f
concentraton of A s ncreased four tmes, cacuate order of reacton.
Answers
1. 4 10
10
mo L
1
sec
1
. 2.
1
(
2
5.# $alf%&ife of a n
t"
order Reaction
Let us venture on to fnd out the t
1/2
for a n
th
order reacton where
( 1
.
#
11 2
#
[A ]
t
2
(
( (
[A ] #
d[A] d[A] d[A]
k[A] kdt k dt
dt [A] [A]

#
#
#
#1 2
A
[A ]
1 (
( (
11 2 11 2
[A ]
A
2
[A]
[A] d[A] kt kt
1 (
1

1

1 ( 1 (
1 (
1 ( # #
# 11 2 11 2
[A] [A] 1 1
[A] kt 1 kt
1 ( 2 1 ( 2

_ 1
1 _
1

1

, ]
1
] ,
( 1
11 2
( 1
#
1
[1 2 ] kt
)1 (*[A ]

( 1
11 2
( 1
#
)2 1*
kt
)( 1* [A ]
(order n 1)
Therefore for a nth order reacton, the haf fe s nversey reated to the nta
concentraton rased to the power of (n 1).
Note: It can be noted that for a zero order reacton
#
11 2
[A]
t
2k
.
5.' ()a*!les Of First+Order Reaction
A arge number of reactons exhbtng frst-order knetcs are known. A few exampes are
sted beow
(i)
3 3 3 3 3 3 2 4
)CH * COOC)CH * 2CH COCH C H
+
(ii)
2 5 2 2
1
N O )g* 2NO )g* O )g*
2
+
(iii)
3 2 3 2 2 4 14
)CH * CHN NCH)CH * N C H
+
(iv)
2 2 2 2
:O Cl )g* :O )g* Cl )g*
+
(v)
NO2
NO2
NO2
NO2
NO2
NO2
; CO
2
)g*
COOH
(vi)
2 2 2 2
1
H O ).ol(-* H O) * O )g*
2
+ l
(vii) A radoactve decays.
There are reactons n whch more than one speces s nvoved n the rate
determnng step, but the order of the reacton s one. Such reactons are known as
pseudo-unmoecuar reactons and they nvove sovent moecues or a catayst as
one of the reactng speces.
Examples of this type of reactions are:
(viii) Acd hydroyss of an ester: CH
3
COOC
2
H
5
+ H
2
O
H
+
CH
3
COOH + C
2
H
5
OH
(ix) Inverson of cane sugar: C
12
H
22
O
11
+ H
2
O
H
+
C
6
H
12
O
6
(gucose) + C
6
H
12
O
6
(fructose)
(x) Decomposton of benzene dazonum:
4 5 2 4 5 2
C H N NCl H O C H OH N HCl
+
+ + +
5., -oncentrations Re!laced By Ot"er .uantities In First%
Order Inte/rated Rate &aw
-12-
SIIT CHEMISTRY Sri
Vyshnavi
The rate constant for a frst-order reacton, t s necessary to determne the rato of the
concentraton at two dfferent tmes. Ouanttes proportona to the concentraton terms
may be substtuted n these equatons, snce the proportonaty constants cance. We
descrbe beow a few typca cases where concentraton terms are repaced by other easy
measurabe quanttes.
Case I:
Let there be a frstorder reacton of the type, A
B + C. Let us assume that a the

three speces are gases. We are requred to cacuate the vaue of rate constant based on
the foowng data
Tme 0 t
Parta pressure of A P
0
P
t
Strategy:
We know that for a frst-order reacton,
#
t
A 1
k (
t A
At t = 0, the parta pressure of A s P

0
and at tme t, t s P
t
. Accordng to the dea gas aw
(
& RT
!
or
( &
! RT
# t
t # t t
& & ( (
<
! Rt ! RT

_ _

, ,
t # # #
t t
t t
(
A & !
( A &
!
_

,

_

,
#
t
& 1
k (
t &
Case II:
Let there be a frst order reacton, A
B+C. Let us assume a three are gases. We are

requred to cacuate the vaue of rate constant based on the foowng data.
Tme 0 t
Tota
pressure
P
0
P
t
Cacuate the expresson of rate constant.

Strategy:
Tota Pressure means the sum of parta pressures of a the gaseous speces present n
the system.
( ) ( ) ( )
#
#
A g B g C g
At time # & # #
At time t & 3 3 3
+

Snce at t = 0 the tota pressure s P
0
, t must aso be the parta pressure of A at t = 0,
snce n the begnnng ony the reactant w be present. Let the decrease n pressure of A
due to reacton t tme t be x. Thus, at tme t, the tota pressure woud be
(P
0
x) + x + x = P
0
+ x
P
0
+ x = P
t
x = P
t
P
0
(P
0
x) = P
0
(P
t
P
0
) = 2P
0
P
t
#
# t
& 1
k (
t 2& &
Case III:
Tme 0 t
Parta pressure of A + B +
C
P
t P

Strategy:
Let the nta pressure of A be P
0
and the pressure of A reacted t tme t be x.
( ) ( ) ( )
#
#
# #
A g B g C g
At time # & # #
At time t & 3 3 3
At time # & &
+

s the tme when the reacton s compete.
At tme = t, the tota pressure w be
(P
0
x) + x + x = P
t
P
0
+ x = P
t
x = P
t
P
0
At tme = , the tota pressure w be
P
= 0 + P
0
+ P
0
= 2P
0
; 2P
0
= P
;
#
&
&
2
x = P
t
P
0
= P
t

&
2
# t t
& &
)& 3* & & &
2 2

_

,
t
& 1
k (
t 2)& & *
,
-14-
SIIT CHEMISTRY Sri
Vyshnavi
Case IV:
Tme 0 t
Parta pressure of B + C P
t P

Strategy:
Let the nta pressure of A be p
0
and the amount of pressure reacted t tme t be x.
At tme nfnty, the tota pressure of B and C w be
P
0
+ P
0
= 2P
0
= P
#
&
&
2
At tme t, the tota pressure of B and C w be

x + x = 2x = P
t
x =
t
&
2
t
& 1 2 1
k (
t & 1 2 & 1 2
t
& 1
k (
t & &
.
Case V:
A B C +
Tme T
Parta pressure of
B
P
2
P
3
Fnd k.
Now et us assume that A, B and C are substances present n a souton. From a souton of
A, a certan amount of the souton (sma amount) s taken and ttrated wth a sutabe
reagent that reacts wth A. The voume of the reagent used s V
1
at t = 0 and V
2
at t = t.
Tme 0 T
Voume of reagent V
1
V
2
The reagent reacts ony wth A. Fnd k.
It can be understood that the voume of the reagent consumed s drecty proportona to
the concentraton of A. Therefore the rato of voume of the reagent consumed aganst A
at t = 0 and t = t s equa to |A|
0
/|A|
t
# 1
t 2
[A] ! 1 1
k ( (
t [A] t !

.

Ill ustrations
Illustration 3
A
B + C
Tme 0 T
Voume of reagent V
1
V
2
The reagent reacts wth A, B and C. Fnd k.
Soltion
We can use a smar ogc for sovng ths one. That s
1
1
1 1
A B C
At t # ! # #
At t t ! 3 3 3
At t # ! !
+

where x s the voume of the reagent for those moes of a whch have been converted nto
B and C
V
1
+ x = V
2
x = V
2
V
1
V
1
x = 2V
1
V
2
#
t 1 2
[A] 1 1 !
k ( (
t [A] t )2! ! *

Ths s true ony f we make an assumpton n the begnnng of ths probem. The
assumpton s that the n factor of A, B and C wth the reagent s same.
Ths can be made cear as foows. Let y moes of A be converted to B and C. If y
moes of A requre x m of reagent and f the n factor of A s n
1
wth the reagent then the
equvaents of A converted are n
1
y and n x m of reagent n
1
y equvaents of the reagent
are present. Now snce the same y moes of B and C are formed and we fnd the same
voume of reagent used for B and C, t can be cacuated that y moes of B and C aso
contan n
1
y equvaent each, whch mpes that n factor of B and C are aso n
1
.
5.10 1e2uential Or -onsecuti3e Reaction
Reacton n whch a reactant gves product, whch further goes to gve another product,
are caed sequenta or consecutve reacton.
1 2
k k
A B C
The dfferenta rate equaton are
Rate of dsappearance of A,
1
d[A]
k [A]
dt
.(1)
Rate of change of B,
1 2
d[B]
k [A] k [B]
dt
.(2)
Rate of formaton of C,
2
d[C]
k [B]
dt
.(3)
Integratng equaton wthn the mts we get,
|A|
t
= |A|
0

1
k t
e
...(4)
In order to get the vaue of B at any nstant of tme, we need to ntegrate equaton.
Snce ths s a dfferenta equaton, we ntegrate t n the foowng manner.
Frst brngng k
2
|B| to the eft sde of the equaton
2
d[B]
k
dt
+ |B| = k
1
|A| .(5)
-1!-
SIIT CHEMISTRY Sri
Vyshnavi
From equaton (8e), we get
1
k t
2 1 #
d[B]
k [B] k [A] e
dt

+
Integraton of ths equaton s not possbe as we are unabe to separate the two
varabes, |B| and t. Thus, the equaton s to be mutped on both sdes by an ntegratng
factor
2
k t
e
.
2 2 1
k t )k k *t
2 1 #
d[B]
e k [B] k [A] e
dt

_
+

,
2 2 2 1
k t k t )k k *t
2 1 #
d[B]
e k [B] e k [A] e
dt

+ .(6)
Left hand sde of the equaton (6) s equa to
( )
2
k t
d
[B]e
dt
(a dfferenta of
2
k t
[B]e .
( )
2 2 1
k t )k k *t
1 #
d
[B]e k [A] e
dt

( )
2 2 1
k t )k k *t
1 #
d [B]e k [A] e dt
.(7)
Integratng equaton (7) wthn the mts, 0 and t,
( )
k t
2
2 2 1
[B]e t
k t )k k *t
1 #
# #
d [B]e k [A] e dt

2 2
2 2 1
t
)k k *t
k t )k k *t 1
1 # #
2 1 2 1
#
k e
[B]e k [A] [A] e 1
k k )k k *
1
1
1
]

]
|B| =
2 2 1
k t )k k *t 1
#
2 1
k
[A] e e 1
)k k *

1
]
|B| =
1 2
k t k t 1
#
2 1
k
[A] e e
)k k *

1
]
.(8)
In genera, the concentraton of A decreases exponentay, the concentraton of B ntay
ncreases up to a maxmum and then decreases thereafter, and the concentraton of C
ncreases steady.
Tme when |B| becomes maxmum
1 2
d[B]
k [A] k [B] #
dt

k
1
|A| = k
2
|B|
Substtutng equaton (4) and equaton (8), we get
1 1 2
k t k t k t 2 1
1 # #
2 1
k k
k [A] e [A] e e
)k k *

1
]
Rearrangng, we get
1 2
1
k t k t
2 1
k t
2
)k k * [= e
k e

Sri Vyshnavi SIIT CHEMISTRY -1"-

1 2
)k k *t 1
2
k
1 1 e
k

t
max
=
1
1 2 2
k 1
(
)k k * k
.(9)
Maxmum concentraton of B
1 2
k t k t 1
#
2 1
k
[B] [A] e e
)k k *

1
]
1 2 1
1 2 1 2 2
k k k
(
)k k * )k k * k 1
#
2 1
k
[B] [A] e e
)k k *

1
1
1
]
1 1 2 1
1 2 1 1 2 2
k k k k
( (
)k k * k )k k * k 1
#
2 1
k
[B] [A] e e
)k k *

1
1
1
]
2 1 2 2
1 1 2 1 1 2
k k k k
( (
k )k k * k )k k *
1
#
2 1
k
[B] [A] e e
)k k *
_ _

, ,
1
1

1
]
1 2
1 2 1 2
k k
)k k * )k k *
1 2 2
ma3 #
2 1 1 1
k k k
[B] [A]
)k k * k k

1
_ _
1

1
, ,
1
]
.(10)
In order to get the concentraton of |C|, we substtute |B| from equaton ( 8) to (3) and
then ntegrate wthn the mts.
1 2
k t k t 2 1
2 #
2 1
k k d[C]
k [B] [A] e e
dt )k k *

1
]
1 2
k t k t 2 1
#
2 1
k k
d[C] [A] e e dt
)k k *

1
]
Upon ntegratng wthn the mts, 0 to t,

1 2
[C] t
k t k t 2 1
#
2 1 # #
k k
d[C] [A] [e e ]dt
)k k *

1 2
t
k t k t
2 1
#
1 1 1 2
#
k k e e
[C] [A]
)k k * k k

1

1

]
1 2
k t k t
2 1
#
2 1 1 2
k k e 1 e 1
[C] [A]
)k k * k k

1 _ _

1

1 , , ]
1 2
k t k t
2 1
#
2 1 1 2
k k 1 e 1 e
[C] [A]
)k k * k k

1 _ _

1
1 , , ]
1 2
k t k t #
2 1
2 1
[A]
[C] k )1 e * k )1 e
)k k *

1
]
.
-1#-
SIIT CHEMISTRY Sri
Vyshnavi
5.11 (ffect of 4e*!erature on t"e Reaction Rate
56rr"enius 4"eory7
Temperature has very marked effect on the reacton rate. It has been found that the rate
of most homogeneous reacton are neary doubed or trped by 10 rse n temperature.
t 1#
t
k
k
+
= 2 to 3 (neary)
The rato of the rate constant of a reacton at two dfferent temperatures dfferng by
10 .e. k
t+10
/k
t
s known as temperature coeffcent of reacton rate. Ths rato aso depends
upon temperature and two temperatures generay seected are 25C and 35C. If a
reacton has a temperature coeffcent of reacton rate equa to 3, then rasng ts
temperature from 25C to 65C, the rate w ncrease by neary 3 3 3 3 .e. 81 tmes.
In order to expan the effect of temperature on the reacton rate. Arrhenus proposed
a theory of reacton rate whch states as foows:
(i) A chemca reacton takes pace by coson between the reactant moecues, and
coson to be effectve the codng moecues must posses some certan mnmum
energy caed threshod energy of the reacton.
(ii) Reactant moecues havng energy equa or greater than the threshod are caed
actve moecues and those havng energy ess than the threshod are caed passve
moecues.
(iii) At a gven temperature there exsts a dynamc equbrum between actve and
passve moecues. The process of transformaton from passve to actve moecues
beng endothermc, ncrease of temperature ncreases the number of actve
moecues and hence the reacton.
Passve moecues ` `
` `
Actve moecues, H = +ve
(iv) Concept of energy of actvaton (E
a
)
The extra amount of energy whch the reactant moecues (havng energy ess than
the threshod) must acqure so that ther mutua coson may ead to the breakng of
bond(s) and hence the reacton, s known as energy of actvaton of the reacton. It s
denoted by the symbo E
a
. Thus,
E
a
= Threshod energy Actua average energy
E
a
s expressed n kcas moe
1
or k| moe
1
The essence of Arrhenus Theory of reacton
rate s that exsts an energy barrer n the
reacton path between reactant(s) and
product(s) and for reacton to occur the reactant
moecues must cmb over the top of the barrer
whch they do by coson. The exstence of
=a
1
=a
2
Reacta(t
H ' H % H ' =a ' =a & R 1 2
H
R
H
&
=(t>al?@ )H*
&rodAct.
T>re.>old e(t>al?@
or e(erg@
&rogre.. o, Reactio(
)or reactio( coordi(ate*
Sri Vyshnavi SIIT CHEMISTRY -1$-
energy barrer and concept of E
a
can be
understood from the foowng dagram.
R
H
= Summaton of enthapes of reactants

&
H
= Summaton of enthapes of products

H = Enthapy change durng the reacton
Ea
1
= Energy of actvaton of the forward reacton (FR)
Ea
2
= Energy of actvaton of the backward reacton (BR)
!ota"le #oints
(i) H = Energy actvaton of FR Energy of actvaton of BR
(ii) In the dagram mentoned above, FR s exothermc (H s ve) whe BR s
endothermc (H s + ve). The mnmum actvaton energy of FR .e. any exothermc
reacton w be zero whe mnmum actvaton energy for BR .e. any endothermc
reacton w be equa to H.
(iii) Greater the heght of energy barrer, greater w be the energy of actvaton and
more sower w be the reacton at a gven temperature.
(iv) Rate = Coson frequency fracton of the tota number of coson whch s
effectve.
or
= Coson frequency fracton of the tota number of cosons n whch K.E. of the
codng moecues equas to Ea or exceeds over t
Coson frequency s the number of cosons per unt voume per unt tme. It s
denoted by the symbo Z. Z s drecty proportona to
T
. By 10 rse n temperature.
So, t s the fracton of the tota number of effectve, cosons that ncreases
markedy by 10 rse n temperature resutng nto marked ncrease n the reacton
rate.
$rrhenis E%ation
The varaton equbrum constant of a reacton wth temperature s descrbed by Vant
Hoff equaton of thermodynamcs whch s as foows
?
2
d(8
H
dT RT
If k
1
and k
2
be the rate constant of FR and BR, respectvey then Kp = k
1
/k
2
. Further,
H = Ea
1
Ea
2
. Puttng these n the above equaton we get,
1 2
a a
1 2
2 2
= =
d(k d(k
dT dT RT RT

Spttng nto two parts
-2%-
SIIT CHEMISTRY Sri
Vyshnavi
1
a
1
2
=
d(k
/
dT RT
+ (For FR)
2
a
2
2
=
d(k
/
dT RT
+ (For BR)
where Z s constant
Arrhenus sets Z equa to are and wthout specfyng FR and BR, he gave the foowng
equaton caed Arrhenus equaton.
a
2
= d(k
dT RT
.(1)
From ths equaton t s evdent that rate of change of ogarthm of rate constant wth
temperature depends upon the magntude of energy of actvaton of the reacton. Hgher
the Ea
1
smaer the rate of change of ogarthm rate constant wth temperature. That s,
rate of the reacton wth ow Ea ncrease sowy wth temperature whe rate of the reacton
wth hgh E
a
ncreases rapdy wth temperature. It s aso evdent that rate of ncrease of
ogarthm of rate constant w go on decreasng wth ncrease of temperature.
Integratng Equaton (1) assumng Ea to be constant we get,
=a
(k (A
RT
+ .(2)
or
k =a
(
A RT
.(3)
or k = Ae
Ea/RT
Equaton (3) s ntegrated form of Arrhenus equaton. The constant A caed pre-
exponenta factor snce t s somewhat reated wth coson frequency. It s a constant for
a gven reacton. From Equaton (3) t s evdent that as T , k a. Thus, the constant A
s the rate constant of reacton at nfntey temperature. The rate constant goes on
ncreasng wth temperature.
So, when T approaches nfnty, k w be maxmum. That s to say, A s the maxmum
rate constant of a reacton.
It s aso be noted that the exponenta term .e. e
Ea/RT
measures the fracton of tota
number of moecues n the actvated state or fracton of the tota number of effectve
cosons. If
a
=
(
and n be the number of moecues of reactant n the actvated state and
the tota number of moecues of the reactant present n the reacton vesse respectvey,
then
a a
= = 1 RT
(
e
(

Equaton (2) may aso be put as
=a 1
logk logA
2-3#3R T
_
+

,
.(4)
Snce
a
=
2-3#3R
and ogA both are constants for a gven reacton. So from equaton 7 t s
evdent that a pot of og k vs.
1
T
w be a straght ne of the sope equa to
a
=
2-3#3R
and
ntercept equa to ogA as shown beow.
a
=
2-3#3R
= tan = tan (180 ) =

OA
OB
a
OA
= 2-3#3R
OB

ogA = OA
1 " # %
A
l o g 8
O
1 1 T
Thus, from ths pot E
a
and A both can be determned accuratey.
If k
1
be the rate constant of a reacton at two dfferent temperature T
1
and T
2
respectvey then from equaton (4), we may wrte
og k
1
=
a
2
= 1
- logA
2-3#3R T
+
og k
2
=
a
2
= 1
- logA
2-3#3R T
+
Subtractng
a 2
1 1 2
= k 1 1
log
k 2-3#3R T T
_

,
.(5)
Wth the hep of ths equaton t s possbe to cacuate E
a
of a reacton provded, rate
constants of reacton at two dfferent temperatures are known. Aternatvey one can
cacuate rate constant of a reacton at a gven temperature provded that rate constant of
the reacton at some other temperature and aso E
a
of the reacton s known.

Ill ustrati ons
Illustration 4
The haf tme of frst of decomposton of ntramde s 2.1 hour at 15C.
NH
2
NO
2
(aq.) N
2
O(g) + H
2
O(l)
If 6.2 g of NH
2
NO
2
s aowed to decompose, cacuate.
() tme taken for NH
2
NO
2
s decompose 99%
() voume of dry N
2
O produced at ths pont measured at STP.
Solution
O
1#
2-3#3 a
t log
8 )a 3*
-22-
SIIT CHEMISTRY Sri
Vyshnavi
If
1 a
t , 3 <
2 2

11 2 1#
2-3#3 a
t log
a
8
a
2
.(1)
If t = t
99%
,
55a
3 <
1##
t
99%
=
1#
2-3#3 a
log
55a
8
a
1##
.(2)
By Eqs. (1) and (2), t
99%
=
1#
11 2
1#
log 1##
t
log 2

2
2-1
#-3#1#
= 13.&5 hor
Aso Moe of N
2
O formed =
55
1##
moe of NH
2
NO
2
taken
=
55 4-2
#-#55
1## 42

Voume of N
2
O formed at STP = 0.099 22.4 = 2.21' (.
Illustration 5
In I order reacton, the concentratons of reactants 10 and 20 mnute after the begnnng
of reacton corresponds to 13.8 and 8.25 (arbtrary unts). Cacuate the nta
concentraton of the reactants and the veocty constant.
Solution
t = 10, (a x) = 13.8
t = 20, (a x) = 8.25
t = 0,
O
1#
2-3#3 a
8 log
t a 3
1#
2-3#3 a
8 log
1# 13-"
.(1)
1#
2-3#3 a
8 log
2# "-25
.(2)
By sovng Eqs. (1) and (2),
K = 5.1 10
2
mnute
1
a = 23.09.
Illustration 6
Cacuate the factor by whch the rate of I order reacton s ncreased for a temperature
rse of 10C from 25C to 35C. The energy of actvaton s 35 kca mo
1
.
Solution
Gven,
T
2
= 273 + 35 = 308 K, T
1
= 273 + 25 = 298 K
E
a
= 35 10
3
ca mo
1
, R = 1.987 ca
O 2.303 og
10

a 2 2 1
1 1 2
= 8 [T T ]
8 R TT

2.303 og
10

3
2
1
8 35 1# [3#" 25"]
8 1-5"6 3#" 25"

2
1
8
8
= 6.812
or K
2
= 6.812 K
1
The factor by whch the rate constant changes s 6.812
O Rate = K | |
The factor by whch rate changes s aso ).*12.
-24-
SIIT CHEMISTRY Sri
Vyshnavi
Illustration 7
At 380 C, the haf fe perod for the frst order decomposton of H
2
O
2
s 360 mn. The
energy of actvaton of the reacton s 200 k| mo
1
. Cacuate the tme requred for 75%
decomposton at 450C.
Solution
K
1
= 0.693/360 mn
1
at 653 and
E
a
= 200 10
3
|, K
2
= ? at 723 K, R = 8.314 |
From 2.303 og
10
(K
2
/K
1
) = (E
a
/R) |(T
2
T
1
)/(T
1
T
2
)
K
2
= 0.068 mn
1
Now
1#
2-3#3 1##
t log
#-#4" 25
= 2+.3& minte.
Practice Exercise
3. Cataytc decomposton of ntrous oxde by god at 900C at an nta pressure of 200
mm was 50% n 53 mnute of 73% n 100 mnute.
(a) What s the order of reacton?
(b) Cacuate veocty constant.
(c) How much w t decompose n 100 mnute at the same temperature but at an
nta pressure of 600 mm?
4. The decomposton of N
2
O
5
accordng to equaton 2N
2
O
5
4NO
2
(g) + O
2
(g) s a frst
order reacton. After 30 mnute from start of the decomposton n a cosed vesse, the
tota pressure deveoped s found to be 284.5 mm of Hg and on compete
decomposton, the tota pressure s 584.5 mm of Hg. Cacuate the rate constant of
reacton.
5. A 1
st
order reacton s 50% compete n 30 mnute at 27C and n 10 mnute at 47C.
Cacuate the
(a) Rate constant for reacton at 27C and 47C
(b) Energy of actvaton for the reacton.
(c) Energy of actvaton for the reverse reacton f heat of reacton s 50 k| mo
1
.
6. The energy of actvaton for a reacton s 100 k| mo
1
. Presence of a catayst owers the
energy of actvaton by 75%. What w be effect on rate of reacton at 20C; other
thngs beng equa?
Answers
3. 1.308 10
2
minute
1
4. 5.206 kt 10
3
minute
1
5. 43.85 kJ mol
1
, 93.85 kJ mol
1
6. 2.35 10
13
5.12 -atalyst
A catayst s a substance, whch ncreases the rate of a reacton wthout tsef beng
consumed at the end of the reacton, and the phenomenon s caed catayss. There are
some cataysts whch decrease the rate of reacton and such cataysts are caed negatve
catayst. Obvousy, the catayst acceeratng the rate w be postve catayst. However,
the term postve s sedom used and catayst tsef mpes postve catayst.
Catayst are generay foregn substances but sometmes one of the product formed
may act as a catayst and such catayst s caed "auto catayst" and the phenomenon s
caed auto catayss. Therma decomposton of KCO
3
s found to be acceerated by the
presence of MnO
2
. Here MnO
2
(foregn substance) acts as a catayst.
2KCO
3
+ |MnO
2
|
2KC + 3O
2
+ |MnO
2
|
MnO
2
can be receved n the same composton and mass at the end of the reacton.
In the permanganate ttraton of oxac acd n the presence of bench H
2
SO
4
(acd medum),
t s found that the ttraton n the begnnng there s sow dscharge of the coour of
permanganate souton but after sometme the dscharge of the coour become faster. Ths
s due to the formaton of MnSO
4
durng the reacton whch acts as a catayst for the same
reacton. Thus, MnSO
4
s an "auto catayst" for ths reacton. Ths s an exampe of auto
catayst.
2KMnO
4
+ 3H
2
SO
4
+ 5H
2
C
2
O
2
K
2
SO
4
+ 8H
2
O + 10CO
2
,eneral characteristics of catalyst
() A catayst does not ntate the reacton. It smpy fastens t.
() Ony a sma amount of catayst can catayse the reacton.
() A catayst does not ater the poston of equbrum .e. magntude of equbrum
constant G. It smpy owers the tme needed to attan equbrum. Ths means f a
reversbe reacton n absence of catayst competes to go to the extent of 75% t
attanment of equbrum, and ths state of equbrum s attaned n 20 mnutes then
n presence of a catayst aso the reacton w go to 75% of competon before the
attanment of equbrum but the tme needed for ths w be ess than 20 mnutes.
(v) A catayst drves the reacton through a dfferent route
for whch energy barrer s of shortest heght and
hence E
a
s of ower magntude. That s, the functon of
the catayst s to ower down the actvaton.
E
a
= Energy of actvaton n absence of catayst.
Ea = Energy of actvaton n presence of catayst.
Ea Ea = owerng of actvaton energy by catayst.
&rodAct.
=a
a
&-=-
H
R
H
&
Reactio( Coordi(ate
Reacta(t.
If k and k
cat
be the rate constant of a reacton at a gven temperature T, and E
a
and E
a
are the actvaton energes of the reacton n absence and presence of catayst,
respectvey, the
a
='a 1 RT
cat
= 1 RT
k Ae
k Ae
a a
)= =' * 1 RT cat
k
Ae
k

-2!-
SIIT CHEMISTRY Sri
Vyshnavi
Snce E
a
, E
a
s + so k
cat
> k. the rato
cat
k
k
gves the number of tmes the rate of
reacton w ncrease by the use of catayst at a gven temperature and ths depends upon
E
a
E
a
1
. Greater the vaue of E
a
E
a
1
, more number of tmes k
cat
s greater than k.
The rate of reacton n the presence of catayst at any temperature T
1
may be made
equa to the rate of reacton n absence of catayst but for ths sake we w have to rase
the temperature. Let ths temperature be T
2
ths
= 1 RT
a 2
a 1
=' 1 RT e
e

or
a a
1 2
=' =
T T
.(6)
5.13 Radioacti3ity
A radoactve decay foow 1
st
order knetcs and ths s where the smarty ends. Ths w
be expaned n a short whe.
We measured the rate of reacton n chemca knetcs based on the rate of change of
concentraton of reactant or products. But ths procedure w not work for cacuatng the
rate of radoactve reacton. Ths s because most of the tme the radoactve substance s
a sod. Therefore ts concentraton woud be a constant wth tme (assumng t to be pure
and that the product does not reman wth the reactants). Therefore the rate of radoactve
reactons are measured by cacuatng the rate of change of nuce of the radoactve
substance. For a radoactve decay A B, the rate of reacton s cacuated as
A
A
dN
N
dt

Integratng the dfferenta rate aw we get
t
A
o
N t
N
a N o
d
dt
N

og
#
t
N
t
N

Where N
o
= number of nuce of A at t = 0
N
t
= number of nuce of A at t = t
= decay constant
The expresson can be rearranged to gve
N
t
= N
0
e
t
.(1)
Ths suggests that the number of nuce of radoactve substance A at any nstant of tme
can be cacuated, by knowng the number of nuce at t = 0, ts decay constant and the
tme.
-alf.(ife
|ust ke a 1
st
order reacton the haf fe of radoactve decay s gven by
11 2
#-453
t
Note: Let us start wth 10 nuce. If the haf fe s 5 mnutes, then at the end of frst 5
mnutes, number of nuce woud be 5. Now what woud be the number of nuce after next
mnutes? W t be 2.5 or 2 or 3? We can ceary see that t cannot be caed as haf fe.
Ths demma can be overcome by understandng that a formua reatng to knetcs are
ony vad when the sampe sze s very arge and n such a arge sampe sze, a sma
dfference of 0.5 w be nsgnfcant.
The fact that radoactve decay foows the exponenta aw mpes that ths
phenomenon s statstca n nature. Every nuceus n a sampe of a radonucde has a
certan probabty of decayng, but there s no way to know n advance whch nuce w
actuay decay n a partcuar tme span. If the sampe s arge enough that s, f many
nuce are present the actua fracton of t that decays n a certan tme span w be very
cose to the probabty for any ndvdua nuceus to decay. To say that, a certan
radosotope has a haffe of 5 hr., then, sgnfes that every nuceus of ths sotope has a
50 percent chance of decayng n every 5 hr. perod. Ths does not mean a 100 percent
probabty of decayng n 10 hr. A nuceus does not have a memory, and ts decay
probabty per unt tme s constant unt t actuay does decay. A haf fe of 5 hr. mpes a
75% probabty of decay n 10 hr., whch ncreases to 87.5% n 15 hr, to 93.75% n 20 hr,
and so on, because n every 5 hr. nterva the probabty of decay s 50 percent.
$/erage(ife 0ime
Average fe tme s defned as the fe tme of a snge soated nuceus. Let us magne a
snge nuceus whch decays n 1 second. Assumng 1 second tme nterva to be very sma
the rate of change of nuce woud be 1/1 (because dN = 1 and dt = 1). We can aso see
that snce
dN
N
dt
, for a snge soated nuceus N = 1,

dN
dt
. Therefore n ths present

case = 1.
Now et us assume the same nuceus decays n 2 seconds, we can see that
dN
dt
.e.,
s equa to 1/2. You w aso notce that n the 1
st
case the nuceus survved for 1 second
and n the second case t survved for 2 second. Therefore the fe tme of a snge soated
nuceus s
1
aB
1
t
.
-2#-
SIIT CHEMISTRY Sri
Vyshnavi
5.14 6cti3ity
Actvty by defnton s the rate of decay of a radoactve eement. It s represented as A
and s equa to N. By no means shoud be confused wth rate of change of radoactve
nuce represented by
dN
dt
. Ths s because
dN
dt
taks about the overa change n the

number of nuce n a gven nstant of tme whe actvty ony taks about that change
whch s decay. For exampe f you go out to a market wth Rs. 50 n your pocket and you
spend Rs. 20 n 5 mnutes then your rate of change of money n the waet s Rs. 4/ mn
and n fact the rate of spendng the money s aso Rs. 4/mn. Here you can see both are
same. But f whe spendng Rs. 20 n 5 mntues, somebody keeps Rs. 10 n your waet,
then the rate of change of money n you waet woud become Rs. 2.5/mn, whe the rate
of spendng the money s Rs. 4/mn. Ths mpes that as ong as the radoactve substance
s ony decayng the rate of change of nuce and actvty are same and equaton (1) n
terms actvty of a radoactve substance can be wrtten as A
t
= a
0
e
t
. But f the
radoactve substance s aso beng produce ths
dN
dt
= rate of producton actvty, (Of
course ts a dfferent matter, rate of producton may or may not be a constant).
5.15 1!ecific 6cti3ity
Ths s actvty per unt mass of the sampe. Let radoactve sampe weghtng w gms have
a decay constant . The number of nuce n the w gms woud be
0
AB
C
, where M =
moecuar weght of the radoactve substance and Av = Avogadros number.
Specfc actvty =
0
AB
AB C
0 C
_

It shoud be remembered that f a radoactve sampe s pure and the product does
not reman wth reactant then specfc actvty s a constant.
1nit of $cti/ity
The unt of radoactvty of a substance s measured as the rate at whch t changes nto
daughter nuceus. It has been derved on the scae of dsntegraton of Radum.
Let us consder 1 g of radus (atomc mass = 226 and t
1/2
= 1600 yrs) undergoes
decay, then Rate of decay of radus = Number of nuce of Ra n 1 g
=
23
#-453 1 4-#23 1#
14## 345 24 4# 4# 224

= 3.7 10
10
dps = 3.7 10
10
Becquerre.
= 1 cure (O 1 C = 3.7 10
10
dps)
= 3.7 10
4
Rutherford (O 1 rd = 10
6
dps)
The S unt of actvty s dps of Becquerre.

2"3ecti/e 0ype
Example 1
Consder a gaseous reacton, the rate of whch s gven by K|A| |B|, the voume of the reacton
vesse contanng these gases s suddeny reduced to 1/4
th
of the nta voume. The rate of reacton
reatve to the orgna rate woud be
(a) 16/1 (b) 1/16 (c) 8/1 (d) 1/8
Solution
By reducng voume to
1
4
th the concentraton w become 4 tmes hence rate 16 tmes.
4a5
Example 2
The rate of a reacton ncreases 4-fod when concentraton of reactant s ncreased 16 tmes. If the
rate of reacton s 4 10
6
moe L
1
S
1
moe L
1
when concentraton of the reactant s 4 10
4
, the
rate constant of the reacton w be
(a) 2 10
4
moe
1/2
L
1/2
S
1
(b) 1 10
2
S
1
(c) 2 10
4
moe
1/2
, L
1/2
S
1
(d) 25 moe
1
L mn
1
Solution
Rate co(ce( , Rate = k co(ce(
4 4
11 2 4 11 2 2
Rate 4 1# 4 1#
k
)co(ce(* )4 1# * 2 1#

= 2 10
4
moe
1/2
L
1/2
S
1
4a5
Example 3
A catayst owers the actvaton energy of a reacton from 20 k| moe
1
to 10 k| moe
1
. The
temperature at whch the uncataysed reacton w have the same rate as that of the cataysed at
27C s
(a) 123 C (b) 327 C (c) 227 C (d) + 23 C
Solution
a
1 2 2
= =' a 1# 2#
T T 3## T

T2 = 600 K = 327C
4"5
Example 4
A frst order reacton s 87.5% compete n an hour. The rate constant of the reacton s
(a) 0.0346 mn
1
(b) 0.0693 h
1
(c) 0.0693 mn
1
(d) 0.0346 h
1
Solution
For 87.5% change there w be three haf-changes. Hence haf-tme of the reacton w be
1
3
h =
4#
2#
3
mn, snce haf-tme of a frst order reacton s a constant ndependent of nta
concentraton.
-3%-
SIIT CHEMISTRY Sri
Vyshnavi
100%
2# mi( 2# mi( 2# mi(
)A( reacted*
5#7 257 12-57
11 2
#-453 #-453
k
t 2#

= 0.0346 mn
1
4a5
Example 5
The haf-fe a frst order reacton s 24 hours. If we start wth 10 M nta concentraton of the
reactant then conc. After 96 hours w be
(a) 6.25 M (b) 1.25 M (c) 0.125 M (d) 0.625 M
Solution
Number of haf-ves =
54
4
24

Concentraton remanng after 96 hrs =
4
1#
)2*
= 0.625 M
465
Example 6
Durng the partcuar reacton 10% of the reactant decompose n one hour 20% n two hours 30% n
three hours and so on. The unt of the rate constant s
(a) Hour
1
(b) L mo
1
hour
1
(c) mo L
1
hour
1
(d) mo hour
1
Solution
Ths reacton s a zero order reacton.
4c5
Example 7
The temperature coeffcent of a reacton s 2, by what factor the rate of reacton ncreases when
temperature s ncreased from 30C to 80C.
(a) 16 (b) 32 (c) 64 (d) 128
Solution
"#
3#
k
k
= 2
5
= 32
4"5
Example 8
The rate constant, the actvaton and Arrhenus parameter of a chemca reacton at 25C are 3
10
4
s
1
, 104.4 k| mo
1
and 6 10
14
s
1
respectvey. The vaue of the rate constant at T s
(a) 2 10
18
s
1
(b) 6 10
14
(c) (d) 3.6 10
30
s
1
Solution
K = Ae
Ea/RT
when T

vaue s 6 10
14
s
1
4"5
Example 9
If t1/2 does not change wth nta concentraton, then order of the reacton s
(a) zero (b) second (c) frst (d) thrd
Solution
11 2
( 1
1
t
a

K = Ae
Ea/RT
when T

4c5
Example 10
A substance undergoes a frst order decomposton. The decomposton foows two parae frst
order reacton as
A
8
1
8
2
B
C
The percentage dstrbuton of B and C are
(a) 80% B and 20% C (b) 75% B and 25% C (c) 90% B and 10% C (d) 60% B and 40% C
Solution
For parae reacton
1
2
8 [B]
8 [C]
4
5
[B] 1-14 1# 3
[C] 1 3-" 1#
% of B = 75 and percentage of C = 25
4"5
Example 11
A tangent drawn on the curve obtaned by pottng concentraton of product (moe L
1
) of a frst
order reacton vs. tme (mn) at the pont correspondng to tme 20 mnute makes an ange to 30
wth concentraton axs. Hence the rate of formatons of product after 20 mnutes w be
(a) 0.580 moe L
1
mn
1
(b) 1.723 moe L
1
mn
1
(c) 0.290 moe L
1
mn
1
(d) 0.866 moe L
1
mn
1
Solution
Tangent makes an ange of 30 wth concentraton axs so t must make an ange of 60 wth the
tme axs
(ve drecton). The sope of the tangent w be tan 60 .e., 1.723.
4"5
Example 12
For reacton 3A
products, f s found that the rate of reacton ncreases 4fod when

concentraton of A s ncreased 16 tmes keepng the temperature constant. The order of reacton
s?
(a) 2 (b) 1 (c) 1 (d) 0.5
Solution
The rate data suggests the rate aw as foows
Rate A .e., r A
1/2
order = 0.5
465
Example 13
The therma decomposton of acetadehyde: CH3CHO
CH4 + CO, has rate constant of 1.8

10
3
moe
1/2
L
1/2
mn
1
at a gven temperature. How woud
3
d[CH CHO]
dt
w change f concentraton
of acetadehyde s doubed keepng the temperature constant?
(a) w ncrease by 2828 tmes (b) w ncrease by 11.313
tmes
(c) w not change (d) w ncrease by 4 tmes
Solution
Unt of the rate constant moe
1/2
L
1/2
. mn
1/2
suggests that the reacton obeys knetcs of 1.5
order.
Rate = k |CH3CHO|
3/2
-32-
SIIT CHEMISTRY Sri
Vyshnavi
Or
1 1
31 2 1 31 2
3
Rate mole D mi(
k
[CH CHO] )mole D *

= Moe
1/2
, L
1/2
. mn
1
So, by doubng the concentraton of acetadehyde the rate w ncrease 2
1/5
.e., 2.828 tmes.
4a5
Example 14
The reacton ; 2O3
3O2, s assgned the foowng mechansm.

(I) O3 ` `
` `
O2 + O
(II) O3 + O
.lo0
2O2
The rate aw of f the reacton w, therefore be
(a) r |O3|
2
|O2| (b) r |O3|
2
|O2|
1
(c) r |O3| (d) r |O3| |O2|
2
Solution
Step II, beng r.d.s.
Rate of overa reacton = rate of Step II = KII |O3| |O|
Puttng the vaue of |O| from the equbrum of Step I,
Rate =
2
C 3
2
8 8 [O ]
[O ]
4"5
Example 15
For an endothermc reacton where H represents the enthapy of the reacton, the mnmum vaue
for the energy of actvaton w be
(a) Less than H (b) zero (c) more than H (d) equa to H
Solution
=
=
R
H
=
&
Reactio( coordi(ate
4c5
Example 16
The rate aw for a reacton between the substances A and B s gven by
Rate k |A|
n
|B|
m
On doubng the concentraton of A and havng the concentraton of B, the rato of the new rate to
the earer rate of the reacton w be
(a) m + n (b) (n m) (c) 2
(n m)
(d)
)m (*
1
2
+
Solution
Earer rate = k a
n
b
m
New rate k (2 a)
n
(b)
m
( ( m m
( m
Ne0 rae 2 a b 2
=arlier rate a b
= 2
n
. 2
m
= 2
nm
.
4c5
Example 17
The haf-fe of a reacton s haved as the nta concentraton of the reactant s doubed. The order
of reacton s
(a) 0.5 (b) 1 (c) 2 (d) 0
Solution
T1/2
( 1
( 1
11 2 1 # 2 # 2
( 1 ( 1
# 11 2 2 # 1 # 1
)t * [A ] [A ] 1
,
[A ] )t * [A ] [A ]

' ;

( 1
t 2a
t 1 2 a

,
or 2 = (2)
n1
or n 1 = 1 or n = 2.
4c5
Example 18
The rate constant of the reacton at temperature 200 K s 10 tmes ess than the rate constant at
400 K. What s the actvaton energy of the reacton?
(a) 1842.4 R (b) 921.2 R (c) 460.6 R (d) 230.3 R
Solution
At T1 = 200 K, f k1 = k, then
at T2 = 400 K, k2 = 10 k
a
= 1#k 4## 2##
log
k 2-3#3 R 4## 2##
_
,
or Ea = 921.2 R
4"5
Example 19
In the reacton 2A + B
A2B, f the concentraton of A s doubed and that of B s haved, then

the rate of reacton w
(a) ncrease by 4 tmes (b) decrease by 2 tmes (c) ncrease by 2 tmes (d) reman the
same
Solution
Intay rate = k |A|
2
|B| = k a
2
b.
New rate = k (2a)
2

b
2
_

,
= 2 k a
2
b .e. ncreased 2 tmes.
4c5
Example 20
The rate constant k, for the reacton
2 5 2 2
1
N O )g* 2NO )g* O )g*
2
+
Is 2.3 10
2
s
1
. Whch equaton gven beow descrbes the change of |N2O5| wth tme? |N2O5|0 and
|N2O5|t correspond to the concentraton of N2O5 ntay and at tme t.
(a) |N2O5|t = |N2O5|0 + kt (b) |N2O5|0 = |N2O5|te
kt
(c) og |N2O5|t = og |N2O5|0 + kt (d)
2 5 #
2 5 t
[N O ]
( kt
[N O ]

Solution
# 2 5 #
t 2 5 t
C [N O ] 1 a 1 1
k ( ( (
t a 3 t C t [N O ]

-34-
SIIT CHEMISTRY Sri
Vyshnavi
465


S"3ecti/e 0ype
Example 1
A hydrogenaton reacton s carred out at 500 K. If the same reacton s carred out n the presence
of a catayst at the rate, the temperature requred s 400 K. Cacuate the actvaton energy of the
reacton f the catayst owers the actvaton energy by 20 k| mo
1
.
Solution
Suppose actvaton energy n the absence of catayst s Ea and that n the presence of catayst t s
Eb. Then
K =
a b
= 1 5##R = 1 4##R
Ae Ae

(as k s same n both the cases).

Hence,
a b
= =
5## R 4## R
or
b a
4
= =
5
But Ea Eb = 20 k| or
a a
4
= =
5
= 20
or
1
5
Ea = 20 or Ea = 100 k| mo
1
.
Example 2
At constant temperature and voume, X decomposes as
2X(g) 3 Y(g) + 2 Z (g)
Px s the parta pressure of X.
2"ser/ation
!o.
0ime 4in
mintes5
#x 4in mm of
-g5
1 0 800
2 100 400
3 200 200
() What s the order of reacton wth respect to X?
() Fnd the tme for 75% competon of the reacton
() Fnd the tota pressure when pressure of X s 700 mm of Hg.
Solution
() as pressure of X s changng wth tme, t cannot be a zero order reacton. Let us now check t
for 1
st
order.
At t = 100 mn,
o
t
& 2-3#3 2-3#3 "##
log log
1## & 1## 4##
= 6.932 10
3
mn
1
At t = 200 mn,
2-3#3 "## 2-3#3
k log log 4
2## 2## "##

= 6.932 10
3
mn
1
As k comes out to be constant, hence t s a reacton of 1
st
order.
()
657
2-3#3 1##
t log
k 1## 65
=
3 1
2-3#3
log4
4-532 1# mi(

= 2++ min.
-3!-
SIIT CHEMISTRY Sri
Vyshnavi
()
2E)g* 3F)g* 2/)g*
(itial "## mm # #
a,tr time t "## 2? 3? 2?
+
When pressure of X s 700 mm,

800 2p = 700 or p = 50 mm
Tota pressure = (800 2 p) + 3p + 2p
= 800 + 3p = 800 + 3 50 = &5+ mm.
Example 3
Show that for a frst order reacton tme requred for 99% competon s twce for the tme requred
for the competon of 90% of the reacton.
Solution
T99% =
1#
2-3#3 1##
log
k 1## 55
.(1)
T90% =
1#
2-3#3 1##
log
k 1## 5#
.(2)
By Eq. (1) & (2)
557 1#
5#7 1#
t log 1##
2
t log 1#

t99% = 2 t90%.
Example 4
The decomposton of C2O7 at 400 K n the gas phase to C2 and O2 s of 1
st
order. After 55 sec at
400 K the pressure of C2O7 fas from 0.062 to 0.044 atm. Cacuate.
(1) The rate constant (2) Pressure of C2O7 after 100 sec.
Solution
2 6 2 2
6
Cl O Cl O
2
Cole at t #, a # #
63
Cole at t 55 .ec, )a 3* 3
2
+

(a) Snce pressure of C2O7 s gven
a 0.062 (a x) 0.044
2-3#3 a
k log
t a 3
=
2-3#3 #-#42
log
55 #-#44
k = 6.023 10
3
sec
1
.
(b) Let t = 100 sec, (a x) P
3
1#
2-3#3 #-#42
4-#23 1# log
1## &

P = 0.033 atm.
Example 5
A 22.4 tre fask contans 0.76 mm of ozone at 25C. Cacuate
() The concentraton of oxygen atoms needed so that the eementary reacton O + O3 2O3
havng rate
constant equa to 1.5 10
7
tre mo
1
sec
1
can proceed wth a rate of 0.15 mo tre
1
sec
1
() The rate of formaton of oxygen under ths condton.
Solution
The unt of rate constant suggests the second order for reacton. Thus,
Rate of reacton = K|O3| |O| or 0.15 = 1.5 10
7

#-64
[O]
#-#"21 25" 64#
1
1

]
3
( & #-64
,or O
! RT #-#"21 25" 64#
_

,
|O| = 2.45 10
4
n/V for O = 2.45 10
4
&
RT
for O = 2.45 10
4
P0 = 2.45 10
4
0.0821 298
= 5.99 10
3
atm
= 5.99 10
3
760 mm = 4.5 mm
Aso, rate of reacton =
2
d[O ] 1 1
2 dt 2
rate of formaton of O2
Rate of formaton of O2 = 2 0.15 = 0.30 mo L
1
t
1
.
Example 6
(a) In a reacton wth ntay 0.12 M, the concentraton of reacton s reduced to 0.06 M n 10 hour
and to
0.03 M n 20 hour.
() What s order of reacton? () What s rate constant?
(b) The rate of a frst order reacton s 0.04 mo tre
1
s
1
at 10 mnute and 0.03 mo tre
1
at 20
mnute
after ntaton. Fnd the haf fe of the reacton.
Solution
(a) Assumng Ist order, .e., K =
1#
2-3#3 a
log
t )a 3*
a = 0.12 M
(a x) = 0.06 M 7or case I :
1#
2-3#3 #-12
8 log
1# #-#4
= 0.069 hr
1
t = 10 hr
a = 0.12 M
(a x) = 0.03 M 7or Case II:
1
1#
2-3#3 #-12
8 log #-#45 >r
2# #-#3

t = 20 hr
Reacton s of 1 order and rate constant k = 0.069 hr
1
(b) Rate = K |A|
0.04 = K|A|10 and 0.03 = K|A|20
1#
2#
[A] #-#4 4
[A] #-#3 3

Aso
1#
2#
[A] 2-3#3
t log
8 [A]
when t = 10 mn
2-3#3 4
1# log
8 3
-3#-
SIIT CHEMISTRY Sri
Vyshnavi
2-3#3 4
8 log
1# 3
= 0.288 mn
1
11 2
2-453 #-453
t
8 #-#2""
= 24.06 mn.
Example 7
The foowng data represent for the decomposton of NH4NO2 n aqueous souton.
Tme n mnute 10 15 20 25
Voume of N2(n
mL)
6.25 9.0 11.4
0
13.65 33.05
(a) Show that reacton s of 1st order (b) Cacuate veocty constant.
Solution
4 2).* 2)g* 2 ) *
NH NO N 2H O
Cole at t # a # #
Cole at t t )a 3* 3 23
+

l
the voume of N2 formed at any tme s proportona to the amount of NH4NO2 decomposed n that
tme.
At t =
2
N
!
= 33.05 mL
a 33.05
I At t = 10
2
N
!
= 6.25
x 6.25
II At t = 15
2
N
!
= 9.0 mL
x 9.0
III At t = 20
2
N
!
= 11.40 mL
x 11.40
IV At t = 25
2
N
!
= 13.65 mL
x 13.65
Now use,
1#
2-3#3 a
k log
t a 3
Case I
1#
2-3#3 33-#5
k log
1# 33-#5 4-25
k = 2.0 10
2
mn
1
Smary, cacuate k for each case. The vaues of k come amost constant and thus showng that
reacton s 1 order. Average of a k vaue gves rate constant.
Exercise . I

,eneral 0ype 47ill in the "lan8s9 0re or 7alse9 $ssertion :;eason 5
rue!"alse
1. Moecuarty of a reacton can be 0, 1, 2, 3, etc.
2. There s no dfference between rate aw and aw of mass acton.
3. Arrhenus equaton s
E / RT
a
k Ae .
4. Order of reacton s an expermenta parameter.
5. For a zero order reacton t1/2 s proportona to nta concentraton
"ill in t#e $lan%s
1. The nverson of cane sugar s a ______ reacton though ts moecuarty s ______
2. A reacton s sad to be of ______ f the rate s entrey
3. The hydroyss of ethy acetate n ______ medum s a ______ order reacton.
4. When
2
dx
k|A||B|
dt
, the reacton s sad to be of ______ n A and of ______ order n B. The overa
order s ______ .
5. For a frst order reacton t1/2 =
.........
k
Assertion an& 'eason
In the foowng queston, a statement of Asserton (A) s gven whch s foowed by a correspondng
statement of reason (R). Mark the correct answer out of the foowng optons/codes.
(a) If both (A) and (R) are true and (R) s the correct expanaton of (A).
(b) If both (A) and (R) are true but (R) s not correct expanaton of (A).
(c) If (A) s true but (R) s fase.
(d) If both (A) and (R) are fase.
1. A : Haf fe of a certan radoactve eement s 100 days. After 200 days, fracton eft
undecayed w be 50%.
R :
(
#
N 1
N 2
_

,
< where symbos have standard meanng
2. A : Cataysts do not change the heat effect of the reacton .e., exothermc or endothermc
nature of the reacton.
R : Cataysts do not shft chemca equbrum n reversbe processes, but ony hep n
attanment of the equbrum
3. A: Temperature coeffcents of most of the reactons es between 2 and 3.
R: Increase n temperature ncreases the number of cosons.
4. A: The moecuarty of the reacton H2 + Br2 2 HBr s 2.
R: The order of the reacton s 3/2.
5. A: For the reacton RC + NaOH(aq) ROH + NaC, the rate of reacton s reduced to haf on
reducng the concentraton of RC to haf.
R: The rate of the reacton s represented by k |RC|, .e., t s a frst order reacton
Exercise . II

2"3ecti/e 0ype 42nly 2ne Choice Correct5
Level . I
1. At 250C, the haf fe for the decomposton of N2O5 s 5.7 hour and s ndependent of nta
pressure of N2O5. The specfc rate constant s
(a)
#-453
5-6
(b) 0.693 5.7 (c)
5-6
#-453
(d) None
2. For a gven reacton of frst order, t takes 20 mn, for the concentraton to drop from 1 M L
1
to
0.6 ML
1
. The tme requred for the concentraton to drop from 0.6 ML
1
to 0.36 ML
1
w be
(a) > 20 mn (b) < 20 mn (c) = 20 mn (d)
3. In a frst order reacton the
a
a 3
was found to be 8 after 10 mn. The rate constant s
-4%-
SIIT CHEMISTRY Sri
Vyshnavi
(a)
)2-3#3 3log2*
1#
(b)
)2-3#3 2log3*
1#
(c) 10 2.303 2 og 3 (d) 10 2.303 3

og 2
4. For the reacton A + B
Products, t s found that the order of A s 2 and of B s 3 n the

rate expresson. When concentraton of both s doubed the rate w ncrease by
(a) 10 (b) 6 (c) 32 (d) 16
5. The rate aw of the reacton A + 2B
Product s gven by d|Product|/dt = K|A|

2
. |B|. If A s
taken n arge excess, the order of the reacton w be
(a) 0 (b) 1 (c) 2 (d) 3
6. If a reacton wth t1/2 = 69.3 sec, has a rate constant 10
2
sec
1
, the order s
(a) 0 (b) 1 (c) 2 (d) 3
7. The specfc rate constant for a frst order reacton s 60 10
4
sec
1
. If the nta concentraton
of the reactant s 0.01 mo L
1
, the rate s
(a) 60 10
6
M sec
1
(b) 36 10
4
M sec
1
(c) 60 10
2
M sec
1
(d) 36 10
1
M sec
1
8. The rate constant for a zero order reacton s 2 10
2
mo L
1
sec
1
. If the concentraton of the
reactant after 25 sec s 0.05 M, the nta concentraton must have been
(a) 0.5 M (b) 1.25 M (c) 12.5 M (d) 1.0 M
9. A frst order reacton s carred out wth an nta concentraton of 10 M
1
and 80% of the
reactant changes nto the product. Now f the same reacton s carred out wth an nta
concentraton of 5 ML
1
, the percentage of reactant changng to the product s
(a) 40 (b) 80 (c) 160 (d) cant be
cacuated
10. What fracton of a reactant showng frst order remans after 40 mn, f t1/2 s 20 mn?
(a) V (b) 1/2 (c) 1/8 (d) 1/6
11. In Arrhenus equaton, the fracton of effectve cosons s gven by
(a) k = Ae
Ea/R
(b) A (c) e
Ea/R
(d) None of these
12. For a frst order reacton t3/4 s 1368 seconds. The specfc rate constant s (n sec
1
)
(a) 10
3
(b) 10
2
(c) 10
9
(d) 10
5
13. For a reacton A + B
Products, on doubng the nta concentraton of B keepng that of a

fxed the rate doubes and on doubng the nta concentraton of A and B, rate ncreased 4
tmes. The rate aw s
(a) K|A||B| (b) K|A|
2
|B|
2
(c) K|A|
2
|B| (d) K|B|
2
|A|
14. The rate expresson for a reacton s rate = K|A|
3/2
|B|
1
the order of reacton s
(a) 0 (b) 1/2 (c) 3/2 (d) 5/2
15. The rate constant for the reacton 2N2O5
4NO2 + O2 s 3.0 10
5
sec
1
. If the rate s 2.4
10
5
mo L
1
sec
1
, then conc. of N2O5 n mo L
1
s
(a) 1.4 (b) 1 : 2 (c) 0.04 (d) 0.8
16. For a reacton A
products, nta conc. of A s 2M. After 10 mnutes reacton s 10%

competed. If
r = k|A| then haf fe s approxmatey.
(a) 0.693 (b) 69.3 mn (c) 66 mn (d) 0.0693 mn
17. The rate of formaton of C s the foowng reacton 2A + B
2C s 10 Kg mn
1
. Hence the
rate of dsappearance of A w be (kg/mn)
(a) 10 (b) 8 (c) 6.4 (d) 3.2
18. In the presence of catayst Ea s owered by 2Kca at 27C. Hence rate w be
(a) 20 tmes (b) 14 tmes (c) 28 tmes (d) 2 tmes
19. For reacton A2 + 2B
2AB. Then order w.r.t. A2 and B are respectvey

|A2| |B| Rate (M sec
1
)
0.1 0.2 1 10
2
0.2 0.2 2 10
2
0.2 0.4 8 10
2
(a) 1, 2 (b) 2, 1 (c) 1, 1 (d) 2, 2
20. The pot of og K versus
1
T
s near wth a sope of
(a) Ea/R (b) Ea/R (c)
a
=
2-3#3 R
(d)
a
=
2-3#3R
Level . II
21. The radoactve decay foows
(a) frst-order knetcs
(b) secondorder knetcs
(c) a compcated knetcs wth temperature dependence behavour
(d) zeroorder knetcs
22. The rate of a reacton gets doubed when the temperature changes from 7C to 17C. By what
factor w t change when the temperature change from 17C to 27C?
(a) 2 (b) 2.1 (c) 1.91 (d) 2.3
23. Two frst order reactons have haf ves n the rato of 3 : 2. Cacuate the rato of tme ntervas
t1 : t2, the tme t1 and t2 are the tme perod for 25% and 75% competon for the frst and
second reacton respectvey.
(a) 0.311 : 1 (b) 0.420 : 1 (c) 0.273 : 1 (d) 0.119 : 1
24. The rate constant s numercay the same for three reactons of frst, second and thrd order.
Whch of the foowng s correct?
(a) If |A| = 1, then r1 = r2 = r3 (b) If |A| < 1, then r1 > r2
> r3
(c) If |A| > 1, then r3 > r2 > r1 (d) a of these
25. The reacton, 2NO + Br2
2NOBr obeys foowng mechansm,

,a.t
2 2
NO Br NOBr +
` ` `
` ``
.lo0
2
NOBr NO 2NOBr +
The rate expresson of the above reacton can be wrtten as
(a) r = k|NO|
2
|Br2| (b) r = k|NO| |Br2| (c) r = k|NO| |Br2| (d) r = k|NOBr2|
26. The actvaton energy for a reacton, whch doubes the rate when the temperature s rased
from 300 K to 310 K s
(a) 50.6 k| mo
1
(b) 3.6 k| mo
1
(v) 56.6 k| mo
1
(d) 59.6 k| mo
1
27. A substance (nta concentraton, a) reacts accordng to zero-order knetcs. The tme t takes
for the competon of the reacton s
(a) a/k (b) a/2k (c) k/a (d) 2k/a
28. For a frst order reacton, the rato of tmes to compete 99.9% and haf of the reacton s
(a) 8 (b) 9 (c) 10 (d) 12
29. Whch of the foowng statement s not correct?
(a) The effcency of a sod catayst depends upon ts surface area.
(b) Catayst operates by provdng aternate path for the reacton that nvoves a ower
actvaton energy
-42-
SIIT CHEMISTRY Sri
Vyshnavi
(c) Catayst owers the energy of actvaton of the forward reacton wthout affectng the energy
of actvaton of the backward reacton
(d) Catayst does not affect the overa enthapy change of the reacton.
30. Ethyene s produced by the reacton
4 " 2 4
C@clobA ta(e
C H 2C H
The rate constant of the decomposton of cycobutane s 2.48 10

4
sec
1
. In what tme, w the
moar rato of the ethyene to cycobutane n the reacton mxture attan vaue 1 ?
(a) 27.25 mnute (b) 28.25 mnute (c) 25 mnute (d) 20 mnute
31. The nverson of cane sugar proceeds wth a constant haf fe of 50 mnute at pH = 5, for any
concentraton of sugar. However, f pH = 4, the haf fe changes to 50 mnute. The rate aw
expresson for nverson of cane sugar can be wrtten as
(a) r = k |sugar|
2
|H
+
|
0
(b) r = k |sugar|
1
|H
+
|
1
(c) r = k |sugar|
1
|H
+
|
0
(d) r = k |sugar|
0
|H
+
|
1
32. The order of a reacton and rate constant for a chemca change havng og t50% vs og |A|0 curve
as woud be
log t
5#7
459
Dog [A]
#
(a) 0, 1/2 (b) 1, 1 (c) 2, 2 (d) 0, 1
33. Haf fe (t1) of the frst-order reacton and haf fe (t2) of the second-order reacton are equa.
Hence, assumng |A|0 to be same, the rato of the rate at the start of the reacton (assumng
same nta concentraton of the reactant n both the reactons) woud be
(a) 1 (b) 2 (c) 0.693 (d) 1.44
34. The actvaton energes of two reactons are
1 2
a a
= a(d =
. If the temperature of the reactng
systems s ncreased from T1 to T2, predct whch of the foowng aternatves s correct?
(a)
1 2
2
k' k'
k k
(b)
1 2
1 2
k' k'
k k
>
(c)
1 2
1 2
k' k'
k k
<
(d)
1 2
1 2
k' k'
2
k k
<
where k1 & k1 are the rate constant at temperature T1 & T2 K for one reacton and k2 & k2 are
the rate constants at temperature T1 & T2 K for another reacton.
35. The rate constant k1 of a reacton s found to be doube the rate constant k2 of another reacton.
The reatonshp between correspondng actvaton energes of the two reactons at same
temperature
1 2
a a
)= a(d = *
can be represented as
(a)
1 2
a a
= = >
(b)
1 2
a a
= = <
(c)
1 2
a a
= =
(d) none of these
36. The decomposton of a substance foows frst order knetcs. Its concentraton s reduced to
1/8
th
of ts nta vaue n 24 mnutes. The rate constant of the decomposton process s
(1) 1/24 mn
1
(b) 0.693/24 mn
1
(c)
1
2-3#3 1
log mi(
24 "

_

,
(d)
1
2-3#3 "
log mi(
24 1

_

,
37. The chemca reacton, 2O3
3O2 proceeds as foows

O3 ` `
` `
O2 + O ...(fast)
O + O3
2O2 ..(sow)
The rate aw expresson shoud be
(a) r = k|O3|
2
(b) r = k|O3|
2
|O2|
1
(c) r = k|O3| |O2| (d) unpredctabe
38. For a reacton of frst order, t takes 20 mnutes for the concentraton to drop from 1 M to 0.6
M. the ne requred for the concentraton to drop from 0.6 M to 0.3 M w be
(a) > 20 mn (b) < 20 mn (c) equa to 20 mn (d) nfnty
39. For the decomposton of N2O5 at a partcuar temperature, accordng to the equatons
2N2O5
4NO2 + O2
N2O5
2NO2 + O2
the actvaton energes are E1 and E2 respectvey. Then
(a) E1 > E2 (b) E1 < E2 (c) E1 = 2E2 (d) E1 = E2
40. The concentraton of the reactant A n the reacton A
B at dfferent tmes are gven beow

Concentration
4=5
0ime 4=intes5
0.069 0
0.052 17
0.035 34
0.018 51
The rate constant of the reacton accordng to the correct order of reacton s
(a) 0.001 M/mnute (b) 0.001 mnute
1
(c) 0.001 mnute/M (d) 0.001 M
1
mnute
1
Exercise . III

2"3ecti/e 0ype 4=ore than 2ne Choice Correct5
1. The haf-perod T for the decomposton of ammona on tungsten wre, was measured for
dfferent nta pressures P of ammona at 25C. Then
P (mm Hg) 11 21 48 73 12
0
T (sec) 48 92 210 32
0
52
5
(a) zero order reacton (b) Frst order reacton
(c) rate constant for reacton s 0.114 seconds (d) rate constant for reacton s 1.14
seconds.
2. For an somersaton reacton
Catal@.t
A B
n gaseous phase, the equbrum constant at 60C

s 3.60. Both forward and backward reactons are of frst order. Startng wth an nta pressure
of P atm, of A, the pressure became 0.25 P atm n 40 mnutes. The vaues of ndvdua rate
constants for the forward (kf) and backward (kb) reactons are
(a) kf = 3.466 10
2
mn
1
(b) kf = 9.628 10
3
mn
1
(c) kb = 9.628 10
3
mn
1
(d) kb = 3.466 10
2
mn
1
3. For the reacton 2A + B
C wth the rate aw

d[C]
dt
= k |A|
1
|B|
1
and started wth A and B n
stochometrc proporton whch s/are true?
(a) unt of k s Moe ter
1
s
1
(b) |A|, |B| and |C| a w be near functons of tme
(c) |C| = 2kt
(d) |C| = kt
4. Consder the decay of P to a and B by two parae frst order reactons as shown n fgure. Gven
Reacto
n
H Rate
constant
Energy of actvaton
P A HA
kA EA
-44-
SIIT CHEMISTRY Sri
Vyshnavi
P B HB
KB EB
Whch of the foowng s(are) true?
(a) a = EB (b) b = EA (c) HA = b d (d) HB = c a
5. The substance undergoes frst order decomposton. The decomposton foows two parae frst
order reacton as
A
8
1
8
2
B
C
K1 = 1.26 10
4
sec
1
and K2 = 3.8 10
5
sec
1
The percentage dstrbuton of B and C
(a) 76.83% (b) 23.17% C (c) 90% B (d) 40% C
6. A certan reacton obeys the rate equaton (n the ntegrated form) |C
(1n)
C0
(1 n)
| = (n 1) kt
where C00 s the nta concentraton and C s the concentraton after tme, t.
(a) the unt of k for n = 1 s sec
1
(b) the unt of k for n = 2 s tre mo
1
sec
1
(c) the unt of k for n = 3 s mo tre
1
sec
1
(d) the unt of k for n = 3 s tre
2
mo
2
sec
1
7. The ozone ayer n the earths upper atmosphere s mportant n shedng the earth from very
harmfu utravoet radaton. The ozone, O3, decomposes accordng to the equaton 2O3(g)
3O2(g). The mechansm of the reacton s thought to proceed through an nta fast, reversbe
step and then a sow second step.
Step 1: Fast reversbe O3(g) ` `
` `
O2(g) + O(g)
Step 2 : O3(g) + O(g) 2O2(g)
The whch of the foowng s correct?
(a) Step 2 s rate determnng step
(b) the rate expresson for step 2 s
d
dt
|O3| = k|O3| |O|
(c) For step 1, moecuarty s 1
(d) For step 2, moecuarty s 2
8. The forward reactons rate for the ntrc oxde-oxygen reacton
2NO + O2
2NO2 has the rate aw ; rate = K |NO|

2
|O2|
Assume the mechansm:
k
2 2
2NO N O ,
` ` `
```
(rapd equbraton) ;
N2O2 + O2
k'
` ` `
` ``
2 NO2 |sow step|.
Correct optons s/are :
(a) Rate constant = k k (b) |N2O2| = k|NO|
2
(c) |N2O2| = k|NO| (d) rate constant = k
9. Consder the foowng case of COMPETING 1
ST
ORDER REACTIONS
A
8
1
8
2
B
C
After the start of the reacton at t = 0 wth ony a, the |C| s equa to the |D| at a tmes. The
tme n whch a three concentratons w be equa s gven by
(a)
1
1
t ( 3
2k
l
(b)
2
1
t (3
2k
l
(c)
1
1
t (2
3k
l
(d)
2
1
t ( 2
3k
l
10. Takng the reacton, A + 2B
Products, to be of second order, whch of the foowng are

the correct rate aw expressons?
(a)
d3
dt
= k|A| | B| (b)
d3
dt
= k |A| |B|
2
(c)
d3
dt
= k |A|
2
(d)
d3
dt
= k1 |A| + k2|B|
2
11. In acdc medum, the rate of reacton between BrO3
and Br
s gven by the expresson

2 3
3
d [BrO ]
k[BrO ] [Br ] [H ]
dt
+

It means
(a) Rate constant of the reacton depends upon the concentraton of H
+
ons
(b) Rate of reacton s ndependent of the concentraton of the acd added
(c) The change n pH of the souton w affect the rate of reacton
(d) Doubng the concentraton of H
+
ons w ncrease the reacton rate by 4 tmes
12. The rate constant of a reacton s gven by
K = 2.1 10
10
exp ( 2700/RT)
It means that
(a) og k vs. 1/T w be a straght ne wth sope =
26##
2-3#3R
(b) og k vs. 1/T w be a straght ne wth ntercept on og k axs = 2.1 10

10
(c) The number of effectve cosons are 2.1 10
10
cm
3
sec
1
(d) Haf fe of the reacton ncreases wth ncrease of temperature
13. In a hypothetca reacton X
Y, the actvaton energy for the forward and the backward

reacton are 15 and 9 k| mo
1
respectvey. The potenta energy of X s 10 k| mo
1
. Then
(a) Threshod energy of the reacton s 25 k|
(b) The potenta energy of Y s 16 k|
(c) Heat of reacton s 6 k|
(d) The reacton s endothermc
14. A catayst
(a) ncreases the average knetc energy of the reactng moecues
(b) decreases the actvaton energy (c) aters the reacton mechansm
(d) ncreases the frequency of cosons of the reactng speces
15. The rate aw for the reacton
RC + NaOH
ROH + NaC
Is gven by: rate = k |RC|. The rate of ths reacton
(a) s doubed by doubng the concentraton of NaOH
(b) s haved by reducng the concentraton of RC by one haf
(c) s ncreased by ncreasng the temperature of the reacton
(d) s unaffected by change n temperature
16. For a frst order reacton
(a) The degree of dssocaton s equa to 1 e
kt
(b) A pot of recproca of concentraton of reactant vs. tme gves a straght ne
(c) The tme taken for the competon of 75% of reacton s thrce t1/2 of the reacton
(d) The pre-exponenta factor n the Arrhenus equaton has the dmensons of tme
1
17. Whch of the foowng statements are correct?
(a) A pot of og Kp versus 1/T s near
(b) A pot of og |X| versus tme s near for a frst order reacton X
P
(c) A pot of og P versus 1/T s near at constant
(d) A pot P versus 1/V s near at constant temperature
18. For a genera reacton,
-4!-
SIIT CHEMISTRY Sri
Vyshnavi
the rate of reacton may be gve as
(1)
a b A
A B
dC 1
r kC C
dt a
(2)
a b B
A B
dC 1
r kC C
dt b

(3)
a b C
A B
dC 1
r kC C
dt c
(4)
a b D
A B
dC 1
r kC C
dt d

19. Accordng to Arrhenus the reatonshp between rate constant, k and temperature can be gven
by
(1)
=a 1 RT
k Ae
(2)
a 2 2 1
1 1 2
= k T T
log
k 2-3#3R TT

(3)
a
=
logk logA
2-3#3RT
(4)
o
G 2-3#3RTlog8
20. The concept of mechanca veocty or speed cannot be used n measurng the rate of reactons,
because
(1) rate of reacton depends on actve mass of reactants and t decreases wth tme
(2) rate of reacton depends on moar concentraton of reactants and t decreases wth tme
(3) rate of reacton depends on moar concentraton of products and t decreases wth tme
(4) rate of reacton depends on actve mass of products and ts decreases wth tme
Exercise . IV

Comprehensi/e 0ype
Passa(e ) 1
;ea6 the follo>ing comprehension careflly an6 ans>er the follo>ing %estions.
#SE1?2.=2(EC1($; ;E$C0I2!S
There are many reactons whch obey a frst order rate equaton athough n reaty they are b- or
ter-moecuar. As an exampe of these may be taken the decomposton of carbony sufde n water,
namey,
COS + H2O
CO2 + H2S
Accordng to the aw of mass acton ths reacton shoud order wth the rate dependent on the
concentraton of both the carbony sufde and the water. Actuay however, the rate s found to be
frst order wth respect to the carbony sufde and ndependent of the water. Reactons exhbtng
such behavour are sad to be pseudo-moecuar.
The pseudo-unmoecuar nature of ths reacton s expanabe by the fact that water s present n
such excess that ts concentraton remans practcay constant durng the course of the reacton.
Under these condton b x = b, and the rate equaton becomes
2
d3
k
dt
(a x) b
On ntegraton ths eads to
2 1#
2-3#3 a
k bk log
t a 3

whch s the equaton for a frst order reacton. It s evdent, however, that the new constant k s not
ndependent of the concentraton, as s the case wth true frst order constants, but may vary wth b
f the atter s changed apprecaby, When such s the case, the true constant k2 can be obtaned
from k by dvdng the atter by b.
Pseudo-moecuar reactons are encountered whenever one or more of the reactants reman
constants durng the course of an experment. Ths s the case wth reactons conducted n sovents
whch are themseves one of the reactants, as n the decomposton of carbony sufde n water, or
n the esterfcaton of acetc anhydrde n acoho.
(CH3CO)2 + 2C2H5OH
2CH3COOC2H5 + H2O
Agan, ths s aso true of reactons sub|ect to catayss, n whch case the concentraton of the
catayst does not change. The decomposton of dacetone acoho to acetone n aqueous souton s
cataysed by hydroxy ons, wth the rate proportona to the concentraton of the acoho and that of
the base. Snce the concentraton of the base does not change wthn any one experment,
however, the rate equaton reduces to one of frst order wth respect to the acoho. But the rate
constant k obtaned for varous concentratons of base are not dentca, as may be seen from tabe.
To obtan from these the true second order veocty constant, the ks must be dvded by the
hydroxy on concentraton. When ths s done exceent k2 vaues resut, as coumn 3 ndcates.
C Conc. of !a2- K 4min
1
5 K2 @ 89C
0.0205 0.0455 2.22
0.0292 0.0651 2.23
0.0518 0.1160 2.24
0.0710 0.1576 2.22
0.1045 0.2309 2.21
0a"le: ?ecomposition of 6iacetone alcohol in >ater at 25A 4Catalyst: !a2-5
1. Whch of k or k2 s dependent on concentraton?
(a) ony k (b) ony k2 (c) both k and k2 (d) nether k nor k2
2. By what factor does the rate of reacton of dacetone acoho n water souton change f pOH s
ncreased by 2 unts other thngs remanng same?
(a) ncreases 100 tmes (2) decreases 100 tmes (c) ncreases 2 tmes
(d) decreases 2 tmes
3. For the reacton A + B C ; r = k |A| |B| wth |A|0 = 0.001 M and |B|0 = 10 M, the tme n whch
the conc. of A becomes 0.005 M w be neary
(a)
#-453
1#k
(b)
#-453
k
(c)
4-53
k
(d)
453
k
Passa(e ) 2
;ea6 the follo>ing comprehension careflly an6 ans>er the follo>ing %estions.
;eactions 0en6ing 0o E%ili"rim
Not a chemca reactons proceed to a stage at whch the concentratons of the reactants become
vanshngy sma. Here we consder the knetcs of such reactons.
Let a reacton be represented n genera terms by the scheme
1
1
k
k
A B
` ` `
` ``
where k1 and k1 represent the rate constants for the forwards and reverse reactons, respectvey.
The equbrum constant for ths reacton may be wrtten as
K = |B|
/ |A|
= k1/k1 .(1)
Where the subscrpt refers to a tme t, suffcenty ong to estabsh equbrum at the gven
temperature. The nta concentraton of speces A s |A|0, and that of B s |B|0. After a tme t, et
the concentraton of speces A be |A|t and that of B be |B|t. The tota rate of change of |A|t s gven
by
d|A|t = k1|A|t
If, as s usua, |B|0 s ntay zero, t foows from a mass baance that at any tme t, |B|t = |A|0 |A|t,
whence
d|A|t/dt = k1|A|t + k1 (|A|0 |A|t)
-4#-
SIIT CHEMISTRY Sri
Vyshnavi
or d|A|t/dt = (k1 + k1)
1
t #
1 1
k
[A] [A]
k k

+
,
.(2)
Now, from (1) we have |B|
/|A|
= (|A|0 |A|
)/|A|
= k1/k1 or |A|
= |A|0k1/(k1 + k1) Introducng

ths resut nto (2), we obtan
D|A|t/dt = (k1 + k1) (|A|t |A|
)
Integratng
In (|A|t |A|
) = (k1 + k1)t + f
For t = 0, f = In (|A|0 |A|
); hence,
[ ] [ ]
t
#
A A
(
[A] [A]
,
= (k1 + k1)t
1. For the reacton
,
b
k
k
A C
` ` `
` `` (havng both 1
st
order reactons), the concentraton as a functon of
tme are gven for a certan expermenta run aong wth a tangent to the graph at the orgn.
The rato of the magntude of the sopes of the graph of |A| and |C| at the orgn woud be
5 1# 15 2#
1-#
#-"
#-4
#-2
#-4
Co(c-
)C*
Time )mi(-*
[A]
[C]
#
(a) 1 (b)
3
4
(c)
4
3
(d) None of these
2. At What tme s the rate of change of concentraton of A equa to rate of change of
concentraton of C n magntude?
(a) t = 0 ony (b) t tequbrum ony (c) t = 10 ony (d) at a tmes
3. What s the KC of the reacton
2C 2A
` `
` `
?
(a)
2
3
(b)
3
2
(c) 1 (d) None of these
Passa(e ) 3
;ea6 the follo>ing paragraph an6 ans>er the follo>ing %estions nm"ere6
The reacton
2 2
2 " 4 3
: O 3 2:O

+ + s of frst order both wth respect to the persuphate and
odde ons. Takng the nta concentraton as a and b respectvey and takng x as the
concentraton of the trodde at tme t a dfferenta rate equaton can be wrtten.
Two suggested mechansms for the reacton are
(I)
2 2
2 " 4 4
: O :O :O ),a.t*

+ +
` `
` `
(II)
1
k 2 3
2 " 2 "
: O : O ).lo0*

+
1
k 2
4 2 4
:O :O ).lo0*

+ +
2
k 3 2
2 " 4
: O 2 :O ),a.t*
+
+
2
k
2 3
),a.t*

+
3
k
2
),a.t*
+
+
4
k
2 3
),a.t*

+
1. The genera dfferenta equaton for the above reacton s
(a)
d3
dt
= k |a x| |b 3x| (k > 0) (b)
d3
dt
= k |a x| | b 3x| (k > 0)
(c)
d3
dt
= k |a x| |b x| (k > 0) (d)
d3
dt
= k |a x|
|b x| (k > 0)
2. How coud the progress of ths reacton be best montored?
(a) by montorng the coor of the reacton mxture (b) by ttraton of
3
wth
hypo
(c) by precptaton of I
wth Ag
+
(d) by montorng the change n pressure
3. Whch mechansm s consstent wth the facts gven about the reacton rate equaton?
(a) mechansm (I) (b) mechansm (II) (c) both (I) and (II) (d) nether (I) nor (II)
4. For the reacton
2 2
2 2 3 4 4
2: O : O 2

+ +
()
2
2 3 2
d[: O ] d[ ] 1
dt 2 dt
()
2
2 3 2
d[: O ] d[ ]
2
dt dt

()
2
2 3 2 2
d[: O ] d[ ] d[ ]
2
dt dt dt
(v)
2
2 4
d[: O ] 1 d[ ]
dt 2 dt

Correct opton s
(a) ony () (b) () & (v) (c) () & (v) (d) ony ()
5. Statement 4$5: In the reacton,
2 2
2 2 3 4 4
2: O : O 2

+ + , the rate of dsappearance
thosuphate ons s twce the rate of dsappearance of I2.
Statement 4B5: The rate of dsappearance of I2 s one haf the rate of dsappearance of S2O3
2
ons.
(a) Statement (A) & Statement (B) are true (b) Statement (A) s fase & Statement (B) s
true
(c) Statement (B) s fase & Statement (A) s true (d) Statement (A) & (B) are Fase
Passa(e ) 4
Arrhenus studed the effect of temperature on the rate of a reacton and postuated that rate
constant vares wth temperature exponentay as
a
= 1 RT
k Ae
. For most of the reactons, t was

found that t he temperature coeffcent of the reacton es between 2 to 3. The
method s generay used for fndng the actvaton energy of a reacton. Keepng temperature
constant, the effect of catayst on the actvaton energy has aso been studed by studyng how
much the rate of reacton changes n the presence of catayst. In most of the cases, t s observed
that catayst owers the actvaton energy barrer and ncreases the rate of reacton.
1. The pre-exponenta factor n the Arrhenus equaton of a second order reacton has the unts
(a) mo L
1
s
1
(b) L mo
1
s
1
(c) s
1
(d) dmensoness
2. Whch of the foowng pot w be near?
(a) In k versus T wth ve sope (b) k versus 1/T wth ve
sope
(c) In k versus 1/T wth ve sope (d) In k versus 1/T wth + ve sope
3. If the rate of reacton grows 15.6 tmes on ncreasng the temperature by 30 K the temperature
coeffcent of the reacton w be neary
(a) 2 (b) 2.5 (c) 3.0 (d) 3.5
4. If the rate of reacton doubes for 10 rse of temperature from 290 K to 300 K, the actvaton
energy of the reacton w be approxmatey
(a) 40 k| mo
1
(b) 50 k| mo
1
(c) 60 k| mo
1
(d) 70 k| mo
1
5. If x s the fracton of moecues havng energy greater than Ea, t w be gven by
-%-
SIIT CHEMISTRY Sri
Vyshnavi
(a)
a
=
3
RT
(b)
a
=
( 3
RT
(c)
a
= 1 RT
3 e (d) Any of these
*atc#in( +pe ,uestions
1. Match the foowng
Colmn I Colmn II
(a) Decomposton of H2O2 (p) 10t1/2
(b)
308K
298
t
k K
(q) 1
st
order
(c) Arrhenus equaton (r) Temperature coeffcent
(d) t99.9% (s)
a 2 2 1
1 1 2
E k T T
og
k 2.303R T T
_

,
(t) 2 to 3
(a) (a-q), (b-r,t), (c-s), (d-p) (b) (a-r), (b-s), (c-q), (d-p)
(c) (a-s), (b-r), (c-p), (d-q) (d) (a-q), (b-r), (c-p), (d-s)
2. Colmn I Colmn II
(a)
f
t
K t
K
+
(p) Photosenstzer
(b) Rato of number of moecues reactng (q) 1.016
n gven tme to number of quanta of ght
absorbed n same tme
(c) In photochemca dssocaton of H2 to H (r) Temperature coeffcent
atoms Hg s used as
(d) The ncrease n rate of reacton on rasng (s)
t/10
(S)
t/10
the temperature by 10C due to
coson frequency
(c) (a-s), (b-r), (c-p), (d-q) (d) (a-q), (b-r), (c-p), (d-s)
3. Colmn I Colmn II
(a) H2 + I2 2HI (p) Order of reacton = 1.5
(b) C6H5N2C + H2O C6H5OH + N2 + HC (q) Order of reacton = 3
(c) 2FeC3 + SnC2 SnC4 + 2FeC2 (r) Order of reacton = 1
(d) H2 + Br2 2HBr (s) Order of reacton = 2
(c) (a-s), (b-r), (c-p), (d-q) (d) (a-s), (b-r), (c-q), (d-p)
4. Colmn I Colmn II
(a) Rate of reacton (p) Order of reacton = 1.5
(b) Rate constant (q) Order of reacton = 3
(c) Order of reacton (r) Decreases wth ncrease n concentraton
(d) Moecuarty (s) Increases wth ncrease n temperature
(a) (a-q), (b-r,t), (c-s), (d-p) (b) (a-r, s), (b-s), (c-p,q), (d-q)
(c) (a-s), (b-r), (c-p), (d-q) (d) (a-s), (b-r), (c-q), (d-p)
Exercise . V

S"3ecti/e 0ype
1. The progress of the reacton wth tme s presented n the fgure. Determne
A nB
` `
` `
() the vaue of n
() the nta rate of conservaton of A.
C
o
(
c
-

C
o
l
1
l
# - 5
# - 3
1 3 5 6
0ime9-or
2. The foowng data are for the reacton A + B products:
Concn A (M) Concn B (M) Inta Rate (moe L
1
s
1
)
0.1 0.1 4.0 10
4
0.2 0.2 1.6 10
3
0.5 0.1 1.0 10
2
0.5 0.5 1.0 10
2
(a) What s the order wth respect to A and B for the reacton?
(b) Cacuate the rate constant.
(c) Determne the reacton rate when the concentratons of A and B are 0.2 M and 0.35 M,
respectvey.
3. At 100C gaseous reacton s observed to be a frst order reacton. One startng wth pure A,
at the end of 14 mnutes, the tota pressure was found to be 264 mm of Hg. After a ong tme
the tota pressure of the system was found to be 450 mm of hg. From the data cacuate;
() the nta pressure of A
() the pressure at the end of 14 mn.
() the rate constant of the reacton.
(v) the haf-fe perod of the reacton.
4. The sovoyss of cnnamy chorde can be studed spectrophotometrcay by observng the
decrease n absorbance of the absorpton maxmum at 260 nm. The foowng observatons
were made n ethanoc sodum hydroxde at 298 K.
Tme n mnutes 0 10 31 74
Absorbance at 260 nm4.41 0.38 0.34 0.18 0

What are the order and rate constant of ths reacton?
5. 1 g
226
Ra s paced n an evacuated tube whose voume s 5 c.c. Assumng that each Ra
nuceus yeds four He atoms whch are retaned n the tube, what w be the pressure at 27C
of He produced at the end of a year? t
for
226
Ra s 1590 years.
6. The gas phase decomposton of dmethy ether foows frst order knetcs:
-2-
SIIT CHEMISTRY Sri
Vyshnavi
The reacton s carred out n a constant voume contaner at 500C and has a haf fe of 14.5
mnutes. Intay ony dmethy ether s present at a pressure of 0.40 atmosphere. What s the
tota pressure of the system after 12 mnutes? Assume dea gas behavous.
7. The rate constant for the forward reacton s 1.2 10
3
mn
1
at 30C. The enthapes of
actvaton and reacton are 85.48 k| moe
1
and 107.1 k| mo
1
, respectvey. The rate
constant for the reverse reacton s 1.2 10
4
mn1 at 50C. what s ts vaue at 40C.
8. The tme requred for 10% competon of a frst order reacton at 298 K s equa to that
requred for ts 255 competon at 308 K. If the pre exponenta factor for the reacton s 3.56
10
9
s
1
, cacuate ts rate constant at 318 K and aso the energy of actvaton.
9. A sampe of urannte, a uranum contanng mnera, was found on anayss to contan 0.214 g
of Pb
206
for every gram of uranum. Assumng that the ead a resuted from the radoactve
dsntegraton of the uranum snce the geoogca formaton of the urannte and that a
sotopes of uranum other than
238
U can be negected, estmate the date when the mnera
was formed n the earths crust. The haf fe of
238
U s 4.5 10
9
y.
10. In nature a decay chan seres starts wth
90
Th
232
and fnay termnates at
82
Pb
208
. A thorum
ore sampe was found to contan 8 10
5
m of heum at STP and 5 10
7
g of Th
232
. Fnd
the age of the ore sampe assumng the source of heum to be ony due to the decay of Th
232
.
Aso assume compete retenton of heum wthn the ore. (Haf fe of Th
232
= 1.39 10
10
Y).
Exercise . VI

II0.CEE #ro"lems
$ S"3ecti/e #ro"lems
1. The gas phase decomposton of dmethy ether foows frst order knetcs
CH3 O CH3 (g) CH4 (g) + H2(g) + CO(g)
The reacton s carred out n a constant voume contaner at 500C and has a haf-fe of 14.5
mnutes. Intay ony dmethy ether s present at a pressure of 0.40 atmosphere. What s the
tota pressure of the system after 12 mnutes ? Assume dea gas behavour.
2. At 380C, the haf-fe perod for the frst order decomposton of H2O2 s 360 mn. The energy of
actvaton of the reacton s 200 k| mo
1
. Cacuate the tme requred for 75% decomposton at
450C.
3.

The rate constant for the frst order decomposton of a certan reacton s descrbed by the
equaton
og k (s
1
) = 14.34
4
1.25 10 K
T
() What s the energy of a actvaton of ths reacton?

() At what temp. w ts haf-fe perod be 256 mnutes ?
4. The tme requred for 10% competon of a frst order reacton at 298 K s equa to the requred
for ts 25% competon at 308 K. If the pre-exponenta factor for the reacton s 3.56 10
9
s
1
,
cacuate ts rate constant at 318 K and aso the energy of actvaton.
5. The rate constant of a reacton s 1.5 10
7
s
1
at 50C and 4.5 10
7
s
1
at 100C. Evauate the
Arrhenus parameters A and Ea.
6. For the reacton N2O5(g) = 2 NO2 (g) + 0.5 O2(g), cacuate the moe fracton of N2O5(g)
decomposed at a constant voume and temperature, f the nta pressure s 600 mm Hg and
the pressure at any tme s 960 mm Hg. Assume dea gas behavour.
7. The rate constant for an somersaton reacton. A B s 4.5 10
3
mn
1
. If the nta
concentraton of A s 1 M, cacuate the rate of reacton after 1 h.
8. A hydrogenaton reacton s carred out at 500 K. If the same reacton s carred out n the
presence of a catayst at the same rate, the temperature requred s 400 K. Cacuate the
actvaton energy of the reacton f the catayst owers the actvaton energy by 20 k| mo
1
.
9. For the reacton, A + B Products, the foowng nta rates were obtaned at varous gven
nta concentratons
S. !o. D$E DBE ;ate 4mol (
1
sec
1
5
1. 0.1 0.1 0.05
2. 0.2 0.1 0.10
3. 0.1 0.2 0.05
Wrte rate aw and fnd the rate constant of the above reacton.
10. At constant temperature and voume, X decomposes as
-4-
SIIT CHEMISTRY Sri
Vyshnavi
2X (g) 3Y(g) + 2 Z (g)
Px s the parta pressure of X.
2"ser/ati
on !o.
0ime 4in
mintes5
#x 4in mm of
-g5
1. 0 800
2. 100 400
3. 200 200
() What s the order of reacton wth respect to X ?
() Fnd the tme for 75% competon of the reacton.
() Fnd the tota pressure when pressure of X s 700 mm of Hg
$ns>ers
Exercise - .
rue!"alse
1. Fase 2. Fase 3. Fase 4. True 5. True
"ill in t#e $lan%s
1. frst order, two 2. zero order 3. acdc, frst 4. frst, second, thrd
5. 0.693
Assertion an& 'eason
1. (a) 2. (c) 3. (b) 4. (b) 5. (c)
Exercise - ..
/nl+ /ne /ption is correct
(e/el . I
1. (a) 2. (c) 3. (a) 4. (c) 5. (b)
6. (b) 7. (a) 8. (a) 9. (b) 10. (a)
11. (a) 12. (a) 13. (c) 14. (b) 15. (d)
16. (c) 17. (b) 18. (c) 19. (a) 20. (d)
(e/el . II
21. (a) 22. (c) 23. (a) 24. (4) 25. (a)
26. (b) 27. (a) 28. (c) 29. (c) 30. (a)
31. (b) 32. (a) 33. (c) 34. (b) 35. (d)
36. (d) 37. (b) 38. (b) 39. (d) 40. (a)
Exercise - ...
*ore #an /ne 0#oice 0orrect
1. (a, c) 2. (a, c) 3. (a, b, c) 4. (a, b, c) 5. (a, b)
6. (a, b, d) 7. (a, b, c, d) 8. (a, b) 9. (a, b) 10. (a,c)
11. (c, d) 12. (a, b) 13. (a, b, c, d) 14. (b, c) 15. (b, c)
16. (a, d) 17. (a, b, d) 18. (a,b,c) 19. (a,b,c) 20. (a,b)
Exercise ) .1
Passa(e ) 1
1. (a) 2. (b) 3. (a)
Sri Vyshnavi SIIT CHEMISTRY --
Passa(e ) 2
1. (a) 2. (f) 3. (f)
Passa(e ) 3
1. (a) 2. (b) 3. (b) 4. (b) 5. (a)
Passa(e ) 4
1. (b) 2. (c) 3. (a) 4. (b) 5. (b)
*atc#in( +pe ,uestions
1. (a ) 2. (c ) 3. (d ) 4. (b )
Exercise - 1
Su23ecti4e +pe
1. () 2, () 0.1 mo L
1
hr
1
2. (a) a = 2, b = 0, (b) 4 102 mo L1 sec1, (c) 1.6 10
3
mo L
1
sec
1
3. () 150 mm/Hg, () 93 mm/Hg () 3.415 10
2
mn
1
, (v) 20.3 mn
F. Frst order; 1.01 +10
4
sec
1
5. 37.96 10
3

). 0.7488 atm
'. 1.21 10
5
mn
1
*. 9.22 10
4
sec
1
, 18.33 Kca mo
1

&. 1.4 10
9
yrs.
1+. 4.89 10
9
yrs.
Exercise - 1.
..-5EE 6e4el Pro2lem
Section - A
1. 0.749 atm 2. 20.36 mn 3. () 239.34 k| mo
1
() 669 K
4. k = 9.3 10
4
s
1
5. () 22.01 k| mo
1
() 5.433 10
10
s
1
6. 0.4 7. 3.44 10
3
mo L
1
mn
1
8. 100 k| mo
1
9. 0.5 s
1
10. () 6.932 10
3
mn
1
() 200 mn. () 950 mm
2.1............................................................'ate o7 'eaction
........................................................................................1
2.10........................Se8uential /r 0onsecuti4e 'eaction
......................................................................................16
2.11...........E77ect o7 emperature on t#e 'eaction 'ate
9Arr#enius #eor+:.....................................................19
2.12........................................................................0atal+st
......................................................................................26
2.13................................................................'a&ioacti4it+
......................................................................................27
2.14.........................................................................Acti4it+
......................................................................................29
2.15..........................................................Speci7ic Acti4it+
......................................................................................29
2.2...................................................................*olecularit+
........................................................................................4
2.3......................................................./r&er o7 a 'eaction
........................................................................................5
2.4...............;i77erence $etween /r&er an& *olecularit+
........................................................................................7
2.5..................................<inetics o7 "irst /r&er 'eaction
........................................................................................7
2.6............................................=rap#ical 'epresentation
......................................................................................10
2.7.................................>al7-6i7e o7 a nt# or&er 'eaction
......................................................................................11
2.8..............................Examples /7 "irst)/r&er 'eaction
......................................................................................12
-!-
SIIT CHEMISTRY Sri
Vyshnavi
2.9.....0oncentrations 'eplace& $+ /t#er ,uantities .n
"irst-/r&er .nte(rate& 'ate 6aw................................12
Answers..........................................................................55
0#emical <inetics............................................................1
Example 1.......................................................................30
Exercise - .......................................................................39
Exercise - .......................................................................40
Exercise - .......................................................................44
Exercise - .1....................................................................47
Exercise - 1.....................................................................51
Exercise - 1.....................................................................54
Sri Vyshnavi SIIT CHEMISTRY -"-

05 Chemical Kinetics F

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Chemical Kinetics Sri Vyshnavi

does not appear n the

Ths s dfferenta rate equaton and can be soved by ntegraton.

used up per second when |CO

formed per second.

Sri Vyshnavi SIIT CHEMISTRY -11-

B + C. Let us assume that a the

At t = 0, the parta pressure of A s P

B+C. Let us assume a three are gases. We are

Cacuate the expresson of rate constant.

Cacuate the expresson of rate constant.

Cacuate the expresson of rate constant.

At tme t, the tota pressure of B and C w be

Sri Vyshnavi SIIT CHEMISTRY -1"-

Upon ntegratng wthn the mts, 0 to t,

= Summaton of enthapes of reactants

= Summaton of enthapes of products

= tan = tan (180 ) =

Sri Vyshnavi SIIT CHEMISTRY -23-

, for a snge soated nuceus N = 1,

. Therefore n ths present

taks about the overa change n the

products, f s found that the rate of reacton ncreases 4fod when

CH4 + CO, has rate constant of 1.8

3O2, s assgned the foowng mechansm.

A2B, f the concentraton of A s doubed and that of B s haved, then

(as k s same n both the cases).

When pressure of X s 700 mm,

(c) 10 2.303 2 og 3 (d) 10 2.303 3

Products, t s found that the order of A s 2 and of B s 3 n the

Product s gven by d|Product|/dt = K|A|

Products, on doubng the nta concentraton of B keepng that of a

products, nta conc. of A s 2M. After 10 mnutes reacton s 10%

2AB. Then order w.r.t. A2 and B are respectvey

2NOBr obeys foowng mechansm,

The rate constant of the decomposton of cycobutane s 2.48 10

3O2 proceeds as foows

B at dfferent tmes are gven beow

n gaseous phase, the equbrum constant at 60C

C wth the rate aw

2NO2 has the rate aw ; rate = K |NO|

Products, to be of second order, whch of the foowng are

s gven by the expresson

(b) og k vs. 1/T w be a straght ne wth ntercept on og k axs = 2.1 10

Y, the actvaton energy for the forward and the backward

= |A|0k1/(k1 + k1) Introducng

. For most of the reactons, t was

() What s the energy of a actvaton of ths reacton?

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