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CHEMISTRY
Ionic Equilibrium
Introduction
Degreeof dissociation
When an electrolyte is dissolved in a solvent (H
2
O), it spontaneously dissociates into ions.
It may dissociate partially (o << < 1 ) or sometimes completely (o ~ 1 )
Eg. NaCl + aq Na
+
(aq) + Cl

(aq)
CH
3
COOH + aq CH
3
COO

(aq) + H
+
(aq)
The degree of dissociation of an electrolyte (o) is the fraction of one mole of the electrolyte that has
dissociated under the given conditions.
o =
initially taken moles of No.
d dissociate moles of No.
The value of odepends
(a) Nature of electrolyte :
Strong electrolyte dissociate completely where as weak electrolytes dissociate partially.
(b) Nature of solvent :
Asolvent having high value of dielectric constant will favour dissociation.
(c) Dilution :
For weak electrolytes degree of dissociation will increases by dilution (Ostwalds dilution law)
(d) Temperature :
On increasing temperature generally degree of dissociation increases.
(e) Presence of other solute :
When a substance is present it may effect the solubility of the another solute. Generally presence
of common ion supresses degree of dissociation of weak electrolyte.
Ostwalds Dilution Law(for weak electrolytes)
For a weak electrolyte A
+
B

dissolved is water, if o is the degree of dissociation then

AB (aq) AA
+
(aq) + B

(aq)
initial conc C 0 0
conc-at eq. C(1 o) Co Co
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Then according to law of mass action,
K
eq
=
) 1 (
C
) 1 ( C
C . C
] AB [
] B ][ A [
2
o
o
=
o
o o
=
+
= dissociation constant of the weak electrolyte
[C =
V
1
, then V = 1/C(volume of solution in which 1 mole is present) is called dilution, so K
eq
=
V ) 1 (
2
o
o
]
If o is negligible in comparison to unity then, 1 o ~

1. So K
eq
= o
2
C o =
c
K
eq
=
V . K
eq
o
ion concentrat
1
{ Thumb rule }
as concentration increases o decreases
at infinite dilution o reaches its maximum value, unity.
ACIDS BASES AND SALTS :
Arrhenius concept :
Arrhenius Acid : Substance which gives H
+
ion on dissolving in water (H
+
donor)
eg. HNO
3
, HClO
4
, HCl, HI, HBr, H
2
SO
4
, H
3
PO
4
etc.
Types of acids
H
3
BO
3
is not Arrhenius acid.
H
+
ion in water is extremely hydrated (in form of H
3
O
+
, H
5
O
2
+
, H
7
O
3
+
) and high charge density.
The structure of solid HClO
4
is studied by X-ray, It is found to be consisting of H
3
O
+
and ClO
4
.
HClO
4
+ H
2
O H
3
O
+
+ ClO
4
(better representation)
Arrhenius base : Any substance which releases OH (hydroxyl) ion in water (OH ion donor)
Types of base
OH ion also in hydrated form of H
3
O
2
, H
7
O
4
, H
5
O
3

First group elements (except Li.) form strong bases.

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Bronsted - Lowery concept : (Conjugate acid - base concept) (Protonic concept)
Acid : Substances which donate H
+
are Bronsted Lowery acids (H
+
donor)
Base : Substances which accept H
+
are Bronsted Lowery bases (H
+
acceptor)
Conjugate acid - base pairs
In a typical acid base reaction
HX + B X

+ HB
+
Forward reaction Here HX, being a proton donor, is an acid
B, being a proton acceptor, is a base.
Backward reaction Here HB
+
, being a proton donor, is an acid
X

, being a proton acceptor, is a base.

Acid Base Conjugate Conjugate
Acid Base
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+
Conjugate acid - base pair differ by only one proton
Strong acid will have weak conjugate base and vise versa
Reaction will always proceed from strong acid to weak acid or from strong base to weak base.
Examples Acid Conjugate base Base Conjugate acid
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
Amphoteric (amphiprotic) : substances which can act as acid as well as base are known as amphoteric
HCl + H
2
O H
3
O
+
+ Cl
base
NH
3
+ H
2
O NH
4
+
+ OH
acid
Example-1 Ammonium ion is
(A) ALewis acid (B) Lewis base (C) Bronsted acid (D) Bronsted base
Solution Correct answer is (C).
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CHEMISTRY
Lewis concept (electronic concept) :
An acid is a molecule/ion which can accept an electron pair with the formation of a coordinate bond.
Acid e

pair acceptor
e.g. Electron deficient molecules : BF
3
, AlCl
3
Cations : H
+
, Fe
2+
, Na
+
Molecules with vacant orbitals : SF
4
, PF
3
Abase is any molecule/ion which has a lone pair of electrons which can be donated.
Base (electron pair donor)
e.g. Molecules with lone pairs (ligands) : NH
3
, PH
3
, H
2
O, CH
3
OH
Example-2 In which of the following reactions does NH
3
act as an acid ?
(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) None of these
Solution (B)
In the following reaction, NH
3
changes to NaNH
2
which contains NH
2

ion. This means that NH

3
has
donated a proton to Na and hence acts as an acid.
Example-3 Sulphanilic acid is a I an
(A) Arrhenius acid (B) Lewis base
(C) Neither (A) or (B) (D) Both (A) and (B)
Solution (D) Sulphanilic acid is . The SO
3
H group
is capable of donating H
+
and hence it acts as arrhenius acid while nitrogen in the NH
2
group
contains lone pair of electrons and hence can act as lewis base by donating it.
PROPERTIESOF WATER:
Amphoteric (amphiprotic) Acid/base nature:
Water acts as an acid as well as base according to Arhenius and Bronsted-Lowry theory but according to
Lewis concept it can be generally taken as base.
In pure water [H
+
] = [OH

] so it is Neutral.
Molar concentration / Molarity of water :
Molarity = No. of moles/litre =
mole / gm 18
litre / gm 1000
= 55.55 mole /litre = 55.55 M (density = 1 gm/cc)
Ionic product of water : According to Arrhenius concept
H
2
O H
+
+ OH

so, ionic product of water, K

w
= [H
+
][OH

] = 10
14
at 25 (exp.)
dissociation of water, is endothermic, so on increasing temperature K
eq.
increases
K
w
increases with increase in temperature.
Now pH = log[H
+
] = 7 and pOH = log[OH

] = 7 for water at 25 (experimental)

pH = 7 = pOH neutral
pH < 7 or pOH > 7 acidic at 25C
pH > 7 or pOH< 7 Basic
Ionic product of water is always a constant whatever has been dissolved in water since its an
equilibrium constant so will be dependent only on temperature.
Degree of dissociation of water :
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CHEMISTRY
H
2
O H
+
+ OH

taken initially moles of . no total
d dissociate moles of . no
= o
= % 10 x 8 . 1 or 10 x 18
55 . 55
10
7 10
7

=
Absolute dissociation constant of water :
H
2
O H
+
+OH

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


=

So, pK
a
of H
2
O = pK
b
of H
2
O = log (1.8 10
-16
) = 16 log 1.8 = 15.74
Acidity and pH scale :
Acidic strength means the tendency of an acid to give H
3
O
+
or H
+
ions in water.
So greater the tendency to give H
+
, more will be the acidic strength of the substance.
Basic strength means the tendency of a base to give OH

ions in water.
So greater the tendency to give OH

ions, more will be basic strength of the substance.

The concentration of H
+
ions is written in a simplified form introduced by Sorenson known as pH scale.
pH is defined as negative logarithm of activity of H
+
ions.
pH = log +
H
a
(where +
H
a
is the activity of H
+
ions)
Activity of H
+
ions is the concentration of free H
+
ions or H
3
O
+
ions in a dilute solution.
The pH scale was marked from 0 to 14 with central point at 7 at 25C taking water as solvent.
If the temperature and the solvent are changed, the pHrange of the scale will also change. For Example
0 14 at 25C Neutral point, pH = 7
0 13 at 80C (K
w
= 10
13
) Neutral point, pH = 6.5
pH can also be negative or > 14
pH Calculations of Different Types of Solutions :
(a) Strong acid Solution :
(i) If concentration is greater than 10
6
M
In this case H
+
ions coming from water can be neglected,
so [H
+
] = normality of strong acid solution.
(ii) If concentration is less than 10
6
M
In this case H
+
ions coming from water cannot be neglected,
So [H
+
] = normality of strong acid + H
+
ions coming from water in presence of this strong acid
Example-4 Calculate pH of 10
8
M HCl solution.
Solution 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
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CHEMISTRY
(b) Strong base Solution :
Calculate the [OH

] which will be equal to normality of the strong base solution and then use
K
W
= [H
+
] [OH

] = 10
14
, to calculate [H
+
].
Example-5 Calculate pH of 10
7
Mof NaOH solution.
Solution [OH

] from NaOH = 10
7
M
[OH

] from water = x < 10

7
M (due to common ion effect)
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) pH of mixture of two strong acids :
If V
1
volume of a strong acid solution of normality N
1
is mixed with V
2
volume of another strong acid
solution of normality N
2
, then
m. equi. of H
+
ions from I-solution = N
1
V
1
m. equi. of H
+
ions from II-solution = N
2
V
2
If final normality is N and final volume is V, then
NV = N
1
V
1
+ N
2
V
2
[dissociation equilibrium of none of these acids will be disturbed as both are strong acid]
[H
+
] = N =
2 1
2 2 1 1
V V
V N V N
+
+
(d) pH of mixture of two strong bases :
similar to above calculation
[OH

] = N =
2 1
2 2 1 1
V V
V N V N
+
+
& [H
+
] =
] OH [
10
14
Example-6 Calculate pH of mixture of (400ml ,
200
1
M H
2
SO
4
) + (400ml,
100
1
M HCl) + ( 200 ml of water).
Solution N
1
V
1
=
1000
4
1000
400
100
1
=
, N
2
V
2
=
1000
4
, H
+
ions from water will be neglected
N
1
V
1
+ N
2
V
2
= 8 10
3
[H
+
] =
1
10 8
3

= 8 10
3
M
pH = 3 log 8 =2.1
Example-7 500 ml of 10
5
M NaOH is mixed with 500 ml of 2.5 x 10
5
M of Ba(OH)
2
. To the resulting
solution 99 L water is added. Calculate pH.
Solution [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
no. of moles of [OH

] initially = no. of moles of [OH

] of resulting solution
3 10
5
= M
2
100
M
2
= 3 10
7
< 10
6
H
2
O H
+
+ OH

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

\
|

2
3 13
10
7
M = [H
+
]
So, pH = 7 log 0.303 = 7.52
(e) pH of mixture of a strong acid and a strong base :
Acid Base neutralisation reaction will take place.
The solution will be acidic or basic depending on which component has been taken in excess.
If V
1
volume of a strong acid solution of normality N
1
is mixed with V
2
volume of a strong
base solution of normality N
2
, then
Number of m. eq. H
+
ions from I-solution = N
1
V
1
Number of m. eq. OH

ions from II-solution = N

2
V
2
Example-8 Calculate pH of mixture of (400ml,
200
1
M Ba(OH)
2
) + (400ml,
50
1
MHCl) + ( 200ml of Water)
Solution [H
+
] =
1000
2
200
1
400
50
1
400 |
.
|

\
|
|
.
|

\
|

= 410
3
M, so pH = 3 2 log 2 = 2.4
(f) pH of a weak acid(monoprotic) Solution :
Weak acid does not dissociated 100%therefore we have to calculate the percentage
dissociation using K
a
dissociation constant of the acid.
We have to use Ostwalds Dilution law(as we have been derived earlier)
HA H
+
+ OH

t = 0 C 0 0
t = t
eq
C(1o) Co Co K
a
=
] HA [
] OH [ ] H [
+
=
o
o
1
C
2
If o <<1 (1 o ) ~ 1 K
a
~ Co
2
o =
C
K
a
( is valid if o < 0.1 or 10%)
[H
+
] = Co = C
C
K
a
= C K
a
So pH =
( ) C log pK
2
1
a

on increasing dilution C + o | and [H
+
] + pH |
Example-9 Calculate pHof (a) 10
1
MCH
3
COOH (b) 10
3
M CH
3
COOH (c) 10
6
MCH
3
COOH
Take K
a
= 2 10
5
.
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CHEMISTRY
Solution (a) CH
3
COOH CH
3
COO

+ H
+
C 0 0
C(1o ) Co Co
K
a
=
o
o
1
C
2
o =
C
K
a
=
1
5
10
10 2

=
4
10 2

(o << 0.1)
So, [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)
So we have to do the exact calculations
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) If approximation is used then, o =
6
5
10
10 2

=
20
> 1,
so we have to do the exact calculation, 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.
At very low concentration (at infinite dilution) weak electrolyte will be almost 100%
dissociate, so behave as strong electrolyte
(pH) of 10
6
M HCl
~
pH of 10
6
M CH
3
COOH
~
6)
(g) pH of a mixture of weak acid(monoprotic) and a strong acid Solution :
Weak acid and Strong acid both will contribute H
+
ion.
For the first approximation we can neglect the H
+
ions coming from the weak acid solution
and calculate the pH of the solution from the concentration of the strong acid only.
To calculate exact pH, we have to take the effect of presence of strong acid on the
dissociation equilibrium of the weak acid.
If [SA] = C
1
and [WA] =C
2
, then [H
+
] from SA = C
1
the weak acid will dissociate as follows.
HA H
+
+ A

C
2
0 0
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 )
(The weak acids dissociation will be further suppressedbecause of presence of strong acid, common
ion effect)
K
a
= (C
2
o + C
1
)o
Total H
+
ion concentration = C
1
+ C
2
o
If the total [H
+
] from the acid is greater than 10
6
M, then contribution from the water can be
neglected at 25C temp., if not then we have to take [H
+
] from the water also.
(h) pH of a mixture of two weak acid (both monoprotic) solutions :
Both acids will dissociate partially.
Let the acid are HA
1
& HA
2
and their concentrations in the mixture are C
1
& C
2
respectively, then
HA
1
H
+
+ A
1

HA
2
H
+
+ A
2

t= 0 C
1
0 0 C
2
0 0
At eq. 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
a1
=
) 1 ( C
) C C ( C
1 1
2 2 1 1 1
o
o + o o
K
a2
=
) 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)
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CHEMISTRY
K
a1
= (C
1
o
1
+ C
2
o
2
)o
1
;

K
a2
= (c
1
o
1
+ c
2
o
2
)o
2

2 a
1 a
K
K
=
2
1
o
o
[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 +
If the dissociation constant of one of the acid is very much greater than that of the second
acid then contribution from the second acid can be neglected.
So, [H
+
] = C
1
o
1
+ C
2
o
2
~ C
1
o
1
Example-10 Calculate pH of solution obtained by mixing equal volume of 0.02 M HOCl & 0.2 M CH
3
COOH
solutions.
given that K
a1
(HOCl) = 2 10
4
K
a2
(CH
3
COOH) = 2 10
5
also calculate [OH

] , [OCl

], [CH
3
COO

] at equilibrium.
Solution Volume of final solution become double.
So concetration become half
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) pH of a Solution of a polyprotic weak acid :
Diprotic acid is the one, which is capable of giving 2 protons per molecule in water.
Let us take a weak diprotic acid (H
2
A) in water whose concentration is C molar.
In an aqueous solution, following equilbria exist.
o
1
= degree of ionization of H
2
A in presence of HA K
a1
= first ionisation constant of H
2
A.
o
2
= degree of ionisation of HA in presence of H
2
A. K
a2
= second ionisation constant of H
2
A.
I step II step
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)
Knowing the values of K
a1
, K
a2
and c, the values of o
1
and o
2
can be calculated using equations (i) and (ii).
After getting the values of o
1
and o
2
[H
3
O
+
] can be calculated as.
[H
3
O
+
]
T
= co
1
+ co
1
o
2
"manishkumarphysics.in"
10
CHEMISTRY
Finally, for calculating pH
If the total [H
3
O
+
] < 10
6
M, the contribution of H
3
O
+
from water should be added
If the total [H
3
O
+
] > 10
6
M, then [H
3
O
+
] contribution from water can be ignored.
Using this [H
3
O
+
], pH of the solution can be calculated.
Approximation
For diprotic acids, K
a2
< < K
a1
and o
2
would be even smaller than o
1
.
1 o
2
~ 1 and 1 + o
2
~ 1
Thus, equation (i) can be reduced to K
a1
=
1
1 1
1
C
o
o o
This is an expression similar to the expression for a weak monoprotic acid.
Hence, for a diprotic acid (or a polyprotic acid) the [H
3
O
+
] can be calculated from its first equilibrium
constant expression alone provided K
a2
<< K
a1
.
Example-11 Calculate pH [HS

], [S
2
] , [Cl

] in a solution which is 0.1 M HCl & 0.1 M H

2
S. Given that K
a1
(H
2
S) = 10
7
, K
a2
(H
2
S) = 10
14
also calculate degree of dissociation of H
2
S & HS

in solution.
Solution HCl + H
2
S
0.1 M C = 0.1 M
pH = 1 (most of [H
+
] comes from HCl)
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

degree of dissociation of H
2
S = 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
degree of dissociation of HS

= o
2
= 10
13
[S
2
] = Co
1
o
2
= 10
6
10
1
10
13
= 10
20
M
Example-12 Calculate pH, [H
+
], [OH

], [CH
3
COO

], [CH
3
COOH], [SH

], [H
2
S], [S
2
] in a solution obtained
by mixing equal volume of 0.2 M H
2
S & 0.02 M acetic acid given that
K
a
(CH
3
COOH) = 2 10
5
, K
a1
(H
2
S) = 10
7
, K
a2
(H
2
S) = 10
14
Solution Now [H
2
S] = 0.1M, [CH
3
COOH] = 0.01 in new solution
(only first [H
+
] of H
2
S is considered).
[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
"manishkumarphysics.in"
11
CHEMISTRY
for acetic acid, 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
[CH
3
COOH] = 0.01 M
for H
2
S, K
a1
=
] S H [
] HS [ ] H [
2
+
=
1 . 0
] HS [ 10 21
4

[HS

] = 2.18 10
5
M
for HS

, K
a2
=
] HS [
] S [ ] H [
2

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

[S
2
] = 4.76 10
16
M
(j) pH of a mixture of a polyprotic weak acid and a strong acid:
pH can be calculated by taking the concentration of strong acid only(for first approximation)
For precise calculations we should take only the first dissociation constant of the weak polyprotic
acid.(As can be predicted from the equations we have presented so far for different cases.)
Example-13 Calculate pH 10
1
M HCl if 10
3
M CH
3
OOH [K
a
= 2 x 10
5
]. Also calculate [H
+
] from CH
3
COOH.
Solution CH
3
COOH CH
3
COO

+ H
+
C(1 o) Co 10
1
+ Co
H
+
ion can be treated completely from HCl due to less dissociation of CH
3
COOH and its low
conc.
2 10
5
=
C
10 C
1
o
o = 2 10
4
[H
+
] from CH
3
COOH = Co = 2 10
7
M
All these steps can be followed for the calculation of pOH for weak base and their mixtures
(we just have to replace K
a
with K
b
.).
(k) pH of a mixture of a weak acid/ weak base with weak/strong base/acid respectively.
For this type of mixtures there can be two cases in general,
(i) if the acids and bases are mixed in equal amounts (equivalents)
(ii) if the acids and bases are mixed in different amounts (equivalents)
First case will lead tophenomenon of SALT HYDROLYSISand second case will leadto formation of BUFFER
SOLUTIONS.
SALT HYDROLYSIS (REVERSE OF NEUTRALISATION)
Salt + Water acid +base
Whenacids andbases aremixedinequal amounts(equivalents), thenwewill behavingsalt solutions onlyinthe
water and we have to calculate pHof salt solutions.
When a salt is added to water, the solid salt first dissolves and breaks into ions completely(unless otherwise
specified). The ions of the salt may or may not react with water, the cations when react with water will produce
H
3
O
+
ions andtheanions onreactionwithwater will produceOH

ions. Dependingontheextent of hydrolysis and

on the amounts of H
3
O
+
and OH

ions the solution can be acidic, basic or neutral. If salt is BA, then
BA(s) BA(aq) B
+
(aq) +AA

(aq)
A

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

(aq) (anionic hydrolysis)

B
+
(aq) + 2H
2
O(l) BOH (aq) + H
3
O
+
(aq) (cationic hydrolysis)
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12
CHEMISTRY
ANIONICHYDROLYSIS
Anions can function as a base on reaction with water and hydrolyse as follows :
A

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

(aq)
The extent of hydrolysis of a given anion depends on its basic strength
(a) Complete hydrolysis
The anions, which are stronger base than OH

and the conjugate acids of the anions are weaker acid than
H
2
O, they will show complete hydrolysis in aqueous medium.
For Example H

+ H
2
O H
2
+ OH

; NH
2

+ H
2
O NH
3
+
2
1
H
2
(b) Hydrolysis to a limited extent
The anions, which are weaker base than OH

and the conjugate acids are stronger acid than H

2
Obut weaker
acid than H
3
O
+
will hydrolyse to a limited extent in aqueous medium
For Example CN

+ H
2
O HCN + OH

Other Examples are CH

3
COO

, NO

2
, S
2
etc.
(c) Nohydrolysis
The anions that are weaker base than OH

and the conjugate acids are stronger than both H

2
Oand H
3
O
+
do
not hydrolyse at all.
Cl

+ H
2
O HCl + OH

Other Examples include SO

4
2
, NO
3

, ClO
4

etc.
CATIONICHYDROLYSIS
Cations can function as acid on reaction with water and hydrolyze as follows.
B
+
(aq) + 2H
2
O(l) BOH(aq) H
3
O
+
(aq)
The extent of hydrolysis of a given cation depends on its acidic strength.
(a) Complete hydrolysis
The cations, which are stronger acid than H
3
O
+
and their conjugate bases are very much weaker than H
2
O
will show complete hydrolysis. Example is PH
+
4
ion.
PH
+
4
+ H
2
O H
3
O
+
+ PH
3
(b) Hydrolysis to a limited extent
The cations, which weaker acid than H
3
O
+
ion and their conjugate bases are stonger than H
2
Obut weaker
than OH

, show hydrolysis to a limited extent. For Example

NH
+
4
+ 2H
2
O NH
4
OH + H
3
O
+
Other ions showing hydrolysis to limited extent are C
6
H
5
NH
3
+
, CH
3
NH
3
+
etc.
(c) Nohydrolysis
The cations, which are weaker acid than H
3
O
+
and their conjugate bases are stronger than both H
2
O and
OH

do not hydrolyze at all. Example is alkali and alkaline earth metal ions.
Na
+
+ 2H
2
O NaOH + H
3
O
+
Therearefour types of salt.
(i) Salt of strong acid and strong base
(ii) Salt of strong acid and weak base
(iii) Salt of weak acid and strong base
(iv) Salt of weak acid and weak base
Salts of first type does not undergo hydrolysis and rest three types undergo hydrolysis.
(i) Salt of strong acid and strong base
Neither of the ions will undergo hydrolysis so the Solutioncontain only the equilibrium of ionization of water.
2H
2
O(l) H
3
O
+
+ OH

Thus, the pH of Solution will be 7(neutral Solution).

(ii) Salt of strong acid and weak base
The Examples can be NH
4
Cl, (NH
4
)
2
SO
4
, AlCl
3
Only the cation will undergo hydrolysis and the solution will be acidic in nature. For Examplein the solution
of NH
4
Cl of concentration c, we will have
"manishkumarphysics.in"
13
CHEMISTRY
NH
4
+
+ H
2
O NH
4
OH + H
+
t = 0 c 0 0 0
at eq. c(1 h) ch ch (h - degree of hydrolysis)
K
h
=
] NH [
] H ][ OH NH [
4
4
+
+
= hydrolysis constant of the salt
NH
4
OH NH
4
+
+ OH

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

, K
w
= [H
+
] [OH

]
From above equations we can get
K
h
K
b
= K
w
K
h
=
) h 1 ( c
ch . ch

=
) h 1 (
ch
2

(genarally 1-h 1) so we get, 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]
Example-14 Calculate degree of hydrolysis, K
h
and pH of 1 M urea hydrochloride solution in water, K
b
(Urea)
= 1.5 x 10
14
.
Solution NH
2
CONH
3
Cl is a salt of (SA + WB)
So h =
C . K
K
b
w
=
1 x 10 x 5 . 1
10
14
14

or h = 0.816 > 0.1 so we use actual relation

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
Example-15 Equal vol. of 0.2 M NH
4
OH (or ammonia) of 0.1 M H
2
SO
4
are mixed calculate pH of final
solution. Given that : K
b
of NH
3
= 1.8 10
5
Solution pH = 1/2 {14 4.74 + 1} =
2
26 . 10
= 5.13
(iii) Salt of weak acid and strong base
The Examples can be CH
3
COONa, KCN, Na
2
C
2
O
4
, K
3
PO
4
Similar to above analysis we will get
K
h
=
) h 1 ( c
ch . ch

=
) h 1 (
ch
2

(genarally 1-h 1) so we get, h =

c
K
h
K
h
K
a
= K
w
[OH

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

"manishkumarphysics.in"
14
CHEMISTRY
pH = log [H
+
] = ] c log K log K log [
2
1
a w
+ = c] log pK [pK
2
1
a w
+ +
Example-16 If the equilibrium constant for reaction of HCNwith NaOHis 10
10
, then calculate pHof 10
-3
MNaCN
soulition.
Solution HCN + NaOH H
2
O + NaCN K = 10
10
CN

+ H
2
O HCN + OH

K
h
= 10
10
10
-3
M 0 0
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
Example-17 Caluclate degree of hydrolysis(h) and pHof solution obtanied by dissolving 0.1 mole of CH
3
COONa
in water to get 100 lt. of solution ( take K
a
of acetic acid = 2 10
-5
)
Solution 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
(iv) Salt of weak acid and weak base
Examples can include CH
3
COONH
4
, NH
4
CN, Ca(CH
3
COO)
2
, MgC
2
O
4
CH
3
COO

+ NH
4
+
+ H
2
O CH
3
COOH+ NH
4
OH
t = 0 c c 0 0
at eq. 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)
H
2
O H
+
+ OH

, K
w
= [H
+
] [OH

] ......(iv)
So, 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
= |
.
|

\
|

from(ii) equation
[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
]
"manishkumarphysics.in"
15
CHEMISTRY
Example-18 Calcluate pHand degree of hydrolysis of 10
-2
MNH
4
CNsolution.
Given that K
a
of HCN = 510
10
andK
b
of (aq .NH
3
) =210
5
.
Solution 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
Hydrolysis of polyvalent anions or cations.
The hydrolysis of these species will take place in steps( just like dissociation of weak acids).
Out of different steps generally first step hydrolysis dominates mainly because of two reasons
The hydrolysis constant of second and further steps is generally negligible in comparison to first
step hydrolysis constant.
The second and further step hydrolysis will be suppressed in presence of ions produced due to first
step hydrolysis.
For a polyprotic acid (H
2
S, H
3
PO
4
,H
2
CO
3
,H
2
C
2
O
4
) we already know that the disscociation always takes
place in steps, so for Examplefor H
3
PO
4
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)
For all acids we always have K
a1
>> K
a2
>> K
a3
pH of the solution can be caculated from I
st
step only because [H
+
] from II
nd
& III
rd
step can be neglected as
(a) K
a1
>> K
a2
>> K
a3
(b) [H
+
] from I
st
dissociation will suppress the dissociation of II
nd
& III
rd
step.
Now for the hydrolysis of polyvalent ions( of salts like K
3
PO
4
, Na
2
CO
4
, ZnSO
4
, FeCl
3
, (NH
4
)
2
C
2
O
4
or ions
like PO
4
3
,
C
2
O
4
2
, Zn
2+
, Fe
3+
etc.)
Consider the hydrolsis in steps
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)
Fromabove equations we get,
K
a1
K
h3
= K
w
K
a2
K
h2
= K
w
K
a3
K
h1
= K
w
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CHEMISTRY
Genarally pH is calculated only using the first step Hydrolysis
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

So pH =
c] log pK [pK
2
1
a3 w
+ +
Example-19 What is the pH of 1.0 M Na
3
PO
4
in aqueous solution ?
PO
4
3
+ H
2
O HPO
4
2
+ OH

; K
b
= 2.4 x 10
2
Solution 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.
Hydrolysis of Amphiprotic Anion.
(Cation is not Hydrolysed)
NaHCO
3
, NaHS, etc., can undergo ionisation to fromH
+
ion and can undergo hydrolysis to formOH (Na
+
ion
is not hydrolysed)
(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
(b) Similarly for H
2
PO
4
and HPO
4
2
amphiprotic anions.
pH(H
2
PO
4

) =
|
.
|

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

\
| +
2
pK pK
3 a 2 a
Buffer Solution
(if the acids and bases are mixed in different amounts (equivalents))
Buffer Solutions are those, which resist a change in pH upon addition of small amount of small amount of
acid or base. this does not mean that the pH will not change, and all it means is that the pH change would
be less than the change that would have occurred had it not been a buffer.
There are various types of buffers :
(i) Buffer of weak acid and its salt with a strong base ;
(ii) Buffer of a weak base and its salt with a strong acid.
(iii) The Solution of the salt of a weak acid and a weak base.
To calculate the pH of a buffer Solution made up of a weak acid and its salt with a strong base. We have
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 [
"manishkumarphysics.in"
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CHEMISTRY
Taking log of both sides. log [H
+
] = log K
a
+ log
] Salt [
] Acid [
pH = pK
a
+ log
] Acid [
] Salt [
This is known as the Hendersons equation of a buffer.
For a buffer made up of weak base and its salt with a strong acid the Hendersons equation looks like this :
pOH = pK
b
+ log
] Base [
] Salt [
Buffer Capacity :
It is defined as the amount mole of a strong acid or strong base required to change the pHof a buffer by one
unit. For 1 L Buffer solution.
Maximumbuffer capacity :
It can be proved that the maximum buffer is achieved when the salt and acid or base concentration is equal.
Example-20 Calculate the amount of (NH
4
)
2
SO
4
in grams which must be added to 500ml of 0.2 MNH
3
to give a
Solution of pH =9.3. Given pK
b
for NH
3
= 4.7
Solution pOH = pK
b
+ log
] Base [
] acid Cojugate [
4.7 = 4.7 + log
2 . 0
x
x = 0.2, so concentration of (NH
4
)
2
SO
4
required = 0.1 M
moles of (NH
4
)
2
SO
4
needed = 0.05
mol weight of (NH
4
)
2
SO
4
= 132 gm/mole
weight of (NH
4
)
2
SO
4
needed = 132 0.05 = 6.6 gm
Example-21 The pHof a blood streamis maintained by a proper balance of H
2
CO
3
and NaHCO
3
. What volume of
5 MNaHCO
3
Solutionshould be mixed with 10ml of a sample of Solutionwhich is 2.5 Min H
2
CO
3
(assume no NaHCO
3
), in order to maitain a pH = 7.4.(pK
a
for H
2
CO
3
= 6.7, log 2 = 0.3)
Solution pH = pK
a
+ log
base
salt
7.4 = 6.7 + log
base
salt

base
salt
= 5
5 2.5 10 10
3
= 5 V required volume = 25 ml
Example-22 Calculate the buffer capacity of 1lt of
(i) 0.1M CH
3
COOH and 0.1M CH
3
COONa
(ii) 0.2M CH
3
COOH and 0.2M CH
3
COONa
pK
a
CH
3
COOH = 4.74
which will be a better buffer
Solution
dpH
x o
=
b a
) x b )( x a ( 303 . 2
+
+
b a
ab 303 . 2
+
x << a,b
(i) Buffer capacity =
1 . 0 1 . 0
303 . 2 1 . 0 1 . 0
+

= 0.11515
(ii) Buffer capacity =
2 . 0 2 . 0
303 . 2 2 . 0 2 . 0
+

= 0.2303
Second buffer Solution can be said better buffer
"manishkumarphysics.in"
18
CHEMISTRY
INDICATOR :
Indicators are the substance, which indicates the end-point of a titration by changing their colour. They are in
general, either weak organic acids or weak organic bases having characteristically different colours in the
ionised and unionised forms. For Example, methyl orange is a weak base (having red colour in ionised form
and yellowcolour in the unionised form) and phenolphthalein is a weak acid (having pink colour in the ionized
form while its unionised form is colourless)
Let us consider the equilibrium between the ionised and unionsed form of an acid indicator (HIn)
HIn H
+
+ In
K
In
=
] n H [
] n ][ H [
I
I
+
[K
In
= indicator constant or dissociation constant of indicator]
or [H
+
] = K
In

] n [
] n H [
I
I
Taking negative logarithm of both sides
log [H
+
] = log K
In
log
] n [
] n H [
I
I
pH = pK
In
= log
] n H [
] n [
I
I
pH = pK
In
+ log
] form Unionised [
] form Ionised [
In general, the intensity of a coloured solution depends on the concentration of the colour imparting species.
If the solution contains two coloured species, then the colour of the solution depends on the relative
concentration of the colour imparting species. When the solution contains two coloured species as HIn and
In, then it is seen that the solution acquires a distinct colour of In only when the concentration of In is
approximately at least 10 times greater than the concentration of HIn and vice versa.
Let us consider two cases.
Case-I
In order for the solution to show colour due to In the minimum ratio of
] n H [
] n [
I
I
should be 10.
pH = pK
In
+ log (10) = pK
In
+ 1
At this stage, the percentage of the indicator in In form would be given by
] n H [ ] n [
] n [
I + I
I
100 =
1 10
10
+
100 ~ 91.
Thus, nearly 91% of the indicator has been present in the ionised form (In). In fact pH = pK
In
+ 1 is the
minimumpH up to which the solution has a distinct colour characteristic of In. At pHgreater than this value,
some more indicator will be present in the ionised form. Thus at pH > pK
In
+ 1, the solution has a colour
characteristic of In.
Case - II
In order for the solution to show colour due to HIn, the minimum ratio of
] n H [
] n [
I
I
should be
10
1
.
pH = pK
In
+ log
10
1
= pK
In
1.
At this stage, the percentage of the indicator in In form would be given by
] n H [ ] n [
] n [
I + I
I
100 =
1 10
1
+
100 ~ 9.1
Thus, nearly 9.1% of the indicator has been present in the ionised from (In) and
91 ~
% of the indicator is
present in the unionzed from (HIn). In fact pH = pK
In
1 is the maximum pH up to which the Solution has
a distinct colour characteristic of HIn. At pH smaller than this value, some more indicator will be present in
the unionised form. Thus at pH s pK
In
= 1, the solution has a colour characteristic of HIn.
"manishkumarphysics.in"
19
CHEMISTRY
Example-30 pH of 0.1 Msolution of NaA is 8.92. Caculate pK
a
of HA. If a drop of HPh (pK
In
= 9.52 ) be added to
the above solution predict whether the pink colour will visible or not under the medical fact our eyes
can see the pink coler if the molar % ionised from of indicator is 25% or more .
Solution 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
unionised
ionised
8.92 = 9.52 + log
unionised
ionised
] HIn [
] In [
=
unionised
ionised
=
4
1
Since [In] = 20% Colour will not be visible.
ACID-BASE TITRATION :
Titration of SA v/s SB :
Ex. 40 ml 0.1 M HCl v/s NaOH 0.1 M
Volume of NaOH added pHof solution
7
1
13
40 ml
Volume of NaOH
pH
MeOH
HPh
0 ml 1
10 ml 1.22
20 ml 1.48
30 ml 1.84
39 ml 1.90
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
Indicator should change its colour sharply for indication of reaction to be complete so its pH - range should
lie perfectly with in sharp change to avoid experimental error.
MeOH and HPh both can use for titration of SA and SB.
Titration of SB is WA :
Ex. Volume of NaOH pH value
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
* In sharp change of titration HPh is suitable indicator.
* Initially fast change in pH is due to free ions available fram weak acid.
"manishkumarphysics.in"
20
CHEMISTRY
* Slow down of pH change is due to Buffer formation, which is maximum at pH = pK
a
.
* Near equivalence point pH again increases fastly due to salt formation.
* After equivalent point pHchanges very sharply due to presence of strong base.
Titration of SA + wB
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
Equivalence point
7
1
13
20 ml
Volume of HCl
pH
MeOH
HPh
Sharp change between 4 to 7
Titration of W.A. S.B. salt + S.A.
50 mL of 0.1 M CH
3
COONa is titrated with 0.1 M HCl. Calculate pH when vol. of HCl added is.
(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) At equivalent point, weak acid solution.
[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
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CHEMISTRY
W.B.S.A salt + S.B.
(NH
4
Cl + NaOH)
(F) Titration of Poly protic acid v/s S.B. :
50 mL of 0.1 M H
3
PO
4
agent 0.1 M NaOH. Calculate pH when vol. of NaOH added is
(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 M mol 2.5 M mol 0
2.5 M mol 2.5 M mol
pH = pK
a1
+ log 1/1 = pK
a1
= 3
(c) Solution of H
2
PO
4

amphoteric specis
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 M mol 2.5 M mol 0
2.5 M mol 2.5 M mol
pH = log 1/1 + pK
a2
= 7
(e) HPO
4
2
solution (amphoteric speces)
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) 3
rd
eq. pt Na
3
PO
4
solution
[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
(h) 200 mL
hydrolysis of Na
3
PO
4
can be neglected in presence of NaOH
[NaOH] = 5/250 = 1/50 pOH = 1.7
pH = 12.3
"manishkumarphysics.in"
22
CHEMISTRY
(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
Example-31 Predict graph for (Na
2
CO
3
+ HCl) . (W.A.S.B Vs S.B.)
Solution Na
2
CO
3
+ HCl NaHCO
3
+ NaCl
pH =
2
pK pK
2
a
1
a
+
Na
2
HCO
3
+ NaCl H
2
CO
3
+ NaCl
pH = 1/2 {pK
a1
log C}
SIGNIFICANCE OF INDICATORS :
Indicators work in specific pH range i.e. they change their colour distinctly once a specific pH range is
crossed. e.g. phenolphthalein works in pH range 810 while methyl orange in the range 3 to 4.4

Extent of reaction of different bases with acid (HCl) using these two indicators is summarised below
Phenolphthalein Methyl Orange
NaOH 100% reaction is indicated 100% reaction is indicated
NaOH + HCl NaCl + H
2
O NaOH + HCl NaCl + H
2
O
Na
2
CO
3
50%reaction upto NaHCO
3
100% reaction is indicated
stage is indicated
Na
2
CO
3
+ HCl NaHCO
3
+ NaCl Na
2
CO
3
+ 2HCl 2NaCl + H
2
O + CO
2
NaHCO
3
No reaction is indicated 100% reaction is indicated
NaHCO
3
+ HCl NaCl + H
2
O + CO
2
.
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CHEMISTRY
Solubility(s) and SolubilityProduct (K
sp
)
This is generally used for sparingly soluble salts, We will be dealing with the solubilities in the following tyupe
of solutions
1. Simple solution in H
2
O
2. Effect of common ions on solubility
3. Simultaneous solubility
4. Precipitate
1
+ electrolyte
1

Precipitate
2
+ electrolyte
2
5. Condition for precipitation
6. Solubility in a buffer solution
7. Solubilty due to complex formation
Solubility product (K
sp
) is a type of equilibriumconstant, so will be dependent only on temperature
for a particular salt.
Following Examples will illustrate the different type of solubilities and the effects of different factors or
situations on solubility of a salt.
Simple Solubility
Let the salt is A
x
B
y
, in Solution in water, let the solubility in H
2
O = s M, then
A
x
B
y
xA
y+
+ yB
x
xs ys K
SP
= (xs)
x
(ys)
y
= x
x
.y
y
.(s)
x+y
Example-23 Calculate K
SP
of Li
3
Na
3
[AlF
6
]
2
Solution K
SP
= 3
3
.3
3
.2
2
(s)
8
= 3
6
.4.(s)
8
= 2916 s
8
Effect of common ions on solubility :
Because of the presence of common ion the solubility of the salt decreases.
Example-24 Calculatesolubilityof silver oxalate in10
2
Mpotassiumoxlalate solutiongiven that K
SP
of silver oxalate
= 10
10
.
Solution [oxalate] = 10
2
+ x, where x is the solubility of silver oxalate, this can be neglected in comparison
to 10
2.
. So
K
sp
= 10
10
= 10
2
(2x)
2

2 2
10
8

= x
2
x = 510
5
M
Calculation of simultaneous Solubility
When two sparingly soluble salts are added in water simultaneously, there will be two simultaneous
equilibria in the solution.
Example-25 Calculate simultaneous solubility of silverthiocyanate and sliver bromide in water given that K
SP
of
silver thiocyanate = 10
12
and K
SP2
of silver bromide = 510
13
respectively.
Solution Let the solubility of AgSCN be x and that of AgBr is y, then
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)
On solving we get, x = 2y
So y = 4.08 10
7
M and x = 8.16 10
7
M
Condition of precipitation
For precipitation ionic product (K
IP
) should be greater than solubility product K
SP
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CHEMISTRY
Example-26 You are given 10
5
MNaCl solution and 10
8
MAgNO
3
solution, they are mixed in 1:1 volume ratio,
predict whether AgCl will be precipitated or not, if solubility product of AgCl is = 10
10
.
Solution Ionic product =
2
10
5

2
10
8
= 2510
15
< K
sp
Hence no precipitation will take place.
Solubility in appropriate buffer Solutions.
Appropriate buffer means that the components of buffer should not interfere with the salt or only H
+
or OH

ions should be interacting with the ions of the salt.

Example-27 Caculate solubility of MnSin a buffer solution of given pH, K
sp
of MnS and K
1
& K
2
for H
2
Sare given.
Solution let the new solubility of MnS = x
[Mn
2+
] = x = Initial concentration of S
2
ions, but free S
2
ions will be less because some of the S
2
ions will react with H
+
from buffer to form HS

and H
2
S.
[Mn
2+
] = x = [S
2
] + [HS

] + [H
2
S] .....(1)
free
Let us calculate the value of [HS

] & [H
2
S], from of the free [S
2
] ion, for that consider .
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)
and [H
2
S] =
1
K
] HS [ ] H [
+
=
2 1
2 2
K K
] S [ ] H [
+
....(3)
Put (2) & (3) in (1)
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
Selective Precipitation
When the Ksp values differ then one of the salt can be selectively precipitated.
"manishkumarphysics.in"
25
CHEMISTRY
Example-28 What [H
+
] must be maintained in a saturated H
2
S (0.1 M) to precipitate CdS but not ZnS, if [Cd
2+
] =
[Zn
2+
] = 0.1 initially ?
K
sp
(CdS) = 8 x 10
27
; K
sp
(ZnS) = 1 x 10
21
; K
a
(H
2
S) = 1.1 x 10
21
Solution In order to prevent precipitation of ZnS,
[Zn
2+
] [S
2
] < K
sp
(ZnS) = 1 x 10
21
(Ionic product)
or (0.1 . [S
2
] < 1 x 10
21
or [S
2
] < 1 x 10
20
M
This is the maximum value of [S
2
] before ZnS will precipitate. Let [H
+
] to maintain this [S
2
] be x.
Thus for H
2
S 2H
+
+ S
2
,
K
a
=
] S H [
] S [ ] H [
2
2 2 +
=
1 . 0
) 10 x 1 ( x
20 2
= 1.1 x 10
21
or x = [H
+
] = 0.105 M
No ZnS will precipitate at a concentration of H
+
greater than 0.105 M.
Effect on solubility because of complex formation
Example-29 What must be the concentaration of aq. NH
3
(eq.) which must be added to a solution containing
4 10
3
M Ag
+
and 0.001 M NaCl, to prevent the precipitation of AgCl. Given that K
sp
(AgCl) =
1.8 10
10
and the formation constant of [Ag(NH
3
)
2
]
+
is K
formation
=
6
10
8
.
Solution Silver ion concentration which can be allowed to remain in the solution,
1.8 10
10
= [Ag
+
] [Cl

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

= 1.8 10
7
M,
This quantity is so small that almost all the Ag
+
ion will be consumed.
Ag
+
+ 2NH
3
[Ag(NH
3
)
2
]
+
K =
6
10
8
4 10
3
b 0
1.8 10
7
(b 810
3
) 410
3
K =
2 3 7
3 8
) 10 8 b ( 10 8 . 1
10 4
6
10

=
b = 0.0445
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CHEMISTRY
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"manishkumarphysics.in"
29
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
1. If equal concentrations are mixed (of products &reactants) then which of the reaction will proceed to the right
and which will proceed to the left.
(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) Right; (B) Left
2. (a) Write conjugate acids of
SO
4
2
, RNH
2
, NH
2

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

(b) Write conjugate base of

HNO
2
, OH

, H
2
CO
3
, HClO
4
.
(c) Write conjugate acids and conjugate base of amphoteric species.
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) Conjugate acids : H

2
S , NH
4
+
, C
2
H
5
OH
2
+
, H
3
O
+
Conjugate base : S
2
, NH
2

, C
2
H
5
O

, OH

3. Which of the following is the strongest base-

(A) C
2
H
5

(B) C
2
H
5
COO

(C) C
2
H
5
O

(D) OH

Ans. (A)
Sol. Acidic strength, C
2
H
6
< C
2
H
5
OH < H
2
O < C
2
H
5
COOH.
4. In the reaction
(A) C
2
H
5
NH
2
+ HI (C
2
H
5
NH
3
)
+
I

. which reactant would be considered as Bronsted acid, is it also an

arrhenius acid is it also a lewis acid.
Ans. [HI, yes, no]
(B) What about the other species (C
2
H
5
NH
2
) in the above reaction is it Arrhenius base is it Bronsted base, is it
lewis base.
Ans. [No, yes, yes]
5. Calculate the pH of solution obtained by mixing 10 mL of 0.1 M HCI and 40 mL of 0.2 M H
2
SO
4
.
Sol. Milli equivalent of H
+
from HCI = 10 0.1 = 1
Milli equivalent of H
+
from H
2
SO
4
= 40 0.2 2 = 16
Total Meq.of H+ in solution = 1 + 16 = 17
[H+] =
50
17
= 3.4 10
1
|
|
.
|

\
|
=
+
mL in
V
. Meq
] H [
pH = log [H
+
] = log 0.34
pH = 0.47
6. Calculate pH of a KOH solution having :
(a) 5.6 g of KOH mixed in 50 water
(b) if it is further diluted to make 100 ml.
Ans. (a) 14.3 (b) 14
Sol. (a) Mole of KOH =
56
6 . 5
= 0.1
[OH

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

] = 1 M
pOH = 0 pH = 14
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30
CHEMISTRY
7. Calculate the pH of a solution which contains 100 mL of 0.1 M HCI and 9.9 mL of 1.0 M NaOH.
Sol. HCI + NaOH NaCI + H
2
O
Meq. before reaction 100 0.1 9.9 1 0 0
= 10 = 9.9
Meq. after reaction 0.1 0 9.9 9.9
[H
+
] left from HCI =
9 . 109
1 . 0
= 9.099 10
4
M
pH = log H+ = log 9.099 10
4
pH = 3.04
8. Calculate [H
+
] in a solution containing 0.1 M HCOOH and 0.1 M HOCN. K
a
for HCOOH and HOCN are
1.8 10
4
and 3.3 10
4
.
Sol. In this problem both the acids contribute for [H
+
] due to appreciable dissociation, Thus,
HCOOH H
+
+ HCOO

x + y x
HOCN H
+
+ OCN

x + y y
Because [H
+
] will remain common in solution. Thus,
K
HCOOH
=
] HCOOH [
] HCOO ][ H [
+
= 1.8 10
4
.............(1)
K
HOCN
=
] HOCN [
] OCN ][ H [
+
= 3.3 10
4
.............(2)
or K
HCOOH
=
1 . 0
x ) y x ( +
= 1.8 10
4
.............(3)
K
HOCN
=
1 . 0
y ) y x ( +
= 3.3 10
4
..............(4)
Thus, by Eqs. (3) and (4)
3 . 3
8 . 1
y
x
=
or y = 1.83x .............(5)
From Eq. (3) (x + 1.83x). x = 1.8 10
5
x = 2.52 10
3
Therefore, y = 4.61 10
3
Thus, [H
+
] = x + y = 2.52 10
3
+ 4.61 10
3
= 7.13 10
3
M
9. Calculate the pH 0.001 M HOCl having 25% dissociation. Also calculate dissociation constant of the
acid.
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. Calculate the concentrations of all species of significant concentrations present in 0.1 M H
3
PO
4
solution.
K
1
= 7.5 10
3
, K
2
= 6.2 10
8
, K
3
= 3.6 10
13
.
Sol. I step H
3
PO
4
H
+
+ H
2
PO
4

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

H
+
+ HPO
4
2
; K
2
= 6.2 10
8
III step HPO
4
2
H
+
+ PO
4
3
; K
3
= 3.6 10
13
For I step: 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"
31
CHEMISTRY
[H
+
] = 0.024 M
[H
2
PO
4

] = 0.024 M
[H
3
PO
4
] = 0.1 0.024 = 0.076 M
The value of K
1
is much larger than K
2
and K
3
. Also dissociation of II and III steps occurs in presence of H
+
furnished in I step and thus, dissociation of II and III steps is further suppressed due to common ion effect.
For II step: H
2

4
PO H
+
+ H
2
4
PO
0.024 0.024 0
(0.024 y) (0.024 + y) y
The dissociation of
H
2

4
PO occurs in presence of [H
+
] furnished in
Step I.
Thus, K
2
=
] PO H [
] HPO ][ H [
4 2
2
4

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

+
y is small 0.024 y ~ 0.024 and neglecting y
2
.
6.2 10
8
=
024 . 0
y 024 . 0
y = 6.2 10
8
M
or [H
2
4
PO ] = K
2
= 6.2 10
8
M (Insignificant)
For III step: 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

+

Again neglecting x
2
and assuming, 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 (Insignificant)
NOTE: For weak polyprotic acid having no other electrolyte, the anion concentration produced in II step of
dissociation is always equal to K
2
if concentration is reasonable.
11. A solution contains 0.1 MH
2
S and 0.3 MHCI. Calculate the conc. of S
2
and HS

ions in solution. Given K

a1
and K
a2
for H
2
S are 10
7
and 1.3 10
13
respectively.
Sol. H
2
S H
+
+ HS

; K
a1
= 10
7
HS

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

Due to common ion effect the dissociation of H

2
S is suppressed and the [H
+
] in solution is due to HCI.
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
Further 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"
32
CHEMISTRY
12. 20 mL of 0.2 M NaOH are added to 50 mL of 0.2 M acetic acid (Ka = 1.8 10
5
).
(1) What is pH of solution ?
(2) Calculate volume of 0.2 MNaOH required to make the pH of solution 4.74.
Sol. (1) NaOH + CH
3
COOH CH
3
COONa + H
2
O
Millimole added 20 0.2 50 0.2
= 4 = 10 0 0
Millimole after reaction 0 6 4 4
[Molarity] =
volume Total
ole lim mil
[CH
3
COOH] =
70
6
[CH
3
COONa] =
70
4
pH = log 1.8 10
5
+ log
70 / 6
70 / 4
= 4.57
(2) Let V mL of 0.2 M NaOH is required to make pH 4.74 then
NaOH + CH
3
COOH CH
3
COONa + H
2
O
Millimole added 0.2 V 50 0.2
= 0.2 V = 10 0 0
Millimole after reaction 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. Calculate the ratio of pH of a solution containing 1 mole of CH
3
COONa + 1 mole of HCI per litre and of other
solution containing 1 mole CH
3
COONa + 1 mole of acetic acid per litre.
Sol. Case I: pH when 1 mole CH
3
COONa and 1 mole HCI are present.
CH
3
COONa + HCI CHCOOH + NaCI
Before reaction 1 1 0 0
After reaction 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
Case II : pHwhen 1 mole CH
3
COONa and 1 mole of CH
3
COOH; a buffer Solution.
pH
2
= log K
a
+ log
] Acid [
] Salt [
] Salt [ = 1 M
pH
2
= log K
a
] Acid [ = 1 M

2
1
pH
pH
=
2
1
14. Calculate the amount of NH
3
and NH
4
CI required to prepare a buffer Solutionof pH9. when total concentra-
tion of buffering reagents is 0.6 mol litre
1
. pK
b
for NH
3
= 4.7, log 2 = 0.30
Sol. pOH = log K
b
+ log
] Base [
] Salt [
5 = 4.7 + log
b
a
b
a
= 2 a = 2b
"manishkumarphysics.in"
33
CHEMISTRY
Given a + b = 0.6
2b + b = 0.6
3b = 0.6
or b = 0.2 mole and a = 0.4 mole
Thus, ] Salt [ = 0.4 M and [Base] = 0.2 M
15. The solubility product of SrF
2
in water is 8 10
10
. Calculate its solubility in 0.1 M NaF aqueous solution.
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. A solution contains a mixture of Ag
+
(0.10 M) and
+ 2
2
Hg (0.10 M) which are to be separated by selective
precipitation. Calculate the maximum concentration of iodide ion at which one of them gets precipitated
almost completely. What % of that metal ion is precipitated?
K
sp
of AgI = 8.5 10
17
and K
sp
of Hg
2
I
2
= 2.5 10
26
Sol. The [I

] needed for precipitation of Ag

+
and
+ 2
2
Hg are derived as :
For AgI: [Ag
+
][I

] = K
spAgI
(0.1)[I

] = 8.5 10
17
[I

] = 8.5 10
16
M .......(1)
For Hg2I2: [
+ 2
2
Hg ] [I

]
2
= 2.5 10
26
(0.1) [I

] = 2.5 10
26
[I

] = 5 10
13
M .......(2)
Since [I

] required for precipitation of AgI is less and thus AgI begins to precipitate first. Also it will
continue upto addition of [I

] = 5 10
13
when Hg
2
I
2
begins to precipitate and thus,
Maximum [I

] for AgI precipitation = 5 10

13
M
Now at this concentration of I

, [Ag
+
] left in solution is [Ag
+
]
left
[I

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

= 1.7 10
4
M
0.1 M Ag
+
will be left = 1.7 10
4
M Ag
+
in solution
100 MAg
+
will be left = 0.17% M Ag
+
% of Ag
+
precipitated = 99.83%
17. Calculate solubility of BaSO
4
when CaSO
4
and BaSO
4
are dissolved in water simultaneously K
sp
of CaSO
4
=
p, K
sp
of BaSO
4
= q and solubility of CaSO
4
is b mol/litre.
Ans. bq / p
Sol. For BaSO
4
,
[Ba
2+
] [SO
4
2
] = K
sp
of BaSO
4
= q
For CaSO
4
,
[Ca
2+
] [SO
4
2
] = K
sp
of CaSO
4
= p
] Ca [
] Ba [
2
2
+
+
=
p
q
[Ba
2+
] =
p
bq
18. A solution of HCI has a pH = 5. If one mL of it is diluted to 1 litre, what will be pH of resulting solution.
Sol. HCI
I
= 10
5
M since pH = 5
Meq. of HCI
I
in 1 mL = 10
5
1
Meq. of HCI
II
in 1000 mL = N 1000
Since II is prepared by diluting I and Meq. does not change on dilution.
i.e., Meq. of CHI (concentrated) = Meq. of HCI (dilute)
10
5
1 = N 1000
[H
+
] = 10
8
Now, pH = 6.97