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CONTENTS
S.NO.

TOPIC

PAGE NO.

1.

SALT

2.

IONIC DISSOCIATION

3.

OSTWALDS DILUTION LAW

4.

STRENGTHS OF ACIDS AND BASES

5.

SELF IONIZATION OF WATER

6.

HYDROGEN ION / HYDROXYL ION CONC. OF ACID / BASE

7.

pH SCALE

8.

COMMON ION EFFECT

9.

BUFFER SOLUTIONS

10.

BUFFER ACTION

11.

SOLUBILITY

12

12.

HYDROLYSIS OF SALT

14

13.

DEGREE OF HYDROLYSIS

14

14.

THEORY OF INDICATOR

18

Ionic Equilibrium

IONIC EQUILIBRIUM
1. SALT
A substance which ionizes in water to produce ions other than H+ and OH is called a salt.
Types of Salts:
Neutral Salts : Those salts whose aqueous solutions neither turn blue litmus red nor red litmus blue are
called neutral salts. These are prepared by the neutralization of strong acid and strong base. e.g. NaCl,
K2SO4, KNO3 etc.
Basic Salts : Those salts whose aqueous solution turn red litmus blue are called basic salts. These are
formed by the neutralization of strong bases with weak acids. e.g. Na2CO3, CH3COONa
Mixed salts : Salts formed by the neutralization of one acid by two bases or one base by two acids are
called mixed salts. e.g. CaOCl2
Double Salts : Acompound of two salts whose aqueous solution shows the tests for all constituent ions
is called double salt e.g.
Mohr Salt FeSO4. (NH4)2 SO4. 6H2O
PotashAlum K2SO4.Al2 (SO4)3. 24H2O.
Complex Salts : Acompound whose solutions does not give test for the constituent ions is called a
complex salt. e.g.
K4 [Fe(CN)6]
Li (AlH4)

2. IONIC DISSOCIATION
The process in which molecules (acids, bases, and salts) when dissolved in water or when melted break
into ions is called ionic dissociation.
Electrolytes. Hence substances which dissociate into ions in aqueous solutions are called electrolytes.
e.g. NaCl, NaNO3, HCl, K2SO4 etc.
Strong Electrolyte And Weak Electrolyte and Non Electrolytes:
Those electrolytes which dissociate almost completely into ions are known as strong electrolytes.
e.g. HCl, HBr, HI, HClO4, NaCl, Na2SO4, KNO3 etc.
Those electrolytes which dissociate partially are called weak electrolytes. e.g. H3PO4, HF,
H2CO3,HCN, CH3COOH, NH4OH, etc.
.Those electrolytes which do not dissociate into ions in aqueous solutions are called non electrolytes. Molecules
of the substances which do not dissociate into ions in aqueous solutions are called non- electrolytes. e.g. sugar,
urea, etc.

3. OSTWALDS DILUTION LAW

Ostwalds pointed out that like chemicalequilibriuminionic equilibriumwe can applylawof mass action. An
equilibriumbetweenionized and unionized molecules. Considera binary electrolyte having conc. C and degree of
dissociation is.
A B
0
0
C
C(1 ) C
C
AB
At time = 0
At time = t

K aq

[A ][B ]

1 1

[AB]

C C

C(1 )

, for a weak electrolyte

Ionic Equilibrium

K eq C 2 ,

K eq

C
If 1 mole ofAB is present in Vlitre of solution.
C

1
V

K eq V
C C

Conc. of A+ = Conc. B

(i)
(ii)

K eq
C

K eq C

Limitation :
This is only for weak electrolytes not for strong electrolytes.
This law is not applicable for strong electrolyte because strong electrolytes are almost completelyionC
ized at all dilution and hence does not give accurate results.

Dissociation of Weak Acids and Bases :

Dissociation of Weak acids : Consider the dissociation of a weak acid HAin water, represented by the
equation

H3O + A
HA + H2O
C

Initial conc. moles/litre

HA

Final concentration

(C C)

in moles/lit.

H+ + A

C C in moles/lit.

C 2
Ka = 1

This equation is referred to as Ostwald dilution law. In case of weak acids the degree of dissociation
is very small, therefore (1 ) may be taken to be equal to unity
Hence

Since
Also as =

Ka
C

VK a

This shows that decree of dissociation is inversely proportional to square root of concentration and
directly proportional to square root of dilution of the solution.
Dissociation of Weak Base in Water :
The dissociation of a weak base can be represented in the same manner as a weak acid.
e.g.
(initial)

C
BOH

Final concentration in moles/lit. C C

B + OH

C.

Ionic Equilibrium

Where C = Initial conc. in moles/litre

= Degree of dissociation

Kb =

As the base is weak

1
Kb = C 2

= Kb / c
Hence,

CB COH
CBOH

C 22 C2

C(1) 1

1 = 1.

Kb
C

[OH] = C = C
[OH] =

Kb C

4. STRENGTHS OF ACIDS AND BASES

(i)
(ii)

(iii)
(iv)

The strength of an acid/base depend upon the number H+/OH present in solution.
Since = V K a or = V Kb

increases when V increase

Ionization increases with dilution, hence number of H+ /OH increases.

At infinite dilution the ionization of all acids and bases tends to become almost equal and all acids
and bases behave equally strong at infinite dilution.
All mineral acids or bases which ionize fully at all dilutions are considered as strong acids. While
acids/bases like CH3COOH/NH4OH respectively which ionize to a less extent are called weak
acids/bases. The relative strenths is generally compared in terms of their dissociation constants.
We known
Ka1 = C1 1 2 1 1
Ka2 = C2 2 2 2 1
K a1
C1
K a2
C2

(v)
Ex.1
Sol.

K a1 C 2

1
2
K a2 C1

K a1
Ka 2

K b1 C 2

K b2
C1

K b1
K b2

when C1 C2

when C1 C2
when C1 C2
when C1 C2

Strength of all strong acids/bases in water is same. This is called levelling effect

Calculate the degree of ionization of 0.01 M solution of HCN, Ka of HCN is 4.8 1010. Also
calculate hydronium ion concentration.
The ionization of HCN may be represented as,
HCN(aq) H 2O()

CN - (aq) H 3O (aq)

If degree of ionization of HCN is then equilibrium concentration of given species are

Ionic Equilibrium

[HCN] C(1 )
[CN ] C
[H3O ] C
where C = concentration of HCN.
Applying law of chemical equilibrium
C2
[CN ][H 3O ] (C)(C)

C(1 )
(1 )
[HCN]
Since is very small as compared with unity therefore, 1 in the denominator may be taken as 1.
Ka

K a C 2

Ka
4.8 1010
2.2 104 .

C
0.01

[H3O ] C 0.01 2.2 10 4 2.2 10 6 mol L1.

Ex.2
Sol.

The Ka for formic acid and acetic acid are 2 104 and 2 105 respectively. Calculate the
relative strength of acids with same molar concentration
Relative strength of weak acid
2 1
1

=
1
2
2
Ka

Relative strength =

K a2

( C1 = C2)

2 104
2 105

Relative strength for HCOOH to CH3COOH =

Ex.3

10 : 1

Calculate the degree of ionization of 0.02 M acetic acid if its K a 1.8 10 5 . What would be the
degree of ionization if the solution also contains 0.01 M sodium acetate ?

Sol.

CH 3COOH(aq)

CH COO3 (aq) H (aq)

The degree of ionization of this weak acid can be calculated by the approximate relation :
Ka
1.810 5
0.03 310 2 .

C
0.02
Now let us calculate the degree of ionization when the solution also contains 0.01 M sodium acetate.
Sodium acetate being a strong electrolyte would be completely ionized in solution. Let x mol L1 of
acetic acid be ionized.

CH 3COOH(aq)
(0.02 x )M

CH3 COO (aq) H (aq)

xM

xM

CH 3COONa(aq)
CH3 COO (aq)

Na (aq)
0.01 M

Ionic Equilibrium

[H ] x mol L1
[CH3COO ] (x 0.01) mol L1 0.01 mol L1
[ x is very small as compared to 0.01]
[CH3COOH] (0.02 x) mol L1 0.02 mol L1
Ka

[H ][CH3COO ]
[CH3COOH]

1.8105

(x)(0.01)
(0.02)
5

1.8 10 0.02
3.6 105 M
0.01
5
x
3.6 10
1.810 3

Degree of ionization,
0.02
0.02
Thus, it may noted that the degree of ionization of acetic acid has decreased from 3102 to 1.8 103
due to the presence of sodium acetate.
x

5. SELF IONIZATION OF WATER

Water can behave both as an acid as well as a base. This behaviour of water is due to ionization ofwater
to form protons and hydroxyl ions.
H2O
Hence K =

H+ + OH
C H COH
CH 2 O

K CH2O = CH+ COH

CH2O = Kw = CH+ COH
K
Kw is the Ionic Product of water and may be defined as the product of concentration of ions
[(H+) and (OH)] ions. Its value depends only on temperature and is found to be 1 1014 at 25C
At
Kw = 0.11 1014 mol 2/lit 2
OC
Kw = 0.30 1014 mol2/lit2
10C
25C
Kw = 1 1014 mol2 /lit2
14
2
2
100C
Kw = 7.5 10 mol /lit
For pure water CH+ = COH = 10 7 mol/lit at 25C
Degree of dissociation of pure water at 25C
For pure water CH+ = COH.
Also at room temperature CH+ COH = 1014 mol2 /lit2

CH+ = 107 mol/lit

C = 107 mol/lit
107
107

= 1.8 109
C
55.6
Hence degree of dissociation = 1.8 109

% degree of dissociation = 1.8 107

=

6. HYDROGEN ION / HYDROXYL ION CONC. OF ACID/ BASE

(i)

In case of strong acids (or bases) concentration in water solution is taken as equal to normality
of the acid/base since they ionize completely.
[H+] = Normality of acid = Molarity Basicity
[OH] = Normality of base = Molarity Acidity

Ionic Equilibrium

(ii)

In case of weak acids/Bases, the H+/OH concentration is less than normal and may be calculated
by using Oswald's dilution law.
[H+] =

K aC

[OH] =

= C = N
= C = N

K bC

7. pH SCALE :
It may be defined in number of ways.
(i)
The pH value of a solution is equal to the negative power to which 10 must be raised in order to
express [H+] concentration [H+] = 10pH.
(ii)
It can also be defined as the negative logarithmof its [H+] ion concentrations
pH = log[H+]
(iii)
pH values do not give instantaneous idea above the relative strengths of the solution
pH calculation of solution of a mixture of two weak Acids in water :
Let two weak acids be HA and HB and their conc. are C1 and C2, 1 is the degree of dissociation of HA
in presence of HB (due to common ion effect) and 2 be degree of dissociation of HB in presence of
HA. In aqueous solution of HAand HB following equilibrium exists.
conc. at eq.

A
C1 1

+
(C1 1 + C2 2)

B
C2 2

HA+ H 2O(l)

H3O+

C1(1 1)

C11 + C22

HB + H2O(l)

H3O+

C2(1 2)

K a[HA]

[H3O ][A ] [C11 C12 ][C12 ]

C1 (1 1 )
[HA]

K a[HB]

[H3O ][B ] [C11 C22 ][C22 ]

[C2 (1 2 )]
[HB]

pH log[H ] log[C11 C2 2 ]
pH of a DibasicAcid and PolyproticAcid :
Lets take the eg. of a dibasic acid H2A.Assuming both dissociation is weak. Let the initial conc. of H2A
is C and 1 and 2 be degree of dissociation for first and second dissocation.
HA
C1 (1 2)

H2A

C(1 1)
HA
C1 (1 2)

H+
+
C1 + C1 2

H+
C1 + C1 2
A
C1 2.

Ka1

[HA ][H ]
[H 2A]

Ka1

[C1 (1 2 )][C1 C1 2 ]
C(1 1 )

Ionic Equilibrium

Ka 2

Ex.4
Sol.

Ex.5
Sol.

[H ][A ] [C1 C12 ][C12 ]

[C1 (1 2 )]
[HA ]

After solving for 1 and 2. We can calculate the H+ conc.

[H+] = C1 + C1 2
pH = log [C1 + C1 2]
pOH SCALE :
It is defined as the negative logarithms of hydroxyl ions concentration.
pOH = log (OH).
Also it is known that [H+] [OH] = 1014 = Kw
log[H+] (+) log[OH] = 14 = pK w
pH + pOH = pKw = 14.

The pH of a 0.05 M solution of H2SO4 in water is nearly?

pH= log10 H +
The concentration of H+ ions is expressed in gm equivalent
Molarity of H2SO4 = 0.05
Normality = 0.05 2 = 0.1

pH = log 0.1

pH = 1
or
Calculate the pH of solution having H+ ion concentration of 5 104 mole/litre
[H+] ion concentration = 5 104 mole/litre
pH
= log [5 104]
= (log 5 + log 104)
= 0.7 + 4
= 3.3

8. COMMON ION EFFECT

When a solution of weak electrolyte is mixed with another electrolyte which provides one or more ion
common with the weak electrolyte the dissociation of weak electrolyte is suppressed. This suppression
of dissociation of weak electrolyte on addition of a common ion is called common ion effect.
For example if we consider dissociation of CH3COOH in the presence of CH3COONa we get following
situation :

+
CH3COOH CH3COO + H
CH3COONa
CH3COO + Na +
In this case the CH3COO ion contributed by CH3COONa suppresses the dissociation of CH3COOH.
This suppression of dissociation of CH3COOH is called common ion effect.

9. BUFFER SOLUTIONS
A buffer is a solution which resists any change in its pH value on either (a) dilution or (b) addition of
acid/base. The process by which the added H+/OH are removed to maintain the pH of solution, is
known as buffer action.
Types of Buffer :
1.
Simple buffers : Asalt of weak acid and weak base in water e.g.
(a)
NH4CN or CH3COONH4.
(b)
Proteins and amino acids.
(c)
Amixture of an acid salt and normal salt of a poly basic acid e.g.
NaHCO3 + Na2CO3
Na2 HPO4 + Na3PO4.

Ionic Equilibrium

2.

Mixed Buffer : These are of two types

(a)
Acid Buffer Solution : An acidic buffer solution of a weak acid and its salt with strong
base.
e.g. CH 3COOH + CH3COONa

+
CH3COOH
CH3COO
+ H (Weakly ionized)

CH3COO + Na+ (Highly ionized)

CH3COONa
The sodium acetate, being a salt ionizes completely to form CH3COO and Na+ ion. But acetic
acid being a weak acid is ionized to a less extent.Also its ionizations is further suppressed by the
acetate ion from sodium acetate.
Let C moles/litre be the concentration of CH3COOH taken and C1 be the concentration of
CH3COONa.
The degree of dissociation of CH3COOH is in the presence of sodium acetate
Initial conc. (mol/lit.)
C
0
0

CH3COOH
H+
CH3COO +

C
Final conc. (mol/lit.) (C C)
C
Initial conc.(mol/lit.)

Final conc.(mol/lit.)
Hence in the solution

C1
CH3COONa
0

0
0

+
CH3COO + Na
C1
C1

CH3COOH concentration = (C C)
CH3COO concentration = C + C1
H+ concentration = CH+ = C.
But since is very small [CH3COOH] = (C C) C. [CH3COO-] = C + C1 C1
Ka =

CCH 3COO CH
C CH3COOH

=> CH+ = Ka

pH = log CH+ = PKa + log

pH = pKa + log [Salt]

C
C1

C1
C

[Acid]

This equation is called Hendersons Equation.

10. BUFFER ACTION :

When a few drops of acid is added then the H+ ions from the acid combines with excess of CH3COO
ions to form CH3COOH. Hence there is no rise in [H+ ] ion concentrations but due to the consumptions

of CH3COO the concentration of CH3COO decreases and the concentration of CH3COOH increases
hence the ratio of

[Salt]
[Acid]

decreases slightly. Thus the pH change is minimal, meaning the solution has

resisted the change in pH. In other wards one can saythat the pH change which is very minimal is not due to
change in the concentration of [H+] but due to change in buffer capacity of solution.
On the other hand when NaOH is added, the [OH] ions of the base reacts with the unionized CH3COOH
to form acetate ion and water. OH + CH3COOH CH3COO + H 2O
Ex.6
Sol.

Calculate the ratio of pH of a solution containing 1 mole of CH COONa + 1 mole

of HCl per litre and
3
of other solution containing 1 mole CH3COONa + 1 mole of acetic acid per litre.
Case I. pH when 1 mole CH3COONa and 1 mole HCl are present.
0
0
1
1
CH
COOH
+
NaCl
CH3COONa + HCl

3
After reaction
1
1
0
0

Before reaction

Ionic Equilibrium

[CH3COOH] = 1 M

[H+] = C. = C

pH1 =

pH2 = log Ka + log

K a (K .C) (K )
a
a
C

C=1

log Ka
2
Case II : pH when 1 mole CH3COONa and 1 mole of CH3COOH; a acidic buffer solution forms
[Salt] = 1 M, [Acid] = 1 M

[Salt]
[Acid]

pH2 = log Ka

pH1 1

pH 2 2

Basic Buffers :
Abasic buffer solution consists of a mixture of a weak base and its salt with a strong acid.
e.g. mixture of NH4OH and NH4Cl.

NH4OH

NH4+ + OH

Weakly ionized
Highlyionized
NH4Cl
NH4+ + Cl
+
The NH4 ions of NH4Cl suppress the ionization of NH4OH due to common ion effect.
Let the concentrations of NH4OH taken be C moles/lit. and -be the degree of ionization after
adding NH4Cl. Let C1 be the concentration of NH4Cl taken.
Initial conc. (mol/lit.)
C
0
0
+
NH4OH
NH4 OH
Final conc. (mol/lit.) (C C)
C
C
C1
Initial conc.(mol/lit.)
0
0
+
NH4 + Cl
NH4Cl
0
Final conc.(mol/lit.)
C1
C1
The concentration of
[NH4+] = C1 + C C1 [ 1]
[NH4OH] = C C C [ 1]
[OH] = C.
Kb =

C NH C OH
4

C NH 4 OH

COH = Kb
C NH

C NH 4 OH
C NH 4
C

pOH = pKb + log C

= pKb + log C1
NH 4 OH

pOH = pKb + log [Base]

[Salt]

BufferAction :
When few drops of base say NaOH is added then the OH ions added react with NH 4+ to form

10

Ionic Equilibrium

[NH 4 ]

NH4OH and thus the concentration of [OH ] remains unchanged. But the ratio of [NH OH] changes.
4
Thus the change in pH is very small and that too due to change in buffer capacity.
On the other hand when a few drops of acid (Say HCl) is added, then the [H+] ions of acid combine with
excess of NH4OH to form H2O and NH4+ ions. i.e. NH4OH + H+
NH4+ + H2O.
+
Thus the addition of acid does not increase the H ions but since the concentration of NH4 OH decreases
[NH ]

4
and [NH4+] ion conc. increases, the ratio [NH OH]
increases and thus pH changes infinitively.
4

Ex.7

Abuffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of ammonia into
100 mL solution. If pKb of ammonia is 4.74, calculate value of x.

Sol.

(NH4)2SO4

2 NH4 + SO42

Thus, every one mole of (NH4)2SO4 gives two moles of NH4 .

millimoles of NH3, (NH4OH) = 100 0.1 = 10 millimol

millimoles of (NH4)2SO4 = 100 x = 100 x 1000 millimol
millimoles of NH4 = 200 x = 200 x millimol
pH = 9.26
pOH = 14 9.26 = 4.74

pOH pK b log
4.74 = 4.74 + log

[NH 4 ]
[ NH4OH]
200x
10

log 20x = 0
20 x = 1
x=

1
= 0.05.
20

Buffer Capacity :
It is defined as the number of moles of the acid/base added to the buffer solution to produce a change in
pH by one unit.
Buffer Capacity =

number of moles of acid/base added

change in pH

In general Buffer Capacity would be maximum when both components are present in equimolar
proportions.
Agiven acid must have a pH ranging between pKa + 1 to pKa 1 if it is to be used in buffer solution. The
best buffer will have the acid with pH = pKa.
Ex.8
Sol.

What amount of sodium propanoate should be added to one litre of an aqueous solution containing
0.02 mole of propanoic acid (Ka = 1.0 105 at 25C) to obtain a buffer solution of pH 6.
Using the expression
pH = pKa + log

[Salt]
[Acid]

11

Ionic Equilibrium
[Salt]

we get, 6 = log(1.0 105)+ log [0.02 M]

[Salt]

Which gives 6 = 5 + log [0.02 M]

[Salt]
[0.02 M]

= 10 or [Salt] = 0.2 M

Ex.9

What will be the pH of the solution, if 0.01 mole of HCl is dissolved in a buffer solution containing
0.03 mole of propanoic acid (Ka = 1.0 105) and 0.02 moles of salt, at 25C.

Sol.

pH = pKa + log

[Salt]
[Acid]
(0.02 0.01)

= log(1.0 105) + log (0.03 0.01)

1

= 5 + log 4 = 5 0.6 = 4.4

Ex.10 What amount of HCl will be required to prepare one litre of a buffer solution (containing NaCN
and HCN) of pH 10.4 using 0.01 mole of NaCN. Given Kion (HCN) = 4.1 1010
Sol. The addition of HCl converts NaCN into HCN. Let x be the amount of HCl added. We will have.
[NaCN] = (0.01 x)
[HCN] = x
Substituting these values along with pH and Ka in the expression.
pH = log Ka + log

[Salt]
[Acid]

We get 10.4 = log[4 1010] + log

0.01 x
x

or

10.4 = 9.4 + log

or

log

or

0.01 x
x

or

x = 9.9 104 M

0.01 x
x

0.01 x
x

=1

= 10 11x = 102

11. SOLUBILITY
It is the amount of the solute in gram that can be dissolved in 100 gm of a solvent to obtain a saturated
solutions at a particular temperature.
However solubility can also be expressed in moles/litre.
Solubility in gm/lit.

Solubility of solution in moles/litre = Molecular weight of solute

The factors affecting solubility are.
(a)
Nature of solvent
(b)
Nature of solute
(c)
Temperature
(d)
Pressure

12

Ionic Equilibrium

Solubility Product :
If a sparingly soluble salt is added in water, very little amount of it dissolves in water, and thus solution
becomes saturated, but a highly soluble salt saturation is reached on dissolving more of salt.
For all salts at saturation an equilibrium is achieved between the undissolved salt and the ions insolutions.
B+(aq) + + A (aq)

BA(s)
Applying law of mass action we get
K=

[A ] [B ]
[BA]

K[BA] = [B+] [A]

Since only little of salt dissolves so the concentration of salt remains constant
K[AB] = K Constant = Ksp = [B+] [A]

For any salt

BxAy
xBy+ (aq) + yAx(aq)
Ksp = [By+ ]x [Ax] y
Ksp = Kc This expression shows that in a saturated solution of a sparingly soluble salt the ionic product is
equal to the solubility product.
Ksp = Solubility Product
It is defined as the product of the molar concentrations of its ion raised to the power equal to its number
of ions present at equilibrium representing the ionization of one molecule of salt at a given temperature.
Points to Remember:
When Ksp = Ki solution saturated
(1)
When Ki < Ksp unsaturated solution
(2)
(3)
When Ki > Ksp super saturated solution.
Hence precipitation occurs to keep Ki = Ksp
Relationships Between Solubility and Solubility Product:
(1)
Let the solubility of a salt
Bx Ay in water be s moles/lit.
Thus at equilibrium
BxAy
xBy+ (aq) + yAx(aq)
At equilibrium
xs mol/lit
ys moles/lit.
Ksp
= [By+ ]x [Ax] y

(xs)x (ys)y
=
Ksp
= xxyy sx + y
Hence for salts of type MA (AgCl, BaSO4, etc.)

s=

Ksp = 4 s 3

s=

Ksp = 27 s 4

s = 4 K sp /27

Ksp = s2
For M2Atype of salts

K sp

K sp /4

For MA3
Ex.11 A salt M2 X3 dissolves in water such that its solubility is x g. mole/litre. What is KSP of salt ?
Sol. Solubility of M2X3 = x gm mole/litre
2M+3 + 3X 2
M2 X3
+3
[M ] = 2x

[X2] = 3x
Solubility product KSP = (2x) 2.(3x) 3 =108 x 5
Ex.12 The solubility of AgCl in water, in 0.02 M CaCl2, in 0.01M NaCl and in 0.05 M AgNO3 are S0,
S1,S2,S3 respectively. What is the relationships between these quantities ?

13

Ionic Equilibrium

Sol.

(B) Solubility =

S1 =

Solubility Product
Concentration of Common ion

K SP
0.02
K SP

= 50 KSP

S2 = 0.01 = 100 KSP

K sp
= 20 KSP
S =
3

So,

0.05

S2 > S1 > S3 Again solubility will be greatest in water. So, S0 > S2 > S1 > S3

12. HYDROLYSIS OF SALT :

It is the process involving action of water on a salt to form a mixture of acid and alkali.
The hydrolysis of a salt is reverse of neutrilization.
Let there be a salt BA. The hydrolysis of such a salt can be represented as
H2O + AB
water salt

HA+ BOH
acid base

[HA] [BOH]

K = [AB][H O]
2

Kh =

[HA] [BOH]
[AB]

K[H2O] =

[HA] [BOH]
[AB]

where Kh = hydrolysis constant.

The hydrolysis constant is dependent on nature of acid or base which is formed as a result of hydrolysis.
Degree of Hydrolysis : It is defined as the fraction of the total salt, which is hydrolysed at equilibrium.
Anionic Hydrolysis : It is the Hydrolysis of salts of Weak acids and Strong Base e.g. CH3COONa,
Na2CO3, K2CO3, KCN, Na2S etc.
Let the salt hydrolysis be represented as
BA + H2O
(1)

BOH + HA
B +A
BA
SinceA is a strong base is under hydrolysis according to the equation
+

HA + OH

A + H 2O

This is called anionic hydrolysis

Kh =

[HA] [OH ]
[A ]

Multiplying and dividing RHS by H+ we get

Kh =

K w [H ][OH ], K a [H ][A ]

[HA]

[HA] [OH ][H ] K w

Ka
[A ][H ]

Kw

Hence hydrolysis constant = Kh = K

Kh K i.e. hydrolysis constant varies inversely with dissociation constant of acid.

a

13. DEGREE OF HYDROLYSIS :

Let C moles/Lof salt be taken then C moles/Lof cation and anion will be formed respectively.
BA
C

B+
C mole/L

A
C mole/L.

14

Ionic Equilibrium

Let hbe the degree of hydrolysis ofA

Ch moles/lit. of Awill take part in hydrolysis and Ch moles/lit. of HAand Ch moles/L of [OH]
will be formed.
C

A + H2O

(C Ch)

At equilibrium
conc. in moles/L.

Ch

[HA][OH ]

Kh =

[A ]

When h <<<< 1

Kh
C

h=

HA + OH

Ch

Ch 2
1 h

Kh Ch2
K hV .

This shows degree of hydrolysis increases with dilution.

Degree of hydrolysis is directly proportional to the square root of volume of solution in litres containing
one mole of salt.
Also

1
C

Degree of hydrolysis in inversely proportional to the square root of concentration of salt in moles/lit.
pH of solution :
Kh
C

[OH] = Ch = C
(OH) =

K hC

Kw
C
Ka

=
pOH

= 2 pKw 2 logC 2 log K

a
= 2 pKw 2 logC 2 log K
a

pOH

= 2 pKw 2 logC 2 pKa

=

1
2

14
1
2

1
2

logC 2 pKa
1

pOH

=7

logC 2 pKa

pH = 14 pOH = 7 + 2 pKa + 2 logC

Cationic Hydrolysis :
It involves the hydrolysis of a salt of strong acid with a weak base e.g. NH4Cl, (NH4)2SO4, NH4NO3,
BaSO4, FeCl3, etc.
These solutions are acidic solution
BA + H2O HA + BOH
salt

stong acid

weak base

15

Ionic Equilibrium

Here the salt dissociates to form the cation and the anion. Let C moles of salt be taken in one litre
solution and hbe the degree of hydrolysis.
B+ +A
BA
Initial conc. (mole/lit.) C
0
0
B+ + H2O BOH + H+
Ch
Ch
Final conc. (mole/lit.) (C Ch)
[H ][BOH]

Kh =

[B ]

(Ch) 2
1 h

[H ][OH ]

Kw

Kh = K =
=

b
[B ][OH ]

[H ][OH ]

[B ]

[BOH]
1

Kh K
b
2
Since h <<< 1 (Ch) = K h

h=

Kh /C

1
C

K hV

and h V

pH of solution :
Kw
C
Kb

[H+]

= Ch =

pH

= 2 logKw 2 log Kb 2 logC = 2 pKw 2 pKb 2 logC

pH

= 7 2 [pKb + logC]

K hC =

Cationic andAnionic Hydrolysis :

Salts of Weak Acids and Weak Bases :
Here both cation and anion undergo hydrolysis.
BA + H2O
HA + BOH
weak acid

weak base

Let C moles per litre of salt solution be taken.

Let the degree of hydrolysis be h
(1)
BA
+
B+
A
C moles/lit.
C moles/lit

Cationic Hydrolysis
conc. of B+

+ H2O
equilibrium (C Ch)
BA

BOH +
Ch Ch
B+ + A

Anionic Hydrolysis
A + H2O
equilibrium (C Ch)
conc. of

B+ + A + H 2O

BOH +
weak base

[BOH][HA]

HA + OH
Ch Ch

HA
weak acid

[H ][OH ][HA][BOH]

Kh = [B ][A ] =
[OH ][B ][A ][H ]

16

Ionic Equilibrium

Kw

[BOH][HA]

Kh

= K K = [B ][A ]
a b

Kh

= C(1h) C(1h) =
(1 h) 2

Ch Ch

h2

When h <<< 1
h2 = Kh or h =

Kh

So degree of hydrolysis is independent of the concentration of salt taken.

Also, pH = 21 (pKw + pKa pKb)

When pKa > pKb then solution's alkaline and anionic hydrolysis takes place more than cationic hydrolysis
when pKa < pKb then solution acidic and cationic hydrolysis takes place more than anionic hydrolysis.
When pKa = pKb solution neutral and extent of anionic and cationic hydrolysis are equal.
Ex.13 Ka for cyanoacetic acid is 4 103 . What is the value of degree of hydrolysis of 0.4 M sodium
cyano acetate solution ?
14

Sol.

Kh =

Kw
10

K a 4 10 3

= 0.25 1011
h=

Kh
0.25 1011

c
0.4

= 2.5 106

Ex.14 The dissociation constants for aniline, acetic acid and water at 25C are 4 1010, 2 105 and
1014 respectively. Calculate degree of hydrolysis of aniline acetate in a deci normal solution ?
Sol.

Aniline++Acetate+H 2O

Before hydrolysis
1
1
After hydrolysis
1h 1h
Let conc. salt be C mole litre1
Ch . Ch

Aniline +Acetic acid

0

h2

Kh = C(1 h) . C(1 h) = (1 - h)2

h
1-h

Kw
Ka. Kb
1014

2 10 6 4 10 10

% hydrolysis = 54.95 %
h = 0.035
Ex.15 Calculate the pH of aqueous solution of 1.0 M HCOONH4 assuming complete dissociation (pKa
of COOH = 3.8 and pKb of NH3 = 4.8) ?
Sol. Ammonium formate undergoes hydrolysis as
NH4+ + HCOO+H2O NH4OH + HCOOH
Kh

KW
K a . Kb

17

Ionic Equilibrium

Moreover in the solution we have

[NH4OH]
= [HCOOH]
Hence Kh =

[HCOOH]2
[HCOO ] 2

or

KW
Ka . Kb

[H+]2 =

or

2pH

or

pH =

[H ] 2
[K a ]2
KW . Ka
Kb

= pKW + pKa pKb

1
[pK W
2
1
2

+ pKa pKb ]

[14 + 3.8 4.8] = 6.5

Ex.16 A certain weak acid has Ka=1.0104. Calculate the equilibrium constant for its reaction with a
strong base.
Sol. HA + BOH
BA + H2O

weak strong
B+ + A + H2O or HA + A + H2O
HA + B+ + OH
or

K =

[A ]
[HA] [OH ]

Also for weak acid HA

H+ + A
HA
Ka =

[H ] [A ]
[HA]

Ka
KW
K

or

Ka

10 4

K = K =
= 1010
10 14
W

14. THEORY OF INDICATOR

It was first given by Ostwald. According to him, acid-base indicators are either weak organic acids
(HIn) or bases (InOH) having different colours for the ionised and unionised forms. For example, litmus
contains azolitmic acid in which the unionised acid molecules are red while the anionic form is blue.
HIn
H+ + In
blue
red
When litmus is dissolved in water, it appears violet due to presence of unionised acid molecules aswell
as the anionic form. When some acid is added to the solution, equilibrium shift left and the solution turns
red. Similarly, when base is added to the solution, equilibrium shift right and the solution turns blue.
pH Range of Indicator :
The ability of the human eye to preceive colours is limited. Nomally the eye fails to detect the presence of
one of the coloured forms of an indicator together with the other if the concentration of the former is onetenth of the concentration of the latter. Now for the process :
HIn
H+ + In
[H ][In ]
Dissociation or indicator constant, KIn =
[HIn]
[HIn]
[In ]

or,

[H+] = KIn .

or,

[In ]
pH = pKIn + log
[HIn]

18

Ionic Equilibrium

For the solution to appear only in the colour of In,

[In ]
10, or pH (pKIn + 1) For the solution to
[HIn]

[HIn]
[In ]
1
or pH (pKIn 1)
appear in the colour of HIn, [In ] 10 or

[HIn] 10
The pH values of the solution below and above which the solution appears in a single colour is called pH
range of indicator. Normally, pH range of an indicator is (pK In 1) to (pK In+ 1).

pH range of some indicators

Indicator

Colour in acidic
solution
Colourless
Red
Red
Red
Yellow

Nature

Phenolphthalein
Methyl red
Methyl orange
Litmus
Bromphenol blue

acidic
Basic
Basic
acidic
Acidic

pH range
8.0 10.0
4.2 6.2
3.1 4.4
5.0 8.0
3.0 4.6

Colour in baisc
solution
Red
Yellow
Yellow
Blue
Blue

Selection of Indicator in a particular Acid-Base Titration :

The pH range of the resulting solution just before and after adding one drop of titrate is called pH range
of titration. All the indicators for which pH range lie within the pH range of titration, are correct indicator
for that titration. The selection of correct indicator for the titration can be understood from the
following examples :
Titration of strong acid (say 25 mL of 1 M-HCl solution) against strong base (say 1 M-NaOH
solution) : By simple calculation, it may be determined that the complete neutralisation will occur on
adding 25 mL of the NaOH solution. Now, see the pH values of resulting solution on adding different
volumes of NaOH solution, assuming that the volumes are additive and one drop of solution occupy
0.05 mL.
Volume
(in mL)
pH

0
0

10

20

24

24.9 24.95

0.37 0.95 1.69 2.69

3.0

25.05 25.1
11.0

26

30

40

11.3 12.3 12.9 13.4

19

Ionic Equilibrium

pH range of this titration is 3.0 11.0. pH range of almost all indicators lie in this range and hence almost
all indicators are correct for this titration. However, a maximum error of one drop may occur. For
example, pH range of methyl orange is 3.1 4.4. pH of solution on adding 24.95 mL NaOH solution
(just one drop before the equivalent point) is 3.0 and hence, the solution will appear red (pink). When
one more drop of solution is added, pH increases to 7.0 and the colour of solution suddenly become
yellowish. This sudden colour change helps us in deciding end point of titration. However, if the titration
is performed in presence of phenolphthalein indicator, the sudden colour change will occur on adding
one more drop of solution after equivalent point.
If NaOH solution will be titrated against HCl solution, the titration curve will be just opposite. In this
case, phenolphthalein will be the perfect indicator but methyl orange will give error of one drop.
Volume
0
10 20 24 24.9
(in mL)
pH
2.37 4.56 5.34 6.12 7.14

24.95

25.05 25.1

7.44

11.0

26

30

40

11.3 12.3 12.9 13.4

pH range of this titration is 7.44 11.0 pH range of phenolphthalein lies in this range and hence, it is
suitable indicator for the titration. If methyl orange is used, it will show gradual colour change much
before the equivalent point.
With the help of titration curves, it may be determined that methyl orange, not phenolphthalein, is
correct indicator for the titration of strong acid and weak base.
The titration curve of weak acid and weak base do not have any large jump in pH of the solution
and hence such titration can not be performed by using any of such indicators.

When polyprotic acid or base are titrated, the different stage of titration can be identified by
different indicators. For example, when H2CO3 solution is titrated against NaOH solution, the
first stage of titration can be identified by
methyl

20

Ionic Equilibrium

SOLVED EXAMPLES
Ex.1

Sol.

The self ionizationconstant for pure formic acid,

K = [HCOO H 2 ][HCOO ] has been
estimated as 106 at room temperature. What
percentage of formic acid molecules in pure
formic acid are converted to formate ion? The
density of formic acid is 1.22 g/cm3.
Given density of formic acid = 1.22 g/cm3
Weight offormic acid in 1 litre solution
= 1.22 103
1.22 103
26.5 M
46

Thus, [HCOOH] =

Calculate the concentration of all species of

significant concentrations present in 0.1 M
H3PO4 solution. K1 = 7.5 103,
K2 = 6.2 108, K 3 = 3.6 103.

K3 = 3.6 1013

y = 6.2 108
[HP O42 ] = K2 = 6.2 108.

H+ + P O34
(6.2 108 x) (0.024 + x) x
K3

[H ][PO43]
(0.024 x).x

2
[HPO4 ]
(6.2 108 x)

H+ + HP O42 ;

H+ + P O34 ;

Again neglecting x2 and assuming,

6.2 108 x = 6.2 108

for I step : H3PO4

0.1
0.1 C

H+ + H2P O4
0
0
C
C

C.C
K1 [H ][H 2 PO4 ]
[H3PO4 ]
(0.1 C)

C2
7.5 10 = (0.1 C)
3

6.2 108 =

For III step : HP O24

H+ + H 2P O 4;

0.024y
0.024

or

K2 = 6.2 108
III step HP O 24

The dissociation of H2P O4 occurs in presence

of [H+] furnished in step I.

or

[HCOO ]100 103

100 = 0.004%

[HCOOH]
26.5

K1 = 7.5 103
II step H2P O4

HP O42 ;
H+ +
0.024
0
(0.024 + y)
y

(0.024 y)y
6.2 108 = (0.024 y)
y is small 0.024 y 0.024 and

neglecting y2.

[HCOO] = [HCOO H 2 ] = 103.

Now % dissociat ion of HCOOH =

I step H3PO4

For II step H2P O 4

0.024
(0.024 y)

[H ][HPO 2
]
4
Thus, K2 =
[H 2PO4 ]

Since in case of auto ionization [HCOO H 2 ]

[HCOO] = 106

Ex.2

The value of K1 is much large than K2 and K3.

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.

C = 0.024 [H+] = 0.024 M

[H2 PO 4 ] = 0.024 M
[H3PO4] = 0.1 0.024 = 0.076 M

13

3.6 10

0.024x
6.210 8
8

6.2 10
9.31019 .
0.024
If CH3COOH (Ka = 105) reacts with NaOH
at 298 K, then find out the value of the maximum rate constant of the reverse reaction at
298 K at the end point of the reaction. Given
that the rate constant of the forward reaction is
1011 mol1 L sec1 at 298 K. Also calculate
Arrhenius parameter for backward reaction if
H298 = 44 kcal and Ea(f) = 94 kcal.
x

Ex.3

3.6 1013 =

21

Ionic Equilibrium

Sol.

CH3COOH+NaOH
CH 3COONa+H 2O;
11
1
1
Kf = 10 mol L sec
The backward reaction is of hydrolysis of sodium acetate

Ka

Ka
KW
K
1
for
K C K (K h ) K K
W
bac
a
K for
10 10
K bac K K W
105
a
11

14

10

Ex.6
20

Sol.

H = E a f E a b
44 = 94 E a b

Ex.4

Sol.

Ea b A b e

Eabac / RT

Ab = 2.71 10+16.

The pH of pure water at 25C and 35C are 7

and 6 respectively. Calculate the heat of formation of water from H+ and OH.
[H+] = 107
At 25C;

KW = 1014
[H+] = 106
At 35C;
12
KW = 10

Kw2

2.303 log10 K
w1

H T2 T1

R T1 T2

1012 H 308 298

2.303 log10 1014
2 298 308

H = 84551.4 cal/mol
= 84.551 kcal/mol
Thus H2O
H+ + OH
H = 84.551 kcal/mol
H+ + OH H O;2

Ex.7
H = 84.551 kcal/mol
The pH of a 0.10 M hydrocyanic acid solution
is 5.2. What is the value of Ka for hydrocyanic Sol.
acid ?
H3O+ + CN
HCN + H2O
x
x
(0.1 x)
5.2 = log[H3O+]
[H3O+] = 6.3 106
or
x = [H3O+]
6
= 6.3 10 M/l

Ex.5

Sol.

6.3 10 6 6.3 10 6
0.1 6.3 10

An aqueous solution contains 10% ammonia

by mass and has a density of 0.99 g cm3.
Calculate hydroxyl and hydrogen ion
concentration in this solution.
(Ka for NH4+ = 5.0 1010 M)
[OH] in aqueous solution of NH4OH can be
determined from the following relation.
[OH] =

50 103
20
10 = A b e 2 298

[HCN]

xx

= 0.1 x

= 39.6 1011

Given, H298 = 44 kcal and E a f = 94 kcal

[H3O ][CN ]

Kb c

(a) Determination of the value of Kb

14
Kw
110
5
Kb = K =
10 = 2 10
5.0

10
a

(b) Determination of concentration (molarity)

C of NH4OH solution Wt . o f NH 3 in 100
ml of NH 4 O H solution=10gm

Vol. of 100 g of NH4OH solution =

w 1000

10 1000 0.99

Molarity = m V =
17 100

(c) Determination of [OH ]

[OH] =

100
0.99

99
17

Kb C

99
5
= 2 10 17 = 102

19.8
17

= 102 1.16
[OH] = 102 1.077 mol l1
= 1.077 102 mol l1
14

[H+] =

10
13 mol l1
2 = 9.28 10
1.077 10

Calculate the pH of solution obtained by mixing 10 mL of 0.1 M HCl and 40 ml of 0.2 M

H2SO4.
Milli-equivalent of H+ from HCl = 10 0.1 =1
Milli-equvalent of H+ from H2SO4
= 40 0.2 2 = 16
Total meq. of H+ in solution = 1 + 16 = 17

[H+] =

17
3.4 101
50

22

Ionic Equilibrium

Ex.10 A0.1 M solution of weak acid HAis 1% dissociated at 25C. What is its Ka ? If this solution is with respect to NaA 0.2 M, what will
be the new degree of dissociation of HA and
pH ?
Sol. For weak acid HA :

[H ] Meq.

Vin mL

pH = log [H+] = log 0.34

pH = 0.4685

Ex.8

Calculate the pH of a solution which contains

100 mL of 0.1 M HCl and 9.9 mL of 1.0 M
NaOH.
Sol. HCl + NaOH
NaCl + H2O
t = 0 100 0.1 9.9 1
9.9
t = t 109.9
9.99.9 = 0 9.9

Sol.

1
= 0.01, [HA] = 0.1 M
100

K a C 2 0.1 (0.01) 2 10 5

Now 0.2 M NaA, a salt of HA,is added to it

resulting a buffer solution of [HA] = 0.1 M and
[NaA] = 0. 2 M.

0.1
9.099 104 M
109.9
pH = log [H +] = log 9.099 104
pH = 3.0409

[H+] left from HCl =

Ex.9

HA

Calculate [H+] in a solution containing 0.1 M

HCOOH and 0.1 M HOCN. K a for HCOOH
and HOCN are 1.8 104 and 3.3 104.
In this problem both the acids contribute for
[H+] due to appreciable dissociation. Thus,
H+ + HCOO
HCOON
x
0.1 x
x+y
H+
HOCN
+ OCN
0.1y
x+y
y
+
Because [H ] will remain common in solution.
Thus,

KHCOOH =

[H ][HCOO ]
1.8 10 4 (1)
[HCOOH]

[H ][OCN ]
3.3104 (2)
KHOCN =
[HOCN]
or KHCOOH =

(x y)x
0.1

1.8 104 (3)

(x y)y
3.3 10 4
0.1
Thus, by (3) and (4)

KHOCN =

(4)

x 1.8
y 3.3
y = 1.83 x
or
(5)
From (3) (x + 1.83x) . x = 1.8 105
x = 2.52 103

Therefore y = 4.61 103

Thus, [H+] = x + y = 2.52 103
+ 4.61 103 = 7.13 103M

pH = log 105 + log

0.2
0.1

pH = 5.3010
H+ +
A
Also HA
0
0
1
(1 )

[A] is provided by NaA since disso

ciation ofHAin presence ofNaAis suppressed
due to a common ion effect.
[H ][A ] (C) 0.2
105

C(1 )
[HA]

Ka

5 105

Ex.11 Calculate the amount of (NH4)2SO4 in g which

must be added to 500 mL of 0.2 M NH 3 to
yield a solution of pH = 9.35. Kb for NH 3 =
1.78 105.
Sol.

pOH = log Kb + log

or

[Salt]
[Base]

[NH 4 ]
pOH = log Kb + log
[NH 4OH]

[NH 4 ] is obtained from salt (NH4) 2SO 4.

pH = 9.35
pOH = 14 9.35 = 4.65

Millimole of NH 4OH in solution

= 0.2 500 = 100
Let millimole of NH4 added in solution = a

23

Ionic Equilibrium

a
100
[NH ]
; [NH 4OH]
500
500

4.65 = log 1.78 105 + log

a / 500
a

100
a = 79.51
Millimole of (NH4)2SO4 added

a 79.51 39.755
2
2

w
1000 39.755
132

Nic + H+
HNic
(1 )C
C
C
where is the dissociation of the acid and c is
the concentration of nicotinic acid.

100 / 500

4.65 = 4.7496 + log

Sol.

Ka =
c=

[H ][Nic ]
c c
= (1)c
[HNic]

or

c
1

0.1 mol
= 0.05 mol/litre
2.0 litre

1.4 105 =

0.05
1

= 0.016594
Percent dissociation
= 0.016594 100 ~ 1.66%.

Ex.14 How many moles of calcium hydroxide must

be dissolved to produce 250 ml of an aqueous
Ex.12 A solution contains 0.10 M H2S and 0.3 M
solution of pH 10.65 ? Assume complete
2
dissociation.
HCl. Calculate the concentration of S and

pH + pOH = 14
Sol.
HS ions in the solution. For H2S,
7
13
Ka1 = 1.0 10
Ka2 = 1.3 10
pOH = 14 10.65 = 3.35
Sol. Dissociation of H2S can be represented as
[OH] = 4.47 104 mol/litre
H2S H+ + HS
No. of OH moles in 250 ml
(a)

+
2
HS
(b)
H +S
4
= 4.47 10 = 1.12 104
From the first ionisaiton of
w ( NH 4 ) 2 SO4 5.248 g

[H ][HS ]
H2S =
= Ka1
[H 2S]

No. of moles of Ca(OH)2 dissolved = 1

2

Since H2S is weakly ionised and its ionisation

1.12 104 = 0.56 10 4
is further decreased in presence of highly
Ex.15 Saccharin (Ka = 2 1012) is a weak acid
ionised HCl, concentration of H+ in solution
represented by formula HSac. A 4 104 mole
will be mainly due to HCl. Thus [H+] = 0.3
amount of saccharin is dissolved in 200 cm3
Substituting the values in the above equation
water of pH 3. Assuming no change in volume,

calculate the concentration of Sac ions in the

0.3[HS ]
7
= 1 10
resulting solutionat equilibrium.
0.1
Sol. Calculation of [H+] and [HSac] at start
[HS] = 3.33 108 M
We know that [H +] = 10 pH = 10 3 = 0.001M
From the second ionisation of H2S,
4 10 4 1000

[H ][S2 ]
[HS ]
0.3 [S2 ]
3.33 108

[S2]

= Ka2 or
= 1.3

1013

= 1.44 1020 M

Ex.13 Nicotinic acid (Ka = 1.4 105) is represented

by the formula HNic. Calculate its percent
dissociation in a solution which contains 0.10
mol. of nicotinic acid per 2.0 litre of solution.

[Hsac] =

200

= 0.002 M

The dissociation of HSac is as below

HSac.
+
H+
0.002
0.001
At start
At equb
0.002 x
0.001 + x
Ka =

Sac
0
x

[H ][Sac ] (0.01 x) x
=
= 2 1012
[H Sac- ]
0.002 x

x = 4 1012 M
[Sac]equb = 4 1012 M

24

Ionic Equilibrium

Ex.16 Calculate the pH value ofthe mixture containing

50 c.c. of N HCl and 30 c.c. of N NaOH
solution both to be completely dissociated in
normal solution.
Sol. Since we know 30 c.c. of N NaOH will
neutralise 30 c.c. of N HCl.
Amount of N HCl left un-neutralised

= 50 30 = 20 c.c.
Ex.18
Total volume after mixing = 50 + 30 = 80 c.c.
In other words 20 c.c of N HCl has been
diluted to 80 c.c.
Now since 1000 c.c. of N HCl contain
Sol.
= 1 g eq of HCl
20 c.c. of N HCl contain = 1

20
1
=
1000
50

= 1.8 mole/litre
1000 ml contains 1.8 moles
500 ml contains 1.8 = 0.9 moles
2

Weight of gms.
= Numbers of moles Mol. wt. of NH4Cl
= 0.90 53.5 = 48.150 gm
Calculate the pH at the equivalence point when
a solution of 0.10 M acetic acid is titrated with
a solution of 0.10 M sodium hydroxide. Ka for
acetic acid is 1.9 105.
We know that pH of a mixture of solution
containing weak acid and strong base can be
calculated as below.
pH

gram eq.

1
This 50g eq. is the amount of HCl present in

=7+

= 7 + 2 pKa + 2 logc
1
2

4.7212 +

1
log 0.05
2

= 7 + 2.3606 0.65 = 8.71

Ex.19 Calcium lactate is a salt of a weak organic acid
1
Thus 80 c.c. of the mixture contain = 50 g eq.
and represented as Ca (Lac)2. A saturated
solution of Ca (Lac)2 contains 0.13 mol of this
of HCl
salt in 0.50 litre solution. The pOH of this
1 1000
solution is 5.60. Assuming a complete
1000 c.c of the mixture contain = 50 80 g
dissociation of the salt, calculate Ka of lactic
eq. = 0.25 g eq.
acid.
[H+] = 0.25 g eq. per litre
Ca2+ + 2 Lac
Sol. Ca (Lac)2
We know that
2 0.26 M
0.13 2 M
pH = log [H+] = log [0.25] = 0.6021
Concentration of the lactate ion

Ex.17 How many grams of NH 4Cl should be

C = 0.52
dissolved in 500 ml of water to have solution
Also we are given
of pH 4.5 ? Kb for ammonium hydroxide is
pOH = 5.6
pH = 14 5.6 = 8.4
1.8 105.
14
K
log Kw = 14
=
10
or
w
Sol. pH = log[H+]
Substituting the values inthe following equation
log[H+] = log 1 4.5 = 5.5
for the salt of a weak acid and strong alkali.
+
5
[H
]
=
Antilog
[5.5]
=
3.162

10

= 1 (log Kw + log Ka log c)

pH
mole per litre
80 c.c. of the mixture.

[H+] = hc =
or

[H+]2 =

[H ]2 K b
Kw

Kw c
Kb

Kw c
Kb

8.4

= 2 (14 + log Ka log 0.52)

Ka

= 8.26 104

Ex.20 What is the pH of 0.10 M CH 3COONa

solution. Hydrolysis constant of sodium acetate is 5.6 1010?

3.162 10 5 3.162 10 5 1.8 105

c=

1 10 14

25

Ionic Equilibrium

Sol.

Hydrolysis of the salt may be represented

as
CH3COO + Na+ + H2O CH3COOH+Na++OH
CH3COOH + OH
or CH3COO + H2O
0
C

At eq = 0 C
At C(1 )

0
C

equilibrium
Kh =

C 22
C(1 - )

Kh
C

= C2 when < 1

5.6 X 10
0.10

10

= 7.5 105
[OH]

= C = 0.10 7.5 105

pOH

= log (7.5 106) = 5.126

pH

= 14 pOH = 14 5.126
= 8.874

26

Ionic Equilibrium

EXERCISE - I
Q.1

The degree of dissociation of acetic acid in a

0.1 N solution is 1.32 10 2. At what
concentration of nitrous acid, its degree of
dissociation willbe same as that of acetic acid?
Ka (HNO2) = 4104

Q.2

How many times is the H+ concentration in the

blood (pH = 7.36) greater than in the spinal
fluid (pH = 7.53) ?

Q.3

A 0.400 M formic acid solution freezes

at 0.758C. Calculate the Ka of the acid at
that temperature. (Assume molarity equal to
molality). Kf (H2O) is 1.86 mol1 kg.

Q.4

Asample ofAgCl was treated with 5 mL of

1.5 M Na2CO3 solution to give Ag 2CO 3. the
remaining solutioncontained 0.00266625 g/litre
Cl ion. Calculate the solubility ofAgCl in
(a) 0.1 M AgNO 3
(b) 0.1 M BaCl2
(c) 0.2 M NaNO3.
Given that solubility ofAg2CO3
in500 mL H 2O = 13.8 mg.

Q.5

100 mL of solution S 1 contains 0.17 mg of

AgNO3 .Another 200 mLsolution S2 contains
0.117 mg of NaCl. On mixing these two
solutions predict whether the precipitate of
AgCl will appear or not Ksp AgCl = 1010 M2

Q.6

An indicator is a weak acid and the pH range

of its colour is 3.1 to 4.5. If the neutral point of
the indicator lies in the centre of the hydrogen
ion concentrations corresponding to given pH
range, calculate the ionization constant of the
indicator.

Q.7

Calculate the hydrolysis constant of NH4Cl ;

determine the degree of hydrolysis of this salt
in 0.01 M solution and the pH of the solution.
Kb (NH4OH) = 1.8 105

Q.8

Calculate the pH of 0.1 M acetic acid solution

if its dissociation constant is 1.8 105. If 1
litre of this solution is mixed with0.05 mole of
HCl, what will be the pH of the mixture ?

Q.9

What is the solubility product ofAg 2CrO 4 if

0.0166 g ofthe salt dissolves in 500 ml of water
at 18C?

Q.10

When a 40 mL of a 0.1 M weak base is titrated with 0.16 M HCl, the pH of the solution
at the end point is 5.23. What will be the pH if
15 mL of 0.12 M NaOH is added to the
resulting solution.

Q.11

A chemist needs a buffer with pH 4.35. How

many milliliters of pure acetic acid (density
= 1.049 g/mL) must be added to 465 mL of
0.0941 M NaOH solution to obtain such
buffer? (Ka = 1.8 105)

Q.12

It is found that 0.1 M solution of three sodium

salts NaX, NaY and NaZ have pHs 7.0, 9.0
and 11.0, respectively. Arrange the acids HX,
HY and HZ in order of increasing strength.
Where possible, calculate the ionisation
constants of the acids.

Q.13

Given a solution that is 0.5 M CH3COOH. To

what volume at 25C must one dm3 of this
solution be diluted in order to (a) double the
pH; (b) double the hyd roxide-ion
concentration.
Given that Ka = 1.8 105 M.

Q.14

The solubility of Mg(OH)2 is increased by

addition of NH4+ ion. Calculate
(a) KC for the reaction,
2NH3+ 2H2 O+Mg2+
Mg(OH)2+2NH 4+
(b) Find solubility of Mg(OH)2 in a solution
containing 0.5 M NH4Cl before addition of
Mg(OH)2 (Ksp of M g(OH)2 = 1 1011, Kb
for NH4O H = 1.8 105 )

Q.15

Abuffer solution was prepared by dissolving

0.05 mol formic acid and 0.06 mol sodium formate in enough water to make 1.0 L of solution. Ka for formic acid is 1.80 10-4.
(a) Calculate the pH of the solution.
(b) If this solution were diluted to 10 times its
volume, what would be the pH?
(c) If the solution in (b) were diluted to 10 times
its volume, what would be the pH?

27

Ionic Equilibrium

Q.16

An unknown volume and unknown Q.22

concentration of weak acid HX is titrated with
NaOH of unknown concentration. After
addition of 10.0 cm3 of NaOH solution, pH of
solution is 5.8 and after the addition of 20.0
cm3 of NaOH solution, the pH is 6.4. Calculate Q.23
the pH of aqueous solution of 0.1 M NaX.

The ionization constant of acetic acid is

1.74 105. Calculate the degree of dissociation of acetic acid in its 0.05 M solution. Calculate the concentration of acetate ion in the
solution and its pH.

It has been found that the pH of a 0.01 M

solution of an organic acid is 4.15. Calculate
the concentration of the anion, the ionization
Q.17 Asolution containing zinc and manganese ions
constant of the acid and its pKa .
each at a concentration of 0.01 mol dm3 is
saturated with H S.2 Calculate (i) pH at which Q.24 Assuming complete dissociation, calculate the
pH ofthe following solutions:
the MnS will form a precipitate (ii) conc. of
(a) 0.003 M
(b) 0.005 M NaOH
Zn+2 ions remaining.
(c) 0.002 M HBr
(d) 0.002 M KOH
Given : [H2S] = 0.1 mol/lit, Ksp(ZnS) = 1
22
2
2
16
2
10 mol lit , Ksp(MnS) = 5.6 10 mol
Q.25 Calculate the pH of the following solutions:
lit2.
(a) 2 g of TlOH dissolved in water to give 500 ml
K1 and K2 for H 2S are 1107 and 1.11014.
of solution.
(b) 0.3 g of Ca (OH)2 dissolved in water to
Q.18 For the indicator thymol blue, the value of pH
give 2 litre of solution
is 2.0, when half of the indicator is present in
(c) 0.3 g of NaOH dissolved in water to give
an unionized form. Calculate the percentage
200 mLof solution.
ofthe indicator in the unionized formina solution
(d) 1 mL of 13.6 M HCl is diluted with water to
of 4.0 10 3 mol/dm 3 hydrogen ion
give 1 litre of solution
concentration.
Q.26 If the solubility product of silver oxalate is
Q.19 One of the substances sometimes responsible
1 1011, what will be the weight ofAg2C2O4
for the hardness of water is CaSO4.Aparticular
in 2.5 litres of a saturated solution ?
water sample has 131 ppm CaSO (131
g
4
CaSO4 per 106 g of water). If this water boiled Q.27 Calculate the hydrolysis constant of KF.
Determine the degree of hydrolysis of salt in a
in a tea kettle, approximately what fraction of
0.01 M solution and the pH of the solution.
water must be evaporated before CaSO4(s)
Ka(HF) = 6.6 104.
begins to deposit ?Assume that solubility of
CaSO4 does not change with temperature in Q.28 Assuming that the buffer in blood is
CO3HCO3 , calculate the ratio of conjugate
the range 0 to 100C, Ksp (CaSO4) = 9.1
base to acid necessary to maintain blood at its
106.
proper pH, 7.4 K1 (H2CO3) =4.5 107.
Q.20 The indicator phenolred is half inthe ionic form
when pH is 7.2. If the ratio of the undissociated Q.29 How does the solubility of CaC2O4 in a 0.1 M
solution of ( NH 4 ) 2 C 2 O 4 decrease in
form to the ionic form is 1 : 5, find the pH of
comparison with its solubility in water ?Assume that
the solution. With the same pH for solution, if
the ionisation of (NH4)2C2O4 is complete. [Ksp
indicator is altered such that the ratio of
(CaC2O4) = 2 109]
undissociated formto dissociated formbecomes
1 : 4, find the pH when 50% of the new indicator Q.30 How many moles of sodium hydroxide can be
is in ionic form.
added to 1.0 L of a solution 0.10 M in NH3 and
0.10 M in NH4Cl without changing the
Q.21 The first ionization constant of H 2S is
pOH by more than 1 unit. Assume no change in
9.1 108. Calculate the concentration of
volume.

HS ion in its 0.1 M solution. How will this

Kb = 1.8 105.
concentration be affected if the solution is 0.1
M in HCl also? If the second dissociation
constant of H2S is 1.2 1013. Calculate the
concentration of S2 under both conditions.

28

Ionic Equilibrium

EXERCISE - II
Q.1

Calculate the number of H+ present in one ml Q.11

of solution whose pH is 13.

Q.2

Calculate change in concentration of H+ ion in

one litre of water, when temperature changes
from 298 K to 310 K.
Given Kw(298)=1014Kw(310)=2.56 1014. Q.12

Q.3

(i) Kw for H2O is 9.62 1014 at 60C.

What is pH of water at 60C.
(ii) What is the nature of solutionat 60C whose
(a) pH = 6.7
(b) pH = 6.35

Q.4

The value of K w at the physio logical

temperature (37C) is 2.56 1014. What is
the pH at the neutral point of water at this
temperature?

Q.5

Calculate pH of following solutions :

(a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl 50
(ml)
(b) 0.1 M HA + 0.1 M HB [ Ka (HA) = 2
105 ; Ka (HB) = 4 105 ]

Q.6

What are the concentration of H+, H2C2O4,

2
HC 2O 4 and C 2O 4 in a 0.1 M solution of
oxalic acid ?
[K1 = 102 M and K2 = 105 M ]

Q.7

What are the concentrations of H + ,

Q.14

Calculate OH concentration at the equivalent

point when a solution of 0.1 M acetic acid is
titrated with a solution of 0.1 M NaOH. Ka
for the acid = 1.9 105.

Q.15 Calculate the hydronium ion concentration and

pH at the equivalence point in the reaction of
22.0 mL of 0.10M acetic acid, CH3COOH,
with 22.0 mL of 0.10 M NaOH.
[Ka = 1.8 105]
Q.16 The values of Ksp for the slightly soluble salts
MX and QX 2 are each equal to 4.01018.
Which salt is more soluble? Explain your
answer fully.
Q.17

Calculate the SimultaneoussolubilityofAgSCN

and AgBr. K sp (AgSCN) = 1.1 1012 ,
Ksp(AgBr) = 5 1013.

Q.18

A recent investigation of the complexation of

SCN with Fe3+ led of 130, 16, and 1.0 for
K1, K2, and K3, respectively. What is the
overall formation constant of Fe(SCN)3 from
its component ions, and what is the dissociation
constant of Fe(SCN)3 into its simplest ions on
the basis of these data ?

Q.19

Calculate the percent error in the [H O+] 3

concentration made by neglecting the ionization
of water in a 106 M NaOH solution.

Q.20

A solution was made up to be 0.01 M in

chloroacetic acid, ClCH2COOH and also
0. 002 M in so d ium chlo r o a cet a t e
ClCH2COONa . What is [H+] in the solution?
Ka = 1.5 103.

Given : H2SO4 H+ + HSO 4 ; strong

2
HSO4 l H+ + SO 2
4 ; K2 = 10 M

Calculate the pH of a solution which results

from the mixing of 50.0 ml of 0.3 M HCl with
50.0 ml of 0.4 M NH3 .
[Kb (NH3) = 1.8 105]
Q.9 Calculate the pH of a solution made by mixing
50.0 ml of 0.2M NH4Cl & 75.0 ml of 0.1 M
NaOH. [ Kb (NH3 ) = 1.8 10 5 ]
Q.10 What indicator should be used for the titration
of 0.10 M KH2BO3 with 0.10 M HCl ?
Ka (H3BO3) = 7.2 1010 .

What is the OH concentration of a 0.08 M

solution of CH3COONa.
[Ka(CH3COOH)=1.8 105]

Q.13 Calculate the pH of a 2.0 M solution of NH4Cl.

[Kb (NH3) = 1.8 105]

HSO4 , SO 2
4 and H2SO4 in a 0.20 M solution
of sulphuric acid ?

An acid indicator has a K aof 3 105. The

acid form of the indicator is red & the basic
form is blue. By how much must the pH change
in order to change the indicator form 75% red
to 75 % blue?

Q.8

29

Ionic Equilibrium

A solution contains HCl, Cl2HC COOH &

Q.27 How many moles of sodium hydroxide can be
CH3 COOH at concentrations 0.09 M in HCl,
added to 1.00 L of a solution 0.1 M in NH3 &
0.1 M in NH4Cl without changing the pOH by
0.09 M in Cl2HC COOH & 0.1 M in CH3
COOH. pH for the solution is 1.
more than 1.00 unit ? Assume no change in
Ionization constant of CH3 COOH = 105.
volume. Kb(NH3) = 1.8 105.
What is the magnitude of K for dichloroacetic
Q.28 20 ml of a solution of 0.1 M CH3COOH
acid ?
solution is being titrated against 0.1 M NaOH
Q.22 Determine the [S2] in a saturated (0.1M) H2S
solution. The pH values after the addition of 1 ml
solution to which enough HCl has been added
& 19 ml of NaOH are (pH) &1(pH) , what
2
to produce a [H+] of 2 104 . K1 = 107,
is
pH
?
K2 = 1014.
Q.29 Aweak base BOH was titrated against a strong
Q.23 What is the pH of a 1.0 M solution of acetic
acid . The pH at 1/4th equivalence point was
acid ? To what volume must 1 litre of the
9.24. Enough strong base was now added
solution be diluted so that the pH of the resulting
(6m.eq.) to completely convert the salt. The
solution will be twice the original value. Given
total volume was 50ml. Find the pH at this
Ka = 1.8 105.
point.
Q.24 It is desired to prepare 100 ml of a buffer of
Q.30 An organic monoprotic acid [0.1M] is titrated
pH 5.00.Acetic, benzoic and formic acids and
against 0.1M NaOH. By how much does the
their salts are available for use. Which acid
pH change between one fourth and three fourth
should be used for maximum effectiveness
stages of neutralization? If at one third stage of
against increase in pH? What acid-salt ratio
neutralization, the pH is 4.45 what is the
should be used ? pKa values of these acids are:
dissociation constant of the acid? Between
acetic 4.74; benzoic 4.18 and formic 3.68.
what stages of neutralisation may the pH change
Q.25 When a 40 mL of a 0.1 M weak base is titrated
by 2 units ?
with 0.16M HCl, the pH of the solution at the
end point is 5.23. What will be the pH if 15
mL of 0.12 M NaOH is added to the
resulting solution.
Q.21

Q.26 Abuffer solution was prepared by dissolving

0.05 mol formic acid & 0.06 mol sodium
formate in enough water to make 1.0 L of
solution. Ka for formic acid is 1.80 104.
(a) Calculate the pH of the solution .
(b) If this solution were diluted to 10 times its
volume, what would be the pH ?
(c) If the solution in (b) were diluted to 10 times
its volume,what would be the pH?

30

Ionic Equilibrium

EXERCISE- III
Q.1

The conjugate acid of NH2 is

(A) NH3
(B) NH2OH

(D) N2H4
(C) NH 4

Q.2

Out of the following, amphiprotic species are

II
I: HPO32 III
OH

IV
H2PO4 (A) I,
HCO3
III, IV (C) III
(B) I and III
and IV
(D)All

Q.3

Q.9

Which of the following solution will have pH

close to 1.0?
(A) 100 ml of M/100 HCl + 100 ml of M/10
NaOH
(B) 55 ml of M/10 HCl + 45 ml of M/10
NaOH
(C) 10 ml of M/10 HCl + 90 ml of M/10
NaOH
(D) 75 ml of M/5 HCl + 25 ml of M/5 NaOH

pH of an aqeous solution of NaCl at 85C

should be
(A) 7
(B) > 7
(C) < 7
(D) 0

Q.10

Asolution with pH 2.0 is more acidic than the

one with pH 6.0 by a factor of:
(A) 3
(B) 4
(C) 3000
(D) 10000

Q.4

1 cc of 0.1 N HCl is added to 99 cc solution

of NaCl. The pH of the resulting solution will
be
(A) 7
(B) 3
(C) 4
(D) 1

Q.11

The first and second dissociation constants of

an acid H2A are 1.0 105 and 5.0 1010
respectively. The overall dissociatio n
constant of the acid will be :
(A) 5.0 105
(B) 5.0 1015
(C) 5.0 1015
(D) 0.2 105

Q.5

10 ml of

Q.6

Q.7

M
H SO is mixed with 40 ml of
200 2 4

Q.12 An aqueous solution contains 0.01 M RNH2

(Kb = 2 106) & 104 M NaOH.
M
H2SO4. The pH of the resulting solution
The concentration of OH is nearly :
200
(A) 2.414 104
(B) 104 M
is
(B) 2
(A) 1
(C) 1.414 104
(D) 2 104
(D) none of these
(C) 2.3
Q.13 The degree of hydrolysis of a salt of weak acid
If pKb for fluoride ion at 25 C is 10.83, the
and weak base in its 0.1 M solution is found
to be 50%. If the molarity of the solution is 0.2
ionisation constant of hydrofluoric acid in water
M, the percentage hydrolysis of the salt should
at this temperature is :
(A) 1.74 105
(B) 3.52 103
be
4
2
(C) 6.75 10
(D) 5.38 10
(A) 100%
(B) 50%
(C) 25%
(D) none of these
The pH of an aqueous solution of 1.0 M
solution of a weak monoprotic acid which is
1% ionised is
(A) 1
(B) 2
(C) 3
(D) 11

Q.8

If K1 & K2 be first and second ionisation

constant of H3PO4 and K1 >> K2 which is
incorrect.
(A) [H+] = [ H 2PO4 ]
(B) [H+] = K1[H 3PO 4 ]
(C) K2 = [HPO4 ]

Q.14 What is the percentage hydrolysis of NaCN in

N/80 solution when the dissociation constant
for HCN is 1.3 109 and Kw = 1.0 1014
(A) 2.48
(B) 5.26
(C) 8.2
(D) 9.6
Q.15

The compound whose 0.1 M solution is basic

is
(A) Ammonium acetate
(B) Ammonium chloride
(C) Ammonium sulphate
(D) Sodium acetate

(D) [H+] = 3[PO3

]
4

31

Ionic Equilibrium

Q.16

The pH of the neutralisation point of 0.1 N

ammonium hydroxide with 0.1 N HCl is
(A) 1
(B) 6
(C) 7
(D) 9

Q.24

The solubility of A2X3 is y mol dm3. Its

solubility product is
(A) 6 y2
(B) 64 y4
(C) 36 y5
(D) 108 y5

Q.17

If equilibrium constant of
CH3COOH + H2O CH3COO + H3O+
Is 1.8 105, equilibrium constant for
CH3COOH + OH l CH3COO + H2O is
(A) 1.8 109
(B) 1.8 109
(C) 5.55 109
(D) 5.55 1010

Q.25

If Ksp for HgSO4 is 6.4 105, then solubility

of this substance in mole per m3 is
(A) 8 103
(B) 6.4 105
6
(C) 8 10
(D) None of these

Q.26

The solubility of a sparingly soluble saltAB2 in

water is 1.0 105 mol L1. Its solubility
product is:
(A) 1015
(B) 1010
15
(C) 4 10
(D) 4 1010

Q.18

Q.19

The pKa of a weak acid, HA, is 4.80. The pKb

of a weak base, BOH, is 4.78. The pH of an
aqueous solution ofthe corresponding salt, BA,
will be :
Q.27
(A) 8.58
(B) 4.79
(C) 7.01
(D) 9.22
The range of most suitable indicator which
should be used for titration of X Na+ (0.1 M,
10 ml) wit h 0.1 M HCl sho uld be
(Given: k b(X ) =106)
(A) 23
(C) 68

Q.20

(B) 35
(D) 810

How many gm of solid NaOH must be added

to 100 ml of a buffer solution which is 0.1 M
each w.r.t. Acid HA and salt Na+ A to make
Q.29
the pH of solution 5.5. Given pka (HA) = 5.
(Use antilog (0.5) = 3.16)
(A) 2.08 101
(B) 3.05 103
2
(C) 2.01 10
(D) None of these

Q.21

If 40 ml of 0.2 M KOH is added to 160 ml of

0.1 M HCOOH [Ka = 2104], the pOH of
the resulting solution is
(A) 3.4
(B) 3.7
(C) 7
(D) 10.3

Q.22

1 M NaCl and 1M HCl are present in an

aqueous solution. The solution is
(A) not a buffer solution and with pH < 7
(B) not a buffer solution with pH > 7
(C) a buffer solution with pH < 7
(D) a buffer solution with pH > 7

Q.23

Q.28

The pKa of a weak acid (HA) is 4.5. The pOH

of an aqueous buffered solution of HAin which
50% of the acid is ionized is :
(A) 4.5
(B) 2.5
(C) 9.5
(D) 7.0

Which ofthe following is most soluble in water?

(A) MnS (K sp= 81037)
(B) ZnS (Ksp= 71016)
(C) Bi2S3 (Ksp= 11072)
(D) Ag3(PO4) (Ksp= 1.81018)
When equal volumes of the following solutions
are mixed, precipitation of AgCl (Ksp = 1.8
1010) will occur only with:
(A) 104 M (Ag+) and 104 M (Cl )
(B) 105 M (Ag+) and 105 M (Cl )
(C) 106 M (Ag+) and 106 M (Cl )
(D) 1010 M (Ag+) and 1010 M (Cl )

The precipitate of CaF2(Ksp = 1.7 1010) is

obtained when equal volumes of the following
are mixed
(A) 104 M Ca3+ + 104 M F
(B) 102 M Ca2+ + 103 M F
(C) 105 M Ca2+ + 103 M F
(D) 103 M Ca2+ + 105 M F
Q.30 50 litre of a solution containing 105 mole of
Ag+ is mixed with 50 litre of a 2 107 M HBr
solution. [Ag+] in resultant solution is : [Given :
Ksp (AgBr) = 5 1013]
(A) 105 M
(C) 107 M

Q.31

(B) 106 M
(D) None of these

pH of a saturated solution of silver salt of

monobasic acid HAis found to be 9.
Find the Ksp of sparingly soluble saltAgA(s).
Given : Ka (HA) = 1010
(A) 1.1 1011
(B) 1.1 1010
12
(D) None of these
(C) 10

32

Ionic Equilibrium

Q.32 The solubility of metal sulphides in saturated

solution of H2S {[H2S]= 0.1 M} can be
represented by
MS + 2H+ M2+ +H2S;Keq=

[M 2 ][H S]
2

[H ]

The value of Keq is given for few metal sulphide.

If conc. of each metal ion in solution is 0.01
M, which metal sulphides are selectively ppt at Q.37
total [H+]= 1M in saturated H2S solution.
Metal sulphides
MnS
ZnS CoS PbS
[M 2 ][H2S]
7
10
2
Keq =
3 10 3 10
3 3 10
[H ]2
(A) MnS, ZnS, CoS
(C) PbS, ZnS
Q.33

Q.34

Select incorrect statement(s).

(A) Phenolphthalein is suitable indicator for the
titration of HCl (aq) with NH4OH (aq).
(B) An acid-base indicator in a buffer solution
of pH = pKIn + 1 is ionized to the extent of
90%.
(C) In the titration of a monoacidic weak base
with a strong acid, the pH at the equivalent point
is always calculated by

(B) PbS, ZnS, CoS

(D) PbS

Solid Ba(NO3) 2 is gradually dissolved in a

1.0 104 M Na2CO 3 solution. At what
concentration of Ba2+ will a precipitate begin
to form ? (Ksp for BaCO3 = 5.1 109)
(A) 4.1 105 M
(B) 5.1 105 M
(C) 8.1 108 M
(D) 8.1 107 M
Ksp of MX4 and solubility of MX4 is S
mol/litre is related by :
(A) S = [KSP /256]1/5
(B) S = [128 KSP ]1/4
(C) S = [256 KSP]1/5
(D) S = [KSP /128]1/4

(A) Kb of base is less than 106

(B) Concentration of salt (C) at equivalent point
is 0.25 M
(C) Volume of HCl is used at equivalent point
is 100 ml
(D) Weight percentage of base in given sample
is 80%.

1
pH = 2 [pK w pK b log C]

(D) When Na3PO 4 (aq) is titrated with HCl

(aq), the pH of solution at second equivalent
point is calculated by
Q.38

Q.35 Which of the following statement(s) is/are

correct ?
(A) the pH of 1.0108 M solution of HCl is 8
(B) the conjugate base of H2PO4 is HPO42
Q.39
(C) autoprotolysis constant of water increases
with temperature
(D) when a solution of a weak monoprotic acid is
titrated again a strong base, at half
neutralization point pH = (1/2) pKa .
Q.36 A 2.5 gm impure sample containing weak
monoacidic base (Mol. wt. = 45) is dissolved
in 100 ml water and titrated with 0.5 M HCl Q.40
th
1
when of the base was neutralised the
5
pH was found to be 9 and at equivalent point
pH of solution is 4.5 . Given :All data at 25C
& log 2 = 0.3.
Select correct statement(s) .

1
[pK a1 pK a 2 ]
2

Which of the following is true for alkaline

aqueous solution?
pk w
(A) pH >
(B) pH > pOH
2
pk w
(C) pOH <
(D) pH < pOH
2
An acid-base indicator has a Ka of 3.0 105.
The acid form of the indicator is red and the
basic form is blue. then:
(A) pH is 4.05 when indicator is 75% red
(B) pH is 5.00 when indicator is 75% blue.
(C) pH is 5.00 when indicator is 75% red
(D) pH is 4.05 when indicator is 75% blue.
The equilibrium constant for the reaction
HONO(aq) + CN (aq)
HCN(aq)

+6
+ ONO (aq) is 1.1 10 . From the
magnitude of this Keq one can conclude that
(A) CN is stronger base than ONO
(B) HCN is a stronger acid than HONO
(C) The conjugate base of HONO is ONO
(D) The conjugate acid of CN is HCN

33

Ionic Equilibrium

Q.41

Q.42

All of the following are acid-base conjugate

pairs:
(A) HONO, NO 2
(B) H3O+, OH
(C) CH3NH3+, CH3NH 2
(D) HS, S 2
In the following reaction:

(A)Ais an acid and B the base

(B) Ais a base and B the acid
(C) C is the conjugate acid ofA, and D is the
conjugate base of B
(D) C is the conjugate base ofA, and D is the
conjugate acid of B
Q.43 Which does not react with NaOH or which is
not acid salt?
(A) NaH2PO2
(B) Na2HPO3
(C) Na2HPO4
(D) NaHCO3
Q.44 pH of the following solution is not affected by
dilution:
(A) 0.01 M CH 3COONa
(B) 0.01 M NaHCO3
(C) buffer of 0.01 M CH 3COONa and 0.01
M CH3COOH
(D) 0.01 M CH 3COONH 4
Q.45 Which of t he following mixtures
constitute a buffer?
(A) CH3COOH + CH 3COONa
(B) Na2CO3 + NaHCO 3
(C) NaCl + HCl
(D) NH4Cl + (NH 4) 2SO 4
Q.46 Which of t he following mixtures
constitute a buffer?
(A) Na2CO 3 + HCl
(B) NaOH + CH 3COOH
(C) NH3 + CH 3COONH 4
(D) NaOH + BaCl 2
Q.47 In which of the following pairs of
solutions is there no effect on the pH
upon dilution?
(A) 0.1 M NH 3 and 0.1M(NH4) 2SO 4
(B) 0.1 M NaH 2PO 4 and 0.1 M
Na 2HPO 4
(C) 0.1 M HCl and 0.01 M NaOH
(D) 0.1 M KCl and 0.1 M HCl

Q.48 Which of the following will suppress the

ionization of phthalic acid in an aqueous
solution.
(A) KCl
(B) H 2SO
(C) HNO3
(D) NaOH
Assertion and Reason :
Q.49 Statement-1 : pH of 107 M NaOH solution
is exist between 7 to 7.3 at 25C.
Statement-2 : Due to common ion effect
ionization of water is reduced.
(A) Statement-1 is true, statement-2 is true and
statement-2 is correct explanation for
statement-1.
(B) Statement-1 is true, statement-2 is true and
statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.50 Statement-1 : In general phenolphthalein is
used as an indicator for the titration of weak
acid (HA) against strong base (NaOH).
Statement-2 : At equivalent point solution is
basic.
(A) Statement-1 is true, statement-2 is true and
statement-2 is correct explanation for
statement-1.
(B) Statement-1 is true, statement-2 is true and
statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.51

Statement-1 : Moles of Sr2+ furnished by

sparingly soluble substance Sr(OH)2 decreases due
to dilution.
Statement-2 : Solubility product constant of
Sr(OH)2 is not affected by dilution.
(A) Statement-1 is true, statement-2 is true and
statement-2 is correct explanation for
statement-1.
(B) Statement-1 is true, statement-2 is true and
statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

34

Ionic Equilibrium

Paragraph 1
Paragraph 2
1.2 g of a monoprotic acid HA, is titrated with
Potash alum is K Al(SO4)212H2O. As a
strong electrolyte, it is considered to be 100
0.222 M NaOH solution. The pH of the
% dissociated into K+, Al3+ and SO42. The
solution is monitored with pH meter. Aportion
solution is acidic because of the hydrolysis of
of the titration curve is shown in the diagram.
Al3+, but not so acidic as might be expected,
Expanded titration
because the SO42 can sponge up some of the
12.00 curve of
H3O+ by forming HSO4. Given a solution
HA
vs
NaOH
11.00
ma de by disso lving 11. 85 g m o f K
10.00
Al(SO4)212H2O in enough water to make
pH 9.00
100 cm3 of solution. What is [H3O+] of the
8.00
solution if
7.00
6.00
5.00
15 16

Q.55
17 18

19

20

Volume of NaOH (mL)

Q.52

Q.53

Q.54

How many mL of NaOH is required to bring

about the titration to its equivalence point ?
(A) 4.00
(B) 9.00
(C) 19.00
(D) None of these

Q.56

What is the pH of solution at the equivalence

point ?
(A) 3.50
(B) 7.00
(C) 8.40
(D) None of these

Q.57

What is the molar mass of HA ?

(A) 180
(B) 222
(C) 282
(D) None of these

Q.58

Match the column

Q.59 Match the following
List I
(A)
(P)
CH3COOH
(B)
(Q)
H2SO4
NaOH
(C)
(R)
NH3
(D)
(S)
Q.60
Column I
(pH of resultant solution)
200 ml of H2SO4 solution
(A)
(specific gravity 1.225 containing
25% H2SO4 by weight) + 800 ml of
0.525 M strong triacidic base
X (OH)3
50 ml of 0.1 M HCO3 +
(B)

None of the ion is hydrolysing.

(A) 107 M
(B) less than 107 M
(C) More than 107M
(D) 0.0
OnlyAl3+ is hydrolysing and its first hydrolysis
constant is 1.4 105 M
(A) 1.87 103 M
(B) 6.24 104 M
(C) 0.09 M
(D) None of these
2
Only SO4 is hydrolysing and acid dissociation
constant of HSO4 in water is 1.25 102.
(A) 1.26 103 M
(B) 6.32 107 M
8
(C) 1.58 10 M
(D) None of these
3+
2
BothAl and SO4 are hydrolysing.
(A) 2.93 104 M
(B) 0.0114 M
(D) None of these
(C) 5.43 106 M

List II weak
Base
Weak acid
Strong acid
Stronge base
Column II
(Exist between Colour transition
range of an indicator)
(P)
Phenol Red (6.8 to 8.4)
(Q)

Propyl red (4.6 to 6.4)

(R)

Phenolphtalein (8.3 to 10.1)

(S)

Malachite green (11.4 to 13)

2
50 ml of 0.8 M CO3

(C)

(H2CO3 : K a1 = 4 10 7 , K a 2 = 2 10 11)
50 ml of 0.2 M HA (aq) (Ka = 105)
+ 50 ml of 0.1 M HCl (aq)
+ 100 ml of 0.13 M NaOH (aq)

35

Ionic Equilibrium

ANSWER KEY
EXERCISE -I
Q.1
Q.4
Q.6
Q.9
Q.12
Q.14
Q.16
Q.18
Q.21
Q.22
Q.24
Q.26

1.44 104
2.3 mol/lit
Q.2. 1.5 times
Q.3
4
5
(a) 1.76 10 mg/L, (b) 8.8 10 mg/L, (c) 1.588 mg/L
Q.5
No
4
10
4
Q.8
2.87, 1.3
4.11 10 M
5.6 10 , 2.4 10 , 5.63
Q.7
Q.10 pH = 9.168
Q.11 8.7 mL
Ksp (Ag2CrO4) = 4 1012
HZ < HY < HX , K a(HY) = 105 M, K a(HZ) = 109 M
Q.13 (a) 3.7 104 dm3 (b) 4 dm3
Q.15 (a) pH = 3.83 (b) pH = 3.85 (c) 3.99
KC = 3.02 102, S = 0.123 M
Q.17 (i) pH = 4.35 (ii) 1.79 109 mol/lit
9.55
(i) 28.57% (ii) 4.11 104mol dm3
Q.19 67% Q.20 pH = 7.3
[HS] 9.54 105, in 0.1M HCl [HS] = 9.1 108 M,
[S2] = 1.2 1013 M, in 0.1 M HCl [S2] = 1.09 1019 M
[Ac] = 0.00093, pH = 3.03
Q.23 [A] = 7.08 105 M, K a = 5.08 107, pK a = 6.29
(a) 2.52 (b) 11.70 (c) 2.7 (d) 11.30 Q.25 (a) 11.65 (B) 12.21 (c) 12.57 (d) 1.87
Q.27 pH = 7.59, kH = 1.5 1011 Q.28 11
0.103 g

Q.29

1
of its solubility in water solubility decreases
2200

Q.30

0.082 mol of NaOH can be added

EXERCISE - II
107

Q.1
Q.4
Q.7
Q.10
Q.12
Q.16
Q.18
Q.21
Q.24
Q.26

6.022
Q.2
0.6 107
Q.3
(i) 6.51 ; (ii) (a) Basic , (b) Acidic
Q.5
Q.6
0.027 M, 0.073 M, 0.027 M, 105 M
6.81
(a) 0.522 , (b) 2.61
Q.8
0.2116 M, 0.1884 M, 0.0116 M, 0
8.7782
Q.9
9.7324
Q.11 pH = 0.954
(methyl red), one with pH = 5.22 as midpoint of colour range
Q.14 5.12 106 M Q.15 8.71
[OH] = 6.664 106 Q.13 pH = 4.477
QX2 is more soluble Q.17 4 107mol/LAgBr, 9 10 7mol/LAgSCN
Kd = 1/Kf = 4.8 104 Q.19 error = 1%
Q.20 [H+]=2.510-3
2-15
-2
Ka = 1.25 10
Q.22 [S ] = 2.5 10
Q.23 V = 2.77 104 litre
Q.25 9.168
acetic acid, salt-acid molar ratio 1.8 :1
Q.27 0.0818 moles Q.28 2.558
(a) pH = 3.83 (b) pH = 3.85 , (c) = 3.99

Q.29

11.22

Q.30

0.9542, pKa = 4.751,

Q.1
Q.8
Q.15
Q.22
Q.30
Q.37
Q.44
Q.51
Q.54
Q.60

A
Q.2
C
Q.9
D
D
Q.16 B
D
A
Q.23 C
C
Q.31 A
A,B,C Q.38 A,B,C
B
Q.45 C
A, B Q.52 B,C
C
Q.54 A
(A) S, (B) S, (C) Q

Q.3
Q.10
Q.17
Q.24
Q.32
Q.39
Q.46
Q.53
Q.56

C
D
B
D
D
A, B
B,C
B
A

1
10
th &
th stages of neutralisation
11
11

EXERCISE - III
Q.4
Q.11
Q.18
Q.25
Q.33
Q.40
Q.47
Q.40
Q.57

B
Q.5
B
Q.6
Q.12 D
Q.13
C
Q.19 B
Q.20
C
D
Q.26 C
Q.27
B
Q.34 A
Q.35
A, C, D Q.41 D
Q.42
A, B Q.48 B, C, D Q.49
Q.41 D
B
Q.42
Q.58 A
C
Q.59

C
Q.7
B
Q.14 A
B
Q.21 D
A
A
Q.29 B
B,C Q.36 B,C
A, C, DQ.43 A
A,B Q.50 A,B
C
Q.43 C
A-Q, B-R, C-S, D-P

36

ROUGH WORK

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