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"manishkumarphysics.

in"
1
CHEMISTRY
i4fa+ ui4
saiai
f4ia +t +ifa
(+ lni+ (n) n (+ - ~i +i ii ni i-i t . -i t -- ti ~i-i n li l- ti i-i t
t i -i ~i lzi+ = (o << < 1 ) i +ii +ii i -i (o ~ 1) li l- ti -i t
NaCl + aq Na
+
(aq) + Cl

(aq)
CH
3
COOH + aq CH
3
COO

(aq) + H
+
(aq)
(+ - ~i + li - +i nizii (o) - ~i + 1 ni n +i t ii t i l+ <i n: ll-il-i
li l- ti i-i t
o =
k dh la[; eksyksa s x; fy, a izkjEHk es
dh la[;k ftr eksyks ks fo;
o+i ni- l--- l-i +-i t
(a) ua sia4 +t s+fa n - ~i i - li l- ti i- t l+ < n - ~i ~i lzi+ = li l-
ti- t
(b) fni4+ +t s+fa t lni+. l=+ ln( --- i -i + -ii --- lni+- -i (n n ni -) t . li -
+ ~- + n tini
(c) aaai + z - ~ii + ln( -- -i ,ii li - +i nizii n lz ti -i t (~i-i- +i -- -i l-n)
(d) ais -ini- ci- =ini-- li - +i nizii c-i t
(e) -4 fn4 s<iii +t asfifa l+=i ~- <ii +i -l-il- < = ln <ii +i li - +i nizii iil- + =+-i
t =iiii- =n ~i- +i -l-il- n < n - ~i + li- +i nizii i-i t
iai +i aaai fa4 {<n ua sia4i + fny)
(+ <n -~i A
+
B

+i n n ii ni i-i t -ii o li - +i nizii ti -i


AB (aq) AA
+
(aq) + B

(aq)
ili+ =i-< -i C 0 0
=i- =i-<-i C(1 o) Co Co
"manishkumarphysics.in"
2
CHEMISTRY
-i <ni- l+i + l-n (=l+ <ni- +i l-n) + ~-=i.
K
eq
=
) 1 (
C
) 1 ( C
C . C
] AB [
] B ][ A [
2
o
o
=
o
o o
=
+
= <n - ~i +i li- l--i+
[C=
V
1
, -i V = 1/C (ln- +i t ~i-- l=n 1 nin -l-i- ti) ---i +tni-i t. :=ln( K
eq
=
V ) 1 (
2
o
o
]
o
lkUnzrk
1
(u<)
l< 1 +i -n-i n o -n t -i. 1 o ~

1. :=ln( K
eq
= o
2
C o =
c
K
eq
=
V . K
eq
== =i-<-i n lz ti-i t o n +ni ~i-i t
~--- ---i o +i ni- :=+ ~li+-n ni- :+i: (1) -+ t- i-i t
n, +ii aii ni
ifa4u n
<ii i l+ n n ln +- H
+
~i- <- t (H
+
- <i-i)
eg. HNO
3
, HClO
4
, HCl, HI, HBr, H
2
SO
4
, H
3
PO
4
:il<
ni + s+i
H
3
BO
3
~i l-= ~-n -ti t
H
+
~i- n n ~li+ nil- ti - t (H
3
O
+
, H
5
O
2
+
, H
7
O
3
+
+ n ) -ii --- ~izi i- i- t
ai = HClO
4
+i = --i +i ~- X-l+ii = +- ii ni l+ t H
3
O
+
~i ClO
4

= lnn+ -i ti -i
t
HClO
4
+ H
2
O H
3
O
+
+ ClO
4
(=ti <zi-)
ifa4u +ii : +i: <ii i n n OH (ti:il+=n) ~i- < -i t (OH - <i-i)
+iii + s+i
OH

~i- ii :-+ ni H
3
O
2
, H
7
O
4
, H
5
O
3
n t-i t
in n + - (Li + ~l-l+-) n -ii -i- t
"manishkumarphysics.in"
3
CHEMISTRY
siaiat u+sai/i-anit u+sai {u4t n+ii u+sai)
n t <ii . i l+ i i - (H
+
) <i- +- t . i -- ~-n ti - t
+ii t <ii . i l+ i i - (H
+
) n ti +- t . i -- -ii ti - t
u4t n+ii 4
(+ il+ ~-n -ii ~lil+i n
HX + B X

+ HB
+
~n ~lil+i ti HX i i - < - ini t . ~- ~-n t
B i i - n - ini t. ~- -ii t
z- ~lil+i ti HB
+
ii - <- ini t ~- ~-n t
X

i i - n - ini -ii t ~- -ii t


n +ii u4t u4t
n +ii
HCl + H
2
O H
3
O
+
+ Cl
HSO
4

+ NH
3
NH
4
+
+ SO
4
2
[Fe(H
2
O)
6
]
3+
+ H
2
O H
3
O
+
+ [Fe(H
2
O)
5
(OH)]
2+
=ni ~-n - -ii n n +n (+ ii - +i ~-- ti-i t
n ~-n +i = ni -ii < n ti ni. :=+i li- ii =ti t
~lil+i =< n ~-n = < n ~-n +i ~i (l<zii n ) ti -i t ~ii n -ii = < n -ii +i ~i (l<zii
n ) ti -i t
a<iri n u4t +ii +ii u4t n
HCl Cl NH
3
NH
4
+
H
2
SO
4
HSO
4
H
2
O H
3
O
+
HSO
4
SO
4
2
RNH
2
RNH
3
+
H
2
O OH
ai4rit (ai4sifa+) : t <ii . i l+ ~-n -ii -ii <i-i + =ni- ti +- t . -i i l- <ii +tni- t
HCl + H
2
O H
3
O
+
+ Cl
-ii
NH
3
+ H
2
O NH
4
+
+ OH
~-n
a<i1. ~ni l-n ~i- t
(A) (+ n:= ~-n (B) n:= -ii (C) i-= ~-n (D) i-= -ii
rn. =ti -- (C) t
"manishkumarphysics.in"
4
CHEMISTRY
nru u+sai {rnaifa+ u+sai)
(+ ~-n t ~i~i- t. i (+ :n+i- n nti + -=t=ii -i -i =+-i t
~-n :n+i- n niti
e.g. :n+ i- ---i i- in ~i (:n+i- -- iln+) : BF
3
, AlCl
3
i-i- : H
+
, Fe
2+
, Na
+
l+- +-i+ in ~i : SF
4
, PF
3
(+ -ii t ~i ~i- t i (+i+i :n +i- n <i- + =+-i t
-ii (+i+i :n+i- n <i-i
e.g. (+i+i n i- in ~i (lnn ) : NH
3
, PH
3
, H
2
O, CH
3
OH
a<i2 l--- n l+= ~lil+i n NH
3
~-n +i -t +i +-i t ?
(A) NH
3
(aq) + H
+
(aq) NH
4
+
(B) NH
3
(l) + Na (s) NaNH
2
(aq) +
2
1
H
2
(g)
(C) NH
3
(g) + HCI (g) NH
4
CI (s) (D) :-n = +i: -ti
rn. (B) := ~lil+i n NH
3
. NaNH
2
n <n-i t l=n NH
2

~i- t :=+i ~i t l+. NH


3
,Na +i (+ i i - <i- < -i
t := +i t ~-n + =ni- ti +-i t
a<i3. =-+ l-ln+ ~-n t
(A) ~il-= ~-n (B) n:= -ii (C) (A) (B) <i-i ti -ti (D) (A) ~i (B) <i-i ti
rn. (D) =-+l-ln+ ~-n t.
SO
3
H=n t. H
+
< - +i -in-i i-i t . ~- t ~i l-= ~-n + =ni- ti +-i t . l+ NH
2
=n t n -i: i -
(+ (+i+i :n + i- n i-i t ~- t :n+i- n <i- <- +i l- i-i t ~i :-t <i- ++ n: = -ii +
=ni- ti +-i t
n + ni
n +ii s+fa (ai4sifa+) ~i l-= -ii i -- ni i l=zi-- + ~- =i n. ~-n + =ii=ii -ii ii t
nl+- n := +i iiii + ~- =i := + n -ii + n lni i =+-i t
zi z n n [H
+
] = [OH

] :=ln( t -<i=i- t
in ui-<ai/n +t inai
n + nini +i =i l- ni = n +i nin =i-<-i =
eku nzO; dk vkf.od ty
eku dk nzO; d yhVj ty ,
nin-i = nini +i =i/ni =
xzke@yhVj
xzke@yhVj
18
1000
= 55.55 ninni = 55.55 M (i- = 1 gm/cc)
n +i i4fa+ nia+n ~i l-= = +--i + ~- =i
H
2
O H
+
+ OH

:=ln(. n +i ~il-+ ni-+n 25 K


w
= [H
+
][OH

] = 10
14
(inin+)
-ini- ci- K
w
c-i t (n +i li- -niziiii +n t. :=ln( -ini- ci- K
eq.
c-i t)
~ 25C n + ln(. pH = log[H
+
] = 7 -ii pOH = log [OH

] = 7 ( i nin+)
pH = 7 = pOH -<i=i-
pH < 7 i pOH > 7 ~-ni at 25C
pH > 7 i pOH< 7 -iii
n n + z ii ln l+i i(. n +i ~il-+ n i-+n =< l-- t-i t - l+ t (+ =i- l--i + t :=ln(
+ n -ini- l-i +-i t
"manishkumarphysics.in"
5
CHEMISTRY
n + f4ia +t iii
H
2
O H
+
+ OH

o =
dh la[;k eksyksa izkjfEHkd
dh la[;k ksa ksftr eksy fo;
=
% 10 x 8 . 1 or 10 x 18
55 . 55
10
7 10
7

=
n +i f4ia fa4ai+
H
2
O H
+
+OH

K
a
= K
b
=
] O H [
] OH ][ H [
2
+
=
16
7 7
10 8 . 1
55 . 55
10 10


=

:=ln( n +i pK
a
= n +i pK
b
= log (1.8 10
-16
) = 16 log 1.8 = 15.74
nt4ai aii pH siai
~-ni =in ~ii- n n ~-n +i H
+
~ii H
3
O
+
<- +i l-
~- H
+
~i- < - +i l--i i<i l- ti ni. <ii +i ~-ni =in -i ---i ti ~li+ ti ni
-iii =in-i ~ii- n n -ii +i OH

~i- <- +i l-
~- OH

~i- <- +i l- l--i i<i tini. -iii <ii +i =in-i ---i ti ~li+ tini
H
+
~i- +i =i-< -i +i =i -=- ,ii --il- (+ =iiii ni- = +- l+i i =+-i t . l= pH ni-i +t-
t pH+i H
+
~i- +i =l+-i + +iin+ ni n i+ + n liili- l+i i-i t
pH = log +
H
a
(ti +
H
a
, H
+
~i- +i =l+-i t)
H
+
~i- +i =l+-i -- ln- n n+- H
+
~i- ~ii H
3
O
+
~i- +i =i-<-i t
n +i lni+ n- t( 25C +-<i l-< 7 ni-- t( pH ni-i 0 = 14 -+ ~l+- l+i i-i t
l< -ini- -ii lni+ ll-- ti i- t. -i ni- +i pHi= <n i-i t -<iti + ln(
25C 0 14 -<i=i- l-<, pH = 7
80C (K
w
= 10
13
) 0 13 -<i=i- l-<, pH = 6.5
pH +iin+ ~ii > 14 ti =+-i t
ffi-a s+i + fn4ai + fny pH +t niai
( a) s n n fn4a
(i) l< =i-< -i 10
6
M= ~li+ t -i
:= ll-il- n n = l-+n t( H
+
~i- +i -n ni-i i =+-i t.
:=ln( [H
+
] = n ~-n ln- +i -inn-i
(ii) l< =i-<-i 10
6
M= +n ti -i.
:= ll-il- n n = l-+n H
+
~i- =i-<-i +i -n -ti ni-i i =+-i t
:=ln( [H
+
] = n ~-n +i -inn-i + := n ~-n +i -l-il- n n = l-+n H
+
~i-i +i =i-<-i
a<i4. 10
8
M, HCl ln- + pH +i ni-i +i
rn. H
2
O H
+
+ OH
10
8
+ x x
K
w
= [H
+
] [OH]
10
14
= x(x 10
8
)
x
2
+ x 10
8
10
14
= 0
x =
2
10 x 4 10 10
14 16 8
+
=
2
100
1
4 10 10
7 8
+ +

=
2
10 ) 1 401 (
8

= 0.95 x 10
7
[H
+
] = 10.5 x 10
8
= 1.05 x 10
7
M
pH = 7 log 1.05
~
6.98
for 10
9
M HCl pH
~
7
for 10
12
M HCl pH
~
7
"manishkumarphysics.in"
6
CHEMISTRY
( b) sn +ii fn4a
= in [OH

] l+ ni-i +- t i l+ n -ii ln- l+ -in n-i + i ti -i t -ii l+ [H


+
] +i ni-i +-
+ ln( K
w
= [H
+
] [OH

] = 10
14
+i +- +- t
<
a<i5. 10
7
M+ NaOH ln- +i pH+i ni-i +i
rn. NaOH = i-- [OH

] = 10
7
M
n = i-- [OH

] = x < 10
7
M (=n~i- ii + +ii)
H
2
O OH

+ H
+
(x + 10
7
) x
K
w
= [H
+
] [OH

] = 10
14
= x (x + 10
7
)
x
2
+ 10
7
x 10
14
= 0
x =
2
1 5
10
7
= 0.618 10
7
M = [H
+
] (
5
= 2.236)
pH = 7.21
( c) <i sn ni + fi +i pH
l< -inn-i N
1
+ (+ n ~-n ln- + ~i-- V
1
+i -ii -in n-i N
2
+ < = n ~-n ln- +
~i-- V
2
+i ~i= n lnl- l+i i-i t . -i
I-ln- = H
+
~i-i + lnni --i+ = N
1
V
1
II-ln- = H
+
~i- + lnni --i+ = N
2
V
2
l< ~l--n -inn-i Nt -ii ~l--n ~i-- V t -i
NV = N
1
V
1
+ N
2
V
2
:- ~-ni n = l+=i +i ii li - =i- l-i i -ti ti ni. +i l+ <i -i ~-n n ~-n t
[H
+
] = N =
2 1
2 2 1 1
V V
V N V N
+
+
( d) <i sn +ii + fi +i pH
-i+- ni-i + =ni-
[OH

] = N =
2 1
2 2 1 1
V V
V N V N
+
+
-ii [H
+
] =
] OH [
10
14
a<i6. (400ml ,
200
1
MH
2
SO
4
) + (400ml,
100
1
M HCl) +( 200 ml n) + lni + pH +i ni-i +i
rn. N
1
V
1
=
1000
4
1000
400
100
1
=
, N
2
V
2
=
1000
4
, n = i-- H
+
~i- -n tin
N
1
V
1
+ N
2
V
2
= 8 10
3
[H
+
] =
1
10 8
3

= 8 10
3
pH = 3 log 8 =2.1
a<i7. 10
5
M NaOH + 500 ml +i 2.5 x 10
5
M Ba(OH)
2
+ 500 mL + =ii lnnii i-i t i-- ln- n 99 ni.
n lnnii i-i t liini ln- +i pH +i ni-i +i
rn. [OH

]
1000
) 10 5 . 2 2 500 ( ) 10 500 (
5 5
+
= = 3 10
5
M
M
1
= 3 10
5
M
V
1
= 1 L ; V
2
= 100 L
i-i n [OH

] + nini +i =i = liini ln- n [OH

] + +n ni ni +i =i
3 10
5
= M
2
100
M
2
= 3 10
7
< 10
6
H
2
O H
+
+ OH

x (x + 3 10
7
)
"manishkumarphysics.in"
7
CHEMISTRY
K
w
= x (x + 3 10
7
) = 10
14
x =
|
|
.
|

\
|

2
3 13
10
7
M = [H
+
]
:=ln(, pH = 7 log 0.303 = 7.52
( e) y+ sn n aii y+ sn +ii + fi +i pH:
ti ~-n. -ii -<i=i-i+i ~lil+i ln- ti -i t liini ln- ~-ni t ~ii -iii t t :=
l-i +-i t l+ +i -=i ~ ~ili+ n lni ni t
l< -in n-i N
1
+ (+ n ~-n ln- + ~i-- V
1
+i -in n-i N
2
+ (+ n -ii ln- + V
2
~i--
+ =ii lnl- l+i i-i t . -i
I-ln- = H
+
~i-i + lnni --i+ = N
1
V
1
II-ln- = OH

~i-i + lnni --i+ = N


2
V
2
a<i8. (400ml,
200
1
MBa(OH)
2
) + (400ml,
50
1
MHCl) + ( 200ml n) + lni n pH +i ni-i +i
rn. [H
+
] =
1000
2
200
1
400
50
1
400 |
.
|

\
|
|
.
|

\
|

= 410
3
M, so pH = 3 2 log 2 = 2.4
( f ) <n n {iaisifa+) + fn4a +i pH:
< n ~-n 100%lil- -ti ti -i ~- tn ~-n + li - l-ii + K
a
+i -i n + li - + l-zi-
+i ni-i +-i -ilt(
:=+ ln( ~i-i- + ---i l-n +i +in n n - t
HA H
+
+ OH

t = 0 C 0 0
t = t
=i-
C(1o) Co Co K
a
=
] HA [
] OH [ ] H [
+
=
o
o
1
C
2
l< o < <1 (1 o ) ~ 1 K
a
~ Co
2
o =
C
K
a
(o < 0.1 ~ii 10%)
[H
+
] = Co = C
C
K
a
= C K
a
~- pH =
( ) C log pK
2
1
a

---i ci- C + o | -ii [H
+
] + pH |
a<i9. pH +i ni-i +i (a) 10
1
MCH
3
COOH (b) 10
3
M CH
3
COOH (c) 10
6
MCH
3
COOH
l<i ni t K
a
= 2 10
5
rn. (a) CH
3
COOH CH
3
COO

+ H
+
C 0 0
C(1o ) Co Co
"manishkumarphysics.in"
8
CHEMISTRY
K
a
=
o
o
1
C
2
o =
C
K
a
=
1
5
10
10 2

=
4
10 2

(o << 0.1)
~-, [H
+
] = 10
1

2
10
2
pH = 3
2
1
log 2 = 2.85 Ans.
(b) o =
C
K
a
=
3
5
10
10 2

=
2
10 2

(o > 0.1)
:=ln tn =ti ni-i +i -in +- t
K
a
=
o
o
1
C
2
210
5
=
o
o

1
10
2 3
o = 13.14%
[H
+
] = 10
3
0.1314 =1.314 10
4
pH = 4 log (1.314) ~ 3.8 Ans.
(c) l< ~-nil-- +i -in + -, o =
6
5
10
10 2

=
20
> 1,
:=ln =ti ni-i +i -in +- t, 210
5
= 10
6
o
o
1
2
o ~ 0.95 or 95%
[H
+
] = 0.95 10
6
= 9.5 10
7
pH = 7 log (9.5) = 6.022 Ans.
t- +n =i-<-i (~--- -- -i ) <n - ~i 100% li l- ti i- t :=ln n - ~i
+i -t ti +- t
(pH) of 10
6
M HCl
~
pH of 10
6
M CH
3
COOH
~
6)
( g) <n n {iaisifa+) aii sn n + fn4a + fi +i pH:
ln- n <n ~-n -ii n ~-n <i -i H
+
~i- <- t
in =l--+- + ln( < n ~-n ln- = l-+n H
+
~i- +i -n ni- =+- t -ii + n n ~-n
+i =i-< -i = ln- + pH +i l+ln- + =+- t
iii ni-i + ln( tn < n ~-n + li - =i- n ~-n +i -l-il- +i ii ni-- t
l< [SA] = C
1
-ii [WA] =C
2
, -i SA = [H
+
] = C
1
-ii WA = [H
+
] = C
2
ni-i HA (+ < n ~-n t . i l--- +i li l- ti-i t
HA H
+
+ A

t = 0 C
2
0 0
t = t
(eq)
C
2
(1o) C
2
o + C
1
C
2
o K
a
=
) 1 ( C
C ) C C (
2
2 1 2
o
o + o
( o<<<1 )
( n ~-n +i -l-il- + +ii < n ~-n +i li - ~in ~z ti i-i t ),
K
a
= (C
2
o + C
1
)o
H
+
+i +n =i-<-i = C
1
+ C
2
o
~-- n . l< ~-n = + n [H
+
] 10
6
M= ~li+ t . -i n + i n<i- +i -n ni-i i =+-i t . l< -ti
-i tn n = ~i- in ii [H
+
] n - -ilt(
( h) <i <n ni {iaisifa+) + fn4a + fi +i pH:
ni-i l+ HA
1
-ii HA
2
~-n t -ii --+i lni n =i-<-i +nzi C
1
-ii C
2
t. -i
HA
1
H
+
+ AA
1

HA
2
H
+
+ AA
2

t = 0 C
1
0 0 C
2
0 0
=i- C
1
(1 o
1
) C
1
o
1
+C
2
o
2
C
1
o
1
C
2
(1 o
2
) C
2
o
2
+C
1
o
1
C
2
o
2
K
a
1
=
) 1 ( C
) C C ( C
1 1
2 2 1 1 1
o
o + o o
K
a
2
=
) 1 ( C
C ) C C (
2 2
2 2 1 1 2 2
o
o o + o
(Since o
1
, o
2
both are small in comparision to unity)
K
a
1
= (C
1
o
1
+ C
2
o
2
)o
1
;

K
a
2
= (c
1
o
1
+ c
2
o
2
)o
2

2 a
1 a
K
K
=
2
1
o
o
"manishkumarphysics.in"
9
CHEMISTRY
[H
+
] = C
1
o
1
+ C
2
o
2
=
2 a 2 1 a 1
1 a 1
K C K C
K C
+
+
2 a 2 1 a 1
2 a 2
K C K C
K C
+
[H
+
]=
2 a 2 1 a 1
K C K C +
l< (+ ~-n + li - l--i + +i ni- < = ~-n + li - l--i + = t - ~li+ t -i l,-i ~-n =
in<i- +i -n ni-i i =+-i t :=ln( [H
+
] = C
1
o
1
+ C
2
o
2
~ C
1
o
1
a<i10. =ni- ~i-- n 0.02 M HOCl ~i 0.2 M CH
3
COOH ln- +i lnni+ - ln- + pH +i ni-i +i
l<i ni t K
a1
(HOCl) = 2 10
4
K
a2
(CH
3
COOH) = 2 10
5
=i- ln- n [OH

] , [OCl

], [CH
3
COO

] +i ii ni-i +i
rn. ~l--n ln- +i ~i-- <n-i tini
C
1
= 0.01 M, C
2
= 0.1 M
[H
+
] =
2 2 a 1 1 a
C K C K + =
1 . 0 10 2 01 . 0 10 2
5 4
+

=
6 6
10 2 10 2

+
= 2 10
3
M
pH = 3 log2 = 2.7
HOCl H
+
+ OCl

CH
3
COOH H
+
+ CH
3
COO
C
1
(1 o
1
) C
1
o
1
+C
2
o
2
C
1
o
1
C
2
(1 o
2
) C
1
o
1
+C
2
o
2
C
2
o
2
o
1
=
3
4
10 2
10 2

= 0.1 o
2
=
3
5
10 2
10 2

= 0.01
[OCl

] = C
1
o
1
[CH
3
COO

] = C
2
o
2
= 0.01 10
1
= 0.1 10
2
= 1 10
3
M = 1 10
3
M
[OH

] =
] H [
K
w
+
=
3
14
10 2
10

= 5 10
12
M
( i ) rsifa+ <n n + fn4a +i pH:
l,il+ ~-n (+ t t i n n <i ii- <- +i -in-i i-i t
n n (+ < n l, i l+ ~-n (H
2
A) n - t l=+i =i-< -i c Mt l, i l+ ~-n + (+ ni ln- n l--- =i-
i-- ti-i t
4f<
o
1
= HA

+i -l-il- n H
2
A + ~i-- +i +il K
a1
= H
2
A +i in ~i-- l--i+
o
2
= H
2
A n -l-i- HA + ~i-- +i +il K
a2
= H
2
A +i l,-i ~i-- l--i+
I s< II s<
H
2
A HA + H
+
HA A
2
+ H
+
c(1 o
1
) co
1
(1 o
2
) (co
1
+ co
1
o
2
) co
1
(1 o
2
) co
1
o
2
(co
1
+ co
1
o
2
)
K
a1
=
] A H [
] HA [ ] H [
2
+
K
a2
=
] HA [
] A [ ] H [
2

+
K
a1
=
) 1 ( c
)] 1 ( c )[ c c (
1
2 1 2 1 1
o
o o o o + o
K
a2
=
) 1 ( c
) c c )( c c (
2 1
2 1 2 1 1
o o
o o o o + o
=
1
2 1 2 1
1
)] 1 ( )][ 1 ( c [
o
o o o + o
........(i) =
2
2 2 1
1
)] 1 ( c [
o
o o + o
..........(ii)
K
a1
, K
a2
c + ni- i-- t =ni. (i) ~i (ii) +i -in + o
1
~i o
2
+i ni-i +i i =+-i t
o
1
~i o
2
, [H
3
O
+
] +i ni-i l--- -t +i i =+-i t
[H
3
O
+
]
T
= co
1
+ co
1
o
2
~l--n, pH +i ni-i + ln
l< +n [H
3
O
+
] < 10
6
M, n + +ii H
3
O
+
+ in<i- +i i-i -ilt
"manishkumarphysics.in"
10
CHEMISTRY
[H
3
O
+
] > 10
6
M, - n + +ii H
3
O
+
, +i in<i- +i -ti i-i -ilt .
[H
3
O
+
] +i -in + ln- + pH +i ni-i +i i =+-i t
uf-a+aa
i:il+ ~-n + ln(
2
a
K
< <
1
a
K
-ii o
2
, o
1
= ii zii tini
1 o
2
~ 1 -ii 1 + o
2
~ 1
~- =ni+i (i) +i l--- -i+ n = =l-i-- l+i i =+-i t
1
a
K
=
1
1 1
1
C
o
o o
t + < n ni -i i l+ ~-n + + + =ni- t ~- i: i l+ ~-n + ln( (~ii t i l+ ~-n + ln()
[H
3
O
+
], in =i- l--i+ + = l+ln- l+i i-i t
a<i11. (+ ln- n l=n 0.1 M HCl ~i 0.1 M H
2
S t , [HS

], [S
2
], [Cl

] -ii pH +i ni-i +i
l<i ni t K
a1
(H
2
S) = 10
7
, K
a2
(H
2
S) = 10
14
, H
2
S -ii HS

+i li i- +i nizii +i ii ni-i +i
rn. HCl + H
2
S
0.1 M C = 0.1 M
pH = 1 (~li+- [H
+
] HCl = ~i- t )
H
2
S H
+
+ HS

C
1
C
1
C
1
o
1
0.1 + C
1
o
1
Co
1
K
a1
=
) 1 ( C
10 C
1 1
1
1 1
o
o

H
2
S + li i- +i nizii o
1
=
1
7
10
10

= 10
6
HS S
2
+ H
+
C
1
o
1
(1 o
2
) C
1
o
1
o
2
0.1
10
14
= 0.1 o
2
HS

+i lii- +i nizii = o
2
= 10
13
[S
2
] = Co
1
o
2
= 10
6
10
1
10
13
= 10
20
M
a<i12. =ni- nizii n 0.2 M H
2
S ~i 0.02 M (l=l+ ~-n + lnni- - ln- n [H
+
], [OH

], [CH
3
COO

]
[CH
3
COOH] [SH

], [S
2
], [H
2
S], -ii ln- +i pH +i ni-i +i
l<i t. K
a
(CH
3
COOH) = 2 10
5
K
a
(H
2
S) = 10
7
K
a
(H
2
S) = 10
14
rn. [H
+
] =
) 10 2 10 ( ) 10 10 (
5 2 7 1
+
=
7
10 x ) 2 1 . 0 (

+ =
21
10
4
M
pH = 4
2
1
log 21 = 3.34
[OH

] =
] H [
K
w
+
= 2.18 10
111
M
(=il+ ~-n + ln(. K
a
=
] COOH CH [
] COO CH [ ] H [
3
3
+
=
01 . 0
] COO CH [ 10 21
3
4

[CH
3
COO

] = 4.36 10
4
M
"manishkumarphysics.in"
11
CHEMISTRY
[CH
3
COOH] = 0.01 M
H
2
S + ln(, K
a1
=
] S H [
] HS [ ] H [
2
+
=
1 . 0
] HS [ 10 21
4

[HS

] = 2.18 10
5
M
HS

+ ln(, K
a2
=
] HS [
] S [ ] H [
2

+
=
5
2 4
10 18 . 2
] S [ 10 21


[S
2
] = 4.76 10
16
M
( j ) y+ rsifa+ <n n aii sn n + fi +i pH:
+ n n ~-n +i =i-<-i +i n - t( pHl+ln- l+i i =+-i t (in =l--+-)
iii l+n- + ln( < n t i l+ ~-n +i + n in li - l--i + n -i -ilt( (i l+ tn ~ii -+ lli--
ll-il- + ln( <lzi - +- ~i t )
a<i13. 10
1
M HCl -ii 10
3
M CH
3
COOH + ln- + pH +i ni-i +i l< [K
a
= 2 x 10
5
] t
Solution CH
3
COOH CH
3
COO

+ H
+
C(1 o) Co 10
1
+ Co
CH
3
COOH + +n li - + +ii H
+
~i- +i HCl = --il- +- t
2 10
5
=
C
10 C
1
o
o = 2 10
4
CH
3
COOH = [H
+
] = Co = 2 10
7
M
=ii < < n -ii + ln( pOH-ii --+ lni + l+n- + ln( +in n n - t (tn + n K
a
+i K
b
+ =ii
l-ii- +-i t )
( k) +zi <n n/sn +ii/n + uii <n n/<n +ii + fi +i pH:
:= +i + lni + ln( =ini-- <i -t +i ll-il-i ti-i t
(i) l< =ni- nizii (- -i +) n ~-n -ii -ii +i lnl- l+i i-i ti
(ii) l< ~nn~nn nizii (- -i +) n ~-n -ii -ii +i lnl- l+i i-i ti
in ll-il- ni n ~i- +i li-i +i -i-i t -ii l,-i ll-il- + ln- + -- +i -i-i t
ni nsiaa {a<iutat+i +i fsta)
ni + n n + +ii
=ni- nizii (- -i +) n ~-n -ii -ii lnni i- t -i tn n n + n ni +i ln- --i t -ii tn ni
+ ln- +i pH l+ln- +-i ti -i t
ni +i n + =ii lnnii i-i t . -i ai = ni tn ln ti -i t -ii i -i ~i-i n i-i t ( -+
l+ -i+ - - l+i ni ti ) ni + ~i-. n + =ii l+i + =+- t ~ii -ti ii + =+- t
n + =ii i-i- tn zii H
3
O
+
~i- -ii l< n + =ii +ii- +i ~lil+i ti -i OH

~i- < -i t ln-.


~-ni. -iii ~ii -<i=i- ti =+-i i l+ n ~i - +i nizii -ii H
3
O
+
-ii OH

+i nizii l-i +-i t


l< ni BA t -
BA(s)

BA(aq)

B
+
(aq) + AA

(aq)
A

(aq) + H
2
O(l) HA(aq) + OH

(aq) (+iil-+ n~i-)


B
+
(aq) + 2H
2
O(l) BOH (aq) + H
3
O
+
(aq) (i-il-+ n~i-)
"manishkumarphysics.in"
12
CHEMISTRY
wii4fa+ nsiaa
+ii- n + =ii ~lil+i ++ -ii + n +i +- t -ii n~i- +i l--- v+i <zii i i =+-i t
A

(aq) + H
2
O(l) HA (aq) + OH

(aq)
l< n +ii- +i n~i- +i nizii :=+ -iii =in l-i +-i t
(a) si nsiaa
+ii- i l+ OH

= ~li+ n -ii t -ii +ii- + =ni ~-n. H


2
O = <n ~-n t ni
nin n i-i n~i- <zii- t
-<iti + ln( H

+ H
2
O H
2
+ OH

; NH
2

+ H
2
O NH
3
+
2
1
H
2
(b) utfa iii a+ nsiaa
+ii- i OH

~i- = < n -ii t -ii --+ = ni ~-n i l+ H


2
O= n ~-n t n l+- H
3
O
+
= < n ~-n
t . +i ni nin n =iln- nizii -+ n~il- l+i i-i t
a<iri + fny
CN

+ H
2
O HCN + OH

~- -<iti CH
3
COO

, NO
2

, S
2
:il< t
(c) +ir nsiaa art
t +ii-. i l+ OH

= < n -ii ti- t -ii l-+ =ni ~-n H


2
O-ii H
3
O
+
<i-i = vn ti - t . +ii ii
n~il- -ti ti- t
Cl

+ H
2
O HCl + OH

~- -<iti n SO
4
2
, NO
3

, ClO
4

:il< t
riai4fa+ nsiaa
i-i- n + =ii ~lil+i +- ~-n + n +i +- t . -ii l--- +i = n~il- ti - t
B
+
(aq) + 2H
2
O(l) BOH(aq) + H
3
O
+
(aq)
l< n i-i- n~i- +i nizii :=+ ~-ni =ni l-i +-i t
(a) si nsiaa
t i-i-. i H
3
O
+
~i- = n ti- t -ii l-+ =ni -ii H
2
O= <n ti-i t i n~i- <zii- t
-<iti PH
+
4
~i-
PH
+
4
+ H
2
O

H
3
O
+
+ PH
3
(b) y+ utfa iii a+ nsiaa
t i-i-. i H
3
O
+
= < n ~-n t -ii --+ = ni -ii H
2
O= n t n l+- OH

= < n t (+ =iln- nizii -+


n~i- l<ii-i t -<iti + ln(
NH
+
4
+ 2H
2
O NH
4
OH + H
3
O
+
~- ~i- i =iln- nizii -+ n~i- <zii- t t C
6
H
5
NH
3
+
, CH
3
NH
3
+
:il< t
(c) +ir nsiaa art
i-i- i H
3
O
+
= < n ~-n t -ii --+ = ni -ii. H
2
O-ii OH

<i -i = n t +ii ii n~i - -ti l<ii-


t -<iti + ln( -iii -ii -iii n <i ii- ~i + ~i-
Na
+
+ 2H
2
O NaOH + H
3
O
4ri i s+i + ni r
(i) n ~-n -ii n -ii + ni
(ii) n ~-n -ii < n -ii + ni
(iii) < n ~-n -ii n -ii + ni
(iv) < n ~-n -ii < n -ii + ni
in +i + ni +i n~i- -ti ti-i t -ii zi i -i- +i +i n~i- ti -i t
"manishkumarphysics.in"
13
CHEMISTRY
( i ) sn n aii sn +ii + ni
+i : ii ~i- n~i- -ti +-i t :=ln( ln- n +n n + ~i-- +i =i- -iil- t-i t
2H
2
O(l) H
3
O
+
+ OH

~-. ln- +i pH7 tini (-<i=i- ln-)


( i i ) sn n aii <n+ii +i ni
-<iti, NH
4
Cl (NH
4
)
2
SO
4
, AlCl
3
ti =+- t
+ n i-i-. n~i- + ~--n - ~i- t -ii ln- +l- n ~-ni ti- t
-<iti + ln( C=i-<-i + NH
4
Cl ln- + ln(
NH
4
+
+ H
2
O NH
4
OH + H
+
t = 0 c 0 0 0
=i- c(1 h) ch ch (h - n~i- +i nizii)
K
h
=
] NH [
] H ][ OH NH [
4
4
+
+
= ni +i n~i- l--i+ +tni-i t
NH
4
OH NH
4
+
+ OH

, K
b
=
] OH NH [
] OH ][ NH [
4
4
+
H
2
O H
+
+ OH

, K
w
= [H
+
] [OH

]
-i+- =ni+i = tn i-- + =+- t
K
h
K
b
= K
w
K
h
=
) h 1 ( c
ch . ch

=
) h 1 (
ch
2

(=ini-- 1-h 1) :=ln( tn i-- + =+- t h =


c
K
h
[H
+
] = ch = c K
h
=
c
K
K
b
w

pH = log [H
+
] =
2
1
[log K
w
log K
b
+ log c] =
2
1
[pK
w
pK
b
log c]
a<i14. 1Mli ti:i+nii: ln- n K
h
, n ~i- +i nizii -ii pH. l<i t li + ln( K
b
=1.5 x 10
14
.
rn. NH
2
CONH
3
Cl (SA + WB) +i ni t
~- h =
C . K
Kw
b
=
1 x 10 x 5 . 1
10
14
14

i h = 0.816 ~- tn =ti =zi -i n +-i t


K
h
=
b
w
K
K
=
14
14
10 x 5 . 1
10

= 6.667 x 10
1
K
h
=
b
w
K
K
=
h 1
Ch
2

=
5 . 1
1
1.5 h
2
+ h 1 = 0 h = 0.55
[H
+
] = ch = 0.55 M
pH = 0.26
a<i15. 0.1 M H
2
SO
4
-ii 0.2 M NH
4
OH (i ~ni l-i) + =ni- ~i-- +i lnni- vi-- ~l--n ln- + pH +i ni-i
+i K
b
of NH
3
= 1.8 10
5
"manishkumarphysics.in"
14
CHEMISTRY
rn. pH = 1/2 {14 4.7 + 1} =
2
26 . 10
= 5.13
(iii) <n n aii sn +ii +i ni
-<iti CH
3
COONa, KCN, Na
2
C
2
O
4
, K
3
PO
4
ti =+- t -i+- lzn ii + =ni-.
K
h
=
) h 1 ( c
ch . ch

=
) h 1 (
ch
2

(=ini-- 1-h 1)
:=ln( tn i-- +n h =
c
K
h
K
h
K
a
= K
w
[OH

] = ch = c K
h
=
c
K
K
a
w

pH = log [H
+
] = ] c log K log K log [
2
1
a w
+ = c] log pK [pK
2
1
a w
+ +
a<i16. HCN +i NaOH+ =ii ~lil+i + ln =i- l--i + 10
10
t - 10
-3
MNaCNln- +i pH+i ni-i +i
rn. HCN + NaOH H
2
O + NaCN K = 10
10
CN
-
+ H
2
O HCN + OH
-
K
h
= 10
10
10
-3
M O O
10
3
(1 h) 10
-3
h 10
-3
h
K
h
= 10
10
=
) h 1 ( 10
h 10 h 10
3
3 3

c
K
h
h
=
=
7
10

,
pH = 7
2
1
log 10
10
+
2
1
log 10
3
= 7 + 5
2
3
= 10.5
a<i17. 0.1 ni n CH
3
COONa +i n n ii n+ 100 ni ln- i-- ti -i t := ln- +i pH~i ni - +i +i l
(h) +i ni-i +i ( (=il+ ~-n +i K
a
= 2 10
-5
l<i t)
rn. c =
3
10 1
100
1 . 0

=
M
10
5
14
a
w
h
10 5
10 2
10
K
K
K

= =

c
k
h
h
= =
5
10
10 2
10 5

= 5 10
3
= 0.5%
pH =
2
1
[pK
w
+ pK
a
+ log c] =
2
1
[14 + 5 log 2 + log 10
3
] =
2
1
[15.7] = 7.85
( i v) <n n aii <n +ii + ni
-<iti n CH
3
COONH
4
, NH
4
CN, Ca(CH
3
COO)
2
, MgC
2
O
4
ziilnn t
CH
3
COO

+ NH
4
+
+ H
2
O CH
3
COOH+ NH
4
OH
t = 0 c c 0 0
ui4 s c ch c ch ch ch
K
h
=
] NH [ ] COO CH [
] OH NH [ ] COOH CH [
4 3
4 3
+
.....(i)
CH
3
COOH CH
3
COO

+ H
+
, K
a
=
] COOH CH [
] H ][ COO CH [
3
3
+
.....(ii)
NH
4
OH NH
4
+
+ OH

, K
b
=
] OH NH [
] OH ][ NH [
4
4
+
......(iii)
"manishkumarphysics.in"
15
CHEMISTRY
H
2
O H
+
+ OH

, K
w
= [H
+
] [OH

] ......(iv)
:=ln(, K
h
K
a
K
b
= K
w
,
K
h
=
2
h 1
h
) h 1 ( c . ) h 1 ( c
ch . ch
|
.
|

\
|

=

h
K
h 1
h
= |
.
|

\
|

=ni+i (ii) =
[H
+
] = K
a
] COO CH [
] COOH CH [
3
3

= K
a
) h 1 ( c
ch

= K
a

h 1
h

= K
a

h
K = K
a

b a
w
K K
K

=
b
a w
K
K K
pH = log [H
+
] =
2
1
[pK
w
+ pK
a
pK
b
]
a<i18. 10
-2
M, NH
4
CNln- +i pH-ii n~i- +i nizii +i ni-i +i
l<i ni t HCN +i K
a
= 510
10
-ii NH
3
+i K
b
= 210
5
.
rn. pH =
2
1
[14+ pK
a
pK
b
] =
2
1
[14 + 10 log 5 5 + log 2 ] =
2
1
[18.6] =9.3
h
K
h 1
h
=

=
b a
w
K K
K

=
5 10
14
10 2 10 5
10


= 1
2h = 1
h =
2
1
= 0.5
ru4it wii4a ii riai4a +i n siaa
:- -i=i +i n ~i- lli-- <i n l+i i-i t (< n ~-n + li - +i -t)
lli-- <i n ti - + i< =ini-- in < +i n~i- n- <i +ii = nt i ti-i t
in < + n~i- l--i+ +i -n-i n =ini-- l,-i (n ~in + <i + n~i- l--i+ -n
ni- i- t
l,-i -ii ~in + <i +i n~i-. in < + n ~i- + +ii - t ( ~i- +i -l-il- + +ii
-n ni-i i-i t
(+ t i l+ ~-n (H
2
S, H
3
PO
4
,H
2
CO
3
,H
2
C
2
O
4
) + ln( tn tn = i-- t l+ li - tn zii <i n l+i i-i
t :=ln( H
3
PO
4
+ -<iti + ln(
H
3
PO
4
H
+
+ H
2
PO

4
K
a1
=
] PO H [
] PO H [ ] H [
4 3
4 2
+
...(1)
H
2
PO
4

H
+
+ HPO
4
2
K
a2
=
] PO H [
] HPO ][ H [
4 2
2
4

+
...(2)
H
2
PO
4
2
H
+
+ PO
4
3
K
a3
=
] HPO [
] PO ][ H [
2
4
3
4

+
...(3)
=ii ~-ni + ln( tn tn zii i- t K
a1
>> K
a2
>> K
a3
+ n I
st
< = ln- +i pHl+ln- l+i i =+-i t -ii II
nd
-ii III
rd
< = vi-- [H
+
] +i -n ni-i i =+-i
t +i l+
(a) K
a1
>> K
a2
>> K
a3
(b) I
st
li - = i-- [H
+
], II
nd
-ii III
rd
< + li- +i +n + <-i t
~ t = i i ~i-i + n~i- + ln( (ni = K
3
PO
4
, Na
2
CO
4
, ZnSO
4
, FeCl
3
, (NH
4
)
2
C
2
O
4
~ii ~i-
= PO
4
3
,
C
2
O
4
2
, Zn
2+
, Fe
3+
:il<)
"manishkumarphysics.in"
16
CHEMISTRY
<i n n~i- +i ~ni+- +il(
PO
4
3
+ H
2
O HPO
4
2
+ OH

c 0 0
c(1 h) ch ch K
h1
=
] PO [
] HPO ][ OH [
3
4
2
4


...(4)
HPO
4
2-
+ H
2
O H
2
PO
4

+ OH

K
h2
=
] HPO [
] PO H ][ OH [
2
4
4 2


...(5)
H
2
PO
4

+ H
2
O H
3
PO
4
+ OH

K
h3
=
] PO H [
] PO H ][ OH [
4 2
4 3

...(6)
H
2
O H
+
+ OH

, K
w
=[H
+
] [OH

] ...(7)
-i+- =ni+ii = tn i-- +- t
K
a1
K
h3
= K
w
K
a2
K
h2
= K
w
K
a3
K
h1
= K
w
=ini-- +n in < n~i- +i -in + pH l+ln- +i i =+-i t
K
h1
=
) h 1 ( C
Ch . Ch

=
h 1
Ch
2

~ Ch
2
h =
c
K
1 h
[OH

] =ch = c K
1 h
[H
+
] =
] OH [
K
w

=
c K
K
K
w
3 a
w =
c
K K
3 a w

:=ln( pH =
c] log pK [pK
2
1
a3 w
+ +
a<i19. ni ln- n 1.0 M, Na
3
PO
4
+i pH+i ti ni ?
PO
4
3
+ H
2
O HPO
4
2
+ OH

; K
b
= 2.4 x 10
2
rn. K
b
=
x 1
x
2
= 2.4 10
2
= K
b
x
2
+ (2.4 10
2
) x 2.4 10
2
= 0
x = 0.143 = [OH

]
[H
+
] =
] OH [
K

w
= 7 10
14
M
pH = 13.15.
ai4sifa+ wii4a +i nsiaa
{riai4a nsifaa art riai r)
NaHCO
3
, NaHS, :il< ~i-- + ~--n- H
+
-i =+- t -ii n~i- + OH -i =+- t (Na
+
~i-
n~il- -ti ti- t)
(a) (i) HCO
3
+ H
2
O
2
3
CO +
(ii) HCO
3
+ H
2
O H
2
CO
3
+
pH(HCO
3

) =
|
.
|

\
| +
2
pK pK
2 a 1 a
"manishkumarphysics.in"
17
CHEMISTRY
(b) :=i +i H
2
PO
4
-ii HPO
4
2
-iil+ +ii- ti- t.
pH(H
2
PO
4

) =
|
.
|

\
| +
2
pK pK
2 a 1 a
-ii pH(HPO
4
2
) =
|
.
|

\
| +
2
pK pK
3 a 2 a
+ fn4a
{4f< n y +ii ffi-a iiii {a4i+) fniy n4 ri)
+ ln- ln- t i l+ ~-nizii n ~-n i -ii lnni- pHn l- - +i li i +- t . :=+i n-n t
-ti t l+ pHn l-- -ti ti -i t . nl+- pHn l--. ln- i l+ + -ti t +i - n-i n t - +n ti ni
+ fn4a + s+i
(i) < n ~-n ( < n ~-n +i l+=i n -ii + =ii -i ni
(ii) < n -ii ( < n -ii +i l+=i n ~-n + =ii -i ni
(iii) < n ~-n (n < n -ii + ni +i ln-
< n ~-n -ii < n ~-n + n -ii + =ii + ln- + pH+i ni-i + ln
CH
3
COOH CH
3
COO + H
+
K
a
=
] H CO CH [
] H [ ] COO CH [
2 3
3
+
=
] Acid [
] H ][ Salt [
+
[H
+
] = K
a

] Salt [
] Acid [
<i-i ~i log n- log [H
+
] = log K
a
+ log
] [
] [
yo.k
vEy
pH = pK
a
+ log
] [
] [
vEy
yo.k
:= + +i t-=- =ni+i +t- t
+ ln- i l+ < n -ii ( :=+ n ~-n + ni = -i t . :=+i t -=- =ni+i l--- ti ni
pOH = pK
b
+ log
] [
] [
{kkj
yo.k
+ ui4
:=+i := +i liili- l+i i-i t . + +i pHn (+ :+i: = l- - + ln( (+ ni + ln- n ~iz+
n ~-n ( n -ii +i nizii
fri+a + ui4
:= l=z l+i i =+-i t l+ ni ( ~-n i -ii +i =i-< -i( =ni- ti -i ~li+-n =in +i + --i t
a<i20. (NH
4
)
2
SO
4
+i nizii +i ni-i n in n +i l= 0.2 M, NH
3
+ 500 ml ln- n lnni- -=+i pH=9.3 i-- ti -i
t l<i ni t NH
3
+i pK
b
= 4.7
rn. pOH = pK
b
+ log
] [
] [
{kkj
vEy qXeh l;
4.7 = 4.7 + log
2 . 0
x
x = 0.2,
~- (NH
4
)
2
SO
4
+ ln ~iz+ =i-< -i = 0.1 M
(NH
4
)
2
SO
4
+ ~iz+ ni n = 0.05
(NH
4
)
2
SO
4
+i ~iz+ <ni- = 132 0.05 = 6.6 gm
"manishkumarphysics.in"
18
CHEMISTRY
a<i21. +- +i pH, H
2
CO
3
~i NaHCO
3
,ii =-- ln- l+i i-i t 5 M, NaHCO
3
ln- +i l+--i ~i-- +- + -n -
+ 10ml n lnni l+ l=n 2.5 MH
2
CO
3
(ni-i +i: NaHCO
3
-ti), -l-i- t -il+ ln- +i pH= 7.4 l-i
t (H
2
CO
3
+ ln pK
a
= 6.7, log 2 = 0.3)
rn. pH = pK
a
+ log
{kkj
yo.k
7.4 = 6.7 + log
{kkj
yo.k

{kkj
yo.k
= 5
5 2.5 10 10
3
= 5 V ~iz+ ~i-- = 25 ml
a<i22. l--- + 1lt +i + -in-i +i ni-i +i
(i) 0.1M CH
3
COOH ~i 0.1M CH
3
COONa
(ii) 0.2M CH
3
COOH ~i 0.2M CH
3
COONa
pK
a
CH
3
COOH = 4.74
:-n = +i-=i ~-zi + t
rn.
dpH
x o
=
b a
) x b )( x a ( 303 . 2
+
+
b a
ab 303 . 2
+
x << a,b
(i) + -in-i =
1 . 0 1 . 0
303 . 2 1 . 0 1 . 0
+

= 0.11515
(ii) + -in-i =
2 . 0 2 . 0
303 . 2 2 . 0 2 . 0
+

= 0.2303
l,-i + ln- ~-zi +ti i =+-i t
u+ (Indicator) :
= -+ <ii t i ~- ni- + ~l--n l-< +i (~- n n l- - + ,ii) <zii - t =ini--i < n +i l-+ ~-n
i < n +i l-+ -ii ti - t i ~il-- ( ~-~il-- ~-ii~i n llzia n <zii - t
-<iti + ln( n lin ~i - < n -ii (l=+i ~il-- ~-ii n nin n ( ~-~il-- ~-ii n ini n ti -i
t ) ( l+-i+i ni- (+ < n ~-n (~il-- ~-ii n n nii n l+ ~-~il-- ~-ii n nti- ti -i t )
~-ni = -+ (HIn) +i ~il-- ( ~- ~il-- ~-ii~i + n =i-i-ii +i ~- +- t
HIn H
+
+ In
K
In
=
] n H [
] n ][ H [
I
I
+
[K
In
= =-+ l--i+ i =-+ +i li- l-ii+]
i [H
+
] = K
In

] n [
] n H [
I
I
<i-i ~i +iin+ log n- log [H
+
] = log K
In
log
] n [
] n H [
I
I
pH = pK
In
= log
] n H [
] n [
I
I
pH = pK
In
+ log
| |
| | voLFkk vuvk;fur
voLFkk vk;fur
=ini--i ni- ln- +i -i -i (intensity), -= -izii +i =i-< -i l-i +-i t l=+ +ii n - ~i-i
t l< ln- n <i -izii -l-i- t . - ln- +i n ni- -izii +i =i l-i+ =i-< -i~i l-i +-i t
ln- n <i ni- -izii = HIn ( In -l-i- t . - t ii ni t l+ l< In +i =i-< -i HIn +i =i-< -i
+i +n = +n 10 n -i ~li+ ti -i ln- In -izii +i n <zii -i t :=i +i :=+i li- ii = t
"manishkumarphysics.in"
19
CHEMISTRY
fifa I : ln-. In + +ii n <zii :=
] n H [
] n [
I
I
+i ---n ~-i- 10. ti-i -ilt(
pH = pK
In
+ log (10) = pK
In
+ 1
:= l-il- n. =-+ n In +i l-zi- l--- ,ii l<i ini
] n H [ ] n [
] n [
I + I
I
100 =
1 10
10
+
100 ~ 91.
:= +i = -+ +i nnin 91%~il-- ~-ii (In) n -l-i- ti -i t i-- n pH= pK
In
+ 1 - --n pHt l=
ln- +i llzi n In + +ii ti -i t := ni- = ~li+ pH = -+ +i ~il-- ~-ii + z ~li+ nizii
n ti ni
:= +i pH > pK
HIn
+ 1 ln- In +i llzi n <zii-i t
fifa II : ln-. HIn + +ii n <zii :=+ ln(
] n H [
] n [
I
I
+i ~li+-n ~- i-
10
1
ti -i -ilt
pH = pK
In
+ log
10
1
= pK
In
1.
:= l-il- n . =-+ n In ~-ii +i l-zi- l--- + ,ii l<i ini
1 . 9 100
1 10
1
100
] n H [ ] n [
] n [
~
+
=
I + I
I
:= +i = -+ +i nnin 9.1%~il-- ~-ii (In) n -l-i- ti -i t ( = -+ +i 91%~-~il-- ~-ii (HIn)
n -l-i- t i-- n pH= pK
HIn
1 ~li+-n pHt l= ln- +i llzi n HIn + +ii ti -i t := ni-
= +n pH = -+ +i ~-~il-- + z ~li+ nizii n ti ni
:= +i pH < pK
HIn
= 1 ln- HIn +i llzi n <ziini
a<i30. 0.1MNaA ln- +i pH8.92 t -i +- ln- n l< (+ < HPh (pK
In
= 9.52 ) +i lnnii i( -i HA+ pK
a
+i ni-i +il ~- ni- nni: l+ n nii n l<ii: < ni i -ti n l+n ~iii tnii ~i i n nii n +i < i
=+-i t l< = -+ +i n nii ~-ii +i l-zi- 25%i ~li+ ti
rn. pH=
2
1
(pK
a
+ pK
w
+ log c)
8.92 = 7 +
2
1
pK
a
+
2
1
(1)
2
1
pK
a
= 8.92 6.5 = 2.42
pK
a
= 4.84
pH = pK
In
+ log
] [
] [
voLFkk vuvk;fur
voLFkk vk;fur
8.92 = 9.52 + log
] [
] [
voLFkk vuvk;fur
voLFkk vk;fur
voLFkk vuvk;fur
voLFkk vk;fur
=
] HIn [
] In [
=
4
1
-l+ [In] = 20% :=ln n l<ii: -ti <ni
"manishkumarphysics.in"
20
CHEMISTRY
n-+ii aisa :
n ~-n (SA) +i n -ii (SB) + =ii ~-ni- :
40 ml 0.1 M HCl +i 0.1 M NaOH = ~-ni-
fni4 n4 NaOH+i i4aa fn4a +i pH
0 ml 1
10 ml 1.22
20 ml 1.48
30 ml 1.84
39 ml 1.84
39.9 ml 2.90
40.0 ml 3.90
40.1 ml 7
41 ml 10.1
50 ml 11.1
60 ml 12.05
60 ml 12.30
n n l- - t <zii -i t l+ ~lil+i i ti - +i t ~- :=+i pH- i= n - i = l- - +i i ln+ zi l ni-+
-n ni-- t
SA ~i SB + ~-ni- + ln MeOH ~i HPh <i-i +i -in + =+- t
SB (n -ii) +i <n -ii WB + =ii ~-ni-
NaOH +i i4aa pH ia
0 2.5
5 ml 4.23
10 ml 4.7
15 ml 4.7 log 3 = 5.17
19 ml 4.7 + log 19/1 = 6
20 ml 7 + 1/2 (4.7) + 1/2 log (1/4) = 9.05
21 ml 12.4
30 ml 13.23
* ~- ni- n -i = l-- ti -i HPh ~-zi =-+ t
* i-i n pHn - i = l-- < n ~-n n -l-i- n+- ~i-i + +ii t
* pH n iini l-- + l--ii i + +ii ti -i t l=+i + =in pH = pK
a
~li+-n t
* ni l-nii + +ii - -i + l-< + =ni pHl+ -i = c-i t
* n -ii +i -l-il- + +ii - -i + l-< + i< pHn - i = lz ti -i t
SA (n ~-n) + <n -ii WB +i ~-ni-
4 = 7 + i- -i = l--
"manishkumarphysics.in"
21
CHEMISTRY
W.A. S.B. ni + S.A. +i ~-ni-
0.1 M, CH
3
COONa + 50 ml +i 0.1 M, HCl + =ii ~- ni- +- t HCl + l--- ~i-- lnni- pH +i ni-i
+i
(a) 0 mL (c) 25 mL (e) 50 mL (g) 75 mL (b) 10 mL (d) 40 mL (f) 60 mL
pK
a
of CH
3
COOH = 4.74
(a) pH = 1/2 (pK
w
+ pK
a
+ log c) = 1/2 (14 + 4.74 1) = 8.87
(b) CH
3
COONa + HCl NaCl + CH
3
COOH
5 mm 1 mm 0 0
4 mm 0 1 mm
pH = pK
a
+ log 4 = 4.74 + 0.6 = 5.34
(c) pH = pK
a
= 4.74
(d) pH = pK
a
+ log 1/4 = 4.14
(e) --i+ l-< , WAS ln-
[CH
3
COOH] = 5/100 = 1/20 M
pH = 1/2 (pK
a
log C) = 1/2 (4.74 + 2 0.7) =
2
04 . 6
= 3.02
(f) [HCl] = 1/100 M ; pH = 2.1
(g) [HCl] =
125
5 . 2
M ; pH = 1.7
"manishkumarphysics.in"
22
CHEMISTRY
W.B.S.A ni + S.B.
(NH
4
Cl + NaOH)
t i l+ ~-n +i ~- ni- n -ii (S.B.) + =ii :
0.1 M, H
3
PO
4
+ 50 ml, 0.1 M, NaOH + =ii l+i +-i t NaOH + ~i-- +i lnni - pH +i ni-i
+i
(a) 0 mL (b) 25 mL (c) 50 mL (d) 75 mL (e) 100 mL
(f) 125 mL (g) 150 mL (h) 200 mL (i) 90 mL
pK
a1
= 3 pK
a2
= 7 , pK
a3
= 11
(a) pH = 1/2 (pK
a1
log C) = 1/2 (3 + 1) = 2
(b)
H
3
PO
4
+ NaOH NaH
2
PO
4
+ H
2
O
t = 0 5 ln.ni n 2.5 ln.ni n 0
2.5 ln.ni n 2.5 ln.ni n
pH = pK
a1
+ log 1/1 = pK
a1
= 3
(c) H
2
PO
4

+i ln- -iini -izii


pH =
2
pK pK
2
a
1
a
+
=
2
7 3 +
= 5
(d) NaH
2
PO
4
+ NaOH Na
2
HPO
4
+ H
2
O
t = 0 5 ln.ni n 2.5 ln.ni n 0
2.5 ln.ni n 2.5 ln.ni n
pH = log 1/1 + pK
a2
= 7
(e) HPO
4
2
ln- (-iini -izii)
pH =
2
pK pK
3
a
2
a
+
= 9
(f) Na
2
HPO
4
+ NaOH Na
3
PO
4
+ H
2
O
5 2.5 0
2.5 2.5
pH = pK
a3
+ 10 g 1/1 = 0
(g) (g) Na
3
PO
4
ln- +i 3
rd
--i --i+i l-<
[Na
3
PO
4
] = 5/200 = 1/40
pH = 1/2{pK
w
+ pK
a3
+ log C} = 1/2 (14 + 11 2 + 0.4) = 11.7
"manishkumarphysics.in"
23
CHEMISTRY
(h) 200 mL
NaOH +i -l-il- Na
3
PO
4
+i n~i- -n ni-- t
[NaOH] = 5/250 = 1/50 M pOH = 1.7
pH = 12.3
(i) 90 mL
NaH
2
PO
4
+ NaOH Na
2
HPO
4
+ H
2
O
5 4 0
1 0 4
pH = pK
a2
+ log 4 = 7.6
a<i31. (Na
2
CO
3
+ HCl) . (W.A. S.B Vs S.B.) + ln ni+ -i~i
rn. Na
2
CO
3
+ HCl NaHCO
3
+ NaCl
pH =
2
pKa pKa
2 1
+
; 9
Na
2
HCO
3
+ NaCl H
2
CO
3
+ NaCl
pH = 1/2 {log C + pka
1
} ; 3.5 4
u+i +t uii+ai :
pH+i llzi i= ti -i t :-+i i= i ti i-i t -i n <n < -i t l+-i+ini- +i pHi= 810 +
i- ~i lnii:n ~i- +i 3 = 4.4 + i- ti -i t

lli-- -iii +i ~lil+i ~-n (HCl) + =ii <i = -+i = + = ti -i t -i- l<i t
f+aisinta fiirn i-
NaOH 100%~lil+i :ln- ti-i 100%~lil+i :ln- ti-i
NaOH + HCl NaCl + H
2
O NaOH + HCl NaCl + H
2
O
Na
2
CO
3
50%reaction upto NaHCO
3
100%~lil+i :ln- ti-i
~lil+i : ln- ti -i t
Na
2
CO
3
+ HCl NaHCO
3
+ NaCl Na
2
CO
3
+ 2HCl 2NaCl + H
2
O + CO
2
NaHCO
3
+i: ~lil+i : ln- -ti ti -i 100%~lil+i : ln- ti -i t
NaHCO
3
+ HCl NaCl + H
2
O + CO
2
.
"manishkumarphysics.in"
24
CHEMISTRY
fn4ai (s) y fn4ai nia+n (K
sp
)
:= =ni--i ~i lzi+ = ln nii + ln +in n lni i-i t tn l--- +i + ln-i n ln -i + i
n ~- +n
1. H
2
On =iiii ln-
2. ln-i =n ~i-i +i ii
3. =nl-ii+ ln-i (Simultaneous solubility)
4. ~-i
1
+ - ~i
1
~-i
2
+ - ~i
2
5. ~-i i + ln ll-il-i
6. + ln- n ln-i
7. =+n l-nii + +ii ln-i
fn4ai nia+n (K
sp
) y+ s+i +i ui4iii fa4ai+ r, rufn4 4r f+ut ni + fn4 +n ais s fai
+ai r+
l--- -<iti lli-- +i +i ln -i~i ( ni +i ln -i lli-- +i+i ( ll-il-i + ii +i =nni( n
uiriii fn4ai
ni-i l+ ni A
x
B
y
+i i-i n ln- t . ( i-i n ln -i 's' M, t -
A
x
B
y
xA
y+
+ yB
x
xs ys K
SP
=(xs)
x
(ys)
y
=x
x
.y
y
.(s)
x+y
a<i23. Li
3
Na
3
[AlF
6
]
2
+ K
SP
+i ni-i +i
rn. K
SP
= 3
3
.3
3
.2
2
(s)
8
= 3
6
.4.(s)
8
= 2916 s
8
fn4ai s u i4ai +i sii
=n~i-i +i -l-il- + +ii ni +i ln -i i-i t
a<i24. 10
2
Mi lzin ~i + n ln- n l=- ~i + n +i ln -i +i ni-i +il( l<i ni t l=- ~i + n +i
K
sp
= 10
10
rn. [~i+n] = 10
2
+ 2x ti x l=- ~i+n +i ln-i t. := 10
2.
+i -n-i n -n ni-i i =+-i t
K
sp
= 10
10
= 10
2
(2x)
2

2 2
10
8

= x
2
x = 5 10
5
M
uf+ii+ fn4ai +t niai
<i ~-ln ni n n lnni i- t -=i =n ln- n <i =i- -iil- ti i- t
a<i25. i-i n l=- iii=i- ( l=- ini: +i =nl-ii+ =nln-i +i ni-i +il( l<i ni t
l=- iii=i- +i K
sp
= 10
12
(n l=- i ni: +i K
sp
= 510
13
rn. ni-il+ AgSCN+i ln-i x ( AgBr +i y t. -,
AgSCN Ag
+
+ SCN

AgBr Ag
+
+ Br

x + y x x + y y
10
12
= x ( x + y) ------------ (i)
5 10
13
= y (x + y) ------------(ii)
tn +- tn i-- +- t x = 2y
~- y = 4.08 10
7
M and x = 8.16 10
7
M
"manishkumarphysics.in"
25
CHEMISTRY
+isi +t sffifa4i
~-i i + ln( K
SP
+i - n-i n K
IP
~li+ ti -i -ilt(
a<i26. ~i+i 10
5
MNaCl ln- ( 10
8
MAgNO
3
ln- l< n t. :-+i 1:1 + ~i-- ~-i- n lnnii i-i t
~-ni- nni: l+ AgCl ~-il- tini i -ti. l< AgCl ln-i ni-+n = 10
10
ninni
rn. ~il-+ ni-+n =
2
10
5

2
10
8
= 2510
15
< K
sp
:=ln l+=i +i +i ~-i i -ti tini
as4a + fn4ai fn4ai
- +- + +i -i t l+ + + ~. ni = l+i -ti +- i + n H
+
i OH

~i- ti ni + ~i-
+ =ii l+i +- t
a<i27. ai- pH+ + ln- n MnS +i ln-i +i ni-i +il( H
2
S + ln K
1
( K
2
-ii MnS +i K
sp
l<i t
rn. ni-il+ MnS +i -: ln-i =
[Mn
2+
] = x = S
2
~i-i +i ~i li+ =i-< -i. n l+- n +- S
2
~i-i +i = i +n ti ni +i l+ + z S
2
~i-
+ + H
+
~i-i + =ii l+i ++ HS

( H
2
S -i(n
[Mn
2+
] = x = [S
2
] + [HS

] + [H
2
S] .....(1)
free
~ n+- [S
2
] ~i-i = [HS

] ( [H
2
S] +i ni-i +- t . :=+ ln(
HS

H
+
+ S
2
H
2
S H
+
+ HS

K
2
=
] HS [
] S ][ H [
2

+
K
1
=
] S H [
] HS ][ H [
2
+
[HS

] =
2
2
K
] S [ ] H [
+
....(2)
~i [H
2
S] =
1
K
] HS [ ] H [
+
=
2 1
2 2
K K
] S [ ] H [
+
....(3)
=ni+i (1), (2) -ii (3) =
x = [S
2
]
|
|
.
|

\
|
+ +
+ +
2 1
2
2
K K
] H [
K
] H [
1
x =
] Mn [
K
2
SP
+ |
|
.
|

\
|
+ +
+ +
2 1
2
2
K K
] H [
K
] H [
1
x =
|
|
.
|

\
|
+ +
+ +
2 1
2
2
SP
K K
] H [
K
] H [
1 K
4ai-+ +isi
K
sp
+i ni- li-- ti - l+=i (+ ni +i --in+ ~-i i + =+- t
"manishkumarphysics.in"
26
CHEMISTRY
a<i28. = - -- H
2
S(0.1M) ln- n l+--i [H
+
] -i l+ CdS~-i l- ti i n l+- ZnS-ti l< i-i n [Cd
2+
] =[Zn
2+
] =0.1M
t ?
K
sp
(CdS) = 8 x 10
27
; K
sp
(ZnS) = 1 x 10
21
; K
a
(H
2
S) = 1.1 x 10
21
rn. ZnS +i ~-i i = -i i- + ln(
[Zn
2+
] [S
2
] < K
sp
(ZnS) = 1 x 10
21
(~il-+ -i<)
i (0.1) [S
2
] < 1 x 10
21
i [S
2
] < 1 x 10
20
M
ZnS + ~-i l- ti- + tn [S
2
] +i t ni- ~li+-n ti ni ~ := [S
2
] +i -i i- + ln [H
+
], x ti ni
~ H
2
S 2H
+
+ S
2
+ ln(
K
a
=
] S H [
] S [ ] H [
2
2 2 +
=
1 . 0
) 10 x 1 ( x
20 2
= 1.1 x 10
21
i x = [H
+
] = 0.105 M
H
+
+i =i-<-i 0.105 Mtini - +i: ZnS ~-i l- -ti tini
u+n faii + +ii fn4ai s sii
a<i29. ln- l=n 4 10
3
MAg
+
( 0.001 MNaCl t AgCl + ~-i i +i i +- + ln( ni NH
3
+i l+= =i-< -i
+i ln- lnnii i f<4i n4i r K
sp
(AgCl) = 1.8 10
10
( [Ag(NH
3
)
2
]
+
+i = i- l--i+k
formation
=
6
10
8
.
rn. ln- n - t ( l=- ~i-i +i =i-<-i +i ni-i + ln(
1.8 10
10
= [Ag
+
] [Cl

]
[Ag
+
] =
001 . 0
10 8 . 1
10

= 1.8 10
7
M, t nizii :--i +n t l+ nnin =ii Ag
+
~i- in ti - + t
Ag
+
+ 2NH
3
[Ag(NH
3
)
2
]
+
K =
6
10
8
4 10
3
b 0
1.8 10
7
(b810
3
) 410
3
K =
2 3 7
3 8
) 10 8 b ( 10 8 . 1
10 4
6
10



=
b = 0.0445
"manishkumarphysics.in"
27
CHEMISTRY
"manishkumarphysics.in"
28
CHEMISTRY
"manishkumarphysics.in"
29
CHEMISTRY
"manishkumarphysics.in"
30
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
1. l< =ni- =i-< -i~i +i lnni (l+i+i+ ~i -i< +i) - :-n = +i -=i ~lil+i =iii ti ni ~i +i -=i ~lil+i
--i tini
(A) H
2
SO
4
(aq) + NH
3
(aq) NH
4
+
(aq) + HSO
4

(aq)
(B) HCO
3

(aq) + SO
4
2
(aq) HSO
4

(aq) + CO
3
2
(aq)
Sol. (A) =iii; (B) --i
2.. (a) :-+ =ni ~-n lnii SO
4
2
, RNH
2
, NH
2

, C
2
H
5
O C
2
H
5
, F

(b) :-+ =ni -ii lnii HNO


2
, OH

, H
2
CO
3
, HClO
4
.
(c) :-+ =ni ~-n. =ni -ii ~i -iil+ -izii lnii
HS

, NH
3
, C
2
H
4
OH, H
2
O
Sol. (a) HSO
4

, RNH
3
+
, NH
3
, (C
2
H
5
)
2
OH
+
, HF
(b) NO
2

, O
2
, HCO
3

, ClO
4

(c) =ni ~-n : H


2
S , NH
4
+
, C
2
H
5
OH
2
+
, H
3
O
+
=ni -ii : S
2
, NH
2

, C
2
H
5
O

, OH

3. l--- n = +i-=i n -ii t


(A) C
2
H
5

(B) C
2
H
5
COO

(C) C
2
H
5
O

(D) OH

Ans. (A)
Sol. ~-ni =in. C
2
H
6
< C
2
H
5
OH< H
2
O< C
2
H
5
COOH.
4. l--- ~lil+i n
(A) C
2
H
5
NH
2
+ HI (C
2
H
5
NH
3
)
+
I

. +i -=i ~li+n + i -= ~-n +i -t ti +-i t +i t ~ltl-= ~-n


l+ -t ii ~i n l= ~-n +i -t ii ti +-i t
Ans. HI, ti, -ti
(B) < =i -ilzi (C
2
H
5
NH
2
) -i +- ~lil+i n ~ltl-= -ii +i -t ( i -= -ii +i -t ~i n l= -ii +i -t
ti +-i t
Ans. -ti, ti, ti
5. 0.1 MHCI + 10 ml 0.2 MH
2
SO
4
+ 40 ml +i lnl- + i-- ln- +i pHl+ln- +il(
Sol. HCl = H
+
+ ln( lnni --i+ = 10 0.1 = 1
H
2
SO
4
= H
+
+ ln( lnni --i+ = 40 0.2 2 = 16
ln- n H
+
+i +n lnni --i+ = 1 + 16 = 17
[H+] =
50
17
= 3.4 10
1
|
|
.
|

\
|
=
+
esa
kad feyh rqY;
mL
V
] H [
pH = log [H
+
] = log 0.34
pH = 0.47
6. (+ KOH ln- i l--- i-i t + pH +i ni-i +i
(a) 50 mL n n KOH+i 5.6 g lnnii i-i t
(b) l< := ~in -- ++ 100 ml -ii i-i t
Ans. (a) 14.3 (b) 14
Sol. (a) KOH + nin =
56
6 . 5
= 0.1
[OH

] = 2 M
pOH = 0.3 pH = 14.3
(b) [OH

] = 1 M
pOH = 0 pH = 14
"manishkumarphysics.in"
31
CHEMISTRY
7. (+ ln- +i pHai- +il( i 0.1 MHCI +i 100 mL 1.0 MNaOH +i 9.9 mL i-i t
Sol. HCI + NaOH NaCI + H
2
O
~lil+i = lnni - -i + 100 0.1 9.9 1 0 0
= 10 = 9.9
~lil+i + z-i- lnni - -i + 0.1 0 9.9 9.9
HCl = zii - [H
+
] =
9 . 109
1 . 0
= 9.099 10
4
M
pH = log H+ = log 9.099 10
4
pH = 3.04
8. 0.1 MHCOOH0.1 MHOCN i- in (+ ln- n [H
+
] l+ln- +il( HCOOH HOCN+ ln( K
a
+nzi
1.8 10
4
-ii 3.3 10
4
t
Sol. := =n-i n -+- li- + +ii <i-i ti [H
+
] <- t ~-
HCOOH H
+
+ HCOO

x + y x
HOCN H
+
+ OCN

x + y y
+i l+ [H
+
] ln- n =ni- t n ~-
K
HCOOH
=
] HCOOH [
] HCOO ][ H [
+
= 1.8 10
4
.............(1)
K
HOCN
=
] HOCN [
] OCN ][ H [
+
= 3.3 10
4
.............(2)
i K
HCOOH
=
1 . 0
x ) y x ( +
= 1.8 10
4
.............(3)
K
HOCN
=
1 . 0
y ) y x ( +
= 3.3 10
4
..............(4)
:= +i (3) (4) ,ii
3 . 3
8 . 1
y
x
=
i y = 1.83x .............(5)
=ni+i (3) = (x + 1.83x). x = 1.8 10
5
x = 2.52 10
3
:=ln(, y = 4.61 10
3
:= +i, [H
+
] = x + y = 2.52 10
3
+ 4.61 10
3
= 7.13 10
3
M
9. .001 M, HOCl i 25% li l- t + pH +i ni-i +i ~i ~-n + ln li - n ii + +i ni-i +i
Sol. HOCl H
+
+ OCl

a ao ao ao
So, [H
+
] = ao = 10
3

100
25
= 2.5 10
5
So, pH = 4.6
Now, K
a
=
) 1 ( a
) a ( ) a (
o
o o
=
o
o
1
a
2
=
12
1
10
3
10. 0.1 MH
3
PO
4
ln- n -l-i- =ii+ =i-<-i (=ii -izii + ln() + n =i-<-i l+ln- +il( (K
1
= 7.5
10
3
, K
2
= 6.2 10
8
, K
3
= 3.6 10
13
)
Sol. I < H
3
PO
4
H
+
+ H
2
PO
4

; K
1
= 7.5 10
3
II < H
2
PO
4

H
+
+ HPO
4
2
; K
2
= 6.2 10
8
III < HPO
4
2
H
+
+ PO
4
3
; K
3
= 3.6 10
13
I < + ln( : H
3
PO
4
H
+
+ H
2
PO
4

0.1 0 0
0.1 x x x
K
1
=
] PO H [
] PO H ][ H [
4 3
4 2
+

) x 1 . 0 (
x
2

= 7.5 10
3
x = 0.024 M
"manishkumarphysics.in"
32
CHEMISTRY
[H
+
] = 0.024 M
[H
2
PO
4

] = 0.024 M
[H
3
PO
4
] = 0.1 0.024 = 0.076 M
K
1
+ ni- K
2
K
3
= ~li+ ti -i t . =ii ti I < n <i- l+ n H
+
+i -l-il- n II III +i li - l+i i-i
t ~in =n~i- ii + +ii II III < +i li - +n ti i-i t
II < + ln( : H
2

4
PO H
+
+ H
2
4
PO
0.024 0.024 0
(0.024 y) (0.024 + y) y
< I n <i- l+( n [H
+
] +i -l-il- n
H
2

4
PO +i li- ti-i t
:= +i, K
2
=
] PO H [
] HPO ][ H [
4 2
2
4

+
i 6.2 10
8
=
) y 024 . 0 (
y ) y 024 . 0 (

+
y zii t 0.024 y ~ 0.024 y
2
+i -n ni-+
6.2 10
8
=
024 . 0
y 024 . 0
y = 6.2 10
8
M
i [H
2
4
PO ] = K
2
= 6.2 10
8
M (iiiti-)
III < + ln( : H
2
4
PO H
+
+
3
4
PO
(6.2 10
8
x) (0.024 + x) x
K
3
=
] HPO [
] PO ][ H [
2
4
3
4

+
=
) x 10 2 . 6 (
x ). x 024 . 0 (
8

+

- x
2
+i -n n+ ni-il+, 6.2 10
8
x = 6.2 10
8
3.6 10
13
=
8
10 2 . 6
x 024 . 0

x =
024 . 0
10 2 . 6 10 6 . 3
8 13

= 9.3 10
19
M (iiiti-)
aia : < n t il+ ~-n + ln( i +i: ~- - ~i -ti i-i t li - + ln( II < n i-- +ii-
=i-<-i tnzii K
2
+ i ti-i t
11. (+ ln- 0.1 MH
2
S 0.3 MHCI +- t ln- n S
2
HS

~i- +i =i-<-i l+ln- +il( l<i ni


t H
2
S+ ln( K
a1
K
a2
+nzi 10
7
1.3 10
13
ti - t
Sol. H
2
S H
+
+ HS

; K
a1
= 10
7
HS

H
+
+ S
2
; K
a2
= 1.3 10
13
HCI H
+
+ CI

=n~i- ii + +ii H
2
S + li - n +ni ~i-i t -ii HCl + +ii ln- n [H
+
] ti -i t
K
a1
=
] S H [
] HS ][ H [
2
+
10
7
=
] 1 . 0 [
] HS ][ 3 . 0 [

[ [H
+
] from HCI = 0.3]
[HS

] =
3 . 0
1 . 0 10
7

= 3.3 10
8
M
~in K
a2
=
] HS [
] S ][ H [
2

+
1.3 10
13
=
8
2
10 3 . 3
] S ][ 3 . 0 [

[S
2
] =
03 . 0
10 3 . 3 10 3 . 1
8 13

= 1.43 10
19
M
"manishkumarphysics.in"
33
CHEMISTRY
12. 0.2 MNaOH + 20 mL n 0.2 MCH
3
COOH + 50 mL +i lnnii i-i t (Ka = 1.8 10
5
).
(1) ln- +i pH+i t `
(2) ln- +i pH4.74 +- + ln( ~iz+ 0.2 MNaOH+i ~i-- l+ln- +il(
Sol. (1) NaOH + CH
3
COOH CH
3
COONa + H
2
O
lnni n lnninin 20 0.2 50 0.2
= 4 = 10 0 0
~lil+i + z-i- lnnini n 0 6 4 4
[nin-i] =
ru vk; dqy
feyheksy
[CH
3
COOH] =
70
6
[CH
3
COONa] =
70
4
pH = log 1.8 10
5
+ log
70 / 6
70 / 4
= 4.57
(2) ni-i l+ of 0.2 MNaOH+ V mL, 4.74 pH+- + ln( ~iz+ ti - t
NaOH + CH
3
COOH CH
3
COONa + H
2
O
lnni n lnninin 0.2 V 50 0.2
= 0.2 V = 10 0 0
~lil+i + z-i- lnnini n 0 (10 0.2 V) 0.2 V 0.2V
[Acid] =
V 50
V 2 . 1 10
+

; [Salt] =
V 50
V 2 . 0
+
4.74 = log 1.8 10
5
= log
) V 50 /( ) V 2 . 0 10 (
) V 50 /( ) V 2 . 0 (
+
+
V = 25 mL
13. (+ ln- i 1 ni n CH
3
COONa + 1 ni n HCI l- ni i-i t ~- ln- i 1 ni n CH
3
COONa + 1 ni n
(l=l+ ~-n l- ni i-i t +i ~-i- l+ln- +il(
Sol. ll-il- I : pH 1 nin CH
3
COONa 1 nin HCI -l-i- ti
CH
3
COONa + HCI CHCOOH + NaCI
~lil+i = 1 1 0 0
~lil+i + z-i- 0 0 1 1
[CH
3
COOH] = 1 M
[H
+
] = C. o = C
|
.
|

\
|
C
K
a
= ) C . K (
a
= ) K (
a
C = 1
pH
1
=
2
1
log K
a
ll-il- II : pH 1 ni n CH
3
COONa 1 ni n CH
3
COOH +i + ln- ti
pH
2
= log K
a
+ log
] [
] [
vEy
yo.k
[ni] = 1 M
pH
2
= log K
a
[~-n] = 1 M

2
1
pH
pH
=
2
1
14. pH9 in + ln- +i -i- + ln( ~iz+ NH
3
NH
4
CI +i nizii l+ln- +il( + ~li+n + + ln(
+n =i-<-i 0.6 nin ni
1
t NH
3
+ ln( pK
b
= 4.7, log 2 = 0.30
Sol. pOH = log K
b
+ log
] [
] [
{kkj
yo.k
5 = 4.7 + log
b
a
"manishkumarphysics.in"
34
CHEMISTRY
b
a
= 2 a = 2b
l<i ni t. a + b = 0.6
2b + b = 0.6
3b = 0.6
i b = 0.2 nin -ii a = 0.4 nin
:=ln(, [ni] = 0.4 M -ii [-ii] = 0.2 M
15. n n SrF
2
+i ln-i nii+ 8 10
10
t 0.1 MNaF ni ln- n :=+i ln-i l+ln- +il(
Sol. K
sp
= [Sr
2+
] [F

]
2
8 10
10
= s[2s + 0.1]
2
s =
2
10
) 1 . 0 (
10 8

= 8 10
8
M
16. (+ ln- i Ag
+
(0.10 M) Hg
2
2+
(0.10 M) +i (+ lni i-i t -ii l= ii n+ (--in+) ~-i i i+
l+i i-i t ~ii i- ~i- + ln( ~li+-n =i-< -i l+ln- +il( l= l+ +i : (+ i = ~-i l- ti
i-i t := ii- ~i- +i +i %~-i l- ti -i t `
AgI + ln( K
sp
= 8.5 10
17
Hg
2
I
2
+ ln( K
sp
= 2.5 10
26
Sol. Ag
+

+ 2
2
Hg + ~-i i + ln( ~iz+ [I

] l--- +i = -- l+i i-i t


AgI + ln( : [Ag
+
][I

] = K
spAgI
(0.1)[I

] = 8.5 10
17
[I

] = 8.5 10
16
M .......(1)
Hg
2
I
2
+ ln( : [
+ 2
2
Hg ] [I

]
2
= 2.5 10
26
(0.1) [I

] = 2.5 10
26
[I

] = 5 10
13
M .......(2)
- l+ AgI + ~-i i + ln( ~iz+ [I

] +n ti -i t -ii := +i AgI tn ~-i l- ti -i i-i +-i t =ii ti


[I

] = 5 10
13
+ lnni- -+ nni-i ~-i l- ti-i t Hg
2
I
2
~-il- ti -i i-i +-i t -ii := +i,
AgI ~-i i + ln( ~li+-n [I

] = 5 10
13
M
~ I

+i := =i-<-i . ln- n zii -i [Ag


+
], [Ag
+
]
left
[I

] = ( )
AgI
sp
K t
[Ag
+
]
left
=
13
17
10 0 . 5
10 5 . 8

= 1.7 10
4
M
0.1 MAg
+
zii -ni = ln- n 1.7 10
4
MAg
+
100 MAg
+
zii -ni = 0.17%MAg
+
~-i l- Ag
+
+i %= 99.83%
17. BaSO
4
+i ln -i +i ni-i +i CaSO
4
~i BaSO
4
+i n n lnni -= =n CaSO
4
+i K
sp
= p, BaSO
4
+i K
sp
= q ~i CaSO
4
+i ln-i b nin/ni t
Ans. bq / p
Sol. BaSO
4
+ ln(,
[Ba
2+
] [SO
4
2
] = K
sp
of BaSO
4
= q
CaSO
4
+ ln(,
[Ca
2+
] [SO
4
2
] = K
sp
of CaSO
4
= p
] Ca [
] Ba [
2
2
+
+
=
p
q
[Ba
2+
] =
p
bq
"manishkumarphysics.in"
35
CHEMISTRY
18. HCI + (+ ln- +i pH= 5 ti -i t l< :=+i 1 mL +i 1 ni -+ - - l+i i-i t liini ln- +i pH
+i ti ni `
Sol. HCI
I
= 10
5
M -l+ pH = 5
1 ml n HCI
I
+i lnni --i+ = 10
5
1
1000 ml n HCI
II
+i lnni --i+ = N 1000
- l+ I +i --+ II -ii i-i t -ii -- +- lnni --i+ ll-- -ti ti-i t
i.e., HCI +i lnni --i+ (=il-<-) = HCl +i lnni --i+ (--)
10
5
1 = N 1000
[H
+
] = 10
8
~, pH = 6.97

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