Ionic Equilibrium

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1

Electrolytes & Non-Electrolytes
Electrolyte: A compound whose aqueous solution or melt conduct electricity.
Non-electrolyte: A compound whose aqueous solution or melt does not conduct electricity.
Strong electrolytes: An electrolyte which dissociates almost completely into ions in aqueous solution and hence is a
very good conductor of electricity.
Eg. NaOH, KOH, HCl, H
2
SO
4
, NaCl, KNO
3
etc.
Weak electrolyte: A substance with dissociates to a small extent in aqueous solution and hence conducts electricity to
a small extent.
Eg. NH
4
OH, CH
3
COOH
Arrhenius Theory of Ionisation
1. When an electrolyte is dissolved in water it splits into ions, this process is known as dissociation of
ionization.
2. It is not necessary that all the molecules of electrolyte going into solution are completely ionized. The
fraction of total no. of molecules ionized is known as degree of ionization.
Degree of ionization () = No. of molecules ionized / Total no. of molecules present in solution.
3. An electrolyte having high degree of ionization is known as a strong electrolyte and one having low degree
of ionization is known as weak electrolyte.
4. In case of weak electrolyte as molecule of the electrolyte in solution dissociates to give ions at the same time
ions recombined to give back unionized molecules. So there is an equilibrium between ions and unionized
molecules, this is known as ionic equilibrium.
AB (aq) A
+
(aq) + B
(aq)
Applying law of chemical equilibrium
Ki =

) (
) ( ) (
aq AB
aq B aq A

; ki = ionization constant of weak electrolyte.
Difference between dissociation and Ionisation
When an ionic compound is dissolved in water ions already present in the solid separate out, this process is known as
dissociation.
When a polar covalent compound dissolve in water to give ions, this process is known as ionization.
OSTWALDS DILUTION LAW:
Weak acid: In case of a weak acid like acetic acid, acid dissociates to give acetate ion and H
3
O
+
ion and the ions
recombine to give back unionized acetic acid and an equilibrium is established as follows:
CH
3
COOH + H
2
O CH
3
COO
+ H
3
O
+

K =

O H COOH CH
O H COO CH
2 3
3 3

As the solution is dilute, so [H
2
O] is constant. So
Ka =

3
3 3
COOH CH
O H COO CH

; Ka = ionization constant of weak acid.
If C is the initial conc. of acetic acid and is degree of dissociation, then
IONIC EQUILIBRIUM
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2
CH
3
COOH + H
2
O CH
3
COO
+ H
3
O
+

Initial conc. C 0 0
At equi. C(1) C C
a =
1 ) 1 (
2
C
C
C C

In case of weak electrolyte, is very small so it may be taken as negligible as compared to one. So
Ka =
1
2
C
or =
C
Ka

Ka = V Ka
[H
3
O
+
] = C = C Ka
In case of weak base like NH
4
OH equilibrium is established as follows
NH
4
OH NH
4
+
+ OH

Kb =

OH NH
OH NH
4
4

; Kb = ionization constant of NH
4
OH
If initial conc. of NH4OH is C moles/litre and is degree of dissociation then
NH
4
OH NH
4
+
+ OH

Initial conc. C 0 0
At equi. C(1) C C
Kb =
1 ) 1 (
2
C
C
C C

In case of weak electrolyte, is very small so it may be taken as negligible as compared to one. So
Kb =
1
2
C
or =
C
Kb

Kb = V Kb
[OH
] = C = C Kb
Assignment
1. Calculate the degree of ionsation and [H
3
O
+
] of 0.01 M CH
3
COOH solution. The equilibrium constant of
acetic acid is 1.8 10
5
.
2. What will be the percentage of dissociation in 1.0 M CH
3
COOH at equilibrium having dissociation constant
of 1.8 10
5
?
Theories of acids and bases
1. Arrhenius concept of acid and base
Acid: A substance which contains hydrogen atom in its molecule and give hydrogen ions in aqueous solution.
Base: A substance which contains hydroxyl group in its molecule and gives OH
in aqueous solution.
Limitations: This theory is restricted to behaviour in aqueous solution only.
2. Bronsted Lowry concept of acid and base
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Acid: A proton doner is an acid.
Base: A proton acceptor is a base
HCl + H
2
O H
3
O
+
+ Cl

Acid Base Acid Base
CH
3
COOH + H
2
O H
3
O
+
+ CH
3
COO

Acid Base Acid Base
NH
3
+ H
2
O NH
4
+
+ OH

Base Acid Acid Base
CO
3
2
+ H
2
O HCO
3
+ OH

Base Acid Acid Base
HCl + NH
3
NH
4
+
+ Cl

Acid Base Acid Base
Conjugate pair of acid and Base
A pair of acid and base which differs only by one H
+
ion is known as conjugate pair of acid & base.
Acid H
+
= Conjugate base
Base + H
+
= Conjugate acid
The conjugate base of a weak acid is strong and vice-versa.
LEWIS THEORY ACID & BASE
An electron pair acceptor in coordinate bond formation is known as an acid and electron pair doner is known as Lewis
base.
The relative strength of two acid is given by their relative degree of dissociation
2
1
2
1
a
a
K
K
or
2
1
2
1
a
a
K
K
acidHA Strengthof
acidHA Strengthof

1
and
2
are degree dissociation of acid, HA
1
and HA
2
and Ka
1
and Ka
2
are ionization constants of acids HA
1
and
HA
2
.
Normal salt, Acid salt & Basic salt
Normal salt: In which all the replaceable hydrogen atoms of the acid and OH groups of the base have been used. Eg.
NaCl, Na
2
SO
4
, Na
3
PO
4
, NaH
2
PO
3
etc.
Acid salt: A salt in which replaceable hydrogen atom is still left. Eg. NaHSO
4
, NaH
2
PO
4
etc.
Basic salt: A salt in which replaceable OH group of base is still left. Eg. Bi(OH)Cl
2

Self ionization of water Ionic product of water.
Water is a very weak electrolyte which only very few molecules of it ionize, so there is an equilibrium as follows:
H
2
O H
+
+ OH
or 2H
2
O H
3
O
+
+ OH

K =

O H
OH H
2
] [

; K = dissociation constant of water
As water is very weak electrolyte, so at a given temperature [H
2
O] = constant, so
Kw =

OH H ] [ or [H
+
] =

OH
Kw
or [OH
] =

H
Kw

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In neutral water, [H
+
] = [OH
] = Kw
If [H
+
] > [OH
] solution is acidic.
If [OH
] > [H
+
] solution is basic
Value of ionic product of water is only temperature dependent. With increase in the temperature, ionic product of
water increases.
At 298K, Kw = 10
14

pH Scale: This scale was given by Sorensen to express the hydronium ion conc. of a solution.
It is the negative exponent by which 10 is raised to express hydronium ion concentration.
[H
+
] or [H
3
O
+
] = 10
pH

Taking log on both sides
log [H
3
O
+
] = pH
or pH = log [H
3
O
+
]
So pH is the negative logarithm of hydronium ion concentration
I f Ka & Kb are ionization constants of conjugate acid & base then
Ka Kb =Kw
pKa +pKb =14 (at 298 K)
[H
3
O
+
] = antilog of pH.
1. Calculation of [H
3
O
+
] & [OH
]
1. Calculate the [H
3
O
+
] and [OH
] ion concentration at 25
o
C in
(i) 0.02 M HCl solution (ii) 0.005 M NaOH solution
2. If hydrogen ion concentration in a solution is 1 10
5
moles/litre, calculate the conc. of [OH
] ion in the
solution.
2. Calculation of pH of completely ionized acids.
(i) Culculute the pH value of 0.001 N HNO
3
solution
(ii) Calculate the pH value of 10
3
M HCl solution
(iii) 0.049 g of H
2
SO
4
is dissolved per litre of the given solution. Calculate the pH of the solution.
(iv) 13.5 g of an acid HA of molecular mass 135 was dissolved in 10 litres of aqueous solution. Calculate the pH
of the solution, assuming the acid to be completely dissociated.
(v) Calculate the pH of a solution obtained by diluting 25 mL of N/100 HCl to 500
3. Calculation of pH of completely ionized bases
(i) Calculate the pH value of (a) 0.0001 M NaOH (b) 0.01 M NaOH (c) 0.04 M NaOH solution at 25
o
C.
(ii) How many grams of sodium hydroxide must be dissolved to prepare 1 L of N/10 solution, what will be the pH
of the solution?
4. Calculation of pH of weak acid or weak base
(i) Acetic acid has a dissociation constant of 1.8 10
5
. Calculate the pH value of the decinormal solution of
acetic acid.
(ii) Calculate the pH value of a solution of 0.1 M NH
3
. (Kb = 1.8 10
5
)
5. Calculation of pH of mixture of acid & base
(i) What would be the pH of a solution obtained by mixing 100 mL of 0.1 N HCl and 9.9 mL of 1.0 N NaOH
solution?
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(ii) Calculate the pH of a solution obtained by mixing equal volumes of the solutions with pH = 3 and pH = 5.
(iii) Calculate the pH of a solution obtained by mixing 100 cm
3
of a solution with pH = 3 and 400 cm
3
of solution
with pH = 4.
6. Calculation of pH of water
(i) The value of Kw is 9.55 10
14
at a certain temperature. Calculate the pH of water at this temperature.
(ii) Calculate the hydronium ion conc. of a solution having pH 10.6
7. pH of very dilute acid or alkali solution
(i) Calculate the pH of 10
8
M HCl solution
(ii) 10
6
M NaOH solution is diluted 100 times. Calculate the pH of the diluted base.

Common I on effect in the ionization of weak acids & bases
If sodium acetate is added to a solution of acetic acid. Acetic acid is a weak acid, so there is an equilibrium as
follows:
CH
3
COOH CH
3
COO
+ H
+
.(i)
Sodium acetate is a strong electrolyte, so it is completely ionized.
CH
3
COONa CH
3
COO
+ Na
+
(ii)
Due to increase in conc. of CH
3
COO

ion, the reverse reaction is favoured in eq (i) and degree of dissociation of
acetic acid is further supessed.
If NH
4
Cl is added to a solution of NH
4
OH. NH
4
OH is a weak base, so there is equilibrium as follows:
NH
4
OH NH
4
+
+ OH
.(iii)
NH
4
Cl is a strong electrolyte, so it is completely ionized.
NH
4
Cl NH
4
+
+ Cl
(iv)
Due to increase in conc. of NH
4
+
ions degree of dissociation of NH
4
OH is further suppressed.
So when an ion common with the weak electrolyte (acid or base) is added to the solution of weak electrolyte its degree
of dissociation is further suppressed. This effect is known as common ion effect.
Hydrolysis of salt & pH of salt solution
When a salt is dissolved in water it reacts with water to give an acid & a base. This phenomenon is known as
hydrolysis of salt. The solution may be acidic, basic or neutral depending upon the relative strength of acid & base.
This process may be taken as reverse of neutralization.
BA + H
2
O BOH + HA
Salt water Base acid
Hydrolysis of a salt of strong acid and strong base
The salts of this type are NaCl, NaNO
3
, Na
2
SO
4
, KCl, KNO
3
etc.
When such a salt is dissolved in water following process takes place
BA + H
2
O BOH + HA
As acid & base are strong electrolytes so equation may be written as follows:
BA + H
2
O B
+
+ OH
+ H
+
+ A

H
+
+ OH
H
2
O
BA + H
2
O B
+
+ A
+ H
2
O
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So hydrolysis of salt does not take place only salt is ionized and then ions are hydrated. As in the solution neither H
+

ions nor OH
ions are in excess, so solution will be neutral (pH = 7 at 298 K). When such salt is added to any
solution, the pH of solution does not change.
Hydrolysis of a salt of weak acid and strong base
Eg. CH
3
COONa, Na
2
CO
3
, K
2
CO
3
etc.
BA + H
2
O BOH + HA
Strong base Weak acid
Strong base and salt are strong electrolytes, so they are completely ionized whereas acid being weak remains
unionized. So the equation may be written as follows:
B
+
+ A
+ H
2
O B
+
+ OH
+ HA (i)
Or A
+ H
2
O OH
+ HA .. (ii)
In this case as anion is hydrolysed, so it is known as anionic hydrolysis and as OH
ions are in excess, so solution is

basic in nature (pH > 7).
Applying law of chemical equilibrium to equation (ii)
Kh =

O H A
HA OH
2

, As [H
2
O] = constant
So Kh =

A
HA OH
, Kh = hydrolysis constant. (iii)
In case of weak acid [HA]
HA H
+
+ A

So Ka =

HA
H
-
A
, Ka = dissociation constant of acid . (iv)

Kw = [H
+
] [OH
] . (v)
Dividing eq (iv) by (v)

A
OH
Ka
Kw HA
= Kh
If C is the conc. of salt and h is degree of hydrolysis of salt, then for the following equation
A
+ H
2
O OH
+ HA
At equi. C (1h) Ch Ch
So Kh =
) 1 ( h C
Ch Ch
=
h
Ch
1
2

If h is very small then
Kh = Ch
2
. or h =
C
Kh
=
C Ka
Kw

[OH
] = Ch = C Kh =
Ka
C Kw

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[H
+
] =

Ka
C Kw
Kw
OH
Kw
=
C
Ka Kw
,
pH =
2
1
[log Kw + log Ka log C]
pH = 7 +
2
1
[pKa + log C]
Salt of strong acid and weak base
Eg. NH
4
Cl, CuSO
4
, AlCl
3
etc.
BA + H
2
O BOH + HA
Salt Base Acid
As salt & acid are strong electrolytes so they are completely ionized
B
+
+ A
+ H
2
O BOH + H
+
+ A

B
+
+ H
2
O BOH + H
+
. (i)
In this case as cation is hydrolysed so it is known as cationic hydrolysis and as H+ ions are in excess in the solution,
so solution is acidic in nature and pH < 7.
Applying law of chemical equilibrium to equation (i)
Kh =

O B
BOH
2
H
H
, As [H
2
O] = constant, so
Kh =

H
B
BOH
, Kh = hydrolysis constant. (ii)
Kw = [H
+
] [OH
] . (iii)
In case of weak base
BOH B
+
+ OH

Kb =

BOH
B
-
OH
(iv)
Dividing eq (iii) by (iv)

B
H
Kb
Kw BOH
= Kh
If C is the conc. of salt and h is degree of hydrolysis,
B
+
+ H
2
O BOH + H
+
. (v)
At equi. C(1h) Ch Ch
Kh = Ch
2
. or h =
C
Kh
=
C Kb
Kw
or [H
+
] = Ch = C Kh =
Kb
C Kw

pH =
2
1
[log Kw log Kb + log C]
pH = 7
2
1
[pKb + log C]
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Hydrolysis of a salt of weak acid and weak base
Eg. Ammonium acetate, Ammonium carbonate
BA + H
2
O BOH + HA
As salt is the strong electrolyte, so it is completely ionized.
B
+
+ A
+ H
2
O BOH + HA . (i)
The acid-base nature will depend upon relative strength acid and base. In this case both cation and anion are
hydrolysed.
Kh =

-
A
HA
B
BOH
(ii)
Kw = [H
+
] [OH
] . (iii)
In case of weak acid [HA]
HA H
+
+ A

So Ka =

HA
H
-
A
, Ka = dissociation constant of acid . (iv)

In case of weak base
BOH B
+
+ OH

Kb =

BOH
B
-
OH
(v)
Dividing eq (iii) by (iv) & (v)
Kb Ka
Kw

-
A
HA
B
BOH
= Kh
If C is the conc. of salt and h is degree of hydrolysis.
B
+
+ A
+ H
2
O BOH + HA
At equi. C(1h) C(1h) Ch Ch
Kh =
) 1 (( ) 1 ( h C h C
Ch Ch

=
2
2
) 1 ( h
h
if h is very small
Kh = h
2
, or h =
Kb Ka
Kw
Kh

HA H
+
+ A

Ka =

HA
H
-
A

Or [H
+
] =

A
HA Ka
= Ka
h
h
1
= Ka Kh = Ka
Kb Ka
Kw
=
Kb
Ka Kw

pH =
2
1
[log Kw + log Ka log Kb]
pH = 7 +
2
1
[pKa pKb]
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Assignment
1. Calculate the hydrolysis constant, degree of hydrolysis and pH of 0.10 M KCN solution at 25
o
C. For HCN,
Ka = 6.2 10
10
.
2. Calculate the pH of 0.10 M solution of NH
4
Cl. The dissociation constant (Kb) of NH
3
is 1.6 10
5
.
3. Calculate the pH of 0.01 M solution of NH
4
CN. Given that the dissociation constants are: Ka for HCN = 6.2
10
10
and Kb for NH
3
= 1.6 10
5
.
4. The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate the
hydrolysis constant for ammonium acetate at 298 K and also the degree of hydrolysis and pH of
(a) 0.01 M (b) 0.04 M solution.
BUFFER SOLUTIONS
The solutions which resist the change in pH on addition of small amounts of acid or base or the solution pH of
which does not change appreciably on addition of small amounts of acid and base is known as a buffer solution.
Types of Buffer solutions
1. Solutions of single substances: Solution of the salt of weak acid and weak base like CH
3
COONH
4
acts as a
buffer.
2. Solution of mixtures
(i) Acidic buffer It is the solution of a mixture of weak acid & its salt with strong base. Eg.
CH
3
COOH + CH
3
COONa
(ii) Basic Buffer Solution of a mixture of weak base and its salt with strong acid. Eg. NH
4
OH +
NH
4
Cl
Buffer action
Property of a buffer solution to resist the change in pH on addition of small amounts of acid or base is known as buffer
action.
(i) Acidic buffer: Taking an example of the solution of mixture of CH
3
COOH + CH
3
COONa
Acetic acid is a weak acid so there is equilibrium as follows:
CH
3
COOH CH
3
COO
+ H
+

Sodium acetate is a strong electrolyte, so completely ionized.
CH
3
COONa CH
3
COO
+ Na
+

Due to common ion effect the degree of dissociation of acetic acid is further suppressed, so the solution contains
mostly unionized CH
3
COOH and CH
3
COO
ions.
On addition of small amount of acid i.e. H
+
ions
CH
3
COO
+ H
+
CH
3
COOH (unionized)
As H
+
ions added are used so there is no change in pH.
On addition of small amounts of base
CH
3
COOH + OH
CH
3
COO
+ H
2
O
As base added is used so no change in pH.
pH of acidic buffer (Henderson equation)
pH = pKa + log

acid
salt

(ii) Basic Buffer: Taking example of NH
4
OH + NH
4
Cl
NH
4
OH is a weak base so there is an equilibrium as follows
NH
4
OH NH
4
+
+ OH

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NH
4
Cl is a strong electrolyte so completely ionized.
NH
4
Cl NH
4
+
+ Cl

Due to common ion effect degree of dissociation of NH
4
OH is further suppressed and solution contains mostly NH
4
+

ions and unionized NH
4
OH.
On addition of some acid
NH
4
OH + H
+
NH
4
+
+ H
2
O
As acid added is used so there is no change in pH
On addition of some base
NH
4
+
+ OH
NH
4
OH
As base added is used, so there is no change in pH
pH of basic buffer
pOH = pKb + log

base
salt

pH = 14 pOH
(iii) Buffer capacity
No. of moles of acid or base required to be added to 1 litre of buffer solution, so as to change its pH by 1 unit.
Buffer capacity = [No. of moles of acid or base added to 1L of buffer solution] / [Change in pH]
Assignment
1. Calculate the pH of a buffer which is 0.1 M in acetic acid and 0.15 M in sodium acetate. Given that the
ionization constants of acetic acid is 1.75 10
5
. Also calculate the change in pH of the buffer if to 1 litre of the
buffer
(i) 1 cc of 1 M NaOH are added (ii) 1 cc of 1M HCl are added.
2. Calculate the pH of a solution obtained by mixing 5 mL of 0.1 M NH
4
OH with 250 mL of 0.1 M NH4Cl
solution. Kb for NH4OH = 1.8 10
5
.
Solubility of a sparingly soluble salt like AgCl, AgBr, AgI, BaSO
4
etc.
In case of such salts solubility is so small that even in the saturated solution all the molecules of the solid going into
the solution or completely ionized, so there is an equilibrium between solid and ions.
AxBy (s) xA (aq) + yB (aq)
K =

AxBy
A
x y
B

As AxBy is a solid, so
Ksp = [A]
x
[B]
y

Product of conc. of ions, each conc. raised by an exponent which is equal to no. of that ion obtained from 1 molecule
of the solid, in a saturated solution at a given temperature is known as solubility product.
Product of conc. of ions, each conc. raised by an exponent which is equal to no. of that ion obtained from 1 molecule
of the solid, in any solution is known as ionic product.
If ionic product is less than Ksp unsaturated solution.
Ionic product = Ksp Saturated solution.
Ionic product > Ksp Precipitation
Relation between solubility and Ksp
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Solubility: No. of moles of solute dissolved in 1L of saturated solution at a given temperature.
Electrolytes giving only two ions in the solution like AgCl, AgBr, AgI, BaSO
4
etc.
AgCl (s) Ag
+
(aq) + Cl
(aq); Let solubility of AgCl be S

S S
Ksp = [Ag
+
] [Cl
]
Ksp = S S = S
2
. or S = Ksp
Solids giving 3 ions in solution like Pb(OH)
2
, PbCl
2
, AgCrO
4
etc.
Ag
2
CrO
4
(s) 2Ag
+
+ CrO
4
. Let solubility of Ag
2
CrO
4
be S
2S S
Ksp = [Ag
+
]
2
[CrO
4
2
]
Ksp = (2S)
2
S = 4S
3
or S =
3
4
Ksp

Solubility of a sparingly soluble salt in a salt solution having ion common with sparingly soluble salt.
Eg. AgCl (s) in x Molar NaCl solution.
Let the solubility of AgCl (s) in NaCl solution be S.
NaCl + Aq. Na
+
(aq) + Cl
(aq)
x M
AgCl (s) Ag
+
(aq) + Cl
(aq);
S S+x
As S is very small as compared with x so S+x = x.
Ksp = [Ag
+
] [Cl
] = S x or S =
x
Ksp

Higher is the conc. of common ion lower will be the solubility of the solid.
Assignment
1. The solubility of AgCl in water at 25oC is found to be 1.06 10
5
moles per litre. Calculate the solubility
product of AgCl at this temperature.
2. The solubility of Mg(OH)
2
is 8.352 10
3
g/litre at 290oC. Find out its Ksp at this temperature.
3. Calculate the pH of a 0.10 M ammonia solution. Calculate the pH after 50.0 mL of this solution is treated
with 25.0 mL of 0.10 M HCl. The dissociation constant of ammonia, Kb = 1.77 10
5.

4. The solubility product for silver chloride is 1.2 10
10
at 298 K. Calculate the solubility of silver chloride at
298 K.
5. Lead chloride has a colubility product of 1.7 10
5
at 298 K. Calculate its solubility at this temperature.
6. The solubility product of AgCl in water is 1.5 10
10
. Calculate its solubility in 0.01 M NaCl aqueous
solution.
7. Given that the solubility product of BaSO
4
is 1 10
10
. Will a precipitate form when
(i) Equal volumes of 2 10
3
M BaCl
2
solution and 2 10
4
M Na
2
SO
4
solution are mixed?
(ii) Equal volumes of 2 10
8
M BaCl
2
solution and 2 10
3
M Na
2
SO
4
solution are mixed?
MCQs having only one correct answer
1. The pH of a 10
8
molar solution of HCl in water
is
(A) 8 (B) 8
(C) Between 7 and 8 (D) Between 6 and 7.
2. A mixture of a weak acid (say acetic acid) and its
salt with a strong base (say sodium acetate) is a
buffer solution. Which other pair of substance
from the following may have a similar property?
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12
(A) HCl and NaCl
(B) NaOH and NaNO
3

(C) KOH and KCl
(D) NH
4
OH and NH
4
Cl.
3. Assuming complete dissociation, the pH of a 0.01
M NaOH solution is equal to
(A) 2.0 (B) 0.01
(C) 12.0 (D) 14.0.
4. The ionic product of water will increase if
(A) pressure is decreased
(B) H
+
are added
(C) OH
are added
(D) temperature is increased.
5. Of the given anions, the strongest Bronsted base
is
(A) ClO
(B) ClO
2

(C) ClO
3
(D) ClO
4

6. In decinormal solution, CH
3
COOH acid is ionized
to the extent of 1.3%. If log 1.3 = 0.11. What is
the pH of the solution?
(A) 3.89 (B) 2.89
(C) 4.89 (D) unpredictable
7. Neutralization of an acid with a base, invariably
results in the production of
(A) H
3
O
+
(B) H
2
O
(C) H
+
and OH
(D) OH

8. In which of the following solvents AgBr has
highest solubility?
(A) 10
3
M NaBr (B) 10
3
M NH
4
OH
(C) Pure water (D) 10
3
M HBr.
9. Ostwalds dilution law is applicable to
(A) Strong electrolytes only
(B) Weak electrolytes only
(C) Non-electrolytes
(D) Strong as well as weak electrolytes.
10. One litre of water contains 10
7
moles of H
+
ions.
Degree of ionisation of water is
(A) 1.8 10
7
% (B) 0.8 10
9
%
(C) 3.6 10
9
% (D) 3.6 10
7
%
11. Which of the following is most soluble?
(A) Bi
2
S
3
(Ksp = 1 10
70
)
(B) MnS (Ksp = 7 10
16
)
(C) CuS (Ksp = 8 10
37
)
(D) Ag
2
S (Ksp = 6 10
51
)
12. The solubility of PbCl
2
is
(A) Ksp (B) (Ksp)
1/3
(C) (Ksp / 4)
1/3
(D) (8 Ksp)
1/2

13. The conjugate base of HPO
4
2
is
(A) PO
4
3
(B) H
2
PO
4

(C) H
3
PO
4
(D) H
3
PO
3
.
14. The pH of solution formed by mixing 40 ml of
0.10 M HCl with 10 ml of 0.45 M of NaOH is
(A) 10 (B) 12
(C) 8 (D) 6
15. The solubility product of AgCl is 4.0 10
10
at
298 K. The solubility of AgCl in 0.04 M CaCl
2
will be
(A) 2.0 10
5
M (B) 1.0 10
4
M
(C) 5.0 10
9
M (D) 2.2 10
4
M.
16. If a neutral solution has pKw = 13.36 at 50C
then pH of the solution is
(A) 6.68 (B) 7
(C) 7.68 (D) None of these.
17. BF
3
is acid according to
(A) Lewis
(B) Arrhenius
(C) Bronsted and Lowery
(D) Madam Curie.
18. Which of the following solution can not act as a
buffer?
(A) NaH
2
PO
4
+ H
3
PO
4

(B) CH
3
COOH + CH
3
COONa
(C) HCl + NH
4
OH
(D) H
3
PO
4
+ NaH
2
PO
4
19. For preparing a buffer solution of pH 6 by mixing
sodium acetate and acetic acid, the ratio of the
concentration of salt and acid should be (K =
10
5
)
(A) 1 : 10 (B) 10 : 1
(C) 100 : 1 (D) 1 : 100.
20. A monoprotic acid in a 0.1 M solution ionizes to
0.001%. Its ionisation constant is
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13
(A) 1.0 10
3
(B) 1.0 10
6

(C) 1.0 10
8
(D) 1.0 10
11
.
21. The strongest conjugate base is
(A) NO
3
(B) Cl

(C) SO
4
2
(D) CH
3
COO

22. In one litre of water 10
10
moles of HCl were
added. The pH of the solution will be
approximately
(A) 7 (B) 14
(C) 8 (D) 4
23. Given that, the solubility product Ksp, of AgCl is
1.8 10
10
, the concentration of Cl
ions that
must just be exceeded before AgCl will
precipitate from a solution containing 4 10
3
M
Ag
+
ions is
(A) 4.5 10
8
M (B) 4 10
8
M
(C) 1.8 10
8
M (D) 1 10
8
M
24. pH of a solution produced when an aqueous
solution of pH = 6 is mixed with an equal volume
of an aqueous solution of pH = 3 is about:
(A) 3.3 (B) 4.3
(C) 4.0 (D) 4.5
25. Which buffer among the following has pH > 7?
(A) CH
3
COOH / CH
3
COONa
(B) HCOOH / HCOOK
(C) CH
3
COONH
4
(D) NH
4
OH / NH
4
Cl
26. The pH of a buffer containing equal molar
concentration of a weak base and its chloride (Kb
= for weak base = 2 10
5
, log 2 = 0.3) is
(A) 5 (B) 9
(C) 4.7 (D) 9.
27. In the equation I
2
+ I

I
3
, which is Lewis
Base?
(A) I
2
(B) I

(C) I
3
(D) None of these.

28. An example of salt that will not hydrolyse is
(A) NH
4
Cl (B) KCl
(C) CH
3
COONH
4
(D) CH
3
COOK.
29. Which of the following has highest pH?
(A) CH
3
COOK (B) Na
2
CO
3

(C) NH
4
Cl (D) NaNO
3

30. The value of ionic product of water at 393 K is
(A) less than 1 10
14

(B) greater than 1 10
14
(C) equal to 1 10
14

(D) equal to 1 10
7
.
31. At 25C the pH of a solution containing 0.10 M
sodium acetate and 0.03 M acetic acid is (pK
value of acetic acid = 4.57)
(A) 3.24 (B) 4.59
(C) 5.09 (D) 6.67.
32. The solubility of AgCl in 0.2 M NaCl is [Ksp of
AgCl = 1.8
10
]
(A) 1.8 10
11
M (B) 9.0 10
10
M
(C) 6.5 10
12
M (D) 5.6 10
11
M.
33. The solubility product of AgI at 25C is 1.0
10
16
mol
2
L
2
. The solubility of AgI in 10
4
N
solution of KI at 25C is approximately (in mol
L1)
(A) 1.0 10
8
(B) 1.0 10
16
(C) 1.0 10
12
(D) 1.0 10
10
.
34. Which one of the following is NOT a buffer
solution?
(A) 0.8 M H
2
S + 0.8 M KHS
(B) 2 M C
6
H
5
NH
2
+ 2 M C
6
H
5
N
+
H
3
Br
(C) 3 M H
2
CO
3
+ 3 M KHCO
3

(D) 0.05 M KClO
3
+ 0.05 M HClO
4

35. CuSO
4
solution is
(A) acidic (B) basic
(C) neutral (D) none.
36. In the hydrolysis of a salt of weak acid and weak
base, the hydrolysis constant K
h
, is equal to
(A)
Kb
Kw
(B)
Ka
Kw

(C)
Kb . Ka
Kw
(D) Ka Kb
37. The conjugate base of H
2
PO
4

is
(A) PO
4
3
(B) HPO
4
2

(C) H
3
PO
4
(D) P
2
O
5

38. Ksp for Cr(OH)
3
is 2.7 10
13
. What is its
solubility in moles/litre?
(A) 1.7 10
8
(B) 2.7 10
13

(C) 1 10
8
(D) l.36 10
8

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39. The solubility product of a sparingly soluble salt
AX
2
is 3.2 10
11
. Its solubility (in moles/litre) is
(A) 4 10
4
(B) 5.6 10
6

(C) 3.1 10
4
(D) 2 10
4
.
40. 50ml of 0.1 M HCl and 50 ml of 2.0 M NaOH are
mixed. The pH of the resulting solution is
(A) 1.30 (B) 4.2
(C) 12.70 (D) 11.70.
41. The solubility product of a salt having general
formula MX
2
in water is, 4 10
12
. The
concentration of M
2+
ions in the aqueous solution
of the salt is:
(A) 2.0 10
6
M (B) 1.0 10
4
M
(C) 1.6 10
4
M (D) 4.0 10
10
M
42. The conjugate base of OH
is
(A) O
2
(B) H
2
O
(C) O
(D) O
2

43. At 25oC, the dissociation constant of a base,
BOH is 1.0 10
12
. The concentration of
hydroxyl ions in 0.01 M aqueous solution of the
base would become
(A) 2.0 10
6
mol L
1

(B) 1.0 10
5
mol L
1

(C) 1.0 10
6
mol L
1

(D) 1.0 10
7
mol L
1
.
44. When 10 mL of 0.1 M acetic acid (pKa = 5.0) is
titrated against 10 mL of 0.1 M ammonia solution
(pKb = 5.0) the equivalence point occurs at pH
(A) 5.0 (B) 6.0
(C) 7.0 (D) 9.0
45. The Ka value of formic acid and acetic acid are
respectively 1.77 10
4
and 1.75 10
5
. The
ratio of the acid strength of 0.1 N acids is
(A) 100 (B) 3.178
(C) 0.3 (D) 0.1
46. If 0.1 M of a weak monobasic acid is taken and
its percentage degree of ionisation is 1.34%, then
calculate its ionisation constant
(A) 0.8 10
5
(B) 1.79 10
5

(C) 0.182 10
5
(D) None of these.
47. At 90C, pure water has H
3
O
+
ion concentration
of 10.6 mol L
1
. Then Kw at 90C is
(A) 10
6
(B) 10
14

(C) 10
12
(D) 10
8
.
48. Which of the following salts undergoes anionic
hydrolysis?
(A) CuSO
4
(B) Na
2
CO
3

(C) NH
4
Cl (D) FeCl
3
49. When equal volumes of the following solutions
are mixed, precipitation of AgCl (Ksp = 1.8
10
10
) will occur only with
(A) 10
4
M (Ag
+
) and 10
4
M (Cl
)
(B) 10
5
M (Ag
+
) and 10
5
M (Cl
)
(C) 10
5
M (Ag
+
) and 10
6
M (Cl
)
(D) 10
10
M (Ag
+
) and 10
10
M (Cl
).
50. The solubility of A
2
X
3
is y mol dm
3
. Its solubility
product is
(A) 6y
4
(B) 64y
4

(C) 36 y
5
(D) 108 y
5
.

ANSWER

15 D D C D A
610 B B B B A
1115 B C A B C
1620 A A C B D
2125 D A A A D
2630 D B B B B
3135 C B C D A
3640 C B C D C
4145 B D D C B
4650 B C B A D

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Ionic Equilibrium

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ions are in excess, so solution is

, Ka = dissociation constant of acid . (iv)

, Ka = dissociation constant of acid . (iv)

(aq); Let solubility of AgCl be S

(D) None of these.

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