IONIC EQUILIBRIUM

14. 0.10 mol sample of AgNO3 is dissolved in 1.00 L of 1.00 M NH3. If 0.010 mol of NaCl is
added to this solution will AgCls! p"e#ipitate$ [4]
14. Ag
%
% &NH3 AgNH3!&
Initial 0.1 M 1.00 M 0
' 1(0.&! M 0.10 M
It has )een assumed that almost all Ag
%
ion has )een #omple'ed and onl* its pa"t ' is left
+f,
[ ]
[ ] [ ]
-
& &
3
& 3
10 . . 1
! /0 . 0 '
10 . 0
NH Ag
! NH Ag

+
+

', -./10
(-
M , Ag
%
undissolved!
0Cl
(
1 , 1.010
(&
M
0Ag
%
1 0Cl
(
1 , -./10
(-
1.010
(&
, -./10
(11
2 1./10
(10
+3pAgCl
Hen#e AgCls! will not p"e#ipitate
14. 3olid NH4I disso#iates a##o"ding to the "ea#tion at 400 +
NH4Is! NH3g! % HIg! 5 +p , 1. atm
&
. In p"esen#e of #atal*st HI disso#iates in H&
and I& as &HI H& % I&. If pa"tial p"essu"e of H& at this temp is 1 atm in the #ontaine"
when )oth the e6uili)"ium e'ist simultaneousl*7 #al#ulate +p value of se#ond e6uili)"ium fo"
the disso#iation of HI! [5]
14. NH4Is! NH3 g! % HI g!
1. +
1
8


&HI H& % I&
8 ( '
&
'
&
'
$ +
&
8

He"e
&
'
, 1 atm
' , & atm
88 (&! , 1.
8 , 4.1
&
& &
HI
I H
8
10 4 . 10
! 1 . 3
1 1
8
8 8
+
& &
&

19. In a solution of 0.04 M :eCl& and 0.0& M :eCl3 and 0.01 M HCl7 How la"ge ma* )e its pH
without the"e )een p"e#ipitation of eithe" :eOH!& and :eOH!3. +sp of :eOH!& and :eOH!3
a"e /10
(.
and 410
(&/
"espe#tivel*. [5]
19. Che#; the #on#ent"ation of salt whose 0OH
(
1 "e6ui"ed is less fo" p"e#ipitation.
4. Mg3O4 gives a p"e#ipitate with NH4OH )ut not with mi'tu"e of NH4OH and NH4Cl
4. No dou)t NH4OH is wea; )ase )ut it p"ovides app"e#ia)le OH
(
ion to e'#eed the ioni#
p"odu#t of ioni# #on#ent"ation of Mg
&%
and OH
(
than thei" +sp and thus Mg3O4 is p"e#ipitated
out as MgOH!&. On the othe" hand the disso#iation of NH4OH is supp"essed in the p"esen#e
of #ommon ion f"om NH4Cl and thus OH
(
! diminishes to the e'tent that 0Mg
&%
10OH
<
1
&
2 +sp.
=hus Mg3O4 is not p"e#ipitated.
13. 0.10 M of sample of AgNO3 is dissolved in 1.00 L of 1 M NH3. If 0.01 mol of NaCl is added to
the solution will the p"e#ipitation of AgCls! ta;es pla#e
! AgCl sp
+
,1./10
(10

1 ! NH Ag 0 f
& 3
+
+
, 1..10
9
13. Ag
%
% &NH3 AgNH3
%
!&
0.10 M 1.00 M 0 Initial #on#.
' 1(0.&0!M 0.10 M :inal #on#.
It has )een assumed that almost all Ag
%
ion has )een #omple'es and ve"* ( ve"* small pa"t '
is left
+f ,
[ ]
[ ][ ]
&
3
& 3
NH Ag
! NH Ag
+
+

&
! /0 . 0 '
10 . 0

, 1..10
9

' , -./10
(-
M
Cl
(
! , 1.010
(&
M
0Ag
%
1 0Cl
(
1 , -./10
(-
1.010
(&
, -./10
(11
2 +spAgCl!
Hen#e p"e#ipitation of AgCls! will not ta;e pla#e
/. A solution of wea; a#id was tit"ated with )ase NaOH. =he e6uivalen#e point was "ea#hed
when 3..1& ml of 0.1 M NaOH have )een added. Now 1/.0/ ml 0.1 M HCl we"e added to
the tit"ated solution7 the pH was found to )e 4.-&. >hat is +a of the a#id$ 0log1&,1.0/1 [6]
/. :o" #omplete neut"ali?ation
Me6 of a#id , Me6 of NaOH
, 3..1&0.1 , 3..1&
HA % NaOH NaA%H&O
3..1& 3..1& 0 0
0 0 3..1& 0
Now5 1./0. Me6 of HCl 1/.0.0.1! a"e added to this solution #ontaining 3..1& Me6 of NaA
NaA % HCl NaCl % HA
Me6 )efo"e "ea#tion 3..1& 1./0. 0 0
Me6. afte" "ea#tion 1./0. 0 1./0. 1./0.
=he solution has HA and NaA and thus a#ts as a )uffe"
pH , ( log +a%log
/0. . 1
/0. . 1
4.-&, ( log +a
+a , 1.&10
(4
&. Cal#ulate the amount of NH3 and NH4Cl "e6ui"ed to p"epa"e a )uffe" solution of pH -.0.
>hen total #on#ent"ation of )uffe"ing "eagents is 0.. mol@L7
( )
3
+) NH
8 4.9
7 log &,0.30.
&.
0.&8 ' @ 40
8 1

' , / gm
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
4. Mg3O4 gives a p"e#ipitate with NH4OH )ut not with mi'tu"e of NH4OH and NH4Cl
4. No dou)t NH4OH is wea; )ase )ut it p"ovides app"e#ia)le OH
(
ion to e'#eed the p"odu#t of
ioni# #on#ent"ation of Mg
&%
and OH
(
than thei" +sp and thus Mg3O4 is p"e#ipitated out as
MgOH!&. On the othe" hand the disso#iation of NH4OH is supp"essed in the p"esen#e of
#ommon ion f"om NH4Cl and thus OH
(
! diminishes to the e'tent that 0Mg
&%
10OH
<
1
&
2 +sp.
=hus Mg3O4 is not p"e#ipitated.
10. An a#id ( )ase indi#ato"7 HIn+In, 10
(.
! displa*s the #olou" of its a#id fo"m onl* when it is
ionised to a ma'imum of -.0-A7 while it displa*s its )asi# #olou" when it is ionised to the
e'tent of at least -4.&4A. >hat is the pH ( "ange of the indi#ato"$
10. p+In , .
pH , p+In % log
[ ]
[ ] HIn
In

:o" a#idi# #olou" to p"evailB

[ ]
[ ] 10
1
-1 . -0
0- . -
HIn
In

pH . ( 1 , 4
:o" )asi# #olou" to p"evailB
[ ]
[ ]
&0
9. . 4
&4 . -4
HIn
In

pH . % 1.3 , 9.3
pH "ange B 4 ( 9.3
11. 0.10 mol sample of AgNO3 is dissolved in 1.00 L of 1.00 M NH3. If 0.010 mol of NaCl is
added to this solution will AgCls! p"e#ipitate$ +sp , 1./10
(10
7 +fAgNH3!&
%
, 1..10
-
!.
11. Ag
%
% &NH3 AgNH3!&
%

Initial 0.1 M 1.00 M 0
' 1(0.&! M 0.10 M
It has )een assumed that almost all Ag
%
ion has )een #omple'ed and onl* its pa"t ' is left
+f,
[ ]
[ ] [ ]
-
& &
3
& 3
10 . . 1
! /0 . 0 '
10 . 0
NH Ag
! NH Ag

+
+

', -./10
(-
M , Ag
%
undissolved!
0Cl
(
1 , 1.010
(&
M
0Ag
%
1 0Cl
(
1 , -./10
(-
1.010
(&
, -./10
(11
2 1./10
(10
+3pAgCl!
Hen#e AgCls! will not p"e#ipitate
19. =he fi'ing of photog"aphi# plate film involves dissolution of une'posed silve" )"omide in h*po
solution a##o"ding to the e6uation
AgC"s! % &3&O3
&(
e6! Ag3&O3!&
3(
a6! % C"
(
a6!
Cal#ulate mola" solu)ilit* of AgC" in 0.1 M h*po solution assuming its #omplete disso#iation
+sp of AgC" , 4.410
(13
+f of Ag3&O3!&
3(
, &.010
13
19. AgC"s! Ag
%
% C"
(
7 +1,+sp
Ag%

% &3&O3
3(
Ag3&O3!&
3(
7 +& , +f
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
AgC"s! % &3&O3
3(
a6! Ag3&O3!&
3(
a6! % C"
(
a6! +# , +sp. +f , -
0.1 M 0 0 DDDDDDinitiall*
0.1(&'! M 'M 'M DDDDD. at e6uili)"ium
( )
&
&
'
-
0.1 &'

7
'
3
0.1 &'

' , 0.3 ( .'7 4' , 0.37 ' ,

0.3
0.043M
9
M
=hus7 mola" solu)ilit* of AgC" 0.1M h*po , 0.043 M
1/. 30 ml solution of a wea; mono)asi# a#id "e6ui"es .0 ml 0.&4 M NaOH fo" the end point.
Eu"ing tit"ation the pH of the a#id solution upon addition of &0 ml al;ali 0.&4M! was 4...
Cal#ulate pH of the a#id solution at the following two stages
a! Cefo"e addition of an* d"op of al;ali
)! At the e6uivalen#e point7 the #ontents of the #oni#al flas; having )een diluted to 140 ml
)* the addition of distilled wate" log &,0.30! and p+w , 14!
1/. 30 ml HA , .0 mL 0.&4 M NaOH7 so 0HA1 , 0.4 M
No. of millimole of a#id initiall* ta;en , 300.4 , 14
when &0 ml 0.&4 M , 4 millimole! NaOH is added the salt fo"med , 4 millimole and a#id
"emaining un"ea#ted , 10 millimole. =he "esulting mi'tu"e will )e an a#id )uffe" mi'tu"e
whose pH will )e given )* the e6uation
pH , p+a % log
[ ]
[ ] a#id
salt
4.. , p+a % log
10
4
p+a , 4.-
i! pH of a#id solution )efo"e addition of an* d"op of al;ali
pH ,
&
1
0p+a ( log C1 ,
&
1
04.-(log 0.41 , 4..
ii! pH of the solution at the end point whi#h is diluted to 140 ml
No. of millimole of salt fo"med , 14
Folume of solutio , 140 ml
0salt1 , M 1 . 0
140
14

=he salt fo"med will )e h*d"ol*sed to "ende" the solution faintl* al;aline. =he pOH of this
solution ma* )e #al#ulated as
pOH ,
&
1
0p+a ( p+w ( log C1 ,
&
1
04.-(14%11 , 4.04
pH , -.-4
1-. =he solu)ilit* of AgCl Mw,143.4! in pu"e wate" is &./90 ppm at &4C. Cal#ulate its solu)ilit*
mol L
(1
! in &.0 M NH3 solution at &4C. Assume densit* of wate" is 1 g@ml
Given Ag
%
% &NH3 0AgNH3!&1
%
7 + , &.410
9
at &4C.
1-. 10
.
g wate" is asso#iated with &./9 g AgCl i.e.
mol 10 &
4 . 143
/9 . &
&

10
3
g i.e. 1000 mL wate" d,1! is asso#iated with &10
(4
mol
=hus7 solu)ilit* of AgCl in pu"e wate" , &10
(4
mol L
(1

+sp , &10
(4
! &10
(4
! , 410
(10
mol
(&
L
(&

AgCls! Ag
%
% Cl
(
7 +sp , 410
(10
mol
&
L
(&

Ag
%
% &NH3 0AgNH3!&1
%
7 + , &.410
9
mol
(&
L
&

AgCl s! % &NH3 0AgNH3!&1
%
Cl
(
7 +# , +sp , 10
(&
& M 0 0 DDD initiall*
&('! 'M 'M DDDD at e6uili)"ium
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
( )
&
&
&
10
' & &
'

' , 0.1.. mol L

(1
, solu)ilit* of AgCl in & M NH3 soln.
&0. In a solution of 0.04 M :eCl& and 0.0& M :eCl37 how la"ge ma* )e its pH without these )eing
p"e#ipitation of eithe" :eOH!& o" :eOH!3$ Given +sp :eOH!& , 1.10
(.
H
+sp :eOH!3 , /10
(&.

&0. :o" the p"e#ipitation if :eOH!&
, 00.041 0OH
(
1
&
, 1.10
(.
0OH1 , &10
(&
and fo" :e0OH13
0.0&! OH
(
!
3
, /10
(&.
OH
(
! , &'10
(/

:o" :eOH!3 the 0OH
(
1 ions a"e "e6ui"ed less
8OH , / ( log &
8H , .%log &
,..3
1. An indi#ato" HIn has a standa"d ioni?ation #onstant
-
- 10

. =he a#id #olo" is *ellow and

al;aline #olo" is "ed. =he *ellow #olo" is visi)le when the "atio of *ellow to "ed fo"m is 3B1 and
"ed #olo" p"edominates when "ed to *ellow fo"m is &B1. >hat is the pH "ange of the
indi#ato"$
1. HIn H In
+
+
*ellow "ed
pH ,
[ ]
[ ]
In
"ed
p+ log
*ellow
+
( log
-
1
- 10 log
3

+
pH ..4./
&
pH - log- log /.34.
1
+
3o7 pH "ange of indi#ato" is ...4/ to /.34.
3. 8"ove that deg"ee of disso#iation of a wea; a#id is given )*
p+a pH!
1
1 10


+
>he"e +a is its disso#iation #onstant
3. :o" wea; monop"oti# a#id
HA H A
1
+
+

&
C
H C and +a
1
+

1
]

3o7 +a ,
( )
H
1
+
1
]

1 ! 1
H +a log H log
+ +
_
1 1

] ]

,
( log +a
pH, p+a <log
1

log
1
p+a pH

p+a pH!
1
10

p+a pH!
1
1 10


+
.. HCl is p"epa"ed in the la) )* the a#tion of #on#. H&3O4 ove" NaCl o" +Cl. Cut HC" o" HI
#annot )e p"epa"ed in a simila" manne". I'plain )"iefl*.
.. NaJ % H.H3O4 NaH3O4 % HJ
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
HC" J , C"! o" HI J , I! is a "edu#ing agent while #on#. H&3O4 is an o'idising agent. Hen#e
"edo' inte"a#tion )etween them ta;es pla#e "esulting into o'idation of HJ to J& J , C"7 I!
and "edu#tion of H&3O4 to 3O&
H&3O4 % &HJ &H&O % J& % 3O&
>he"e J , C" o" I
HCl )eing ve"*ve"* wea; "edu#ing agent7 "emains uno'idised.
/. =o ma;e a )uffe" solution of pH,. whi#h of the following is a )ette" )uffe"$
a! HA 0.001 M!7 NaA 0.1M!
)! HC 0.01M! 7 NaC 0.1M!
Given +) of A
(
,10
(10
and +) of C
(
, 10
(-
.
/. pH e'p"ession fo" an a#idi# )utte" pH , p+a % log
[ ]
[ ] a#id
K salt
although it is diffi#ult to give an
e'a#t limit up to whi#h a )uffe" #an )e used. It is gene"all* a##epted that a solution has
useful )uffe" #apa#it* p"ovided that the value of salt@a#id lies within the "ange of 10 to 0.1. It
follows the"efo"e that a pa"ti#ula" wea; a#id #an )e emplo*ed )* ma;ing useful )uffe"
solution of pH l*ing within the "ange of p+a ( 1 to p+a %1.
He"e ii! mi'tu"e is )ette" than i!
10. >hen a solution #ontaining Ca
&%
and Mg
&%
ions is at fi"st satu"ated with NH4Cls! and then
t"eated with NH4!&CO37 onl* Ca
&%
is p"e#ipitated as #a")onate. I'plain.
10. +sp of MgCO3 is mo"e than +sp of CaCO3
In the p"esen#e of NH4
%
ions7 the following e6uili)"ia e'ists.
&
4 3 3 3
NH CO HCO NH 7
+
+ +

the"e)* #onve"ting CO3
&<
into HCO3
<
.
=he de#"eased #on#. of CO3
&<
is still suffi#ient to ma;e the ioni# p"odu#t 0Ca
&%
1 0CO3
&<
1
e'#eed the +sp of CaCO3 whe"eas this is not so in the #ase of MgCO3.
1/. In a solution of 0.04 M :eCl& and 0.0& M :eCl37 how la"ge should )e the pH7 without an* of
these eithe" :eOH!& o" :eOH!3 )eing p"e#ipitate$ Given +sp :eOH!&,1.10
(.
H+sp
:eOH!3,/10
(&.

1/. :o" the p"e#ipitation if :eOH!&
, 00.041 0OH
(
1
&
, 1.10
(.
0OH1 , &10
(&
and fo" :e0OH13
0.0&! OH
(
!
3
, /10
(&.
OH
(
! , &'10
(/

:o" :eOH!3 the 0OH
(
1 ions a"e "e6ui"ed less
8OH , / ( log &
8H , .%log &
,..3
1-. =he fi'ing of photog"aphi# plate film involves dissolution of une'posed silve" )"omide in h*po
solution a##o"ding to the e6uation
AgC"s! % &3&O3
&(
e6! Ag3&O3!&
3(
a6! % C"
(
a6!
Cal#ulate mola" solu)ilit* of AgC" in 0.1 M h*po solution assuming its #omplete disso#iation
+sp of AgC" , 4.410
(13
+f of Ag3&O3!&
3(
, &.010
13
1-. AgC"s! Ag
%
% C"
(
+sp , 4.410
(13
Ag%

% &3&O3
3(
Ag3&O3!&
3(
7 +f ,&.010
13
AgC"s! % &3&O3
3(
a6! Ag3&O3!&
3(
a6! % C"
(
a6! +# , +sp. +f , -
0.1 M 0 0 DDDDDDinitiall*
0.1('! M 'M 'M DDDDD. at e6uili)"ium
( )
-
' 1 . 0
'
&
&

7 3
' 1 . 0
'

' , 0.3 ( 3'7 4' , 0.37 ' , 094 . 0

4
3 . 0
M
=hus7 mola" solu)ilit* of AgC" 0.1M h*po , 0.094 M
3. >hethe" the pH of a solution of a wea; a#id will in#"ease o" de#"ease o" "emain #onstant
upon dilution$ Give "eason fo" *ou" answe".
3. =he pH will in#"ease
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
HA H
%
% A
(
C 1(! C C DDDD at e6uili)"ium

C
1
DDDDD.. Loughl*!
:o" eve"* 4( fold in#"ease in dilution7 C will "edu#e to 1@4
th
and hen#e will )e dou)led7 so
0H
%
1 whi#h is C will de#"ease on dilution and hen#e pH will in#"ease.
/. >ill a p"e#ipitate fo"m if &0 ml of 10
(4
M AgNO3 and &0ml of 10
(4
M NaCl a"e mi'ed$ Given
+spAgCl! , 1.910
(10
M
&
/. Afte" mi'ing #on#ent"ation of Ag
%
, 410
(4
and #on#ent"ation of Cl
(
, 410
(.
=he ioni# p"odu#t is
0Ag
%
1 0Cl
(
1 , 410
(4
410
(.
, &410
(1&

=his ioni# p"odu#t is la"ge" than +sp and thus p"e#ipitation of AgCl will o##u".
-. Cal#ulate the amount of NH3 and NH4Cl "e6ui"ed to p"epa"e a )uffe" solution of pH -.0.
>hen total #on#ent"ation of )uffe"ing "eagents is 0.. mol@L7
( )
3
) NH
+ 4.9
7 log &,0.30.
-. pOH , ( log +) % log
[ ]
[ ] Case
3alt
14(-! , 4.9 % log '@*
4 , 4.9% log
*
'
'@* , & DDD.1!
Also7 '%*!,0.. DDD&!
:"om 1! H &!
* , 0.& mol 0.&19,3.4 g@L
', 0.4 mol o" 0.443.4 , &1.4@L
11. An indi#ato" HIn has a standa"d ioni?ation #onstant
-
- 10

. =he a#id #olo" is *ellow and

al;aline #olo" is "ed. =he *ellow #olo" is visi)le when the "atio of *ellow to "ed fo"m is 3B1 and
"ed #olo" p"edominates when "ed to *ellow fo"m is &B1. >hat is the pH "ange of the
indi#ato"$
11. HIn H In
+
+
*ellow "ed
pH ,
[ ]
[ ]
In
"ed
p+ log
*ellow
+
( log
-
1
- 10 log
3

+
pH 9.4.
&
pH - log- log /.34.
1
+
3o7 pH "ange of indi#ato" is 9.4. to /.34.
19. 40 ml of 0.1 M CH3COOH was mi'ed with 40 ml 0.1 M NaOH solution. Cal#ulate the value of
e6uili)"ium #onstant of this "ea#tion. If 40 ml 0.04M HCl was added to this solution what will
)e the final pH of solution$ +a of CH3COOH is 10
(4

19. CH3COOH CH3COO
(
% H
%
Di!
H
%
% OH
(
H&O Dii!
On adding i! and ii!
CH3COOH % OH
(
CH3COO
(
% H&O
Falue of e6. #onstant ,
-
10
+w
+a

4 millimoles of CH3COOH will "ea#t with 4 millimoles of NaOH and will p"odu#e 4 millimoles
of CH3COONa. Now &.4 millimoles of HCl will "ea#t with &.4 millimoles of CH3COONa and
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
will p"odu#e &.4 millimoles of CH3COOH. =his solution is a )uffe" solution and pH of this
solution is given )*
pH , p+a % log
[ ]
[ ] a#id
salt

pH , p+a , 4
1-. =he fi'ing of photog"aphi# plate film involves dissolution of une'posed silve" )"omide in h*po
solution a##o"ding to the e6uation
AgC"s! % &3&O3
&(
e6! Ag3&O3!&
3(
a6! % C"
(
a6!
Cal#ulate mola" solu)ilit* of AgC" in 0.1 M h*po solution assuming its #omplete disso#iation
+sp of AgC" , 4.410
(13
+f of Ag3&O3!&
3(
, &.010
13
1-. AgC"s! Ag
%
% C"
(
+sp , 4.410
(13
Ag%

% &3&O3
3(
Ag3&O3!&
3(
7 +f , &10
13
AgC"s! % &3&O3
3(
a6! Ag3&O3!&
3(
a6! % C"
(
a6! +# , +sp. +f , -
0.1 M 0 0 DDDDDDinitiall*
0.1(&'! M 'M 'M DDDDD. at e6uili)"ium
( )
-
' 1 . 0
'
&
&

7 3
' 1 . 0
'

' , 0.3 ( 3'7 4' , 0.37 ' , 094 . 0

4
3 . 0
M
=hus7 mola" solu)ilit* of AgC" 0.1M h*po , 0.094 M
1. >hat is the solu)ilit* of AgCl in 0.1 M NaCl solution$ +sp AgCl , 1./10
(10
L
(1
3
(1
.
1. +sp , 0Ag
%
1 0Cl
(
1
1./10
(10
, 33%0.1!
3,1./10
(-
&. A #e"tain wea; a#id has a disso#iation #onstant of 110
(4
. :ind the e6uili)"ium #onstant fo"
its "ea#tion with a st"ong )ase.
&. + ,
10
10
+w
+a
+a @ +w
1
+h
1

3. >hethe" the pH of a solution of a wea; a#id will in#"ease o" de#"ease o" "emain #onstant
upon dilution$ Give "eason fo" *ou" answe".
3. =he pH will in#"ease
HA H
%
% A
(
C 1(! C C DDDD at e6uili)"ium

C
1
DDDDD.. Loughl*!
:o" eve"* 4( fold in#"ease in dilution7 C will "edu#e to 1@4
th
and hen#e will )e dou)led7 so
0H
%
1 whi#h is C will de#"ease on dilution and hen#e pH will in#"ease.
11. Eete"mine the pOH of a solution afte" 0.1 moles of NaOH is added to 1L of a solution
#ontaining 0.14M CH3COOH and 0.&M CH3COONa. Assume no #hange in volume.
0+a , 1./10
(4
1 0log 1./,0.&44 log &,0.301 log 3,0.49911
11. 0CH3COOH1 , 0.14M 0CH3COONa1 , 0.&M
CH3COOH % NaOH CH3COONa % H&O
t , 0 .14 0 0.& 0
t , neut"ali?ation .04 0.1 0.&%0.1 0.1
0CH3COONa1 afte" addition of .1M NaOH , .& % .1 , .3 M
0CH3COOH1 afte" addition of .1M NaOH , .04M
pH , p+a % log
1 A#id 0
1 3alt 0
pH , log 1./ 10
<4
! % log
04 .
3 .
4.944 % log . , 4.4&3
pOH , 14 < 4.4&3 , /.499
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
1&. I6ual volumes of 0.0& M CaCl& and 0.0004 M Na&3O4 a"e mi'ed. >ill a p"e#ipitate fo"m$
+sp Ca3O4 , &.4 10
<4
1&. CaCl& % Na&3O4 Ca3O4 % &NaCl
0.0& F 0.0004 F 0 0
3uppose F moles of )oth a"e mi'ed
0Ca
&%
1 ,
F &
F 0& . 0
[ ]

4
3O
,
F &
F 004 . 0
0Ca
&%
1
[ ]

4
3O
,
F &
F 004 . 0
F &
F 0& . 0

,& 10
<.
3in#e 0Ca
%%
1 [ ]

4
3O < +sp
3o7 it will not p"e#ipitate
13. Cal#ulate simultaneous solu)ilit* of AgCN3 and AgC" in a solution of wate". +sp of AgC"
, 4 10
<13
and +sp of AgCN3 , 1 10
<1&
13. Let solu)ilit* of AgCN3 and AgC" in a solution )e a and ) mole@lit"e
AgCN3 a
! ) a
CN3 Ag

+
+
+
AgC"
)
! ) a
C" Ag

+
+
+
:o" AgCN3
AgCN3
sp
+ 0Ag 10CN3 1
+

1 10
<1&
, a % )!a D1!
:o" AgC" +spAgC" , 0Ag
%
1 0C"
<
1
4 10
<13
, a % )!) D&!
o"
&
10 4
10
)
a
13
1&

a , &)
Q +spAgCN3 , 0Ag
%
1 0CN3
<
1
&) % )!&) , 1 10
<1&
) , 4 10
<9
mole@lit"e
a , &) , /10
(9
mole@ lit"e
1. =he solu)ilit* p"odu#t of

-
4
Ca3O is &.4 10 . :ind out the solu)ilit* in 0.& M
&
CaCl
solution.
1. Let M3N )e the solu)ilit* of 4
Ca3O
in the solution
& &
4 4
0.& 3! 3
Ca3O s! Ca a6! 3O a6!
+
+
+
3 2 2 0.&
+sp , 0Ca
%&
103O4
&(
1

&.410
(-
, 0.& 3
3 ,
-
/
0.4 10
1.&4 10
0.&

&. A solution of HCl has a pH , .. If one mL of it is diluted to 1 lit"e7 what will )e the pH of
"esulting solution$
&. pH , .7 mola"it* of HCl , 10
(.
M
when 1 ml is diluted to 1 Lt
the mola"it* of HCl )e#omes , 10
(-
M
the 0H
%
1 due to ioni?ation of wate" ,10
(9
the "esultant 0H
%
1 , 10
(9
%10
(-
, 1.0110
(9
ap"o'!
pH , ..--
11. A solution #ontains a mi'tu"e of ( ) Ag 0.&M
+
and
&
&
Hg
+
0.&0 M! whi#h a"e sepa"ated )*
sele#tive p"e#ipitation. Cal#ulate ma'imum #on#ent"ation of Iodide ion at whi#h one of them
gets p"e#ipitated almost #ompletel*. >hat pe"#entage of that metal ion is p"e#ipitated$
( )
19 &.
sp sp & &
+ fo" AgI /.4 10 7+ fo" Hg I &.4 10


11. :i"st dete"mine7 whi#h ion sta"ts p"e#ipitating
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
0I
(
1 "e6ui"ed to p"e#ipitate AgI ,
19
sp
1.
+ of AgI
/.4 10
4.&4 10 m
0.&
0Ag 1

0I
(
1 fo" Hg&I& ,
&.
sp & &
13
&
&
+ of Hg I
&.4 10
3.4 10
0.&
Hg

1
]
=his mean that AgI will )e p"e#ipitated fi"st as 0I
(
1 "e6ui"ed fo" AgI is less. Cut when 0I
(
1
"ea#hes 3.410
(13
m. =hen p"e#ipitation of Hg&I& also sta"ts
3o 0Ag
%
1 let at that stage in given as
sp
& &
+ of AgI
0Ag 1
I Hg I
+

1
]
19
4
13
/.4 10
&.4 10 M
3.4 10

A of Ag
%
left unp"e#ipitated
4
&.4 10
100 0.1&A
0.&

A age of Ag
%
, --.//A
=his means when Hg&I& sta"ts p"e#ipitating Ag
%
is almost p"e#ipitated
1&. Cal#ulate the simultaneous sta)ilit* of AgCN3 and AgC" in a solution of wate" +sp AgCN3 ,
&10
(1&
7 +sp AgC" , 1010
(13
.
1&. Let the solu)ilit* of AgCN3 and AgC" in wate" )e a and ) "espe#tivel*
AgCN3 Ag
%
% CN3
(
a a
AgC" Ag
%
% C"
(
) )
0Ag
%
1 , a % )7 0CN3
(
1 ,a and 0C"
(
1 , )
+sp AgCN3 , 0Ag
%
1 0CN3
(
1 , aa%)!
&'10
(1&
, aa%)! D1!
+sp AgC" , 0Ag
%
1 0C"
(
1 , ) a%)!
1010
(13
, )a%)! D&!
Eividing I61! )* &!
1&
13
& 10 a
)
10 10

& ,
a
)
o" a ,&)
8utting the value of a in e61!
.)
&
, &10
(1&
)
&
,
1&
& 10
.

) , 4.9910
(9
mol L
(1
a , &4.9910
(9
, 11.4410
(9
mol L
(1
11. A solution of volume F #ontains MaN mole of MCl and M)N mole of NCl whe"e MOH and NOH
a"e two wea; )ases having disso#iation #onstants +17 +& "espe#tivel*. 3how that the pH of
the solution #an )e e'p"essed as pH ,
1 &
10
> & 1
+ + 1 F
log
& + a+ )+
1

1
+
]
11. MCl M
%
% Cl
(

a@v a@v
NCl N
%
% Cl
(

)@v )@v
Now M
%
and N
%
ions unde"goes h*d"ol*sis simultaneousl*
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
M
%
% H&O MOH % H
%
1
a
'
v
_

,
'1 '1 % '& D i!
3imila"it* fo" N
%
7 N
%
% H&O NOH % H
%
&
)
'
v
_

,
'& '1 % '&
:"om i!
( )
1
1 & 1
w
H
1
' ' '
+
+
+ a @ v
+

D iii!
( )
&
1 & &
w
H
&
' ' '
+
+
+ )@ v
+

D iv!
1 &
a a a )
' and '
F F F F
)e#ause of lowe" values of '1 and '& due to #ommon ion effe#t.

0H
%
1 , '1 % '&
C* adding iii! and iv!
0'1%'&1
&
,
w w
1 &
+ + a )
. .
F + F +
+
w w
1 &
1 &
+ + a )
' ' . .
F + F +
+ +
pH , (log H
%
, ( log 0'1 % '&1 , ( log
w w
1 &
+ + a )
F + F +
+
, (
w
1 &
+ 1 a )
log
& F + +
1

+
1 ' ;
1
]
, ( { }
w
& 1
1 &
+ 1
log + a + )
& F+ .+
1
+
1
]
pH ,
1 &
w & 1
+ + 1 F
log
& + a+ )+
1
_
1
+
1 ,
]
13. 0.0&4 moles of a h*d"o#hlo"ide salt of < amino a#id NH& < CH& < COOH! was dissolved in
&40 ml of wate" and the pH of the solution was &.9. 3ame moles of sodium salt of this a#id is
added to &40 ml wate" and the pH of solution now is 117 Cal#ulate the pH of amino a#id at
whi#h isoele#t"i# point will o##u".
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)

COOH
NH
3
Cl

COOH
NH
3
Cl

+
1
+


COOH
NH
3
COO
NH
3
3
H O
+
+
&
H O
1
3
# H & 10
+
1

]
0.1 # 0.1 0.1
& 4
1
+ C 4 10

NH
&
COONa
NH
&
COO
Na
+
+

#onOugate a#id of aminoa#id

#onOugate )ase of amino a#id
NH
&
COO

&
+w @ +
&
H O +


0.1 #
1
OH

+
NH
&
COOH
0.1 0.1
3 & 4 - w
&
&
+
# 10 7 C 10 + 10
+


Now
COO
NH
3
%
1
1@ +
H
+
+


COOH
NH
3
%
COOH
NH
&
&
+

H
+
+
COO
NH
&
At isoele#t"i# point 0C.A.1 , 0C.C.1
0H
%
1 ,
1 &
+ + pH , ..9
1-. 1 g of mono)asi# a#id in 100g of wate" lowe"s the f"ee?ing point )* 0.1./PC. If 0.& g of same
a#id "e6ui"es 14.1 ml of
10
N
al;ali fo" #omplete neut"ali?ation7 #al#ulate deg"ee of
disso#iation of a#id +f fo" H&O , 1./. + mol
<1
+g!
1-. = ,
m>
w + 1000
f
= , 0.1./7 w , 1g7 > , 100 g7 +f , 1./.
ma#id , 110.91 =his is e'p. Mol.wt.!
Now me6 of a#id , Me6 of Al;ali
I
& . 0
1000 , 14.1
10
1
I6. wt , 13&.44 , Mol. wt. Mono)asi# a#id!s
HA H
%
% A
<
Cefo"e disso#iation 1 0 0
Afte" disso#iation 1<
91 . 110
44 . 13&
M
M
e'p
N

, 1 % , 1-..A
1. A wea; a#id t*pe indi#ato" was found to )e 40A disso#iated at pH , -.1&4-. >hat )e A
disso#iation at pH , -$
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
1. HIn In
(
% H
%

C1(! C C
pH , p+In (
C1 !
log
C

-.1&4- , p+In < log

.
4
_

,
, p+In ( 0.19.0
p+In , -.3010
at pH , -
- , p+In (
1
log
_

,
- , -.3010 < log
1 _

,
N
0.3010 ,log
1

i.e. & ,
1

, 0.3
A disso#iation , 33.3A
9. >hen a su)stan#e AC& is dissolved in wate" it disso#iate into A4 and C4 and the following
e6uili)"ium is esta)lished. 4AC& A4 % &C4
AC&7 A4 and C4 all th"ee a"e solu)le in wate" and a"e non(volatile. >hen 0.4 mola" solution of
AC& was ta;en the )oiling point is found to )e 100.&34. Cal#ulate the e6uili)"ium #onstant fo"
the a)ove "ea#tion.+) , 0.4&!
9. =) , i+)m
0.&34 , i0.4&0.47 i, 0.-
4AC& A4%&C4
C1(!
4
C

&
C
i, 1( %
4
C
%
&
C
0.- ,
4
1

1 . 0
4

7 , 0.4
+# ,
4 4
& &
! 1 C
4
C
4
C

,
3
4
1. 0.4 1 !

putting , 0.4
( )

4
3
! . . 0 4 . 0 1.
4 . 0
0.0.19
10. >hat will )e the "esultant pH when &00 mL of an a6ueous solution of HCl pH , &.0! is
mi'ed with 300 ml of an a6ueous solution of NaOH pH , 1&.0!$
0
3010 . 0 & Log
10

1
10. pH of HCl , & 0HCl1 , 10
(&
M
pH of NaOH , 1& 0NaOH1 , 10
(&
M
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HCl % NaOH NaCl % H&O
Initial me6 &0010
(&
30010
(&
0 0
Me6 afte" "ea#tion 0 1 & &
0OH
(
1 left f"om NaOH ,
400
1
, &10
(3
M
pOH , ( log0OH1 , ( log &10
(3
, &..-/-
pH , 11.3010
.. I'plain the followingB
a! >h* is sodium a#etate solution al;aline$
)! >h* pH of a
9
10

M HCl a6ueous solution is not 9.0$

.. a! In a6ueous fo"m7 a#etate ion of sodium a#etate "ea#ts with wate" and p"odu#e OH

ion
whi#h is "esponsi)le fo" al;aline natu"e.
3 & 3
CH COO H O CH COOH OH

+ +


i.e. h*d"ol*sis of sodium a#etate in wate".
)! In a6ueous fo"m of
9
10 MHCl

+
1 +
]

9 9
&
8" odu#e 8" odu#e
)* HCl of H
=otal H 10 10
O
( )
9 9
H 10 1 1 & 10
+
1 +
]
pH, 9(log& , ..9 app"o'.!
9. Cal#ulate the solu)ilit* of AgCl in 0.&0 M
3
AgNO .
10
sp
+ of AgCl is 1 10

.
9. Let the solu)ilit* of AgCl , 3 mol lit
1
He"e7
sp
+ of AgCl Ag Cl
+
1 1
] ]
[ ] [ ]
10
1 10 3 0.& 3

+
3 22 0.&!
10
10 1
10
3 4 10 mol lit
.&

10. Cal#ulate the num)e" of
+
H ions p"esent in 10 mL solution whose pH,1&
10. pH , 1&
1&
H 10 M
+
1
]
Moles ,
1& & 14
10ml
H 10 10 10
1000ml
+
1
]
Mole#ules ,
A
Moles N
14 &3 -
10 ..0&3 10 ..0&3 10

14. At what minimum pH will ( )
3
3
10 M Al OH

go into solution v , 1 lit! as ( )

4
Al OH

and7 at what
ma'imum pH it will disso#iated as
3
Al
+
$
Given ( )
3 34
4
Al OH Al 4OH +e6 1.3 10

+
+


( )
3 33
3
Al OH Al 3OH +sp 4 10
+
+

0log 1.3,0.113-7 log 1.91 , 0.&3301
14. In #ase I7
( )
&
3
4
OH OH
+e6
&.. 10
+sp 10
Al OH

1 1
] ]

1
]
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4
OH &.. 10

1
]
( ) [ ]
4
pOH log &.. 10 4.. pH -.4

In #ase II7
( )
33
10 3
3 3
+spof Al OH
4 10
OH 3 3 1.91 10 M
10 Al

1
]
1
]
( )
10
pOH log 1.91 10 -.9/

pH 14 -.9/ 4.&&
19. Cal#ulate a! H*d"ol*sis #onstant7 )! deg"ee of h*d"ol*sis7 #! pH fo" 0.01 N solution of
sodium a#etate if +a ,
4
1.- 10

fo" a#idi# a#id. 0log&.1/ , 0.33/41

19.
+h
3 & 3
CH COO H O CH COOH OH

+ +


+w
&
+a
3 3
H O H OH
CH COOH CH COO H
+
+

+

' ;






a! H*d"ol*sis #onstant +h!
14
10
4
+w 10
4.&. 10
+a 1.- 10

)! Eeg"ee of h*d"ol*sis h! ,
10
4
4.&. 10
+h@ C &.&- 10
0.01

#! :o" pH dete"mination7 we have to dete"mine
OH

1
]
o"7
4 .
OH 0.01 &.&- 10 &.&- 10 M

1
]

14
-
.
10
H 4.39 10 M
&.&- 10

1
]

( )
-
pH log 4.39 10 /.3.

9. Calomel Hg&Cl& is a #ompound of the diatomi# ion of me"#u"* I! Hg&
&%
H #hlo"ide ion Cl
(
.
Although most me"#u"* #ompounds a"e ve"* poisonous si'teenth #entu"* ph*si#ians used
#alomel as a medi#ation. =hei" patients did not die of me"#u"* poisoning )e#ause #alomel is
6uite insolu)le
& 1/
& & & sp
Hg Cl Hg a6! &Cl a6!7 + 1.1 10
+
+
Cal#ulate the mola" solu)ilit* of Hg&Cl&.
9.
&
& & &
Hg Cl Hg &Cl
+
+
s &s
+sp ,
&
&
&
Hg Cl
+
1 1
] ]
1/ &
1.1 10 / &s!

3 1/
4s 1.1 10

s ,
9
..4 10

-. Compa"e the deg"ee of disso#iation of 0.1M HCNO to that of 0.& M HCN. Given +a0HCNO1
,
4 10
1.& 10 H+aHCN! 4 10


-.
1 1 1 1 &
& & & & 1
+a @ C +a C
+a @ C +a C

4
. 10

, 994.4 times
1&. a! Cal#ulate the pH of 0.1 M Na&H8O4. Given that fo" H38O4
3 9 11
1 & 3
+a 10 7+a 10 7+a 10

+
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)!
I II
C H
&
N
N
C H
&
N
%
N
(

Among the a)ove two #anoni#al fo"ms whi#h is mo"e sta)le and wh*$ [2+2=4]
1&. a! 3in#e H8O4
(&
is the #onOugate )ase of the a#id H&8O4
(
H H8O4
(&
is the a#id of the
#onOugate )ase 8O4
3(

pH of the amphip"oti# anion H8O4

&(
,
& 3
p+a p+a 9 11
-
& &
+ +

)! CH& , N
%
, N
(
II! is mo"e sta)le #anoni#al fo"m )e#ause g"eate" no of #ovalent )onds
and even the o#tet #ompletion in II! fo"m is to a g"eate" e'tent.
14. 0.1 M HCOOH solution is tit"ated against 0.04 M +OH solution. Cal#ulate pH at Q and 3@4
th
stages of neut"ali?ation of a#id. =he pH fo" 0.1 M HCOOH is 3. 0log 3,0.49911 [4]
14. +a fo" CH3COOH
0H
%
1 , 10
(3
C,10
(3
,
&
3
10
1 . 0
10

+a, C
&
7 , 0.110
(&
!
&
, 10
(4
Case I HCOOH % +OH HCOO+ %H&O
Cefo"e adding +OH 0.1 0
Afte" adding +OH 0.1
&
1
0.1
&
1
>hen
&
1
a#id neut"ali?es
pH , ( log +a % log
1 a#id 0
1 salt 0
pH , (log 10
(4
% log
4 . 0
4 . 0
pH , ( log 10
(4
pH , 4
Case II HCOOH % +OH HCOO+ % H&O
Cefo"e adding +OH 0.1 0
Afte" adding of +OH 0.1
4
1
0.1
4
3
fo"
4
3
neut"ali?ation 7pH , ( log 10
(4
% log
&4 . 0
94 . 0
pH , 4.4991
1.. Aniline is an amine that is used to manufa#tu"e d*es. It is isolated as aniline h*d"o#hlo"ide
0C.H4NH31Cl7 a salt p"epa"ed )* the "ea#tion of the wea; )ase aniline and h*d"o#hlo"i# a#id.
>hat is the pH of a 0.&33 M solution of aniline h*d"o#hlo"ide$ 0+) fo" aniline
10
4.. 10

1.
If it is )ehaving as a#id. [4]
1..
. 4 3
C H NH
+
ion is the #onOugate a#id of a wea; )ase
+a fo" C.H4NH3
%
! R +) fo" C.H4NH&! , +w ,
14
1 10

+a fo" C.H4NH3
%
!
14
4
10
) . 4 &
;w 1 10
&.& 10
+ fo" C H NH ! 4.. 10

0H 1 ;a#
+
,
4
&.& 10 0.&33

3
0H 1 &.&. 10 M
+

pH , &..4
19. >hat is the ma'imum possi)le #on#ent"ation of Ni
&%
ions in wate" at &4PC! that satu"ated
with H&3 0.1 M at &4PC! and maintained at pH , 37 with HCl. +sp of Ni3 is
3 10
<&1
. H&3 disso#iates into two steps7 ea#h with e6uili)"ium #onstant.
H&3 H
%
% H3
<
+a1 , -.1 10
</
H3
<
H
%
% 3
&<
+a& , 1.1 10
<1&
[4]
19. =he ove"all disso#iation of H&3 will )e the p"odu#t of +a1 and +a&
/ 1& -
1 &
+a +a +a -.1 10 ! 1.1 10 ! 1 10


3atu"ated H&3 app"o'imatel* 0.1 M and disso#iation of H&3 is ve"* slight
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
& & 1- 1 &0
0H 1 03 1 1 10 10 10
+

3in#e pH , 37 0H
%
1 , 10
3
M
& & &0
& 14
& .
0H 1 03 1 10
03 1 10 M
0H 1 10
+

+

3in#e Ni3 will p"e#ipitate7 if the solu)ilit* p"odu#t is e'#eeded7 the highest value whi#h ni#;el
#on#ent"ation #an have is
&1
& 9
14
3 10
0Ni 1 3 10 M
10

&0. a! >hat is the pe"#entage disso#iation if 1 mole of J&S is int"odu#ed into 1.10 L vessel at
1000 +$ +# fo" the disso#iation of J&S,110
(.
.
&J&Sg! &J&g! % S&g! [2]
)! =he pH of an a6ueous ammonia is 11.4. :ind the mola"it* of the solution. +) fo" NH4OH
is 1./10
(4
. 0Antilog 0.4,3.1.&1 [2]
&0. a! &J& S g! &J&g! %S&g!
moles )efo"e disso#iation 1 0 0
Moles afte" disso#iation 1(! @&
>he"e is deg"ee of disso#iation of J& S7 Folume of #ontaine" , 1.10 L
+# ,
[ ] [ ]
[ ]
.
&
&
&
&
&
&
&
10 1
1 . 1
1
1 . 1 & 1 . 1
S J
S J

,
_

,
_

,
_

Assuming 1( 1 sin#e is small )e#ause +# , 10

(.
, 1.310
(&
o" 1.3A
)! pH , 11.4 i.e. < log 0H
%
1 , 11.4
0H1
%
, 3.1.&10
(1&
0OH
(
1 ,
[ ]
M 0031. . 0
10 1.& . 3
10
H
+w
1&
14

+
Let the initial #on#ent"ation of NH4OH )e ' mole@ L
NH4OH NH4
%
% OH
(
Initial #on#. ' 0 0
#on#. at e6u. '(0.0031.! 0.0031. 0.0031.
+) ,
4
10 / . 1
0031. . 0 '
0031. . 0 0031. . 0

' , 0.44/ M
4. Cal#ulate the solu)ilit* of AgCl in 0.&0 M
3
AgNO .
10
sp
+ of AgCl is 1 10

.
4. Let the solu)ilit* of AgCl , 3 mol lit
1
He"e7 sp
+ of AgCl Ag Cl
+
1 1
] ]
[ ] [ ]
10
1 10 3 0.& 3

+
3 22 0.&!
10
10 1
10
3 4 10 mol lit
.&

.. I'plain the va"iation of pH of a solution of a wea; a#id with dilution$ Give "eason fo" *ou"
answe".
.. =he pH will in#"ease
HA H
%
% A
(
C 1(! C C DDDD at e6uili)"ium

C
1
DDDDD.. Loughl*!
:o" eve"* 4( fold in#"ease in dilution7 C will "edu#e to 1@4
th
and hen#e will )e dou)led7 so
0H
%
1 whi#h is C will de#"ease on dilution and hen#e pH will in#"ease.
9. 100 mL 0.& M solution of CH3COONa and 40 ml 0.& M solution of HCl a"e mi'ed togethe".
>hat is the pH of the "esulting mi'tu"e$ p+)CH3COO
(
! , -.&. and p+w , 14!
9. 8+a , p+w ( p+) , 14 ( -.&. , 4.94
No. of millimole of CH3COONa ta;es , 1000.& , &0
No. of millimole of HCl added , 400.&,10
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
CH3COONa % HCl CH3COOH % Na
%
% Cl
(

=hus7 10 millimoles HCl will "ea#t withe 10 millimole CH3COONa to fo"m 10 millimole
CH3COOH. Hen#e "esulting mi'tu"e will )e an a#id )uffe" mi'tu"e with 10 millimole of salt
and a#id ea#h.
8H , p+a % log
[ ]
[ ] a#id
slat
, 4.94% log
10
10
, 4.94
1&. Cal#ulate pe"#entage h*d"ol*sis of
+
4
NH and CN
<
ions in a 1M NH4CN solution. Given
+aHCN! , 4.4 10
<10
and +)NH4OH! , &10
<4
and +w , 10
<14
1&. Coth
+
4
NH and CN
<
ions h*d"ol*se in solution. Hen#e we have
+
4
NH % CN
<
% H&O NH4OH% HCN
C1(! C1(! C C
+H ,
1 CN 10 NH 0
1 HCN 10 OH NH 0
4
&
+
3in#e 0NH4OH1 , 0HCN1 , C
[ ] ! 1 C 1 CN 0 NH
4

+
+h ,
! 1 C ! 1 C
! C ! C


,
&
&
! 1

o" ,
+h 1
+
h
+
+h ,
14
4 10
10
& 10 !4.4 10 !

, 1.1
,
1.1
1 1.1 +
, 0. 9&4
Hen#e7 9&.4 A of NH4CN is h*d"ol*sed in the solution
14. 14 mL solution of wea; mono)asi# a#id "e6ui"es 30 ml 0.4 M NaOH solution fo" the end
point. =he pH of the a#id solution upon addition of 10 mL 0.4 M NaOH solution du"ing the
tit"ation was 4.4 #al#ulate pH of the a#id solution
i! when no al;ali had )een added and
ii! when e6uivalen#e point was "ea#hed and the solution so o)tained was diluted to 94 mL
)* adding distilled wate". Log &, 0.30 and +w , 10
(14
!
14. Coth a#id and al;ali have thei" n ( fa#to" e6ual to 17 so the* must "ea#t in thei" e6uimole#ula"
p"opo"tion.
30 mL 0.4 M NaOH , 14 millimole NaOH 14 millimole wea; a#id HA!
3o7 14 mL HA solution #ontains 14 millimole HA.
Mola"it* of a#id solution ,
1
14
14

>hen 10 mL 0.4 M NaOH i.e. 100.4 ,4 millimole! added7 4 millimol soda salt NaA! will )e
fo"med at 10 millimoles of HA will "emain f"ee. =he mi'tu"e will )e an a#id )uffe" mi'tu"e fo"
whi#h.
pH , p+a % log
[ ]
[ ] A#id
3alt
4.4 , p+a % log
10
4
p+a , 4./
pH of a#id solution when no al;ali had )een added
Mola" #on#. of a#id )eing app"e#ia)le will )e negligi)le in #omp"ession to unit*7 so
pH ,
1 1
0p+a log#1 04./ log1 1
& &

pH of the solution at the e6uivalen#e point B
No. of millimole of salt fo"med , 14
volume of solution , 94
mola" #on#. of salt solution 14@94 , 1@4 , 0.&
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
=he salt fo"med will )e h*d"ol*sed to ma;e the fee)l* al;aline
pOH ,
[ ] C log p+a p+w
&
1

,
[ ] & . 0 log / . 4 14
&
1

, 4.-4
pH , 14(4.-4 , -.14
&0. Afte" solid 3"CO3 was e6uili)"ated with a pH /.4 )uffe"7 the solution was found to have
03"
&%
1 , 310
(4
moles L
(1
7 what is solu)ilit* p"odu#t #onstant fo" 3"CO3
0+& fo" CO3
(&
is 4.910
(11
1 Anti log 0.4,3.1.&!
&0. CO3
&(
% H&O HCO3
(
% OH
(

+h ,
3
11 &
&
3
OH HCO
+w +w
+
4.9 10 CO


1 1
] ]

1

]
0H3O
%
1 , ( log /.4 , 3.1.&10
(-
3
- 11 &
3
HCO
+w +w
3.1.& 10 4.9 10 CO

1
1
]

1
1
]
]
-
3
11 &
3
HCO
3.1.& 10
4.9 10 CO

]

1

]
.9.&
03"
%&
1 , 0HCO3
(
1 % 0CO3
&(
1
, .9.&0CO3
&(
1 % 0CO3
&(
1
, ./.&0CO3
&(
1 ,310
(4
0CO3
(&
1 ,
4
3 10
./.&

4.410
(.
+ps , 0310
(4
1 04.410
(.
1 ,13.&10
(10
1. >hat is the solu)ilit* of AgCl in 0.1 M NaCl solution$ +sp AgCl , 1./10
(10
L
(1
3
(1
.
1. +sp , 0Ag
%
1 0Cl
(
1
1./10
(10
, 33%0.1!
3,1./10
(-
&. A #e"tain wea; a#id has a disso#iation #onstant of 110
(4
. :ind the e6uili)"ium #onstant fo"
its "ea#tion with a st"ong )ase.
&. + ,
10
10
+w
+a
+a @ +w
1
+h
1

10. An a#id ( )ase indi#ato"7 HIn+in , 10
(.
! displa*s the #olou" of its a#id fo"m onl* when it is
ionised to a ma'imum of -.0-A7 while it displa*s its )asi# #olou" when it is ionised to the
e'tent of at least -4.&4A. >hat is the pH ( "ange of the indi#ato"$
10. p+in , .
pH , p+in % log
[ ]
[ ] HIn
In

:o" a#idi# #olou" to p"evailB

[ ]
[ ] 10
1
-1 . -0
0- . -
HIn
In

pH . ( 1 , 4
:o" )asi# #olou" to p"evailB
[ ]
[ ]
&0
9. . 4
&4 . -4
HIn
In

pH . % 1.3 , 9.3
pH "ange B 4 ( 9.3
1&. Eete"mine the pOH of a solution afte" 0.1 moles of NaOH is added to 1L of a solution
#ontaining 0.14M CH3COOH and 0.&M CH3COONa. Assume no #hange in volume.
0+a , 1./10
(4
1 0log 1./,0.&44 log &,0.301 log 3,0.49911
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
1&. 0CH3COOH1 , 0.14M 0CH3COONa1 , 0.&M
CH3COOH % NaOH CH3COONa % H&O
t , 0 .14 .1 0 0
t , neut"alisation .04 0 .1 .1
0CH3COONa1 afte" addition of .1M NaOH , .& % .1 , .3 M
0CH3COOH1 1 afte" addition of .1M NaOH , .04M
pH , p+a % log
1 A#id 0
1 3alt 0
pH , log 1./ 10
<4
! % log
04 .
3 .
4.944 % log . , 4.4&3
pOH , 14 < 4.4&3 , /.499
13. I6ual volumes of 0.0&M CaCl& and 0.0004 M Na&3O4 a"e mi'ed will a ppt fo"m$
+sp Ca3O4 , &.4 10
<4
13. CaCl& % Na&3O4 Ca3O4 % &NaCl
0.0& F 0.0004 F 0 0
3uppose F moles of )oth a"e mi'ed
0Ca
&%
1 ,
F &
F 0& . 0
[ ]

4
3O ,
F &
F 004 . 0
0Ca
&%
1 [ ]

4
3O ,
F &
F 004 . 0
F &
F 0& . 0
,& 10
<.
3in#e 0Ca
%%
1 [ ]

4
3O < +sp
3o7 it will not p"e#ipitate
14. Cal#ulate simultaneous solu)ilit* of AgCN3 and AgC" in a solution of wate". +sp of AgC"
, 4 10
<13
and +sp of AgCN3 , 1 10
<1&
14. Let solu)ilit* of AgCN3 and AgC" in a solution )e a and ) mole@lit"e
AgCN3
a
! ) a
CN3 Ag

+
+
+
AgC"
)
! ) a
C" Ag

+
+
+
1 10
<1&
, a % )!a
:o" AgC" +spAgC" , 0Ag
%
1 0C"
<
1
4 10
<13
, a % )!)
o" &
10 4
10
)
a
13
1&

a , &)
Q +spAgCN3 , 0Ag
%
1 0CN3
<
1
&) % )!&) , 1 10
<1&
) , 4 10
<9
mole@lit"e
a , &) , /10
(9
mole@ lit"e
3. A solution is 0.0- M in HCl and 0.0- M in
&
CHCl COOH.
=he pH of this solution is 1.
Cal#ulate
a
+
fo"
&
CHCl COOH.
3.
& &
CHCl COOH CHCl COO H
+
+


0.0- 0 0.0- f"om HCl!
0.0- < '! ' 0.0- % '!
pH of the solution is 1 so
1
0H 1 10
+

0.0- % ' , 0.1

' , 0.01
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
& &
a
&
0CHCl COO 1 0H 1 0.01 0.1
+ 1.&4 10
0CHCl COOH1 0.0- 0.01!
+

4. I6uili)"ium #onstant fo" the h*d"ol*sis of

3 &
:e to :eOH!
+ +
and
3
H is ..4 10 .
+
>hat is the
ma'imum pH at whi#h at least -4A of the total
3
:e
+
in a dilute solution e'ists as
3
:e $
+
( log 0.1&34 , 0.-0/3!.
4.
3 &
&
:e H O :eOH! H
+ + +
+ +


C1 < h! Ch Ch
&
C.h 4
+h 7 h
1 h 100

3
C 4 4 100
..4 10
100 100 -4

C , &.49 M
4
0H 1 &.49
100
+

pH , 0.-0/3
-. A solution is 0.1 M in
Cl

and 0.001 M in
&
4
C"O .

If solid
3
AgNO
is g"aduall* added to this
solution7 whi#h will p"e#ipitate fi"st7 AgCl o"
& 4
Ag C"O $
And also find out what is the
#on#ent"ation of ion7 that p"e#ipitates fi"st7 at the time when the se#ond ion sta"ts
p"e#ipitating.
10 &
sp
+ AgCl! 1.9 10 M

1& &
sp & 4
+ Ag C"O ! 1.- 10 M

-. 0Ag 1
+
needed to p"e#ipitate AgCl H
& 4
Ag C"O B
:o" AgCl7
10 &
-
1.9 10 M
0Ag 1 1.9 10 M
0.1M

:o" & 4
Ag C"O 7
1& 3
4
1.- 10 M
0Ag 1 4.4 10 M
0.001M

3o7 AgCl p"e#ipitates fi"st.
& 4
0Cl 1 when Ag C"O

sta"ts p"e#ipitating
10 &
.
4
1.9 10 M
0Cl 1 3./. 10 M
4.4 10 M

10. A mi'tu"e of solid

4
3"3O
and solid
4
Ca3O
is sha;en up with wate" until satu"ation
e6uili)"ium is esta)lished.
Given that +sp3"3O4! , 9.. R 10
(9
M
&
and +sp Ca3O4!,1.4 R 10
(-
M
&
7 #al#ulate the
simultaneous solu)ilit* of
4 4
3"3O and Ca3O .
10. If ' and * a"e the "espe#tive solu)ilities of
4 4
3"3O and Ca3O
in the solution
sp 4
+ 3"3O ! '' *! +
sp 4
+ Ca3O ! *' *! +
9
'' *! 9.. 10 ............i!

+
-
*' *! 1.4 10 ............ii!

+
3olving i! and ii! fo" ' and *
4
' /.9 10 M

.
* 1.9 10 M

11. 0.-. g of HI we"e heated to attain e6uili)"ium7 & &
&HI H I . +


=he "ea#tion mi'tu"e on11.
& &
&HI H I +


3
9.4 10

0 0
3
9.4 10 '!

'
&

'
&
Me6. of
&
I
fo"med at e6uili)"ium , Me6. of h*po used fo" tit"ation
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
&
I
>
1
1000 14.9
I 10

3
&
>
of I 1.49 10
I

_


,
Moles of
&
I
fo"med
3
3
1.49 10
0.9/4 10
&

3
'
0.9/4 10
&


3
' 1.49 10

Eeg"ee of disso#iation of HI
3
3
1.49 10
0.&0-
9.4 10

13. A ve"* impo"tant )uffe" solution in anal*ti#al #hemist"* is the one p"epa"ed )* mi'ing e6ual
volumes of & M
4
NaH3O
and 1.. M
& 4
Na 3O .
One of its uses is to ;eep h*d"ogen < ion
#on#ent"ation stead* du"ing p"e#ipitation of sulfides )* the "ea#tion
&
& g! s!
M H 3 M3 &H
+ +
+ +
a! Given that disso#iation #onstant fo"
&
4 4
H3O H 3O
+
+

is
&
1.&. 10 7

what is the pH
of the a)ove )uffe"$
)! >hat would the pH )e#ome afte" p"e#ipitation of all the
&
Co
+
out of 10 mL of 0.040 M
&
CoCl
using
&
H 3
in the a)ove )uffe"$
&
log1.&. 10 1./-log71.&4 0.0-97log0.9/& 0.10.

1

]
[23 = 6]
13. a!
a
1
pH p+ log
0./
+
, 1.--9
a! 10 mL of 0.04 M has )een p"e#ipitated out using
&
H 3
&
&
Co H 3 Co3 &H
+ +
+ +
0.0004 0.001
If 0.0004 mol of
&
Co
+
is p"e#ipitated7 0.001 mol of
H
+
will )e gene"ated. 3uppose 100
mL ea#h of
4 & 4
NaH3O and Na 3O
a"e added to ma;e the )uffe" initiall*.
&
4 4
3O H H3O
+
+


0.0/ mol 0.001 0.1 mol
Afte" "ea#tion 0.09- 0 0.101
a a
0salt1 0.09-
pH p+ log p+ log
0a#id1 0.101
+ +
, 1.- % 0.10.
, &.00.
14. a! 100 g of NaCl is sti""ed in 100 mL of wate" at
o
&4 C
till e6uili)"ium is attained. Howmu#h
amount of NaCl will go into solution if
sp
+
of NaCl , 39./&
&
M .
If the solution at
e6uili)"ium is diluted to &00 mL7 #al#ulate the new solu)ilit* of NaCl.
)! At 11&9 + and 1 atm p"essu"e7 a gaseous mi'tu"e of CO and
&
CO
in e6uili)"ium with
solid #a")on has -0.44A CO )* mass
s! &g! g!
C CO &CO +


Cal#ulate
#
+
fo" the "ea#tion at the a)ove tempe"atu"e. [2 3 = 6]
14. a! 3olu)ilit* of NaCl , ..14 mol @ lit

..14 4/.4 g@ lit


..14 4/.4
g@ mL 3.g@ 100mL
10

3. g of NaCl goes into solution.
On dilution7 solu)ilit* NaCl does not #hange.
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
)! s! &g! g!
C CO &CO +


-.44 g -0.44 g
&
CO CO
-.44 -0.44
n 0.&1mol n 3.&3 mol
44 &/

&
1
&
CO
p
CO
n ! p 3.&3 3.&3 1
+ 14.44 atm
n 0.&1 3.44 n
_



,

p
#
n 1
+
14.44
+ 0.14. m@ L
L=! 0.0/&1 11&9!

1.. =he solu)ilit* of

3
CaCO
is 9 mg @ L. Cal#ulate the solu)ilit* p"odu#t of
3
CaCO
f"om this
info"mation and f"om the fa#t that when
& 3
Na CO
is added slowl* to a solution #ontaining
e6uimola" #on#. of
& &
Ca and Ca 7
+ +
no ppt. of
3
CaCO
is fo"med until -0A of
&
Ca
+
has )een
p"e#ipitated as
3
CaCO
. [4]
1..
&
3
10
sp 3
9 10
+ of CaCO 4- 10
100

,
>hen
&
Ca
+
is -0A p"e#ipitated then onl*
3
CaCO
sta"ts p"epitating. =hen if the solution
#ontains a m @ L of
& &
Ca H Ca
+ +
ea#h7
& & 10
3
0Ca 1 0CO 1 4- 10
+

10
&
3
4- 10
0CO 1
a

Now fo"
3
CaCO
7
& &
sp 3
+ 0Ca 1 0CO 1
+

10
a 10 4- 10
100 a

/. >hat is the pH of a 0.4 M a6ueous NaCN solution$
)
p+ of CN 4.9

/. a
p+
fo" HCN , 14 < 4.90 , -.30
&
NaCN H O NaOH HCN + +


Initial moles 1 0 0
At e6uili)"ium 1 < h h h
w
a
+ #
0OH 1 Ch
+

[ ]
w a
1
pOH p+ p+ log#
&

[ ]
1
14 -.3 0.3010
&
+
, &.4
pH 14 &.4
, 11.4
-. >hat
3
H O !
+
must )e maintained in a satu"ated
&
H 3
solution to p"e#ipitate
&
8)
+
)ut not
&
Tn
+
f"om a solution in whi#h ?in# ion is p"esent at a #on#ent"ation of 0.01 M$
&&
sp &
+ of H 3 1.1 10

&1
sp
+ of Tn3 1.0 10

-. :o" Tn3 not )e p"e#ipitated f"om a solution of
& &
Tn and 8)
+ +
& &
sp
0Tn 1 03 1 + of Tn3
+
<
& & &1
010 1 03 1 1.0 10

<
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
o" the ma'imum
& 1-
03 1 10

at whi#h Tn3 will )egin to p"e#ipitate o" upto this
#on#ent"ation7 no ppt. >ill o##u"
&
&
H 3 &H 3
+
+


& & &&
0H 1 03 1 1.1 10
+

& 1- &&
0H 1 10 ! 1.1 10
+

&
0H 1 3.3 10 M
+

14. Given7
3 & 3
AgNH ! Ag &NH
+ +
+


/ 10
# sp
+ ..& 10 and + of AgCl 1./ 10

at &-/ +. Cal#ulate the #on#ent"ation of the
#omple' in 1.0 M a6ueous ammonia.
14. 3 & 3
AgNH ! a6! Ag a6! &NH a6!
+
+ +


&
3
#
3 &
0NH 1 0Ag 1
+
0AgNH ! 1
+
+

AgCls! Ag a6! Cl a6!

+
+


sp
+ 0Ag 10Cl 1
+

3
0NH 1 1M
3 &
0AgNH ! 1 0Cl 1 ) )e#ause Ag
+ +

o)tained f"om AgCl passes in
3 &
0AgNH ! 1
+
state
=he"efo"e
&
# 3
&
sp 3 &
+ 0NH 1 1
+ 0Cl 1 0AgNH ! 1 )
+

10
& &
/
1./ 10
) 0.&- 10
..& 10

1
) 0.43- 10

3 &
0AgNH ! 1 0.043- M
+

19. >hat is the ma'imum possi)le #on#ent"ation of Ni
&%
ions in wate" at &4PC! satu"ated with
H&3 0.1 M at &4PC! and maintained at pH , 37 with HCl. +sp of Ni3 is
3 10
<&1
. H&3 disso#iates into two steps7 ea#h with e6uili)"ium #onstant.
H&3 H
%
% H3
<
+a1 , -.1 10
</
H3
<
H
%
% 3
&<
+a& , 1.1 10
<1&
19. =he ove"all disso#iation of H&3 will )e the p"odu#t of +a1 and +a&
/ 1& -
1 &
+a +a +a -.1 10 ! 1.1 10 ! 1 10


3atu"ated H&3 app"o'imatel* 0.1 M and disso#iation of H&3 is ve"* slight
& & 1- 1 &0
0H 1 03 1 1 10 10 10
+

3in#e pH , 37 0H
%
1 , 10
3
M 7
& & &0
& 14
& .
0H 1 03 1 10
03 1 10 M
0H 1 10
+

+

3in#e Ni3 will p"e#ipitate7 if the solu)ilit* p"odu#t is e'#eeded7 the highest value whi#h ni#;el
#on#ent"ation #an have is
&. Cal#ulate the solu)ilit* of Mn3 in pu"e wate". Assume h*d"ol*sis of 3
< <
ions.
+spMn3! , &.4 10
<10
1
a
+
and
&
a
+
of H&3 a"e 1 10
<9
and 1 10
<14
"espe#tivel* [6]
&. a! Let mola" solu)ilit* of Mn3 )e 'M
Mns!
+ &
'
Mn
%
&
'
3
3
< <
% H&O H3
<
% OH
<
14
14
a
>
h
10 1
10 1
+
+
+
&

, 1
H3
<
% H&O H&3 % OH
<
9
14
a
>
h
10 1
10 1
+
+
+
1

, 1 10
<9
As
h h
+ + >>
7 fi"st step h*d"ol*sis is almost #omplete
' , 0Mn
&%
1 , 0H3
<
1 , 0OH
<
1
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Conside" fi"st step h*d"ol*sis 7
1 3 0
1 OH 0 1 H3 0
+
&
h

o"7 03
&<
1 ,
h
+
1 OH 0 1 H3 0

,
1
'
&
At e6uili)"ium7 0Mn
&%
1 03
&<
1 , +sp , &.4 10
<10
O" ' ,
&
10
'
10 4 . &

7 ' , ..3 10
<4
M
4. A wea; )ase 40 ml was tit"ated with 0.1 M HCl. =he pH of the solution afte" addition of 10 ml
and &4 ml we"e found to )e -./4 and -.&4 "espe#tivel*. Cal#ulate +) of the )ase and pH
a! At e6uivalen#e point
)! On addition of &0 ml HCl mo"e afte" e6uivalen#e point.0log 3.-/,0..7 log &.4,0.47 log
1.9,0.&37 log 4,0..-/7 log 1...,0.&&1 [3+3=6]
&1
& 9
14
3 10
0Ni 1 3 10 M
10

&. Cal#ulate the solu)ilit* of Mn3 in pu"e wate". Assume h*d"ol*sis of 3
< <
ions.
+spMn3! , &.4 10
<10
1
a
+
and
&
a
+
of H&3 a"e 1 10
<9
and 1 10
<14
"espe#tivel* [6]
&. a! Let mola" solu)ilit* of Mn3 )e 'M
Mns!
+ &
'
Mn
%
&
'
3
3
< <
% H&O H3
<
% OH
<
14
14
a
>
h
10 1
10 1
+
+
+
&

, 1
H3
<
% H&O H&3 % OH
<
9
14
a
>
h
10 1
10 1
+
+
+
1

, 1 10
<9
As
h h
+ + >>
7 fi"st step h*d"ol*sis is almost #omplete
' , 0Mn
&%
1 , 0H3
<
1 , 0OH
<
1
Conside" fi"st step h*d"ol*sis 7
1 3 0
1 OH 0 1 H3 0
+
&
h

o"7 03
&<
1 ,
h
+
1 OH 0 1 H3 0

,
1
'
&
At e6uili)"ium7 0Mn
&%
1 03
&<
1 , +sp , &.4 10
<10
O" ' ,
&
10
'
10 4 . &

7 ' , ..3 10
<4
M
4. A wea; )ase 40 ml was tit"ated with 0.1 M HCl. =he pH of the solution afte" addition of 10 ml
and &4 ml we"e found to )e -./4 and -.&4 "espe#tivel*. Cal#ulate +) of the )ase and pH
a! At e6uivalen#e point
)! On addition of &0 ml HCl mo"e afte" e6uivalen#e point.0log 3.-/,0..7 log &.4,0.47 log
1.9,0.&37 log 4,0..-/7 log 1...,0.&&1 [3+3=6]
4. Let COH is )ase with no"malit* N
COH % HCl CCl % H&O
Initial Me6. 40 N 10 0.1 0
Me6. of afte" tit"ation 40 N < 1 0 1
Medium is still )asi# as #lea" f"om pH. 3o a#id a#ts as limiting "eagent. :u"the" mi'tu"e
a)ove fo"ms a )asi# )uffe" solution.
pOH , p+) % log
1 )ase 0
1 salt 0
4.1. , p+) % log
1 N 40
1

D1!
3imila"l* afte" addition of &4 ml HCl
4.9. , p+) % log
4 . & N 40
4 . &

D&!
:"om &! < 1!
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0.. ,
( )
1
1 N 40
4 . & N 40
4 . &
log

3.-/ ,
( )
( ) 4 . & N 40
1 N 40 4 . &

N , 0.1
putting N , 0.1 in e6uation 1!
4.1. , p+) % log
1 1 . 0 40
1

+), 1.93 10
<4
At e6uivalen#e point we #al#ulate pH )* salt h*d"ol*sis
C
%
% H&O COH % H
%
C1 < ! C C
C ,
&
1 . 0
&
N

, 0.04 =otal volume is dou)led!

pH ,
&
1
p+w < p+) < log C! , 4.1&
,
&
1
14 < 4.9. < log 0.04!
, 4.&9
Afte" addition of HCl7 the pH is #al#ulated f"om HCl left un"ea#ted onl*
Me6. of HCl left , &0 0.1 , &
No"malit* of HCl ,
1&0
&
, 0.01..
pH , < log 0.01..! , 1.9/
&. >hethe" pH of a solution of wea; a#id will in#"ease o" de#"ease upon dilution$ Give "eason
fo" *ou" answe" in )"ief.
&. =he pH will in#"ease
HA H
%
% A
(

CI ( ! C C D at e6uili)"ium
,
C
1
o"
C
+
a
"oughd"* negativit* in #ompassion to unit*!
=hus on 4 ( fold dilution whe"e #on#. de#"eases to 1@4
th
!7 will )e almost dou)led. =hus C
i.e. 0H
%
1 de#"eases upon dilution and hen#e pH will in#"ease
3. 100 mL 0.& M solution of CH3COONa and 40 ml 0.& M solution of HCl a"e mi'ed togethe".
>hat is the pH of the "esulting mi'tu"e$ p+)CH3COO
(
! , -.&. and p+w , 14!
3. 8+a , p+w ( p+) , 14 ( -.&. , 4.94
No. of millimole of CH3COONa ta;es , 1000.& , &0
No. of millimole of HCl added , 400.&,10
CH3COONa % HCl CH3COOH % Na
%
% Cl
(

=hus7 10 millimole HCl will "ea#t withe 10 millimole CH3COONa to fo"m 10 millimole
CH3COOH. Hen#e "esulting mi'tu"e will )e an a#id )uffe" mi'tu"e with 10 millimole of salt
and a#id ea#h.
8H , p+a % log
[ ]
[ ] a#id
slat
, 4.94% log
10
10
, 4.94
11. 14 mL solution of wea; mono)asi# a#id "e6ui"es 30 ml 0.4 M NaOH solution fo" the end
point. =he pH of the a#id solution upon addition of 10 mL 0.4 M NaOH solution du"ing the
tit"ation was 4.4 #al#ulate pH of the a#id solution
i! when no al;ali had )een added and
ii! when e6uivalen#e point was "ea#hed and the solution so o)tained was diluted to 94 mL
)* adding distilled wate". Log &, 0.30 and +w , 10
(14
!
11. Coth a#id and al;ali have thei" n ( fa#to" e6ual to 17 so the* must "ea#t in thei" e6uimole#ula"
p"opo"tion.
30 mL 0.4 M NaOH , 14 millimole NaOH 14 millimole wea; a#id HA!
3o7 14 mL HA solution #ontains 14 millimole HA.
Mola"it* of a#id solution ,
1
14
14

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>hen 10 mL 0.4 M NaOH i.e. 100.4 ,4 millimole! added7 4 millimol soda salt NaA! will )e
fo"med at 10 millimoles of HA will "emain f"ee. =he mi'tu"e will )e an a#id )uffe" mi'tu"e fo"
whi#h.
pH , p+a % log
[ ]
[ ] A#id
3alt
4.4 , p+a % log
10
4
p+a , 4./
pH of a#id solution when no al;ali had )een added
Mola" #on#. of a#id )eing app"e#ia)le will )e negligi)le in #omp"ession to unit*7 so
pH ,
1 1
0p+a log#1 04./ log01 &.4
& &

pH of the solution at the e6uivalen#e point B
No. of millimole of salt fo"med , 14
volume of solution , 94
mola" #on#. of salt solution 14@94 , 1@4 , 0.&
=he salt fo"med will )e h*d"ol*sed to ma;e the fee)l* al;aline
pOH ,
[ ] C log p+a p+w
&
1

,
[ ] & . 0 log / . 4 14
&
1

, 4.-4
pH , 14(4.-4 , -.04
13. =he solu)ilit* of AgCl Mw,143.4! in pu"e wate" is &./90 ppm at &4C. Cal#ulate its solu)ilit*
mol L
(1
! in &.0 M NH3 solution at &4C. Assume densit* of wate" is 1 g@ml
Given Ag
%
% &NH3 0AgNH3!&1
%
7 + , &.410
9
at &4C.
13. 10
.
g wate" is asso#iated with &./9 g AgCl i.e.
mol 10 &
4 . 143
/9 . &
&

10
3
g i.e. 1000 mL wate" d,1! is asso#iated with &10
(4
mol
=hus7 solu)ilit* of AgCl in pu"e wate" , &10
(4
mol L
(1

+sp , &10
(4
! &10
(4
! , 410
(10
mol
(&
L
(&

AgCls! Ag
%
% Cl
(
7 +sp , 410
(10
mol
&
L
(&

Ag
%
% &NH3 0AgNH3!&1
%
7 + , &.410
9
mol
(&
L
&

AgCl s! % &NH3 0AgNH3!&1
%
Cl
(
7 +# , +sp , 10
(&
& M 0 0 DDD initiall*
&('! 'M 'M DDDD at e6uili)"ium
( )
&
&
&
10
' & &
'

' , 0.1.. mol L

(1
, solu)ilit* of AgCl in & M NH3 soln.
4. >hat is the solu)ilit* of AgCl in 0.1 M NaCl solution$ +sp AgCl , 1./10
(10
L
(1
3
(1
.
4. +sp , 0Ag
%
1 0Cl
(
1
1./10
(10
, 33%0.1!
3,1./10
(-
4. A #e"tain wea; a#id has a disso#iation #onstant of 110
(4
. :ind the e6uili)"ium #onstant fo" its "ea#tion
with a st"ong )ase.
4. + ,
10
10
+w
+a
+a @ +w
1
+h
1

14. Eete"mine the pOH of a solution afte" 0.1 moles of NaOH is added to 1L of a solution #ontaining
0.14M CH3COOH and 0.&M CH3COONa. Assume no #hange in volume.
0+a , 1./10
(4
1 0log 1./,0.&44 log &,0.301 log 3,0.49911
14 0CH3COOH1 , 0.14M 0CH3COONa1 , 0.&M
CH3COOH % NaOH CH3COONa % H&O
t , 0 .14 .1 0 0
t , neut"alisation .04 0 .1 .1
0CH3COONa1 afte" addition of .1M NaOH , .& % .1 , .3 M
0CH3COOH1 1 afte" addition of .1M NaOH , .04M
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pH , p+a % log
1 A#id 0
1 3alt 0
pH , log 1./ 10
<4
! % log
04 .
3 .
4.944 % log . , 4.4&3
pOH , 14 < 4.4&3 , /.499
14. I6ual volumes of 0.0&M CaCl& and 0.0004 M Na&3O4 a"e mi'ed will a ppt fo"m$
+sp Ca3O4 , &.4 10
<4
14. CaCl& % Na&3O4 Ca3O4 % &NaCl
0.0& F 0.0004 F 0 0
3uppose F moles of )oth a"e mi'ed
0Ca
&%
1 ,
F &
F 0& . 0
[ ]

4
3O ,
F &
F 004 . 0
0Ca
&%
1 [ ]

4
3O ,
F &
F 004 . 0
F &
F 0& . 0
,& 10
<.
3in#e 0Ca
%%
1 [ ]

4
3O < +sp
3o7 it will not p"e#ipitate
19. Cal#ulate pe"#entage h*d"ol*sis of
+
4
NH and CN
<
ions in a 1M NH4CN solution. Given +aHCN! ,
4.-3 10
<10
and +)NH4OH! , 1./ 10
<4
and +w , 10
<4
19. Coth
+
4
NH and CN
<
ions h*d"ol*se in solution. Hen#e we have
+
4
NH % CN
<
% H&O NH4OH% HCN
C1(! C1(! C C
+H ,
1 CN 10 NH 0
1 HCN 10 OH NH 0
4
&
+
3in#e 0NH4OH1 , 0HCN1 , C
[ ] ! 1 C 1 CN 0 NH
4

+
+h ,
! 1 C ! 1 C
! C ! C


,
&
&
! 1

o" ,
h
+
1 +h +
+h ,
! 10 -3 . 4 ! 10 / . 1
10
10 4
14

, 1.1&9
,
1.1&9
1 1.1&9 +
, 0.414
Hen#e7 41.4A of NH4CN is h*d"ol*sed in the solution
/. >hethe" the pH of a solution of a wea; a#id will in#"ease o" de#"ease o" "emain #onstant
upon dilution$ Give "eason fo" *ou" answe".
/. =he pH will in#"ease
HA H
%
% A
(
C 1(! C C DDDD at e6uili)"ium

C
1
DDDDD.. Loughl*!
:o" eve"* 4( fold in#"ease in dilution7 C will "edu#e to 1@4
th
and hen#e will )e dou)led7 so
0H
%
1 whi#h is C will de#"ease on dilution and hen#e pH will in#"ease.
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
10. +a fo" HCN is 410
(10
at &4C. :o" maintaining a #onstant pH of -7 find the volume of 4 M
+CN solution "e6ui"ed to )e added to 10 ml of & M HCN solution
10. As pH is maintained to )e #onstant the solution is a#idi# )uffe" of HCN and +CN
3o pH , p+a % log
1
]
1

a#id
salt
- , ( log 410
(10
! % log

,
_

,
_

,
_

10 v
& 10
10 v
v 4
- ,10(log 4 % log
4
F
3olving F F , & ml
1&. Cal#ulate simultaneous solu)ilit* of AgCN3 and AgC" in a solution of wate". +sp of AgC"
, 4 10
<13
and +sp of AgCN3 , 1 10
<1&
1&. Let solu)ilit* of AgCN3 and AgC" in a solution )e a and ) mole@lit"e
AgCN3 a
! ) a
CN3 Ag

+
+
+
AgC"
)
! ) a
C" Ag

+
+
+
1 10
<1&
, a % )!a
:o" AgC" +spAgC" , 0Ag
%
1 0C"
<
1
4 10
<13
, a % )!)
:o" AgCN37
% (
AgCN3
1&
+sp , 0Ag 1 0CN3 1
10 a )! a

+
o"
&
10 4
10
)
a
13
1&

a , &)
Q +spAgCN3 , 0Ag
%
1 0CN3
<
1
&) % )!&) , 1 10
<1&
) , 4 10
<9
mole@lit"e
a , &) , /10
(9
mole@ lit"e
1. >ill a p"e#ipitate of MgOH!& )e fo"med in a 0.001 M solution of MgNO3!& if the pH of
solution is adOusted to -$ +sp of MgOH!& , /.-10
(1&

1. pH , -7 0H
%
1 , 10
(-
M o" 0OH
(
1 , 10
(4
M
Now if MgNO3!& is p"esent in solution of 0OH
(
1 , 10
(4
M7 then7 p"odu#t of ioni# #on#ent"ation
, 0Mg
&%
1 0OH
(
1
&
, 00.0011 010
(4
1
&
, 10
(13
lesse" than +sp of MgOH!& i.e. /.-10
(1&

MgOH!& will not p"e#ipitate.
4. An a#id )ase indi#ato" has its +a , 10
(.
. =he a#id #olou" p"edominates ove" )ase #olou"
when #on#ent"ation of a#id is 10 times that of the )asi# fo"m. On the othe" hand the )asi#
#olou" p"edominates ove" the a#id #olou" when )ase #on#ent"ation is &0 times that of the
a#id. >hat is the pH < "ange of the indi#ato"$
4. 4 to 9.3
1&. An a6ueous solution of a metal )"omide MC"& 0.04M! is satu"ated with H&3. >hat is the
minimum pH at whi#h M3 will p"e#ipitate$ +sp fo" M3 , ..0 10
<&1
. Con#ent"ation of
satu"ated H&3 , 0.1M7 +1 , 10
<9
and +& , 1.3 10
<13
fo" H&3 0log 1.04 , 0.09141 [5]
1&. Given MC"&g! MC"&a6! M
&%
% &C"
<
MC"& % H&3 M3 % &HC"
+sp of M3 , 0H
%&
1 03
<&
1
. 10
<&1
, 00.041 03
&<
1
03
&<
1 , 1.& 10
<1-
M
=hus7 M3 will )e p"e#ipitated if H&3 p"ovides 1.& 10
<1-
M ion of 3
< <
Now H&37 H&3 &H
%
% 3
< <
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
+1 +& ,
1 3 H 0
1 3 0 1 H 0
&
& +
10
<9
1.3 10
<13
,
1 1 . 0 0
1 10 & . 1 0 1 H 0
1- & +

0H
%
1 , 1.04 10
<1
pH , .-&/.
14. a! Cal#ulate the pH of 0.1 M Na&H8O4. Given that fo" H38O4
+a1 , 10
(3
7 +a& , 10
(9
7 +a3 , 10
(11

)!
N N CH N N CH
& &
..
..
..

+
I! II!
Among the a)ove two #anoni#al fo"ms whi#h is mo"e sta)le and wh*$ [2+2=4]
14. a! 3in#e H8O4
&(
is the #onOugate )ase of the a#id H&8O4
(
H H8O4
&(
is the a#id of the
#onOugate )ase 8O4
3(
pH of the amphip"oti# anion H8O4
&(
,
-
&
11 9
&
p+a p+a
3 &

+
)! II! is mo"e sta)le than I! as in II! all the atoms fulfil thei" o#tet7 also II! has highe"
num)e" of #ovalent )onds.
19. A sample of AgCl was t"eated with 4 ml of 1.4 M Na&CO3 solution to give Ag&CO3. =he
"emaining solution #ontained 0.00&. g of Cl
(
pe" lit. Cal#ulate +sp of AgCl +sp of Ag&CO3 ,
/.&10
(1&
! [5]
19. Na&CO3 % &AgCl &NaCl % Ag&CO3
Initial 9.4 a 0 0
9.4 <a e'#ess &a a
Given Cl
(
,
4
10 3& . 9
4 . 34
00&. . 0


Also #on# of Cl
(
fo"mal ,
ml in Folume
mm
,
4
a &

4 . 34
00&. . 0
4
a &

a , 1./310
(4
M
Na&CO3 left ,9.4(a! , 9.4
CO3
&(
! ,
4
4 . 9
+sp , 0Ag
%
1
&
0CO3
&(
1
Ag
%
,
4 @ 4 . 9
+
sp
, &.3410
(.
+sp , AgCl , &.3410
(.

4 . 34
0&. . 0
, 1.9910
(-
.. AlOH!3s! % OH
(
AlOH!
(
4 5 "ate law e'p"ession is given fo" this e6uation as
( ) [ ]

dt
OH Al d
4
410
(4
0OH
(
1 ( &10
(&
0AlOH!4
(
1
Cal#ulate value of e6uili)"ium #onstant fo" "eve"se "ea#tion [2]
.. +e6 ,
40
10 4
10 &
4
&

19. In a solution of 0.04 M :eCl& and 0.0& M :eCl3 and 0.01 M HCl7 How la"ge ma* )e its pH
without the"e )een p"e#ipitation of eithe" :eOH!& and :eOH!3. +sp of :eOH!& and :eOH!3
a"e /10
(.
and 410
(&/
"espe#tivel*. [5]
19. Che#; the #on#ent"ation of salt whose 0OH
(
1 "e6ui"ed is less fo" p"e#ipitation.
1/. An a6ueous solution & lit"e volume ! in MCN mola" w.".t. H& A disso#iation #onstant +a! and & C moles
w.".t. H&3O47 then p"ove that
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)
+

+
& &
+a 0H 1 0OH 1
0A 1 7 &C 0A 1
1.C &
1/.
+
+


&
&
H A &H A
+
+

& &
H 3O
& 4
&
0H 1 0A 1
+a 7 0H 1 4C
0H A1
( )

&
&
4C
0A 1
C

&
+a
0A 1
1.C
Appl*ing the #on#ept of ele#t"i#al neut"alit*7
+
+ +
& &
4
0H 1 &03O 1 &0A 1 0OH 1
+

+ +
& & &
4
0H 1 0OH 1
03O 1 0A 1 &C 0A 1
&
FIITJEE Ltd., ICES House, Sarvapriya Vihar (Near Hauz Khas Bus Termina!, Ne" #ehi$%&,'h( )&*%*+,+, )&-&*%-), )&-*,%.), /a0( )&*%1+,)