IONIC EQUILIBRIUM

PART-1
class-27

Subhasish-orbital

Ionic
equilibria
Part-1
Subhasish-orbital

Ionic equilibrium
The equilibrium between ions
and the undissociated molecules
are known as ionic equilibrium
and this type of equilibrium is
governed by weak acids and
bases and sparingly soluble salts .

Subhasish-orbital

Acid-base Theory
1. Arrhenius (1880s) :
Applied to aqueous solutions only
Acids : Substances that produce hydrogen ions, H+(aq)
when dissolved in water. E.g. HCl
Bases : Substances that produce hydroxide ions, OH(aq)
when dissolved in water.
E.g. NaOH

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Acid-base Theory
Arrhenius Concept
According to Arrhenius concept all substances which
giveH+ionswhen dissolved in water are called acids while
those which ionize in water to furnishOH -ionsare called
bases.
HA = H++ A-(Acid)
BOH= B++ OH-(Base)

Thus, HCl is an acid because it gives H+ ions in water.

similarly, NaOH is a base as it yields OH -ions in water.
HCl = H++ ClNaOH = Na++ OH

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Acid-base Theory
Some acids and bases ionize completely in
solutions and are called strongacids and
bases. Others are dissociated to a limited
extent in solutions and are termedweak acids
and bases.
HCl, HNO3, H2SO4, HCIO4, etc.,
are
examples of strong acids and NaOH, KOH,
(CH3)4NOH are strong bases.

Subhasish-orbital

Acid-base Theory
Every hydrogen compound cannot be regarded
as an acid, e.g., CH4is not an acid. Similarly,
CH3OH, C2H5OH, etc., have OH groups but
they are not bases, they must generate H+or
OH-ions in aqueous solution in order to be
defined as acid or base

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Acid-base Theory
Actually free H+ions are highly reactive so
they do not exist in water. They combine with
water molecules to form hydronium ion (H3O+)
molecules,i.e., have strong tendency to get
hydrated.
HX + H2O = H3O++ X (Hydronium ion)
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Acid-base Theory
The reaction between an acid and a base
is termedneutralization.
According to Arrhenius concept, the
neutralization in aqueous solution
involves the reaction between H+and
OH-ions or hydronium and OH-. This can
be represented as
H3O++ OH- = 2H2O
Subhasish-orbital

Acid-base Theory
Limitations ofArrhenius concept
1. For the acidic or basic properties, the presence
of water is absolutely necessary. Dry HCl shall
not act as an acid. HCl is regarded as an acid
only when dissolved in water and not in any other
solvent.
2 .The concept does not explain acidic and basic
character of substances in non-aqueous solvents.
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Acid-base Theory
Limitations ofArrhenius concept
3. The neutralization process is limited to those
reactions which can occur in aqueous solutions
only, although reactions involving salt
formation do occur in the absence of solvent.
4. It cannot explain the acidic character of
certain salts such as AlCl3in aqueous solution.
5. An artificial explanation is required to explain
the basic nature of NH3and metallic oxides
and acidic nature of non-metal oxides.
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2. Br nsted / Lowry (1923) :

Applied to aqueous and non-aqueous solutions

Acids : Proton donors,

E.g.

Molecule HCl, H2O, CH3COOH

Cation H3O+, NH4+
Anion HSO4Orbital-subhasish-C-27

Bases : Proton acceptors,

eg.

Molecule - H2O, NH3

Anion - Cl, OH, CH3COO, SO42

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Bronsted-Lowry Concept
Example:

HCl + H2O

acid

H3

+
O +

base
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Cl

Bronsted-Lowry Concept
Example:

NH3 + H2O
base

NH4

acid
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++

OH

Conjugate acid base pair

NH3 + H2O
base

acid

NH4

++

acid

Acid-base conjugate pairs

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OH

base

A conjugate acid-base pair is a pair of

species that can be inter-converted by
transfer of proton.

HCl(aq) + H2O(l)

Acid

Cl(aq) + H3O+(aq)

Conjugate base
Loss of H+
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A conjugate acid-base pair is a pair of

species that can be inter-converted by
transfer of proton.

HCl(aq) + H2O(l)

Conjugate acid

Cl(aq) + H3O+(aq)

Base
Gain of H+
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A conjugate acid-base pair is a pair of

species that can be inter-converted by
transfer of proton.
Gain of H+

HCl(aq) + H2O(l)

Cl(aq) + H3O+(aq)

Base

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Conjugate acid

A conjugate acid-base pair is a pair of

species that can be inter-converted by
transfer of proton.
Loss of H+

HCl(aq) + H2O(l)

Cl(aq) + H3O+(aq)

Conjugate base

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Acid

A species can behave as an acid or a

base depending on the situation.
E.g. H2O

Acid

Base

Conjugate base Conjugate acid

HCl(aq) + H2O(l)

Cl(aq)

H3O+(aq)

H2O(l)

OH(aq)

NH4+(aq)

+ NH3(aq)

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Q.(a)

Give the conjugate acid of HSO4(aq).

H2SO4(aq) + H2O(l)

HSO4(aq) + H3O+(aq)

(b) Give the conjugate bases of NH3(aq) and

OH(aq).
NH3(aq) + H2O(l)

NH2(aq)

+ H3O+(aq)

OH(aq) + H2O(l)
(aq)

O2(aq)

+ H3O+

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Concept of Conjugate Acidbase Pairs

Acid

Base

HCl(aq) +
H2O(l)

Conjugate base

H2O(l)
NH3(aq)

CH3COOH(aq) + H2O(l)
H2O(l)

HSO4(aq) +

Cl(aq)

OH(aq) +

Conjugate acid
H3O+(aq)
NH4+(aq)

CH3COO(aq) + H3O+(aq)

H2O(l)

OH(aq)

H3O+(aq)

H2O(l)

SO42(aq) +

H3O+(aq)

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Relative Strengths of Conjugate Acid-base

Pairs
Stronger acid/base produces weaker conjugate base/acid.

stronger + stronger
acid
base
conjugate

weaker +
conjugate
base

The forward reaction is more complete.

The equilibrium position lies to the right.
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weaker
acid

Relative Strengths of Conjugate Acid-base

Pairs
Weaker acid/base produces stronger conjugate base/acid.

weaker + weaker
acid
base
stronger
conjugate

stronger +
conjugate
base

The forward reaction is less complete.

The equilibrium position lies to the left.
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acid

 For a strong acid,

HCl(aq)
stronger acid

H2O(l)
stronger base

Cl(aq) + H3O+(aq)
weaker base

the equilibrium position lies far to the right.

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weaker acid

 For a weak acid,

CH3COOH(aq) + H2O(l)

CH3COO(aq) + H3O+(aq)

weaker acid

stronger base

weaker base

the equilibrium position lies far to the left.

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stronger acid

SOLVENT TYPES

On the basis of proton interaction, solvents can be classified

into four types:
Protophilic solvents: Solvents which have greater tendency
to accept protons, i.e., water, alcohol, liquid ammonia, etc.
Protogenic solvents:Solvents which have the tendency to
produce protons, i.e., water, liquid hydrogen chloride, glacial
acetic acid, etc.
Amphiprotic solvents: Solvents which act both as protophilic
or protogenic, e.g., water, ammonia, ethyl alcohol, etc.
Aprotic solvents: Solvents which neither donate nor accept
protons, e.g., benzene, carbon tetrachloride, carbon
disulphide, etc.

Subhasish-orbital

3. Lewis (1930s) :
More widely applied to systems with and
without solvents

Acids : electron pair acceptors,

e.g. H+, BF3 , AlCl3 , BeCl2
(electron-deficient
species)
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Bases : electron pair donors,

e.g.
NH3, OH

species containing lone pair(s)

H+(aq) + OH(aq)
BF3

+ NH3

Lewis acids

Lewis bases
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H2O(l)
H3NBF3

Lewis Concept
Example:
H
Cl

H+ N H

Lewis acid

Cl + H N H

Lewis base

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Lewis Concept
Example:
H

Ag+ + 2 N H
Lewis acid

H3N Ag NH3

Lewis base

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The pH Concept
The pH of a solution is the negative logarithm of
the hydrogen-ion concentration.

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Self-ionization of Water
H2O(l) + H2O(l)
Kc =

H3O+(aq) + OH(aq)

[ H 3O (aq )][OH (aq )]

[ H 2 O(l )]2

[H O(l)] is approximately a constant,

2

Kc[H2O(l)]2 = Kw = [H3O+(aq)][OH(aq)]
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Kw is known as the ionic product

of water.
Kw is temperature-dependent.

At 298 K, Kw =

[ H 3O (aq )][OH (aq )]

= 1.00 1014 mol2 dm6

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In neutral solution,
[H3O+(aq)] = [OH(aq)]
14
2
6
7
3
1
.
00

10
mol
dm

1
.
00

10
mol
dm
=

pH = log10(1.00107) = 7.00

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In acidic solution,
[H3O+(aq)] > [OH(aq)]
[H3O+(aq)] > 1.00107 mol dm3

pH < 7.00

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In alkaline solution,
[H3O+(aq)] < [OH(aq)]
[H3O+(aq)] < 1.00107 mol dm3

pH > 7.00

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Given the following Kw values at different temperatures,

Temp/oC

18.0

25.0

40.0

75.0

Kw / mol2 dm6

0.6101014

1.00 1014

2.92 1014

16.9 1014

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An increase in T increases the value of Kw

the equilibrium position shifts to the right

the system absorbs heat by shifting to

the right

the forward reaction is endothermic

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In neutral solution,
[H3O+(aq)] = [OH(aq)]
2.92 10 14 mol 2dm 6 1.71 10 7 moldm 3

pH = log10(1.71107) = 6.77

So pH depends on temperature.

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[H3O+], [OH-], and pH Values

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The pH Concept
pH and Significant Figures

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THE pH CONCEPT
pKw = -log(Kw) = -log(1.00 x 10-14) = 14
pOH = -log[OH-]
[H3O+][OH-] = Kw
Implies that
pH + pOH = pKw
pH + pOH = 14.00
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pH of Acids and Bases

pH of Weak Acids and Bases
Weak acids and bases are not completely ionised; an equilibrium is found to have
been established between ions and unionised molecule. Let us consider a weak
acid of basicity 'n'.
AHn= An-+ nH+
C
teq C(1-)

0 0
C nC

[H+] = nC; .. pH = -log10[nC]

For monobasic and, n=1
pH = -log10[C]
Dissociation constant of acid K amay be calculated as
Ka= [An-][H+]n/[AHn] = [C][nC]n/[C(1-)]
= [nC]n/(1-) For weak acids, 1

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pH of Acids and Bases

.. (1-) = 1
= [nC ]n/(1-)
nCKa= nC [nC ]n= [nC ](n+1)
= [nC ] = [nCKa]1/(n+1)
=[H+] = [nCKa]1/(n+1)

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pH of Acids and Bases

.. pH = -1/(n+1) log10(nCKa)
For monobasic acid, n = 1
pH = -logCK
Since Ka= [nC]n
ka/ = (nC)n
[nC ] = [K/]1/n= [H+]
pH = -1/n log10(K/)
For n = 1 pH = -log10(K/)

Subhasish-orbital-C-27

pH of Acids and Bases

Limitations of pH Scale:
pH values of the solutions do not give us
immediate idea of the relative strengths
of the solutions. A solution of pH = 1 has a
hydrogen ion concentration 100 times that
of a solution of pH = 3 (not three times).
A 4 x 10-5NHCI is twice concentrated of
a 2 x 10-5NHCI solution, but the pH
values of these solutions are 4.40 and
4.70 (not double).
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pH of Acids and Bases

Limitations of pH Scale:
pH value of zero is obtained in 1 A' solution of
strong acid. In case the concentration is 2N,
3N, 10N, etc. The respective pH values will
be negative.
A solution of an acid having very low
concentration, say 10-8N, cannot have pH 8,
as shown by pH formula, but the actual pH
value will be less than 7.

Subhasish-orbital-C-27

pH of Acids and Bases

Note:
Normality of strong acid = [H3O+]
Normality of strong base = [OH-]
.. pH = -log [N] for strong acids
pOH = -log [N] for strong acids
Sometimes pH of acid comes more than 7 and that of
base comes less than 7. It shows that the solution is
very dilute; in such cases, H+or OH-contribution from
water is also considered, e.g., in 10NHCI,
[H+]Total= [10-8]Acid+ [10-7]Water
= 11 10-8M= 1.1 10-7M

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Solubility
Product

Meaning of Solubility Product

Consider the dissolution of a sparingly
soluble salt MX(s) (e.g. AgCl) in water to
form M+(aq) and X(aq):
dissolution

MX(s)

M+(aq) + X(aq)

precipitation

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Meaning of Solubility Product

dissolution

MX(s)

M+(aq) + X(aq)

precipitation
(aq)][ X (aq)]
[
M
Kc
[MX(s)]

The amount of MX(s) present in the

solution does not affect its solubility
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Meaning of Solubility Product

Incorporating the [MX(s)] into Kc of the
above equilibrium gives a new constant
known as the solubility product, Ksp
Ksp = [M+(aq)]eq [X(aq)]eq

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Meaning of Solubility Product

Generally,
MaXb(s)

aMb+(aq) + bXa(aq)

the solubility product is given by:

Ksp = [Mb+(aq)]aeq [Xa(aq)]beq

Meaning of Solubility Product

BaSO4(s)

Ba2+(aq) + SO42(aq)

Ksp = [Ba2+(aq)]eq [SO42(aq)]eq

Ksp of BaSO4 at 298 K = 1 1010 mol2 dm6

Meaning of Solubility Product

Ag2CO3(s)

2Ag+(aq) + CO32(aq)

Ksp = [Ag+(aq)]2eq [CO32]eq

Ksp of Ag2CO3 at 298 K = 8 1012 mol3 dm-9

Table 8.5: Ksp Values at 25 C

for Common Ionic Solids

Relationship between solubility and solubility

product :

Let us consider a sparingly soluble salt MXAY

MXAY = xM+ + yAIf molar solubility is S then
CM+ = xS CA- = yS
So KSP = (xS)x (yS)y = xxyy. S(x+y)

Solubility product constant

If the molar solubility of Bi2S3 is s, the molar solubility
of Bi2+ is 2s and the molar solubility of S2- is 3s.
Bi2S3 (s)

2Bi3+ (aq) + 3S2-(aq)

s
2s
3s
This is because, there are 2 ions of Bi3+ produced for
Each molecule of the parent, Bi2S3 and 3 ions of S2produced for each molecule of the parent.

K sp Bi

3 2

2 3

K sp 2 s 3s
2

Solubility product constant

K sp 2 s 3s
2

K sp (4 27) ( s )
5

K sp (108) ( s )
5

Since we already know the value of molar solubility for

Bi2S3, which is 1.70810-15 M

K sp (108) (1.708 10 )

15 5

K sp 1.569 10

72

How to find the molar solubility if

we know is Ksp?
Ca(OH)2 (s)
s

Ca2+ (aq) + 2OH-(aq)

1s
2s

K sp Ca

OH

2 1

K sp 1 s 2 s
1

K sp 4s

Calculate the molar solubility of lead iodide PbI 2,

from its Ksp in water at 25C
PbI2 (s)
s

Pb2+ (aq) + 2I-(aq)

1s
2s

K sp Pb

2 1

K sp 1 s 2 s
1

K sp 4s

K sp 4s

But , K sp 7.9 10
7.9 10 4 s
9

7.9 10
3
s
4
9

1.97 10 s
9

s 1.97 10 1.3 10 M
3

Calculate the molar solubility of lead iodide PbI 2,

in 0.1 M NaI solution
PbI2 (s)
s

K sp ( PbI 2 ) 7.9 10

Pb2+ (aq) + 2I-(aq)

1s
2s

NaI (s)

Na+ (aq) + I-(aq)

0.1M

K sp Pb

2 1

7.9 10 1 s (2 s ) 0.1
9

0.1M

Common
ion

Calculate the molar solubility of lead iodide PbI2,

in 0.1 M NaI solution

7.9 10 1 s (2 s ) 0.1
1

7.9 10 (1s ) 2 s 0.1

9

Because the Ksp of PbI2 is really small, the solubility s is going

to be really small. Hence we can make a simplification.

2s 0.1

0.1
2
9
7.9 10 (1s ) 0.1
7.9 109
s
7.9 10 7 M
0.01

Comparison between Ionic

Product and Solubility Product
1. [M+(aq)] [X(aq)] < Ksp at a given
temperature
the solution is unsaturated
more MX(s) can be dissolved in it

Comparison between Ionic

Product and Solubility Product
2. [M+(aq)] [X(aq)] = Ksp at a given
temperature
the solution is saturated
the system is at equilibrium

Comparison between Ionic

Product and Solubility Product
3. [M+(aq)] [X(aq)] > Ksp at a given
temperature
the solution is supersaturated
precipitation will occur until
[M+(aq)] [X(aq)] = Ksp

Is a precipitate expected to form at

equilibrium when 50.0 cm3 of 1.00103 M
BaCl2(aq) is added to 50.0 cm3 of 1.00 104
M Na2SO4(aq)?
(Given: Ksp for barium sulphate = 1.10 1010
mol2 dm6. Assume that the total volume of
solution, after mixing, equals the sum of the
volumes of the separate solutions.)

[Ba2+(aq)] = 1.00103 mol dm3 2 = 5.0104 mol dm3

[SO42(aq)] = 1.00104 mol dm3 2 = 5.0105 mol dm3
[Ba2+(aq)] [SO42(aq)] = (5.00 104) (5.00 105)
= 2.50 108 mol2 dm6 > Ksp
Barium sulphate precipitate is expected to be formed.

277

Common Ion Effect

Ksp of a salt MX(s) is always constant at a
given temperature
Independent of the concentrations of the M+
(aq) and X(aq) ions
Addition of a common ion (i.e. M+(aq) or X
(aq) ions) will change the position of the
equilibrium

Common Ion Effect

Consider the equilibrium system :
MX(s)
At equilibrium,

M+(aq)
x mol dm3

X(aq)
x mol dm3

where x mol dm3 is the solubility of MX

in water without common ion
E.g. dissolve MX in Pure Water
At a given Temperature, Ksp = x2

Common Ion Effect

In the presence of common ions (M+ and/or X)
MX(s)

M+(aq)

Initial

c mol dm3

At equilibrium,

(y + c) mol dm 3

X(aq)
y mol dm3

where y mol dm3 is the solubility of MX in a

solution containing c mol dm3 of M+
At the same Temperature, Ksp = x2 = (y+c)(y)
y < x The solid is less soluble in the
presence of its common ions.

A solid is always less soluble in the

presence of its common ions.

Common ion effect in qualitative

analysis
1. Dissociation of ammonium hydroxide
decreases in presence of ammonium
chloride.
2. In acidic medium dissociation of
hydrogen sulphide suppressed.
3. In alkaline medium dissociation of
hydrogen sulphide increases

Common ion effect in qualitative

analysis
4.The dissociation of amonium
carbonate decreases in presence of
ammonium chloride

Few related facts

Precipitation of CuS obtained by passing
H2S in acidic medium but pptn of ZnS
occurs by passing H2S in alkaline
medium.
Ammonium chloride is added to
ammonium hydroxide for the pptn of
ferric, aluminium and chromium ions

Qualitativ
e Analysis

General procedure for separating ions in qualitative analysis

add
precipitating
ion

centrifuge

centrifuge

add
precipitating
ion

A qualitative analysis scheme for separating cations into

five ion groups

NH3/NH4+
buffer(pH 8)

add
(NH4)2HPO4
Or ammon carbonate

centrifuge

centrifuge

centrifuge

add
6 M HCl

add

centrifuge

acidify to
pH 0.5;
add H2S

A qualitative analysis scheme for Ag+,Al3+,Cu2+, and Fe3+

Step 2:
Add HCl

centrifuge

centrifuge

Step 1:
Add
NH3(aq)

Step 3: Add
NaOH

centrifuge

Step 4:
Add HCl,
Na2HPO4

Step 5:
Dissolve in
HCl and
add KSCN

Solubility product
Other Applications of Solubility Product
(i)Purification of common salt
Natural common salt consists of many insoluble and soluble
impurities. Saturated solution of common salt is prepared and
insoluble impurities are filtered off. Hydrogen chloride gas (HCl)
is circulated through the saturated solution. HCl and NaCl
dissociate into their respective ions as:
NaCl Na++ ClHCl H++ ClThe concentration of Cl-ions increases considerably in solution
due to ionization HCl. Hence, the ionic product [Na +][Cl-] exceeds
the solubility product of sodium chloride and, therefore, pure
sodium chloride precipitates out from solution.

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Solubility product
(ii) Salting out of soap
Soap is a sodium salt of higher acids. From the solution, soap
is precipitated by the addition of concentrated solution of
sodium chloride. Soap and sodium chloride are present in
the form of ions.
CnH2n+1COONa CnH2n+1COO-+ Na+
Soap
NaCl Na++ ClThus, the concentration of Na+ ions increases considerably on
addition of NaCl solution. Hence, the ionic product
[CnH2n+1COO-] [Na+] exceeds the solubility product of soap
and, therefore, soap precipitates out from the solution.

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Solubility product
(iii)Manufacture of sodium bicarbonate (baking soda):
In Solvay's soda process. CO 2gas is passed through
ammonical brine to precipitate out NaHCO 3.
NH4OH + CO2 NH4HCO3
NH4HCO3+ NaCl NaHCO3+ NH4Cl
NaHCO3is precipitated first because of its lower
solubility product as compared to those of NH 4Cl,
NH3HCO3and NaCl.
Thus, baking soda (NaHCO3) can be quantifiably
estimated.

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Solubility product
(iv)Application of solubility product in quantitative
analysis
Estimation of barium as barium sulphate:
H2SO4as precipitating agent is added to the aqueous
solution of BaCl2.
BaCl2+ H2SO4 BaSO4+ 2HCl
Precipitation of BaSO4takes place when its ionic
product exceeds solubility product. H2SO4is added in
slight excess to ensure complete precipitation. Large
excess of H2SO4is harmful for complex formation.

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