"manishkumarphysics.

in"
1
CHEMISTRY
iui4fa+ nnfa+t
saiai
-ninl-+i n tn t ~- + - + t l+ ~lil+i il- ti -i t i -ti ti -i t -i := l+= =ini -+ il- +i =+-
t := ~i (i=il-+ nnl-+i) n tn ~- + n l+ (+ i=il-+ ~lil+i l+--i - i = ti -i t -ii +i -+i -
= +i+ := i=il-+ ~lil+i +i iil- +- t t ll-il- + = -i: i( -il+ - --n =n n ~li+-n <-i-i i--
+i i =+ . := ~i +i ~l--n iin i=il-+ ~lil+i +i l+illi -ii - + + i n +i -i-i t
iui4fa+ fif+4i +i n / < :
l+=i i=il-+ ~lil+i +i n -=+ ~li+i+ ~ii -i<i +i =i < -i n l- :+i: =n n ti - in l- - +i
+t- t
n =
t
c
A
A
=
lSd.M
yhVj eksy /
= nin ni
1
=n
1
= nin =i ni
3
=n
1
~lil+i + n +i := +i = <lzi - l+i i-i t l+ ~--- t i-in+ = i l-+n
iui4fa+ fif+4i + n + s+i :
(+ ~lil+i R

P + ln(
iua n =
le; k dqy k x; fy;
ifjorZu dqy a lkUnzrk es
ai-+ifn+ n l+=i l-lz-- =n (-ii) ~lil+i +i n
R
-i+iln+
=
0 t
lim

A
A
t
c
=
dt
dc
=
dt
] R [ d
=
dt
] P [ d
=i < -i ~i =n + n ~ili- + +i =ti-i = -i+iln+ n ai- l+i i =+-i t
sifi+ n -i+iln+ n n t = 0 n +i il-i+ n +t- t [t = 0 cin -zi ii]
fif+4i sir ia int ffi-a sifa4i + fif+4i n + r4 u-ri
fif+4i N
2
+ 3H
2
2NH
3
N
2
+ ln( ~lil+i +i n =
dt
] N [ d
2

H
2
+ ln( ~lil+i +i n =
dt
] H [ d
2

NH
3
+ ln( ~lil+i +i n =
dt
] NH [ d
3
t n =ni- -ti t ~lil+i + n +i l--- +i = liili- l+i i-i t
~lil+i +i n =
dt
] N [ d
2

=
dt 3
] H [ d 1
2

=
dt
] NH [ d
2
1
3
aia ~lil+i + n +i ni- ==ni+iln-i l-ii + l-i +-i t . l+ l+=i ~lil+i n l< n <i. -i
~il< l+=i il- + n +i ni- l-- ti -i t
"manishkumarphysics.in"
2
CHEMISTRY
Example-1. lli-- =ni R +i =i<-i -i- <i n: t. RP ~lil+i + ln( lli-- =ni--in ~i=-
n +i ni-i +il( `
t/s 0 5 10 20 30
10
3
[R]/mol L
1
160 80 40 10 2.5
Sol. l< n( lli-- =ni--in tn =i < -i~i n ~ - ai- + =+- t ~i n ai- +- + ln( A[R] n At
+i iin < - t
1
3
1
L mol
10 ] R [

1
3
2
L mol
10 ] R [

s
t
2
s
t
1
1 1
3
av
s L mol
10 r

=
] t t [
10 ] R R [
1 2
3
1 2

160 80 5 0 16
80 40 10 5 8
40 10 20 10 3
10 2.5 30 20 0.75
iui4fa+ fif+4ii + n +i siifa +a in +i+
1. =i<-i 2. -ini- 3. ~li+i+i ~i -i<i +i + l-
4. -+ 5. ln- +i pH 6. nin +i i -i+ l-ii+
7. ll+i ~i +izi 8. <i 9. l -i ~i - -+i -i zi
in -i +i+ =ini-- =ii ~lil+i~i + n +i iil- +- t l+ ~- +i+ + z ~lil+i~i + ln( llzi
+i+ t
1. ui<ai +i sii tn < ~- i-i l-n + ~- =i i-- t l+ n ~li+i+ l+ =i-< -i + =ni- i-i ti -i t :=ln
=n + =ii ~lil+i l+ < i-i t +i l+ =i-< -i i-i t
2. aisia +i sii
3. fi+i+i i a-si<i +t s+fa +i sii
(a) fi+i+ +t ii fa+ ii
n =i ~-ii > < ~-ii > ai = ~-ii
~lil+i l+ < +i i-i +n
+i l+ =ni ni l-+i n = i lini ni l-+i +i - n-i n ~li+ iii ti - t
(b) fi+i+ +i iifa+ i+i : ~li+i+ + +ii +i ~i+i i-i t ~lil+i l+ < c-i t +i l+ a
-i zi+n c-i t
(c) fi+i+i +t iui4fa+ s+fa :
l< ~li+ -i - t -i ~lil+i < n-< ti ini
:= +i -i -i ~li+ ti ni -i ~lil+i < +n ti i ni
4. a-s+ +i sii
i-in+ -+ +i -l-il- =l+i -i +i +n + ~lil+i < +i ci-i t
+iin+ -+ l+ -l-i-i =l+i -i +i ci-i t -ii ~lil+i < +i ii-i t
5. fn4a +t pH +i sii
-<i ti Fe(CN)
6
4

+
) Tl (
3
[Fe(CN)
6
]
3
:= ~lil+i + ln( ~lil+i +i n + n ~-ni nin n ti ai- l+i i =+i t -iii nin n -ti
6. ir4 + siuai+ fii+ +i sii
nin +i i-i+ l-ii + : nin + i -i+ l-ii+ +i ni- i<i ti- ~lil+i +i n +n ~il-+
"manishkumarphysics.in"
3
CHEMISTRY
~lil+i~i +i iil- +-i t
7. ff+i i s+izi +i sii +izi i=il-+ ~lil+i~i + ln( ll+i +i ~iz+-i ti -i t
8. <i +i sii n -ii ~lil+i~i + ln( <i nt i i+ t
9. fuat4 i +t4 +ii +i sii : l< ~lil+i~i n i i ~i t -i l -i ~i - -+i -i zi n l-ii + i+
t
n fa4 {fif+4i + n +t fi+i+ +t ui<ai s faiai)
~lil+i + n +i <zi - ~li+i+ +i =i < -i + = <i n +- := n l-n +t- t := + n ii ln+ -i
-iil- l+i i =+-i t =ini-- n l-n +i <lzi - -ti l+i i =+-i t ~i (+ ti ~lil+i +i ~nn~nn
l-il-i n l+i i-i t -i :=+i ni- ~nn~nn ti -i t n l+- ~li+ = i n ~lil+i( zi z ~li+i+ = i-i
ti-i t -i tn =ini- n l-n i-- ti -i t . :- ~lil+i~i + ln( :
n (ui<ai)
+ifa
n =K (ui<ai)
+ifa
+fna n ut+i 4i n s<zia
ti K= n l--i + = llzi ~lil+i n = ~lil+i +i n =i-<-i :+i: t
K +i :+i: = (=i-<-i)
1 +i l
=n
1
aia l+=i <i ni ~lil+i + ln( K +i ni- l-- t-i t t +n -i l-i +-i t
fif+4i +t +ifa
ni-i l+ ~lil+i m
1
A + m
2
B -i<i
ii ln+ = tn ai- ti-i t l+
R [A]
P
[B]
q
ti p ; m
1
+ i i i -ti ii ti =+-i t q ; m
2
+ i i i -ti ii ti =+-i t
p ~li+i+ A+ =i -i ~lil+i +i +i l t ~i q ~li+i+ B+ =i -i ~lil+i +i +i l t . ~i + n ~lil+i +i
+il (p + q) t
aia ~lil+i +i +i l zi - i ii +. li--i + ~ +i n ti =+-i t ~i t l+=i (+ ~li+i+ + ln( +iin+ ti =+-i
t l+=i ii ~lil+i + ln( i ~lil+i +i +i l +iin+ -ti ti =+-i t
fuEu mnkgj.k ftuds fy, vfHkf;k dh dksfV ds fofHkUu eku gksrs gSA
vfHkf;k % osx fu;e dksfV
(i) 2N
2
O
5
(g) 4NO
2
(g) + O
2
(g) R = K [N
2
O
5
]
1
. 1
(ii) 5Br

(aq) + BrO
3

(aq) + 6H
+
(aq) 3Br
2
()+ 3H
2
O () R = K [Br

] [BrO
3

] [H
+
]
2
1 + 1 + 2 = 4
(iii) H
2
( i) H
2
(~iii ) R = K [H
2 (i)
]
3/2
3/2
(iv) NO
2
(g) + CO (g) NO (g) + CO
2
(g) R = K [NO
2
]
2
[CO] 2 + 0 = 2
(v) 2O
3
(g) 3O
2
(g) R = K [O
3
]
2
[O
2
]
1
2 1 = 1
(vi) H
2
+ Cl
2

v h
2 HCl R = K [H
2
]
0
[Cl
2
]
0
0 + 0 = 0
~lil+i (ii) (+n < n -ti ti -i t t = i -ti t l+ 12 ~i ~li+i+ + (+ =ii l+i n iin n . ~- := +i
+i ~lil+i~i +i ln ~lil+i +t- t ~i t ~lil+i =iiii ~lil+i~i + <i + +n n ti -i t =iiii
~lil+i~i + ln( ==ni+inil- l--i + +i i n = ~lil+i +i +i l +i ln ~lil+i~i + ln( ii ln+
= ai- l+i i =+-i t
"manishkumarphysics.in"
4
CHEMISTRY
Ex.2
C K 1
C K
dt
dC
2
1
+
=

=ni+i + ~-=i. l-lz-- ~lil+i +i n. =i-< -i l-i +-i t :

=i-<-i (C)
(a) ~li+ ---, (b) ~li+ +n
ti -i ~lil+i +i +i l ti ni
Sol. (a)
dt
dC
=
C K 1
C K
2
1
+
=
2
1
K
C
1
K
+
l< C ~li+ --- -i
C
1
+n tini. -i := -n ni- =+- t

2
1
K
K
dt
dC
=

= l--i +. ~- ~lil+i zi - +i l +i ti ni
(b) l< C ~li+ +n t -i 1 + K
2
C ~ K'

K
C K
dt
dC
1
'
=

=
|
.
|

\
|
' K
K
1
=i-<-i
~- ~lil+i in +i l +i ti ni
ui+fna n fa4
(a) zi -4 +i fa fif+4i
zi - +i l +i ~lil+i + ln(,
=ini- n l-n n = k [=i-<-i] = l--i+
l< ~li+i+ +i il-i+ =i-< -i C
0
-ii =n t =i-< -i C
t
ti -i
n = k =
' t '
C C
t 0

i kt = C
0
C
t
i C
t
= C
0
kt
[R]
0
R
l e;
l kUnzr k l h/khj s[ kk
d k <+y ku
K=
K +i :+i: = n +i :+i: = mol lit
1
sec
1
.
i ti- +i =n =
k
C
0
t
1/2
(~z ~i +in) C
t
=
2
C
0
, ~- kt
1/2
=
2
C
0
t
1/2
=
k 2
C
0
t
1/2
= C
0
zi-4 +ifa +t fif+4i + a<iri
=ini--i. n= +i ii- +i =-t ~i- zi- +il nl-+i +i ~-=i +-i t
2PH
3
(g)

Ni
2 P + 3 H
2
n = K [PH
3
]
2HI (g)

Au
H
2
+ I
2
2NH
3
(g)

Pt
N
2
+ 3H
2
H
2
+ Cl
2

hv
2 HCl n = R [H
2
] [Cl
2
]
(b) s i +i fa +t fif+4iy
(i) si +ifa +t fif+4i + fny
A

-i <
a 0 t = 0
ax ............ t = t
ni-il+
dt
dx
= =n t ~lil+i +i n
"manishkumarphysics.in"
5
CHEMISTRY

dt
dx
= k (ax)
1
i
x a
dx

= kdt.
tn +- t =
k
303 . 2
log
x a
a

k =
t
303 . 2
log
t
0
C
C
-rtnrt ui : kt = ln
x a
a

= ln
t
0
C
C
i ln
t
0
C
C
= Kt = ln
0
t
C
C
= Kt C
t
= C
0
e
kt
& i4+in(t
1/2
) k =
2 / 1
t
303 . 2
log
0
0
C
C 2
t
1/2
=
k
2 log 303 . 2
=
k
2 ln
=
k
0.693
si +ifa +t fif+4i + fny, &i4+in y+ fa4a ifzi r+
ii s<zia :
t =
k
303 . 2
log C
t
+
R
303 . 2
log C
0
si +ifa f& fif+4i :
atf4i f& + fny faa sf+sai +i as4in +a r+
lz ~lil+i n -
=n -=i (i +ini-i)
0 a
t = t (a + x)
dt
dx
= k (a + x) or
) x a (
dx
+
= kdt
=ni+ni- +-
log
e
(a + x) = kt + C
at t = 0 ; x = 0 C = log
e
a
kt = log
e
) x a (
a
+
=
t
303 . 2
log
10
|
|
.
|

\
|
+ ) x a (
a
a-si<a u4 :
t s a-si<a u4, x = a
"manishkumarphysics.in"
6
CHEMISTRY
a t =
K
693 . 0
si +ifa +t fif+4i + fny a<iri
1. (i~i:=i i- +i li-
= N (g)
A
N
2
(g) + C
6
H
14
(g)
2. N+nii (=i l-ni: +i p +nii (=il-ni: n l- -

HCl
3. H
2
O
2
H
2
O +
2
1
O
2
(g)
4. NH
4
NO
2
2H
2
O+ N
2
(g)
5. li(l+ l-
+
2
He
4
Ex.3 in +i l +i ~lil+i + ln(
50 . 0
75 . 0
t
t
+i ni-i +il(
Sol. k =
4 / 3
t
303 . 2
log
0
0
C
4
1
C
=
2 / 1
t
303 . 2
log
2
C
C
0
0

2 / 1
4 / 3
t
t
=
2 log
4 log
=
2 log
2 log 2
= 2
Ex.4. ~li+i+ A -i< +n = +n l+-- ~z~i + i< ~lil+i 95% i ti ini ? (log 2 = 0.3)
(A) 4 (B) 5 (C) 6 (D) 7
Sol. (B)
% 0
100
2 / 1
t

% 50
50
2 / 1
t

% 75
25
2 / 1
t

% 5 . 87
5 . 12
2 / 1
t

% 75 . 93
25 . 6
2 / 1
t

% 875 . 96
125 . 3
"manishkumarphysics.in"
7
CHEMISTRY
(c) fzat4 +ifa +t fif+4i
l,-i +i l +i ~lil+i <i +i +i ti-i t
A + A -i<i n A + B -i<i n
a a a b 0
(a x) (a x) a x b x

dt
dx
= k (ax)
2
< l-n

} }
=

kdt
) x a (
dx
x
0
2 dt
dx
= k (a x) (b x)

1
0
) x a ( t
1
|
|
.
|

\
|

= kt
}

x
0
) x b ( ) x a (
dx
=
}
t
0
kdt

) x a (
1

a
1
= kt or
t
C
1

0
C
1
= kt
(d) < si +i fa +t fif+4i
l< l+=i ~li+i+ +i ~ili+ n lni i -i (+ l,-i +i l (i --- +i l ) +i ~lil+i +i in +i l +i ~lil+i
n ll- - l+i i =+-i t := +i in +i l +i ~lil+i +i z<n in +i l +i ~lil+i +t- t
~lil+i A + B -i<i n [n = K [A]
1
[B]
1
k =
) b a ( t
303 . 2

log
) x b ( a
) x a ( b

l< B +i ~ili+ n lni i-i t b > > a.

k =
bt
303 . 2

log
a
) x a (
k =
bt
303 . 2
log
x a
a

b ~li+ ti- := l-i ni--

kb =
t
303 . 2
log
x a
a

k' =
t
303 . 2
log
x a
a

,
k' z<n in +i l +i ~lil+i + ln( n l-ii + t
< si +ifa +t fif+4i + a<iri
(a) n-- +i zi+i +i n ~i-
C
12
H
12
O
11
+ H
2
O C
6
H
12
O
6
+ C
6
H
12
O
6
=+i= ~ili+ n +i ++i
(b) (- +i n ~i-
CH
3
COOCH
3
+ H
2
O
+
H
CH
3
COOH+CH
3
OH
(~ili+)
Ex.5 lnii:n (=i +i ni ln- n n ~i- +i ~- =i ln ti: i +=i: + =ii ~- ni- +- (=il+
~-n l-+n-i t lli-- =n (- +i =i-<-i -i- <i n: t
t/min 0 30 60 90
c/M 0.8500 0.8004 0.7538 0.7096.
~lil+i + <i i- H
2
O +i =i-< -i nnin l-i (51.2 M) ti -i t ~- t z< n in +i l +i ~lil+i t := ~lil+i
+ ln( k +i ni- +i ti ni `
~lil+i +i n = K [CH
3
COOCH
3
] [H
2
O]
"manishkumarphysics.in"
8
CHEMISTRY
Sol. z<n in +i l +i ~lil+i + ln(. [H
2
O] = l-- t -i (- + -i n ~lil+i in +i l +i ti ni
-i +- ~i+i = i-- ti -i t
t c k{H
2
O] =
t
) c / c ( ln
0
min
1
0 0.8500
30 0.8004 2.004 10
3
60 0.7538 2.002 10
3
90 0.7096 2.005 10
3
t <lzi- ti-i t +i k [H
2
O] = l-- t ~i t 2.004 10
3
ln-
1
+ i t ~- t z<n in +il +i
~lil+i t ~ tn l--- + ,ii k +i ni- l-ii l- + =+- t
k [H
2
O] = 2.004 10
3
min
1
k [51.2 M] = 2.004 10
3
min
1
k = 3.914 10
5
M
1
min
1
:=+i :+i: l,-i +i l +i ~lil+i +i t
uiit : zi-4, si, fzat4 aii n
th
+ifa +t fif+4i A a-si< + fin+ii

zi-4 +ifa si +ifa fzat4 +ifa n

th
+ifa

~+ln- l-n
t
A
A
A
= k[A]
t
] A [
A
A

= k[A]
t
] A [
A
A

= k[A]
2
n
] A [ k
t
A
=
A
A

=ni+ln- < l-n [A]

t
= [A]
0
kt In [A]
t
= kt + In [A]
0
t
] A [
1
= kt +
0
] A [
1
kt ) 1 n (
) A (
1
) A (
1
1 n
0
1 n
t
=

li + [A]
t
-ii t [A] -ii t n
] A [
1
-ii t 1 n
t
) A (
1
-ii t
~i ~i t
1/2
=
k 2
] A [
0
t
1/2
=
k
693 . 0
t
1/2
=
0
] A [ k
1
1 n
0
2 / 1
) A (
1
t

([A]
0
l-i t ) ([A]
0
l-i -ti t ) ([A]
0
l-i t )
ffi-a +ifa4i +t iit4 anai
"manishkumarphysics.in"
9
CHEMISTRY
fif+4i +t +ifa fariii +t ffri4i
(a) s ifi+ n ffri
:= lli n (+ il-i+ n (+ ~li+i+ +i =i-< -i +i ll- - + ~- +i l-i i+ ai- l+i i-i t
r = k [A]
a
[B]
b
[C]
c
l< [B] = l--
[C] = l--
~- A+i <i lli-- il-i+ =i-< -i~i + ln(
1
0
r
= k [A
0
]
1
a

a
2 0
1 0
0
0
] A [
] A [
r
r
2
1
|
|
.
|

\
|
=
2
0
r
= k [A
0
]
2
a
~- a =
( )
( )
2 0 1 0
0 0
] A [ ] A [ log
r r log
2 1
(b) ui+fna n fa4 ffri
:= lli n nnl-+i ~i+ ( i nin+ ~i + ) +i i - +- + ,ii :-n = i == - +- =ni +ln- n l-n
+i =il- +-i t -== tn +il l-ii l- +- t := ni+ n ii -i =+- t
Ex.6 CCl
4
ln- n N
2
O
5
+ li - + n +i ~- 318 K -i l+i ni t ~i l--- liin i-- l+( n( t `
t/ln- 0 135 342 683 1693
c/M 2.08 1.91 1.67 1.35 0.57
~lil+i +i +i l ~i n l--i + +i ni-i +il( ~i ~z ~i +in +i ti ni `
Sol. t < i =+- t l+ ~i + zi - +i l + =ni+ln- n l-n +i =il- -ti +- t ~ tn in +i l +i ~lil+i
+i =ni+ln- +- +- t
k =
t
) c / c ( ln
0
t/ln- c/M k =
t
) c / c ( ln
0
min
1
0 2.08 6.32 10
4
135 1.91 6.30 10
4
339 1.68 6.32 10
4
683 1.35 6.32 10
4
1680 0.72 6.31 10
4
tn ( =i < i =+- t l+ k +i ni- =ii i ln+ liini + ln( l-- t ~i t k = 6.31 10
4
min
1
+ =ii in
+i l +i t
t
1/2
=
1 4
min 10 31 . 6
69 . 0

= 1.094 10
3
min
1
+l-+ = l< tn n c + i- (+ ~ii -i- t -i tn cin = k + =ii (+ =iii ii i-- +- t
(c) & i4 +t ffri :
t ii ni t l+ lli-- +i l +i ~lil+i + ln( ~z ~i ~lil+i + il-i+ n lli---i = l-i +-i t
n
th
+i l +i ~lil+i + ln( t
1/2
1 n
0
] R [
1

1 n
0
1 n '
0
'
2 / 1
2 / 1
) R (
) R (
t
t

=
"manishkumarphysics.in"
10
CHEMISTRY
Ex.7 -i:l + n = +i ti: i - = ~-- n t ii ni l+ 210 = + n ~lil+i 50% i ti n: t l+ lni +i
il-i+ <i 200 mm ii. (+ < = i n n 140 = + n ~lil+i ~iii i ti n: t l+ il-i+ <i 300 mm
ii. ~lil+i +i + n +i l +i ni-i +il( `
Sol. n
th
+i l +i ~lil+i + ln( (n = 1), t
1/2

1 n
0
c
1

140
210
=
1 n
200
300

|
.
|

\
|
n = 2
(d) iai si+i (Isolation) ffri :
t lli -- ~lil+i~i + ln( -i ni t l-n ~li+ = i n ~li+i+ ti - t := lli n (+i+i =i < -i +i zi +
=ii ~li+i+i +i =i < -i ~li+ ~ili+ n ni i-i t ~- l<
n = k [A]
a
[B]
b
[C]
c
= k
0
[A]
a
~ a + ni- +i ni-i tn ini llii = + ni i-i t ~i :=i +i b ~i c +i ii ni-i + ni i-i t
Ex.8 ~lil+i :
CH
3
COF + H
2
O CH
3
COOH+ HF
+i ~- l--- il-i+ ll-il-i n l+i i-i t :
sffifa I sffifa II
0
O H
2
c = 1.00 M
0
O H
2
c = 0.02 M
0
COF CH
3
c = 0.01 M
0
COF CH
3
c = 0.80 M
=i<-i +i =n + +n- + n <ii i-i t ~i -i- l<i ni t :
sffifa I sffifa II
t/min
COF CH
3
c / M t/min C
H
2
O
/M
0 0.01000 0 0.0200
10 0.00857 10 0.0176
20 0.00735 20 0.0156
40 0.00540 40 0.0122
~lil+i +i +i l ~i ~lil+i + ln( n l--i + ai- +il( `
Sol. ~- n = k
b
O H
a
COF CH
) c ( ) c (
2 3
ti tn ~i-i- +i i++i lli +- +- t,
0
COF CH
0
O H
3 2
c c >> (ll-il--I) n iln+ ll-il-i,
(ll-il--II) n
0
COF CH
0
O H
3 2
c c << tn n CH
3
COF + = <i n tn ~lil+i zi - +i l +i -ti t +i l+ ~lil+i +i
n =n + =ii ll- - ti -i t ~- tn
t/min
M / c
COF CH
3
1
b
O H
min
) c ( k
2

=
t
c
c
ln
COF CH
0
COF CH
3
3
|
|
.
|

\
|
0 0.01000
10 0.00857 0.0154
20 0.00735 0.0154
40 0.00540 0.0154
"manishkumarphysics.in"
11
CHEMISTRY
~-, k
) c (
O H
2
= 0.0154 min
1
tn ai- ti -i t l+ CH
3
COF + = <i n ~lil+i +i +i l in +i l +i t ~ tn n + = <i n ~lil+i +i +i l
ai- +- t . ~i < ii tn in +i l +i =ni+i nin +- t
t/min
M / c
O H
2
1
b
COF CH
min
) c ( k
3

=
t
c
c
ln
O H
0
O H
2
2
|
|
.
|

\
|
0 0.0200
10 0.0176 0.0128
20 0.0156 0.0124
40 0.0122 0.0124
~i=- = 0.0125 min
1
H
2
O+ ln( ~lil+i in +i l +i t ~i tn i-- ti -i t
) c ( k
COF CH
3
= 0.0125 min
1
~ ll-iil- I n, k =
00 . 1
min 0154 . 0
1
= 0.0154 M
1
min
1
~i ll-il- II n =
800 . 0
0125 . 0
= 0.0156 M
1
min
1
.
fif+4i +t nfa + isa +t ffri4i :
(a) nkc ekiu %
fu;r rki rFkk nkc ij feJ.k dk dqy vk;ru ekfir dj vFkok fuf'pr vk;ru rFkk rkieku ij dqy nkc dks ekfir
dj xSlh; vfHkf;kvksa dh xfr ns[kha tk ldrh gSA mu vfHkf;kvksa ds fy, ;g fof/k ykxw dh tk ldrh gS ftlesa
fd xSlks a dks mRikfnr fd;k tkrk gSA bl dkj.k ,d Bksl ;k nzo dk fo;kstu gks rk gSA ge nkc vFkok vk;ru dks ekfir
dj ,d fuf'pr le; ij f;kdkjd iztkfr dh lkanzrk ds ckjs esa dqN tkudkjh izkIr dj ldrs gSA
Ex.9 K +i P
0
, P
t
~i n + <i n +- +i
Sol. -<iti + ln( ni-i l+ t in +i l ~lil+i t
A(g) nB(g)
ni-i =n t il-i+ <i
P
0
0 t = 0
P
A
= (P
0
x) nx
P
t
(=n t +n <i) = P
0
x + nx = P
0
+ (n 1) x
x =
1 n
P P
0 t

P
A
= P
0

1 n
P P
0 t

=
1 n
P n P
t 0

a p
0
& a x P
A
=
1 n
P nP
t 0

k =
t
2.303
log
t 0
0
P nP
1) ( n P

{n = 1, n +i t ni- ii n ti =+-i t}
~--- ~--- =n z-i- +n <i = P
f
= nP
0
(b) vk;ru ekiu :
(i) - t -i< +i ~i-- ni- = ~lil+i l+ nl- <i-i
"manishkumarphysics.in"
12
CHEMISTRY
Ex.10 zi i -i t: n = +i ~i-- nil- + (+ ~lil+i +i nl- + ~- +i l- nl- l+i i-i t
NH
4
NO
2
(s)
A
2H
2
O() + N
2
(g)
Sol. ni-i +i =n t l--il- N
2
+i ~i-- V
t
t
V

= ~lil+i + ~-- l--i l- N

2
+i ~i-- t
a V

-ii x V
t
(a x) V

V
t
k =
t
303 . 2
log
t
V V
V

(ii) vuqekiu fof/k }kjk :

~- ni- ,ii l+=i =n zi i - ~li+i+ +i nizii ~ii -i( n( -i< +i nizii +i l-i- l+i i =+-i t
Ex.11 l--- ~i + t <lzi - +- t l+ ni ln- n ti: i - ~i+=i: +i li - (+ in +i l +i ~lil+i t
-i n l--i + +i ni- +i ti ni `
u4 faa 0 10 20 30 40
V i4aa ml 25.0 20.0 15.7 12.5 9.6
ti V i lzin n n- +i ml n ni- t i l+ ti: i - i +=i: + l-lz-- ~i-- = l+i +- + ln( ~iz+ t
Sol. in +i l +i ~lil+i + ln( =ni+i t
~li l- H
2
O
2
+ = n- +- l+( n( KMnO
4
+i ~i-- in +i l ~lil+i +i =ni+i + ln( =i- t ~-
KMnO
4
+i +- ~i--. zi - =n il-i+ =i-< -i l-i +-i t ~i t =n z-i- +- ~i-- :=i =n
(a x) l-i +-i t -i+- =ni+i n t ni- i- tn i-- ti-i t
t = 10 ln- k
1
=
10
303 . 2
log
0 . 20
25
= 0.022318 ln-
1
= 0.000372 =+
1
t = 20 ln- k
1
=
20
303 . 2
log
7 . 15
25
= 0.023265 ln-
1
= 0.000387 =+
1
t = 30 ln- k
1
=
30
303 . 2
log
5 . 12
25
= 0.023111 ln-
1
= 0.000385 =+
1
t = 40 ln- k
1
=
40
303 . 2
log
6 . 9
25
= 0.023932 ln-
1
= 0.0003983 =+
1
k l--i + ni ln- n H
2
O
2
+ li - +i <zii -i t i l+ in +i l +i ~lil+i t n l--i + +i ~i =- ni-
0.0003879 = +
1
t
Ex.12 N+ni i (=i-ini: +i p+ni i (=inini: n l--

HCl
-i +- ~lil+i in +i l +i ~lil+i t ~i := ~lil+i +i nl- +i ~ii ln-i ~- ni- ,ii < ii i-i t :=n
l-+n- ini ~ii i- +i ti:i + ni-+ ln- + =ii -i- = -+ +i +- + ~- nil- l+i i-i t := ~lil+i
n KI -i< (P+ni i (=i-ini:) = l+i -ti +-i t n l--i+ +i ti:i + +- ~i-- + =<i n t = 0 ,
V
0
~i =n t, V
t
ai- +il( `
Sol. ni-i l+, V
0
; t = 0 +- t( ti:i +i ~i-- t
:=ln( V
t
= ; t = t +- t( ti:i +i ~i-- t
a V
0
{KI +n ~li+i+ = l+i +-i t}
a x V
t
"manishkumarphysics.in"
13
CHEMISTRY
k =
t
2.303
log
t
0
V
V
Ex.13 (+ (- + ~-ni n ~i- +i ~- +-
CH
3
COOCH
3
+
H O
2
( ) v kf/kD; ) HCl (
H

+
CH
3
COOH+ CH
3
OH
:= ~lil+i +i nl- +i ~lil+i lni +i lli-- =ni--in ni-+ ln- NaOH+i l+-i+iini- = -+ +
=ii +- + ~- ni- + ,ii < ii i ai- l+i i =+-i t := ~lil+i + n l--i + + ni- + =-<i n NaOH
+ +- ~i-- i l+ t = V

~i =n t V
t
t
Sol. ni-i l+, t = 0 NaOH +i +- ~i-- V
0
[t HCl + ln( ~l-i t]
t = t NaOH+i +- V
t
t = NaOH +i +- V

a V

V
0
a x V

V
t
x V
t
V
0
a V

V
0
; k =
t
303 . 2
log
t
0
V V
V V

(c) izdk'kh; ?kw.kZu ekiu :

t lli - +- +i i-i t l< i=il-+ ~lil+i n +n = +n (+ +ilzi+ = =l+ il- ti
~li+i+ ~ii -i< n =l+ il- t
t ii ni t l+
) x a ( ) r r (
a ) r r (
t
0

(a = =i-<-i , x = i- nizii)
ti r
0
, r
t
, r

i+lzi+ ii-i +i +ii t ( =n t = 0, t = t -ii t = t

Ex.14 = +i + n ~i- +i ~- +- := ~lil+i +i nl- +i i inii +i =ti-i = nii i =+-i t +i l+
= +i +i ln- <l-iii- i i + ti -i t ~i n ~i- i-- n +i ~i ++i +i lni ini- i i + ti -i
t :=ln( := ~lil+i +i zi+ i +i -i- ii +t- t
C
12
H
22
O
11
+ H
2
O
+
H
C
6
H
12
O
6
+ C
6
H
12
O
6
~ili+ n+i= ++i
ii- +66.5 +52.7 92.4
i inii n iai + t
t = 0 , u
0
; t = t, u
t
-ii t = u

- :- iai+ + n n l--i+ k +i l-iil- +il(

Sol. := i n +i l=zi-- t l+ i i - n l- - zi+ i +i n ~il- nizii + =ni-i-i ti-i t
a u
0
u

; a x u
t
u

k =
t
303 . 2
log
|
|
.
|

\
|
u u
u u

t
0
fif+4i f+ nfa s ais +i sii
i-i n -i +i ii ~lil+i + n -ini- n ii + + n +- l+i i-i ii i l+ ~lil+i + n +i ~- i-
<i ~nn ~nn -ini- (=iiii-i -ini- 25C-ii 35Clni i-i t) + n liili- ii
T.C. =
t
t
K
10 K +
~ 2 to 3 ( ~li+-n ~lil+i~i n)
"manishkumarphysics.in"
14
CHEMISTRY
+ z ~lil+i~i n -ini- n ii + +i ni- (+ = +n ii i-i t
2NO + O
2
2NO
2
~lil+i +i n -i ci- i-i t
Ex.15 (+ ~lil+i + ln( -ini- n ii+ = 2 t := ~lil+i + ln(
C 25
C 40
k
k
+i ni-i +il(
Sol.
10
t
1
2
.) C . T (
k
k
A
=
8 ) 2 ( ) 2 (
2
3
10
15
= = =
-- := i n n -i n ii + +i ~- -ti l+i t :=ln( ~lil+i + n l-ii + -i +i ii (+
- l=zi-- + ,ii l<i i-i t
fif+4i nfa+t +i irfa4u fu&i-a
:= n += i- -ii llnn n l= - l+l=- l+i ii
t n =i + nl-+ l=zi-- ~iiil- t
~it l-= - ~lil+i +i nl- +i l=zi-- l-il<- l+i i l--- +i = t
i=il-+ ~lil+i ~li+i+ ~i ~i + ++ = ti -i t . ~lil+i lni + (+i + ~i-- n (+i + =n n
ti - ini ++i l+ = i +i ++ ~i l- (z) +t- t
v+ ++ i=il-+ l- - -ti < -i. i-- n -i< viii ++ = --i t viii ++ + ln
l---lnli- <i ~ii i ti - -ilt
ai iri
-i l+ t - --n nizii i ++ +- in ~i +i -ilt l== i=il-+ ~lil+i ti i < tni -i +t- t
-i +i t - --n nizii i ~li+i+ + ~i +i ~lil+i n iin n - + ln ~iz+ ti -i t =l+i -i (E
a
)
+tni-i t
fif-4iu iri
++ l+ viil--i +i + n -i = -ti ni- ~li+i+ ~i l-lz-- l<zii n ++ +- -ilt -ii viii ++
tini
l---lnli- l-zi ++ + ln l-lz-- l<zii + nt- +i ii +-i t
utrit a+
"manishkumarphysics.in"
15
CHEMISTRY
l+i+i+ ~i ~i + n ++ = ti i=il-+ ~lil+i =--- ti -i t -ii iii ++ + ln( (+ - --n
-i +i ~iz+-i ti -i t l= ~lil+i +i <tni -i +t- t
l+i+i+ ~i l-+i -i < tni -i + i i i<i ti-i t =l+ ~i +tni- t -ii l-+i -i
< tni -i = +n ti-i t ~l+ ~i +tni- t
(+ l< n -i ~l+ -ii ~l+ ~i ~i + n (+ nl-+ =i- -l-i- ti -i t ~l+ = =l+ ~i
+i i--i. -ni-i i ti -i t -ii -ini- c - = =l+ ~i ~i +i = i c ni -ii ~lil+i +i nl- ii c ni
~l+ ~i =l+ ~i, AH = +ve
=l+i -i +i ~liiiii (E
a
)
l+i+i+ ~i ~i + ln( ~iz+ ~l-l+- -i -il+ :-+ i- i-l+ ++ ,ii i +i li -
ti =+ := -i +i ti ~lil+i +i =l+i -i +t- t (t < tni -i = +n ti -i t ) := E
a
= +-
+- t ~-
E
a
= <tni -i i--l+ ~i=- -i
E
a
+i nizi+ l+ni + ni i nin
1
i l+ni n nin
1
.
~lil+i +i nl- + ln( ~itl-= l=zi-- +i ~iz+-i :=ln t +il+ l+i+i+ -ii -i< +
~lil+i + ti - + ln(. l+i+i+ ~i ~i n ~i i +i i +-i ti -i t i l+ t ++i ,ii ti -i t -i
~i i i E
a
+i l--- n i+ ,ii =nnii i =+-i t
mRi kn
f; kd kj d
EH
R
EH
P
Ea
1
Ea
2
nsgy ht kZ
A E E H = H H = Ea Ea
p R 1 2
, UFkSYi h(H)
v fHkf; k dhxfr
E
E
A
mRi kn d h, UFkSYi hd k ; ksx
v fHkf; k dsnkSj ku , UFkSYi hi fj or Zu
v xzv fHkf; k dhl f; . k t kZ
i ' p v fHkf; k d hl f; . k t kZ
H =
H =
H =
Ea =
Ea =
R
P
1
2
f; kdkj d d h, UFkSYi hd k ; ksx
- l< n( l-zi = t l-+i l-+n-i t l+ -ni-i i ~lil+i + ln( - --n =l+i -i zi - ti -i t l+ l+=i
-niziiii ~lil+i + ln( ---n =l+i -i AHti-i t
-i ~i i +i - -i: l--i i<i ti ni =l+i -i ii ---i i<i ti ni -ii l<( n( -i ~lil+i +i nl-
iini ti ni
"manishkumarphysics.in"
16
CHEMISTRY
l+=i ~lil+i +i nl- =++i +i ~i l-i + n iii ++i +i ~ zi ~i ~i +i nl- -i . E
a
+ i ~ii
i<i ti
++ ~i l-i. l- ~i-- l- :+i: =n n ++i +i = i ti -i t := 'Z' = +- +- t
'Z'
T
+ =ni- i-i ti -i t l- 10C-i lz = + n iii ++i +i = i -ii ~lil+i +i nl- c -i t (+
~lil+i + =i-i-ii l-ii + +i -i l-i-i i- ti+ + -ninl-+i =ni+i = l--- +i <i n: t
n += n l-i = t ii ni l+ ~i ~i +i li--i + -i< + l-ni i +i < tni -i +i - n-i = ~li+-n -i i-i t
T
2
> T
1
RT / E
a
e

E
a
= ~li+ nl- -i +- +- in ~i ~i +i li--i+
n
RT / E
a
e

k + -i l-i + +ii < -i l-i ti -i t

RT / E
RT / E
a
a
Ae K
e K

[~itl-= =ni+i]
A~i l-i+i+ t i =ti l-i= + =ii = i + -ii- +i +- +-i t A~i E
a
=ini-- -i l-i -ti +- t
E
a
= =+ni ~-ii -+ t-- + ln( ~i~i +i ++i + ln( ~iz+ - --n nl- -i
lnk = ln A
RT
E
a
E
a
> 0
T , K AA
a-+it4 fif+4i
k
f
= A
f
RT / E
af
e

k
b
= A
b
RT / E
ab
e

K
eq
=
b
f
K
K
=
RT / E
b
RT / E
f
ab
af
e A
e A

=
|
|
.
|

\
|
b
f
A
A
RT / ) E E (
ab af
e

ln K
eq
=
RT
H A
+ ln
|
|
.
|

\
|
b
f
A
A
"manishkumarphysics.in"
17
CHEMISTRY
-ini- T
1
n l--i+ = K
1
-ini- T
2
n l--i+ = K
2
lnK
1
= lnA
1
a
RT
E
lnK
2
= lnA
2
a
RT
E
ln
1
2
K
K
=
R
E
a
)
`

2 1
T
1
T
1
(i< +-i)
Ex.16 <i in +i l +i ~lil+i( i l-lz-- -ini i-i n =ni- n i-i t <i -i ~lil+i~i + -ini- =ni- nizii
,ii c - t -i -= ~lil+i +i n l-ii l- +il( i ~li+ nizii ,ii c -i t (~lil+i - --n E
a
i ~li+-n
E
a
+ =ii)
Sol. ln |
|
.
|

\
|
1
2
K
K
=
R
E
a
)
`

2 1
T
1
T
1
.....(i)
ln |
|
.
|

\
|
1
2
K
' K
=
R
' E
a
(

' T
1
T
1
2 1
.....(ii)
(i) (ii) =ni+i.
ln |
|
.
|

\
|
' K
K
2
2
=
R
T A
( E
a
E
a
,)
l< E
a
> E
a
, K
2
> K
2

i K = A
RT / E
a
e

dT
dk
=
RT
EaA
|
.
|

\
|
2
T
1
A
RT / E
a
e

n l--i+ + -i l-ii+
K
1
dT
dK
=
2
a
RT
E
T . K
K
A
A
= li--i+ l-- / :+i: -ini- lz
Ex.17 n l--i + + -i l-ii + + ~iii =nni:( l+ -nizii ii ~lil+i +i =i- -i c i- ~n l<zii n nl- +-i
t l+ -ni-i i ~lil+i +i =i- z- l<zii n nl- +-i t
ln
|
|
.
|

\
|
2
eq
1
eq
K
K
=
R
H A
)
`

2 1
T
1
T
1
"manishkumarphysics.in"
18
CHEMISTRY
Sol. AH = E
af
E
ab
> 0 -niziiii
E
af
> E
ab
-i lz K
f
|
K
b
|
+i - n-i n ~li+
E
af
> E
ab
~lil+i ~n l<zii n nl- + ni
a-s+ aii a-si
- + (+ ( =i <ii t i ~lil+i +i nl- +i l-i iin ln t ( c i-i t := ti - i +t- t + z ( = ii - +
t i ~lil+i +i nl- +i +n + < - t :-t +iin+ - + +t- t - + =ini- -ii (+ ir <ii t --
+ii (+ -i< (+ - + +i -t +i +-i t l= '- - +' +t- t -ii t - - i +tni-i t
KCIO
3
+i -ii li - MnO
2
+i -l-il- = l- ti -i t ~- MnO
2
- + +i +i +-i t
2KClO
3
+ [MnO
2
] 2KCl + 3O
2
|
+ [MnO
2
]
~lil+i + ~-- n MnO
2
=ni- i+ -ii <ni- n i-- ti i-i t
~i+ ln+ ~-n n n n- ~- ni- + i-i n n n- ln- +i n t-+i ti -i t -- + z =n i< n nti
ti i-i t ( =i MnSO
4
+ -- + +ii ti -i t i l+ ~lil+i + - + +i +i +-i t ~- MnSO
4
:= ~lil+i
(+ - - + t
2KMnO
4
+ 3H
2
SO
4
+ 5H
2
C
2
O
2
K
2
SO
4
+ 8H
2
O + 10CO
2
a-s+ + uii-4 niri
- + ~lil+i +i i-i- -ti +i-i t := +n :=+i -i + <-i t
- + +i (+ ~- nizii ~lil+i +i - l- +-i t
(+ - + =i-i-ii +i <n -ti =+-i ~ii - =i-i-ii l-ii + +i ni- ~i AG +i ni- t + n =i-i-ii
+i i-- +- n nn =n +i +n + < -i t ~ii - (+ -+nii ~lil+i n l< - + +i ~- l-il- n 75%-+
i ti-i t =i-i-ii i-- +- n 20 ln- nn- t -i -+ +i -l-il- n t =n 20 ln- = +n tini
(+ - + ~lil+i +i (+ < = i-- = =--- +i-i t ti -i ~i i (+ l----n - -i: +i ti -i t -ii E
a
+i
ni- +n ti i-i t t - + +i =l+i -i +i +n +- +i ni t
E
a
= -+ +i ~-l-il- n =l+i -i
E
a
= -+ +i -l-il- n =l+i -i
E
a
E
a
= -+ ,ii =l+i -i n +ni
Ea
E'a
H
R
H
P
mRi kn
f
L
F
k
h
f
r
t

t
k
Z
v fHkf; k d h i zxfr
(+ l< n( -i T l< k ~i k
- +
~lil+i +i nl- + l--i+ t
-ii E
a
~i E
a
=l+i -i +nzi -+ +i ~-l-il- ( -l-il- n t
RT / Ea
RT / a ' E
Ae
Ae
k
k

=
mRizsjd
=
RT / ) ' E E (
a a
Ae

~- E
a
E
a
i-in+ t (+ l< n( -i k
- +
> k ~- i-
k
k
mRizsjd
~lil+i +i nl- n l+--i n -i lz ti ni (+
-+ ,ii t -ii i-i t
"manishkumarphysics.in"
19
CHEMISTRY
T
1
-i ~lil+i +i nl- +i - + +i -l-il- n ~lil+i +i nl- + i +- t -i T
2
ti i-i t
2 a 1 a
RT / E RT / ' E
e e

=
i
2
a
1
a
T
E
T
' E
=
Ex.18 CO(g) + Cl
2
(g) COCl
2
(g) ~lil+i. (+ =ni- l+i+i+ =i-< i ~lil+i +i nl- 250C , 150C
. 1500 n -i ti i-i t ~lil+i +i =l+i -i ai- +i l< ~i l-i n ii + 2.0 10
10
M
1
sec
1
t -i ~lil+i
l--i+ 150C -i ai- +i
Sol. log
1
2
K
K
=
R 303 . 2
E
(

2 1
1 2
T T
T T
log 1500 =
423 523
100
2 303 . 2
E

E =
100
423 523 2 303 . 2 1761 . 3
= 32.36 kcal mol
1
log K = log A
RT 303 . 2
E
= log (2.0 10
10
)
423 2 303 . 2
32360

= 10.301 16.609 = 6.308
K = 4.92 10
7
litres mol
1
sec
1
Ex.19 (+ +il-+ (- +i ~i- in +il +i ~lil+i +i in- +-i t -ii :=+i n l--i+ l--- +i
+- ti-i t
ln k = 78.09
T
42075
ti k, min
1
n t ~- 227C -i 25% ~lil+i i ti - n nni =n ai- +i
Sol. ln k = 78.09
500
42075
= 6.06
log k =
303 . 2
06 . 6
= 2.63 ; k = 2.344 10
3
min
1
x = 0.25 ; k =
4 / 1
t
303 . 2
log
a 75 . 0
a
t
1/4
=
3
10 344 . 2
303 . 2

log 1.333 = 123.06 min

"manishkumarphysics.in"
20
CHEMISTRY
Ex.20 log k -ii
T
1
+ n n i+ +i cin (+ ~lil+i + ln( 5.4 10
3
ii ni (+ ~lil+i +i =l+i -i ai-
+i l< ~lil+i l--i+ 373 K -i 1.155 10
2
sec
1
t -i ~il- nii+ ai- +i
Sol. (a) cin =
R 303 . 2
E
= 5.4 10
3
E = 5.4 10
3
2.303 1.987 = 24.624 cal mol
1
(b) E = Ae
E/RT
; log 1.155 10
2
= log A
373 987 . 1 303 . 2
624 . 24

i A = 1.764 10
3
sec
1
if+ai aii +ifa
(+ ~i < n l+i +- in ~i ~i +i = i ~i ~lil+i +i ~il+-i +tni-i t + n ~i ~lil+i~i
+ ln( ~il+-i liili- ti-i t -ii =- i ~lil+i +i +- +- + ln( nin -ti ti -i t l=n l+ (+ =
~li+ ~i l+i( ti -i t l+=i ii ~i ~lil+i n -i- = ~li+ ~i -ti ti - . +i l+ -i- = ~li+ ~i ~i n
+i- +i =-ii-i t - +n ti -i t
l+=i ~i ~lil+i + ln( n l-n
aA + bB

-i< n = k[A]
a
[B]
b
, ti a + b = 1, 2 i 3.
l+=i ~i ~lil+i n n l-n +i +i l. l+i+i+ + n ii + + i ti -i t
l+ +il ln-i ~i ~lil+i~i + ln( liili- ti-i t -ii tnzii := iiln+ = ~lil+i +i
l+illi + iin < +i ti ~lil+i +i n l-ii + < +t- t l+=i lzi i ~lil+i + ln( t li--i +, ii + -ii
+iin+ ti-i t
fif+4i +t if+ai aii +ifa anai
"manishkumarphysics.in"
21
CHEMISTRY
fif+4i +t f+4iffri
~lil+i +i l+illi +i <i iini n ii ni t
aif-+ fif+4i
fan fif+4i
aif-+ fif+4i
t ~lil+i l-i n-i + - (+ < n i ti -i t
-il+ ~lil+i + ln ~il+-i ~lil+i n ~i ~i l+ = i + i ti -i t i =l+ = + n -i-i t . l=n ~i
l-lz-- -i -ii =ti l-i= + =ii ++ +-i t
t (+ vi+l-+ =i t
1 (+ ~il+. (+ ~i --l- ti -i t
2 l,~il+
3 lzi~il+
~il+-i < 3 +i l+ 4 ~ii 4 = ~li+ ~i ~i l+ =ti l-i= + =ii ++ l+ vil+-i t - +n ti -i t -il+
~lil+i n + n (+ < t i l+ n l-ii + < ti -i t . :=ln -il+ ~lil+i n +i l ~il+-i ti -i t
-il+ ~lil+i +i +i l ~li+i+ + =i -i = ~lil+i +i = =ni+ilnl- n ii +
H
2
+ I
2
2 HI =n ~lil+i
< = k [H
2
][I
2
]
2H
2
+ 2I
2
4 HI (-il+ -ti t )
i ~lil+i -il+ ~lil+i n l+=i = i +i nii ++ vi-- ti ni -=n -il+ v+ l- -ti ti ni
H
2
+ Cl
2
2HCl
+il = 0
fan fif+4i
~lil+i i <i = ~li+ <i n =--- ti -i t ~ii l+illi ti -i t (-il+ ~lil+i +i ~- +n l==
+i : ln ~lil+i =--- ti-i t )
ln ~lil+i n v + < l+ l+illi l+ ~-i ~il+-i ti ni n l+- liini ~lil+i l+ ~il+-i
liili- -ti ti ni
ln ~lil+i l+ +i l l+=i vil- + =i -i zi - vii -ii i = i + =ii -in+ ii ti =+-i t
~lil+i l+ +i l ~ii < l-n l+ ni-i ~lil+i l+ l+illi +i =ti-i = =i-ii-- l=n n l-ii +
< l< l<i t +i -in ++ +- t
< l-n =< ~li+i+ -i< ~ii -v+ +i =i-<-i + n lni- t. ni-i +i =i-<-i + n
+ii -ti lni-
"manishkumarphysics.in"
22
CHEMISTRY
ln ~lil+i l+ l+illi =< -il+ < + n lni- t . :=ln v + < l+ ~il+-i liili-
ti i ni n l+- liini ~lil+i +i ~il+-i +i +i : ~i -ti ti -i
~li+izi ~lil+i~i l+ l+illi l+ ni-i n - l--- lnli- =l--+-i + vi n = +i i ni
n fa4 +t niai
(A) f+4iffri fu R.D.S. f<4i n4i r+
(i) 4f< R.D.S. +n f+4i+i+, a-si< 4i fi+i+ +t a+ a-s+ uffna r+
R.D.S. +i n fa4 = fif+4i +i n fa4
Ex.21 ~lil+i + n l-n ~i +i l +i ni-i +il(
2NO
2
+ F
2
2NO
2
F l+illi +i =ti-i =
I NO
2
+ F
2

1
K
NO
2
F + F (iini)
II : NO
2
+ F

2
K
NO
2
F (-i)
R.D.S. + ~-=i
n = K
1
[NO
2
] [F
2
]
Ex.22 n l-n +i ni-i +il(
3ClO

ClO
3

+ 2Cl

2ClO

1
K
ClO
2

+ Cl

(iini)
ClO
2

+ ClO

2
K
ClO
3

+ Cl

(-i )
n = K
1
[ClO

]
2
(ii) R.D.S. fi+i+ +t a+ ir4f+ riai r+
+ifa +i aia +a + fny r f+4iffri f<4 n4 uia ui4 s< +t uri4ai u a-s+ ii f+4i+i+, a-si<
+t ui-<ai + s<i n fa4 {< fa4) +i -4a +a r+
Ex-23 2O
3
3O
2
O
3
k
1
k
2
O
2
+ O (-i =i- <)
(niln+)
O + O
3

3
k
2O
2
(iini)
R.D.S. =, < = k
3
[O
3
] [ O]
=i- < + ~-=i
K
eq.
=
2
1
k
k
=
] O [
] O ][ O [
3
2
[O] = (

] O [ k
] O [ k
2 2
3 1
< = k
3
[O
3
] [O] = k
3
[O
3
] (

] O [ k
] O [ k
2 2
3 1
"manishkumarphysics.in"
23
CHEMISTRY
< =
2
3 1
k
k k
] O [
] O [
2
2
3
Ex-24 H
+
+ HNO
2
+ C
6
H
5
NH
2

Br
C
6
H
5
N
2
+
+ 2H
2
O
(niln+)
H
+
+ HNO
2
k
1
k
2
H
2
NO
2
+
(-i) =i- <
(niln+)
H
2
NO
2
+
+ Br


3
k
NOBr + H
2
O (iini)
NOBr

+ C
6
H
5
NH
2
4
k
C
6
H
5
N
2
+
+ Br

+ H
2
O (-i )
Sol. r = k
3
[Br

] [H
2
NO
2
+
]
K
eq
=
2
1
k
k
=
] HNO ][ H [
] NO H [
2
2 2
+
+
[H
2
NO
2
+
] = (

2
1
k
k
[H
+
] [HNO
2
]
r =
2
3 1
k
k k
[H
+
] [HNO
2
] [Br

].
(B) f+4iffri fa RDSfa<fzia art r
sffaa ii uf-a+aai
il-i+. ~li+- ll-i-i n + n ~li+i+i +i lni i-i t ~- n-i + -i<- +i n :=+ -ii n + n
+i - n-i n ~li+ ti -i t n l+- + z =n z-i- n-i + -ii n +i n :=+ -i<- + n + i ti i-i
t := ~lil+i +i ~ll- - ~-ii = i-i i-i t ~-- n ~lil+i i ti - ini ti -i t -i -ii n +i n
:=+ -i<- + n = ~li+ ti i-i t n l+- ~li+- =n ~lil+i ~ll- - ~-ii n t-i t :=ln( ~ll- -
~-ii + <i i- ~lil+i + n l-n +i ~lil+i + ~l--n i + n n + n n =+- t
~ll- - ~-ii .
dt
] [ d ek/;fed
= 0
Ex-25 2O
3
3O
2
O
3
1
k
O
2
+ O
O
2
+ O

2
k
O
3
O
3
+ O

3
k
2O
2
"manishkumarphysics.in"
24
CHEMISTRY
Sol. < =
2
1
dt
] O [ d
3
=
3
1
dt
] O [ d
2
dt
] O [ d
3
= k
1
[O
3
] + k
2
[O
2
][O] k
3
[O
3
] [O]
dt
] O [ d
2
= k
1
[O
3
] k
2
[O
2
] [O] + k
3
[O
3
] [O]
~ll-- ~-ii .
dt
] O [ d
= 0
dt
] O [ d
= k
1
[O
3
] k
2
[O
2
] [O] k
3
[O
3
] [O] = 0
[O] =
] O [ k ] O [ k
] O [ k
3 3 2 2
3 1
+
dt
] O [ d
3
= k
1
[O
3
] +
{ }
] O [ k ] O [ k
] O [ k ] O [ k
3 3 2 2
3 1 2 2
+

] O [ k ] O [ k
] O [ k k
3 3 2 2
2
3 3 1
+
= k
1
[O
3
] +
] O [ k ] O [ k
] O [ k k ] O [ ] O [ k k
3 3 2 2
2
3 3 1 3 2 2 1
+
=
] O [ k ] O [ k
] O [ k k ] O ][ O [ k k ] O [ k k ] O ][ O [ k k
3 3 2 2
2
3 3 1 3 2 2 1
2
3 3 1 3 2 2 1
+
+
=
] O [ k ] O [ k
] O [ k k 2
3 3 2 2
2
3 3 1
+
(

] O [
dt
d
2
1
3 =
] O [ k ] O [ k
] O [ k k
3 3 2 2
2
3 3 1
+
< =
2
1
dt
d
[O
3
]
:=ln(, < (r) =
] O [ k ] O [ k
] O [ k k
3 3 2 2
2
3 3 1
+
l< 3
rd
< RDS t - k
1
>> k
3
k
2
>> k
3
r =
] O [ k ] O [ k
] O [ k k
3 3 2 2
2
3 3 1
+
Ex-26 H
+
+ HNO
2
+ C
6
H
5
NH
2

Br
C
6
H
5
N
2
+
+ 2H
2
O
H
+
+ HNO
2

1
k
H
2
NO
2
+
H
2
NO
2
+

2
k
H
+
+ HNO
2
HNO
2
+
+ Br

3
k
NOBr + H
2
O.
NOBr + C
6
H
5
NH
2

4
k
C
6
H
5
N
2
+
+ H
2
O + Br

"manishkumarphysics.in"
25
CHEMISTRY
Sol.
dt
] NO H [ d
2 2
+
= k
1
[H
+
][HNO
2
] k
2
[H
2
NO
2
+
] k
3
[H
2
NO
2
+
] [Br

] = 0
[H
2
NO
2
+
] = k
1
] Br [ k k
] HNO ]] H [

3 2
2
+
+
rate =
] NH H C [
dt
d
2 5 6 =
] HNO [
dt
d
2
] NH H C [
dt
d
2 5 6 = k
4
[ONBr ] [C
6
H
5
NH
2
]
dt
d
[NOBr ] = k
4
[C
6
H
5
NH
2
][NOBr ] + k
3
[Br

] [H
2
NO
2
+
] = 0
[NOBr] =
] NH H C [ k
] NO H ][ Br [ k
2 5 6 4
2 2

3
+
r =
] NH H C [ k
] NO H ][ Br [ k k
2 5 6 4
2 2

3 4
+
] NH H C [
2 5 6
r =
] Br [ k k
] HNO ][ H ][ Br [ k k

3 2
2

3 1
+
+
si +ifa fif+4i fanaiy
ui-a si +ifa fif+4i
t = 0 [A] = a [B] = [C] = 0
iii ni-i t
1/2
+ ln( [A], [B], [C] [B] / [C]
dt
] B [ d
= k
1
[A] ;
dt
] C [ d
= k
2
[A]
dt
] A [ d
=
dt
] B [ d
+
dt
] C [ d
dt
] A [ d
= (k
1
+ k
2
) [A] = k
eff
[A]
k
eff
= k
1
+ k
2
eff
T
2 n
=
1
T
2 n
+
2
T
2 n
(ti T ~z~i +- +-i t)
`
eff
T
1
=
1
T
1
+
2
T
1
(i< +-i)
~, [A]
t
= a
t k
eff
e

= a
t ) k k (
2 1
e
+
dt
] B [ d
= k
1
[A]
"manishkumarphysics.in"
26
CHEMISTRY
dt
] B [ d
= k
1
a
t ) k k (
2 1
e
+
[B] = |
|
.
|

\
|
+
2 1
1
k k
a k
(1
t ) k k (
2 1
e
+
)
:= +i [C] =
2 1
2
k k
a k
+
(1
t ) k k (
2 1
e
+
)
] C [
] B [
=
2
1
k
k
(i< +-i)
K
eff
= k
1
+ k
2
A
eff
.e
Ea/RT
= A
1
e
Ea
1
/RT
+ A
2
e
Ea
2
/RT
~+ln- +-
R
E
a

|
|
.
|

\
|
2
T
1
AA
efff
.e
Ea/RT
=
R
E
1
a

|
|
.
|

\
|
2
T
1
AA
1
e
Ea
1
/RTT
R
E
2
a

|
|
.
|

\
|
2
T
1
A
2
e
Ea
2
/RTT
2
RT
Ea
k
eff
=
2
1
RT
Ea
k
1
+
2
2
RT
Ea
k
2
E
a
k
eff
= E
a
1
k
1
+ E
a
2
k
2
2 1
2 a 1 a
a
k k
k E k E
E
2 1
+
+
=
a-+it4 si +ifa fif+4i {n sz <iai)
A B
t = 0 a 0
t = t a x x
t = t
eq.
a x
eq.
x
eq.
x
eq.
= -i< +i =i- =i-<-i
dt
] A [ d
=
dt
] B [ d
= 0 ( =i- =i-<-i ll-- -ti t)
dt
] A [ d
= k
f
[A] + k
b
[B]
dt
] B [ d
= k
b
[B] + k
f
[A]
dt
) x a ( d
= k
f
(a x) + k
b
x

dt
dx
= k
f
a + (k
f
+ k
b
)x
}

x
0
b f f
x ) k k ( a k
dx
= }
t
0
dt
b f
x
0 b f f
k k
] x ) k k ( a k [ n
+
+

= t
"manishkumarphysics.in"
27
CHEMISTRY

b f
k k
1
+
t
a k
] x ) k k ( a k
n
f
b f f
=
|
|
.
|

\
|
|
|
.
|

\
| +


b f
k k
1
+
n
|
|
.
|

\
|
+ ] x ) k k ( a k
a k
b f f
f
= t
x =
b f
f
k k
a k
+
( )
t ) k k (
b f
e 1
+
(i< +-i)
K
eq.
=
b
f
k
k
=
. eq
. eq
] A [
] B [
=
) x a (
x
. eq
. eq

f
b f
k
k k +
=
. eq
x
a
x = x
eq.
( )
t ) k k (
b f
e 1
+
(t , x x
eq.
)
k
f
+ k
b
=
t
1
n
|
|
.
|

\
|
x x
x
. eq
. eq
(i< +-i)
ti X
eq
= a (

+
b f
f
k k
k
X
eq
=
b f
f
k k
a k
+

.
l<
b
f
k
k
= 2
a
2 a/3
a/3
+f+ {fa-a) si +ifa fif+4i
A
1
k
B
2
k
C =ii in +i l =ni+i
t = 0 a 0 0
t a x y z
ni-i [A]
t
, [B]
t
~i [C]
t
A + ln(
dt
] A [ d
= r
1
= k
1
[A]
] A [
] A [ d
= k
1
dt
[A]
t
= [A]
0
t k
1
e

a x = a
t k
1
e

x = a(1
t k
1
e

)
B + ln(
r
2
= k
2
[B]
dt
dy
= k
1
ae
kt
k
2
y
dt
dy
+ k
2
y = k
1
ae
-kt
"manishkumarphysics.in"
28
CHEMISTRY
dy + k
2
ydt = k
1
ae
-kt
dt
t k
2
e
dy + k
2
y
t k
2
e
= dt e . ae k
t k t k
1
2 1

}
t
0
t k
2
) ye k ( d
2
= }

t
0
t ) k k (
1
dt ae k
1 2
k
2
y
t k
2
e
=
|
|
.
|

\
|

1 2
1
k k
a k
t ) k k (
1 2
e

+ y
t = 0 y = 0
y =
|
|
.
|

\
|

1 2
1
k k
a k
y =
1 2
1
k k
a k

{
t k
1
e

t k
2
e

} (i< +-i)
=n +i ni-i +il( l= B +i =i-<-i ~li+-n ti i
dt
dy
= 0
k
1
t k
1
e

+ k
2
t k
2
e

= 0
t k
2
e

=
t k
2
1
1
e
k
k

t k
1
e
=
t k
2
1
2
e
k
k
k
1
t = n
2
1
k
k
+ k
2
t
t
max.
=
( )
2 1
k k
1

n
2
1
k
k
(i< +-i)
[B]
max
= a
2 1
2
k k
k
1
2
k
k
(

= [A
0
]
2 1
2
k k
k
1
2
k
k
(

fifa-I : k
1
>> k
2
A
1
k
B
2
k
C
a
a x x
[A] = a
t k
1
e

(---n =i-<-i t)
[B] = a
t k
2
e

[C] = a (
t k
2
e 1

)
k
1
t >> k
2
t

k
1
> k
2
k
1
t << k
2
t
"manishkumarphysics.in"
29
CHEMISTRY

t k
1
e

<<
t k
2
e

y =
1
1
k
a k
(
t k
1
e

) = a
t k
2
e

= [B]
B + ln( t
1/2
iii ~z ~i t
fifa-II : k
2
>> k
1
[B]
t
0
[A] = a
t k
1
e

[C] = a (
t k
1
e 1

)
y =
2
1
k
k
a
t k
1
e

=
2
1
k
k
[A]
|
|
.
|

\
|
0
k
k
2
1
fifa-III : l< +ln+ =ni+i n, k
1
= k
2
= k
y = Ka e
Kt
z = a(1 e
Kt
) K at e
Kt
Ex.27 li =l+-i ~ii -
dt
dN
= N, + ln( =ni+i = i-i +- t + ni ~i =

1
+i -- +il( `
rn (i)
dt
dN
= N :=+i =ni+n- (N = N
0
, ~i =n t = 0 + =ii) +- N = N
0
e
t
i-- ti-i t
ni ~i =
(
(
(
(
(
(

}
}

=
0 t
0 t
dN
tdN
=
}
}

=
0 t
0 t
dt
dt
dN
dt
dt
dN
t
=
}
}

=


0 t
t
0
t
0 t
0
dt e ) N (
dt t e ) N (
=

1
. ni ~i =

1
Ex.28 in +i l +i ~- +nii ~lil+i A
1
k
B
2
k
C (-i<) +i ll-il- n B+i =i-< -i l--- ,ii <i i-i t
C
B
=
) k k (
C k
1 2
0
A 1

| |
t
k
t
k
2 1
e e


.
t = 0 ~li+i zi- C
A
= C
A
0
ni-i i-i t l+ C
B
= C
C
= 0 ni-i i-i t <zii +i C
B
+ ln( t = 0 ~li+-n
ni- t =
|
|
.
|

\
|

1 2
k k
303 . 2
log
|
|
.
|

\
|
1
2
k
k
t
"manishkumarphysics.in"
30
CHEMISTRY
rn
dt
dC
B
=
) k k (
C k
1 2
A 1

| |
t k
1
t k
2
1 2
e k e k


:=+i zi - + i +
t k
1
t k
2
1 2
e k e k

=

1
2
k
k
=
t ) k k (
1 2
e

n
|
|
.
|

\
|
1
2
k
k
= (k
2
k
1
) t t =
|
|
.
|

\
|

1 2
k k
303 . 2
log
|
|
.
|

\
|
1
2
k
k
"manishkumarphysics.in"
31
CHEMISTRY
"manishkumarphysics.in"
32
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
Example-1 l--- <i n: + ~lil+i + ln( [-i<] ~i [~li+i+] +i < l-- +i (+ <= + l- =ti = i
<lzi- +il(
(a) 2O
3
(g) 3O
2
(g) (b) 2HOF(g) 2HF(g) + O
2
(g)
Solution (a)
2
1
dt
] O [ d
3
= +
3
1
dt
] O [ d
2
(b)
2
1
dt
] HOF [ d
= +
2
1
dt
] HF [ d
= +
dt
] O [ d
2
dt
] O [ d
3

=
3
2
dt
d
[O
2
]
dt
] HOF [ d
= +
dt
] HF [ d
= +
dt
] O [ d 2
2
Example-2 t lli N
2
+ 3H
2
2NH
3
n ~lil+i +i n = 2 x 10
4
M.s
1
ai- l+i ni t l< ti +i : iz
~lil+i -ti t -i (a) N
2
, (b) H
2
+ = <i n ~lil+i +i n <lzi - +il( ?
Solution ~lil+i +i < Rate of Reaction = -
dt
] N [ d
2
=
3
1
dt
] H [ d
2
= +
2
1
dt
] NH [ d
3
(a) 2 10
4
=
dt
] N [ d
2
(b) 2 10
-4
3 =
dt
] H [ d
2
= 6 10
-4
MS
-1
.
Example-3 (i) zi - +i l ~lil+i, (ii) ~z +i l, (iii) in +i l, (iv) 3/2 +i l, (v) l,-i +i l, (vi) 5/2 +i l, (vii) - -i
+i l ~lil+i + ln( n l--i + +i nizi+ -i:
Solution < l--i+ +i :+i: = (Mole)
1-n
(Litre)
n-1
Sec
-1
ti n ~lil+i +i +il t
(i) zi- +il + ln( = Mole
(1-0)
(Litre)
(0-1)
Sec
-1
K +i :+i:
n = 0 Mole Litre
(-1)
Sec
-1
:=i -t <=i + ln(
Example-4 ~lil+i CO(g) + NO
2
(g) CO
2
+ NO n 500 K = +n -i NO
2
+ ln(. ~lil+i l,-i +i l +i
~i CO + ln( ~lil+i +i +i l zi - t
(a) ~lil+i + ln( < + lnii
(b) ~n NO
2
+i =i-< -i tn +i ~iii ti -i ~lil+i n n +i l- - ti ni `
Solution (a)
dt
d
[CO] =
dt
d
(NO
2
) = K [NO
2
]
2
~lil+i zi - +i l +i w.r.t. COti ni nl+- =i-<-i <n-i t ni
(b) ~lil+i +i < = K[NO
2
]
2
n NO
2
+i =i-<-i ~iii +- < (+ -i ii: ti ini
Example-5 ~lil+i A + 3B -i<, + ln( n = { d[A] / dt} = k [A]
2
[B] , B +i =i-<-i n l--.
B; { d[B] / dt} = ~lil+i + n +i <zi- <il(
(A) k[A]
2
[B] (B) k [A]
2
[3B] (C*) 3k [A
2
] [B] (D) (1/3) k [A
2
] [B]
Solution <i n: ~lil+i + ln(
dt
] A [ d
=
3
1
dt
] B [ d
= K[A]
2
[B] -
dt
] B [ d
= 3K[A]
2
[B].
Example-6 (+ in +i l +n n n=i =i:+nii-. =i:+niii:- n =nil+ ti i-i t :=+i 153
0
C
k = 3.3 x 10
4
s
1
t :=i -i 40% =nii+i i ti- n l+-- ln- +i =n nnni
Solution in +i l ~lil+i + ln(
t =
K
303 . 2
log
) x a (
a

t =
4
10 3 . 3
303 . 2

log
|
.
|

\
|
60
100
t = 1.54 10
+3
Second. = 25.80 Minute
"manishkumarphysics.in"
33
CHEMISTRY
Example-7 in +i l +i ~lil+i + ln(
25 . 0
5 . 0
t
t
+i ni-i +il(
Solution
25 . 0
5 . 0
t
t
=
)
4
a
a (
a
log
K
303 . 2
)
2
a
a (
a
log
K
303 . 2

=
)
3
4
(log
2 log
Example-8 ~lil+i A + B -i<i + ln( l--- ~i+ i-- l+( n( t
sifi+ n (in/nta u+) 0.030 0.059 0.060 0.090 0.089
[A] (eksy/yhVj) 0.10 0.20 0.20 0.30 0.30
[B] (eksy/yhVj) 0.20 0.20 0.30 0.30 0.50
:= ~lil+i + ln( n =ni+i lnli l< =ti t -i k ai- +il(
Solution < = K[A]
x
[B]
y
in ~i+ = 0.030 = K [0.10]
x
[0.20]
y
(1)
l,-i ~i+ = 0.059 = K [0.20]
x
[0.20]
y
(2)
lzi-i ~i+ = 0.060 = K [0.20]
x
[0.30]
y
(3)
<= =ni+i = tn =ni+i n iin <-
059 . 0
030 . 0
=
y x
y x
] 30 . 0 [ ] 20 . 0 [ K
] 20 . 0 [ ] 10 . 0 [ K
x = 1
-i= =ni+i = <= =ni+i n iin <-
060 . 0
059 . 0
=
y x
y x
] 30 . 0 [ ] 20 . 0 [ K
] 20 . 0 [ ] 20 . 0 [ K
y = 0
x -ii y + ni- (1) =ni+i n i-
0.030 = K[0.10]
1
[0.20]
0
K =
10 . 0
030 . 0
= 0.3 Sec
-1
Example-9 ni ln- n ~nil-n -i: + li- + ~i+ l--- t
Volume of N in cc.
2
Time (minutes)
6.25
9.00
11.40
13.65
35.05
10
15
20
25
infinity
~lil+i +i +i l ti ni
Solution NH
4
NO
2
(s) N
2
(q) + 2H
2
O(l)
ni-i =n 't' (+lzi- N
2
+i ~i-- Vt t
V= ~lil+i + ~-- n N
2
+i (+lzi- ~i--
a ov
(a - x) o V - Vt
- l< n ~i +i = tn ni- =+- t l+ ~lil+i in +i l +i ti ni
"manishkumarphysics.in"
34
CHEMISTRY
K =
t
303 . 2
log
) x a (
a

=
t
303 . 2
log
t
V V
V

I
st
~i +i = K =
10
303 . 2
log
) 25 . 6 05 . 35 (
05 . 35

= 1.96 10
2
sec
1
II
nd
~i +i = K =
15
303 . 2
log
) 9 05 . 35 (
05 . 35

= 1.96 10
2
sec
1
III
nd
~i +i = K =
20
303 . 2
log
) 40 . 11 05 . 35 (
05 . 35

= 1.96 10
2
sec
1
:- =--i = Kni- =ni- ~i-i t -i ~lil+i in +i l +i ti ni
Example-10 H
2
O
2
+i li-
H
2
O
2
H
2
O () +
2
1
O
2
(g)
:= ~lil+i +i nl- +i ~lil+i lni +i KMnO
4
+ =ii lli-- =ni--in ~- ni- + ,ii ai-
l+i i-i t ~lil+i + n l--i+ +i KMnO
4
+ +- ~i-- t = 0, n V
0
-ii t = t V
t
+ n
+- +il(
Solution ni-i l+ H
2
O
2
+i li - in +i l +i ~lil+i t
H
2
O
2
H
2
O(l) +
2
1
O
2
(g)
Kmno
4
+ n H
2
O
2
+ =ii l+i +-i t -
Ist +i l ~lil+i + ln( K =
t
303 . 2
log
) x a (
a

- ao V
o
-ii (a -x) o V
t
- K =
t
303 . 2
log
|
|
.
|

\
|
t
0
V
V
Example-11 A
D
B + C
l e;
0 t
vfHkdkj d dkvk; r u
V
1
V
2
V
3
k l-+iln l< ~li+i+ B, C -ii D = ~lil+i +-i t
Solution A
D
B + C
at t = o a o o
t = t (a - x) x x
t = o a a
t = 0 +n D l+i +-i t
t = 0 + i< ~li+i+ B.C.D. + =ii l+i +-i t
2a o (V
3
V
1
)
a o
2
) V V (
1 3

2x o (V
2
V
1
)
2(a x) o (V
3
V
1
V
2
+ V
1
)
(a x) o
2
) V V (
2 3

-. K =
t
1
ln
) V V (
) V V (
2 3
1 3

"manishkumarphysics.in"
35
CHEMISTRY
Example-12 A B + C
l e;
0 t
vfHkdkj d dkvk; r u
V
1
V
2
k l-+iln l< ~li+i+ A, B -ii C = ~lil+i +-i t
Solution A B + C
t = 0 a 0 0
t = t (a x) x x
ao V
1
(a x) + x + x o V
2
(a + x) o V
2
(a x) o (2V
1
V
2
) ; K =
t
1
ln
t
o
] A [
] A [
=
t
1
ln
) V V 2 (
V
2 1
1

Example-13 A B + C
l e;
T
vfHkdkj d dkvk; r u
V
2
V
3
k l-+iln l< ~lil+i+ A, B -ii C = l+i +-i t l=+i ~li+i+ + =ii n +i+ +i ~-i-
1 : 2 : 3 t
Solution A B + C
t = 0 a 0 0
t = t (ax) x x
t = o a a
~li+i+ A, B, C=ii + =ii l+i + ni -ii l+i n +i+ 1 : 2 : 3 + ~-i- n tini
2a + 3a o V
3
a o
5
V
3
(a-x) 1 + 2x + 3x V
2
(a + 4x) o V
2
5
V
3
+ 4x o V
2
x o
4
1
|
.
|

\
|

5
V
V
3
2
(a-x) o
5
V
3

4
1
|
.
|

\
|

5
V
V
3
2
(a-x) o
5
V
3

4
1
|
.
|

\
|

5
V
V
3
2 .
(a-x) o
20
) v v ( 5
2 3

K =
t
1
ln
) v v ( 5
V 4
2 3
3

Example-14 ni-i ~ A, B -ii C +izi =l+ i ln+ t i =n-n i l- +izi +i ini- ~ii <l-iii- i ni-i t
A(ln-) B(ln-) + C(ln-)
< l--i+ + + ai- +i
"manishkumarphysics.in"
36
CHEMISTRY
Solution in +i l=,i-- t t l+ i i- n l-- =i-< -i + =ii =ni- i-i ti-i t
a o (r
o
- r

)
(a - x) o (r
t
- r

)
- < l--i+ + ln( + l--- +i lnin
K =
t
303 . 2
log

r r
r r
t
o
Example-15 n-- +i zi+ i + n~i- + ~- +izii i n ini + -i n ,ii l+i i-i t . ~i l--- ia i +
ln n
=n (ln-) : 0 84 min
l-i- (i i -) : 50 20 10
(ln i)
lni +izii ~=l+ + tini (log 2 = 0.3, log 3 = 0.48)
Solution n ~i- =
K =
t
303 . 2
log
( )

r r
r r
t
o
=
84
303 . 2
log
10 20
10 50
+
+
K =
84
303 . 2
0.3010 = 8.252 10
3
-n-i +ilzi+ ~=l+ t - lni ni =n 't' t
K =
84
3010 . 303 . 2
=
t
303 . 2
log
10
10 50
+
+
t = 217.14 minute
Example-16 0.5 HCl n 35
0
C -i = +i= +i =n ~--in n i+lzi+ i i- l--- t =nni: l+ ~lil+i +i -=i
+i l +i ti ni
=n (ln- n) 0 10 20 30 4 0
i i - (+il) +32.4 +28.8 +25.5 +22.4 +19.6 11.1
Solution l< ~lil+i in +il +i t - in +il + n K +i ni- =ni- t ni
K =
t
303 . 2
log
( )

r r
r r
t
o
K =
10
303 . 2
log
1 . 11 8 . 28
1 . 11 4 . 32
+
+
=
10
303 . 2 03751 .
= 8.63 10
-3
K =
20
303 . 2
log
1 . 11 5 . 25
1 . 11 4 . 32
+
+
= 8.63 10
-3
K =
30
303 . 2
log
1 . 11 4 . 22
1 . 11 4 . 32
+
+
= 8.63 10
-3
K =
40
303 . 2
log
1 . 11 6 . 19
1 . 11 4 . 32
+
+
= 8.63 10
-3
~lil+i in +i l nl-+i <zii ni
Example-17 ~lil+i + n + ln( -ini- n ii + 3 t l< -ini- 30 K c i l<i i( -i ~lil+i +i n l+-- n -i
c ini`
(A) 3 (B) 9 (C) 27 (D) 81
Solution (C) =ni- =i-< -i + ln(
= = =
10
30
1
2
1
2
3
K
K
R
R
27.
Example-18 ~lil+i A + B -i<
A, B + =i -i in +i l +i ~lil+i t -ii ~lil+i l--i + 27C 6.0

ni n
1
= +
1
t 47C -i
il-i+ ~lil+i l--i + ai- +i l+ A-ii B + =ni- ~i-- l=n + +i =i-< -i 0.02 ni n
ni
1
t +i lnnii i-i t l<i t ~lil+i +i =l+i -i 42 kJ mol
1
t
"manishkumarphysics.in"
37
CHEMISTRY
Solution ~lil+i A + B -i<
tn i-- t log
|
|
.
|

\
|
1
2
K
K
=
R 303 . 2
E A
(

2 1
T
1
T
1
log
|
|
.
|

\
|
1
2
K
K
=
R 303 . 2
E A
(

2 1
1 2
T T
T T
log
|
.
|

\
|
6
K
2
=
320 300 3 . 8 303 . 2
] 300 320 [ 10 42
3


=
03 . 1835
840
log
6
K
2
= 0.4577
6
K
2
= anti log (0.4577)
K
2
= 2.863 6 = 17.178
47
o
C < tini
<
2
= 17.178 [0.01] [0.01]
<
2
= 17.178 10
-4
= 1.7178 10
3
Example-19 (+ n =i ~lil+i A -i<i . (+ in +i l + li - + ln( 400 K -i ~z ~i +in 150
ln- t -ii =l+i -i 65.0 kJ mole
1
, 400 K -i ~i +i ~ zi -i~i i -i< < - + ln( i --
-i i-i ti
Solution
A
K
= e
Ea/RT
= 3.13 10
-6
= ~i +i ii i-- -i t
Example-20 (+ -ni-i i ~lil+i A B +i =l+i -i A+ ln( 17 KJ l- ni n t ~lil+i +i -ni 40 KJ/
mole t z- ~lil+i B A+ ln( =l+i -i tini
(A) 75KJ l- nin (B) 67KJ l- nin (C) 57 KJ l- nin (D) 17 KJ l- nin
Solution (C) AH = E
A
E
B
40 = 17 E
B
E
B
= 57
Example-21 lnii:n -i:i: -ii :ii:n -i:i: + li- +i nl- ~lil+i l--i+ K
1
-ii K
2
+ n t <i-i
~lil+i~i +i =l+i -i ( +nzi 152.30 kJ mol
1
-ii 157.7 kJ mol
1
t . -ii ~i l-i n ii+ +nzi
10
13
, 10
14
t t -i ai- +i l= <i -i ~lil+i~i + ~lil+i l--i + =ni- ti
Solution < l--i+ =ni- tni
K
1
= K
2
A
1
e
RT
Ea
1

= AA
2
e
RT
Ea
2

T =
R
A
A
log 303 . 2
Ea Ea
1
2
1 2

|
|
.
|

\
|

T =
|
|
.
|

\
|

3
4
10
10
log 8 303 . 2
3 . 152 7 . 157
T = 282K
Example-22 l--- l-zi ,ii l--- z-i + --i <il(
(a) ~lil+i -ni-i i i -nizii ii t `
(b) ~n ~lil+i +i A E +i nnin ni- t `
v fHkf; k d hi zxfr
r
a=
k
d
h

t
k
Z
0
20
40
60
(c) + l<zii n =l+i -i +i tini `
(d) (+ -+. =l+i -i +i 10kJ/mol = +n + <-i t l+= -t
- + z- ~lil+i +i < +i iil- + ni `
"manishkumarphysics.in"
38
CHEMISTRY
Solution
(a) ~n ~lil+i -nizii ii ti ni
(b) AE = (Ea Ea
1
) = (50 30) = 20 KJ / Mole.
(c) Eaf = 50 KJ/Mole Eab = 30 KJ/Mole
(d) cni
Example-23 l+=i -i =i- +i =-t HI + li- + ln < l--i+ 1M.s
-1
t
2HI H
2
(g) +I
2
(g)
~lil+i +i +il +i tini` HI +i =i-<-i 2M = 5M ti- n l+--i =n nnni
Solution k +i :+i: = ~lil+i +i +i l zi - t l<i ni t +i ~lil+i +i +i 2A -i< tn lni =+-
t
k
0
=
nt
x
ti n = 2 or k
0
=
nt
) x a ( a
or .1 =
( )
t 2
5 . 0 2
t = 7.5 sec
Example-24 ~lil+i i-i ti - + i< (+ i- +i l ~lil+i +i < 10 ln- 0.05 ni n /L/s -ii 30 ln- 0.04
nin/L/s t ~lil+i + ~z ~i +in +i ni-i +i `
Solution ni-i ~lil+i +i =i-<-i 10 ln- -ii 30 ln- i< +nzi C
1
-ii C
2
t
10 ln- i< < = KC
1
= 0.05 60 and
30 ln- i< < = KC
2
= 0.04 60

2
1
c
c
=
4
5
.
ni-i ~lil+i 10 ln- i< i-i ti -i t
k =
20
303 . 2
log
2
1
c
c
=
20
303 . 2
log
4
5
= 0.011159 1159
t
1/2
=
k
6932 . 0
=
011159 .
6932 . 0
= 62.12 min.
Example-25 A+B -i<. i=l-+ ~lil+i + ln + A-ii B + =-<i n +i l 1 t l< n ~i+ = x -ii
y ai- +i
< (moles/L/s) [A] [B]
0.10 0.1 M 0.1M
0.80 x M 0.1M
0.40 0.2 M y M
Solution < l-n +i l--- +i lni =+- t
< = k [A] [B]
l< n in ~i+i +i < l-n n lni- i-- ti-i t
0.10 = k 0.1 0.1
k = 10
~ lz-i -ii - -i ~i+i +i < l-n n i- tn i-- ti-i t
0.8 = 10 x 0.1
x = 0.80 M
~i 4 = 10 0.2 y
y = 0.20 M.
"manishkumarphysics.in"
39
CHEMISTRY
Example-26 300 K H
2
O
2
+ li- n =l+i -i 16 kcal/ ni n i-- ti -i t l+ 300 K - + +i -l-il-
n li- ti -i t -i t =l+i -i i+ 10 kcal/ ni n t i-i t - + +i -l-il- n ~lil+i
l-i -+ +i -l-il- +i -n-i n l+--i -i = ti-i t
Solution ni-i l+ E
1
-ii E
2
+nzi =l+i -i t ~lil+i +i - + +i ~-l-il- -ii -l-il- n +-
t
-, k
1
=
RT / E
1
Ae

k
2
=
RT / E
2
Ae

n- , In k
1
= In A -
RT
E
1
In k
2
= In A
RT
E
2
In k
2
- In k
1
= -
RT
E
2
+
RT
E
1
or In
1
2
k
k
=
300 002 . 0
1

(16 10) =
300 002 . 0
6

2.303 log
1
2
k
k
= 10
log
1
2
k
k
=
303 . 2
10
= 4.342
(-inin n-
1
2
k
k
= 2.190 10
4
Example-27 l+=i l-lz-- ~lil+i + ln ~ltl-= =ni+i n A -ii E (=l+i -i) +i ni- +nzi
6 10
13
s
-1
-ii 98.6kJ mol
1
t l< ~lil+i +i +il in t - l+= -i :=+i ~z~i +in
20 ln- tini
Solution k = Ae
-E/RT
In k = In A
RT
E
2.303 log k = 2.303 log A
RT
E
~ii log k = log A
RT 303 . 2
E
. .....(1)
l<i t A = 6 10
13
s
-1
, E = 98.6 kJ mol
-1
2
1
t
= 20 60 s.
in +il ~lil+i + ln( k =
2
1
t
6932 . 0
=
1200
6932 . 0
s
-1
:=ln( (1) tini
log
1200
6932 . 0
= log (6 10
13
) -
T 10 314 . 8 303 . 2
6 . 98
3


[R = 8.314 10
-3
kJ/K/mol]
T = 302.26 K.
"manishkumarphysics.in"
40
CHEMISTRY
Example-28 N
2
O
5
+i li- l--- =ni+i + ~- =i in +i l +i ~lil+i t
2N
2
O
5
(g) 4NO
2
(g) +O
2
(g)
(+ < izi n li- + zi ti - + 30 ln- i< + n <i 284.5 mmHg ii i-i t -ii li- i ti -
+n <i 584.5 mm Hg t ~lil+i l+ ln < l--i+ ai- +i
Solution 2N
2
O
5
4NO
2
+ O
2
at t = 0 a
30 ln- i< a - x 2x x/2
(a - x) + 2x +
2
x
= 284.5
or a +
2
x 3
= 284.5 ....(1)
N
2
O
5
. + i li- + i<
2N
2
O
5
4NO
2
+ O
2
0 2a a/2
2a +
2
a
= 584.5
or
2
a 5
= 584.5 ....(2)
(1) ~i (2), = tn i-- ti -i t
a = 233.5, x = 34
l+ 2A -i< +i +i in +i l ~lil+i + ln
k =
t 2
1
log
x a
a

k =
30 2
303 . 2

log
34 5 . 233
5 . 233

= 2.625 10
-3
min
-1
Example-29 Fe
2+
+i = + n l+n ~li+i+ i:llln + =ii. ~n -ii z- <i -i l<zii~i +i ~- nl-+i =
l+i i-i t
Fe
2+
+ 3 dipy Fe(dipy)
3
2+
< (~n) = (1.80 10
13
) [Fe
2+
] [dipy]
3
-ii < (z-) = (1.20 10
-4
) [Fe(dipy)
3
2+
]
= +n + ln -iil l--i+ ai- +i
Solution nl-+ =i-
=+n + -- +i < = =+n + li- +i <
(1.8 10
13
) [Fe
2+
] [dipy]
3
= (1.20 10
-4
) [Fe(dipy)
3
2+
]
K
s
=
3 2
2
3
] dipy ][ Fe [
] ) dipy ( Fe [
+
+
. =
4
13
10 12
10 8 . 1

= 1.5 10
17
Example-30 25
o
C PtCI
4
2-
+ H
2
O Pt(H
2
O)CI
-
3
+ CI

-i +- =i- +i <i -i l<zii~i n nl-+i = l-i- l+i

i-i t t ii ni l+

dt
] PtCI [ d 4
2
= (4.8 10
-5
) [PtCI
2-
4
] - (2.4 10
-3
) [Pt(H
2
O)CI

3
] [CI

] tini
Pt(II) ,ii CI

=+n- + ln( =i- l--i+ +i ni-i +i

Solution =i- ,
dt
] PtCl [ d
2
4

= 0
~-, 4.8 10
-5
[PtCI
2-
4
] = 2.4 10
-3
[Pt(H
2
O)CI
-
3
] [CI
-
]
"manishkumarphysics.in"
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CHEMISTRY
i K =
] CI ][ Ci ) O H ( Pt [
] PtCl [
3
2
2
4

=
5
3
10 8 . 4
10 4 . 2

= 50.
=i- ,
dt
] PtCl [ d
2
4

= 0
~-, 4.8 10
-5
[PtCI
2-
4
] = 2.4 10
-3
[Pt(H
2
O)CI
-
3
] [CI
-
]
i K =
] CI ][ Ci ) O H ( Pt [
] PtCl [
3
2
2
4

=
5
3
10 8 . 4
10 4 . 2

= 50.
Example-31 600
o
C (+ +ni-+ l=n ~l+ n = t . n + z nizii n PH
3
(g) lnnii i-i t PH
3
+ li- = P
4
(g)
~i H
2
(g) - ti t . ~i ~lil+i i ti ti t =n + +n- + =ii + n <i -i- l<i ni t ~lil+i
+i < ai- +i ~i ~lil+i + ln < l--i + +i ni-i +i
Time (s) :
p mm (Hg)
0
262.40
60
272.90
120
275.51
276.40
4PH
3
P
4
+ 6H
2
Solution ni-i +i i-i n PH
3
-ii ~l+ n = +i ~i lzi+ <i +nzi p -ii pi mmt -ii PH
3
+i Pmmlli---
=n ~--ini lil- ti -i t
il-i+ ~i lzi+ <i P
4PH
3
P
4
+ 6H
2
lli-- =ni ~i lzi+ <i : p - p' p'/4 6p'/4
l<i ni t t = 60 =+
p + p' = 262.40 ...(1)
~i, p - p' +
4
' p
+
4
' p 6
+ p' = 272.90 ...(2)
t = :
4
p
+
4
p 6
+ p' = 276.40. ...(3)
=ni+i (1), (2) -ii (3), +i tn +-
p = 18.67 -ii p = 14.
:=i -t t = 120 =+
p - p' +
4
' p
+
4
' p 6
+ p' = 275.51. ...(4)
=ni+i (1), (4) -ii (3), = tn i-- ti-i t
p = 18.67 -ii p = 17.48.
nA -i< +i +i ~lil+i <i n: t ti n = 4, -i in +il nl- + ln =ni+i tini
k
1
=
t 4
303 . 2
log
x a
a

=
t 4
303 . 2
log
' p p
p

.
Thus, at t = 60s; k
1
=
60 4
303 . 2

log
14 67 . 18
67 . 18

= 5.8 10
-3
s
-1
t = 120 s ; k
1
=
120 4
303 . 2

log
48 . 17 67 . 18
67 . 18

= 5.8 10
-3
s
-1.