IONIC EQUILIBRIA

 To study the ionic equilibria it is necessary to study electrolytes.

 Electrolytes are substances which when dissolved in water, break up in to ions. It

is called as Ionization or dissociation. All those substances which dissociates almost
completely are known as strong electrolytes. They may be strong acids like
HCl,HNO3,HClO4

Strong base like NaOH, KOH, Ba(OH)2 Or Salts NaCl,KCl,CaCl2 etc

 The substances which dissociates to a small extent

 (1-10%) in solution are called weak electrolytes. They are weak acids like
CH3COOH,H3PO4,HCN,H2CO3 etc Weak base NH3,C5H5N pyridine etc. Salts like
lead acetate, mercuric chloride etc. these weak electrolyte contains unionized
molecules and ions. Thus for weak electrolytes the ions produced on dissociation are
in equilibrium with un-dissociated molecules in solution. Which is referred to as Ionic
equilibrium?

 Degree of Ionization:α:- It is defined as the fraction of the total number of moles of

weak electrolyte that dissociates into its ions when an equilibrium is reaches.

 It is given by the symbol ‘α’

α = Number of moles or amount of weak electrolyte dissociated

Total number of moles or Initial concentration

Degree of dissociation depends upon:

1) Nature of solute –Strong electrolyte dissociate s completely, the degree of dissociation

is unity. For weak electrolyte which dissociate slightly the degree of dissociation is
much less than 1.(α << 1)

2) Nature of solvent:- The degree of dissociation of an electrolyte insolvent increase.

Water is universal solvent.

3) Concentration of solution: Degree of dissociation increases with dilution of the

solution of electrolyte.

4) Temperature of solution: As temperature increases the degree of dissociation increase.

5) Presence of other ions: Degree of ionization is affected by presence of ions common

to the weak electrolyte. e.g. In presence of CH3COONa the dissociation of weak acid
CH3COOH is decrease or suppressed due to common ion effect (CH3COO- ions).

IONIZATION CONSTANT:-

Consider weak electrolyte BA which dissociates as

 BA⇌B++A- ------------①

 Applying law of mass action

 The rate of forward reaction α [BA]

= k[BA]

 Similarly the rate of backward reaction α [B+][A-]

= k’ [B+][A-]

 At equilibrium

rate of forward reaction = rate of backward reaction

Hence, k[BA] = k’ [B+][A-]

K=k/k’= [B+][A-] /[BA] ….……②

Where ‘K’ is called as ionization or dissociation constant.

 Let for the equation ②, initial concentration of the reactant is ‘c’ and ‘α’ is the degree
of dissociation, then the equilibrium concentration would be

BA ⇌ B+ + A-

Initial concn. c 0 0

Eqm. concn. (1-α)c αc αc

Substituting the above values in eqn. ②, we get

αc  αc
K
1  α c
α 2c
K 
1α
For very very dilute solutions α<<<1, therefore, 1- α ≌ 1

∴ K = α2 c

IONIC PRODUCT OF WATER:-

Water is the most commonly used solvent and it is amphoteric in nature. The dissociation of
water can be represented as-

H2O ⇌ H+ + OH- ……….①

or 2H2O ⇌ H3O+ + OH- ………②

Applying law of mass action to equation ① we get

K
H OH 
 

H O2

or KH2O  H OH 

Since the ionization of water takes place to a very very small extent, the concentration of
undissociated water molecules [H2O] can be regarded as constant.

Hence, the product of K[H2O] can be replaced by new constant Kw-

Kw  KH2O  H OH  ……….③

The constant Kw is termed as ionic product of water.

Equation ② represents no free H+ ion exists in water. Hence the ionic product of water is
given as – Kw  H  OH  

Which is identical with equation ③.

The value of Kw increases with increase in temperature. i.e. the concentration of H + or H3O+
and OH- ions increases with increase in temperature.

The equilibrium of water shows that the formation of one H + ion by the ionization of water
always results in the formation of one OH- ion. Hence in pure water [H+]=[OH-].

In pure water, at 25oC, the concentration of [H+] & [OH-] found to be 1.0 x 10-7 M.

∴Kw = [1.0 x 10-7] [1.0 x 10-7] = 1.0 x 10-14 M

Ostwald’s dilution law:-

It states that, at a given temperature, the degree of dissociation of a weak electrolyte is

inversely proportional to the square root of its concentration.

OR

The degree of dissociation of a weak electrolyte is directly proportional to the square root of
volume of solution containing one gram mole of solute.
Ionization of weak acid—

Consider a weak acid of the type HA that exist in solution partly as undissociated species HA
and partly as H+ and A- ions.

HA⇌ H+(aq) + A- (aq)

The acid dissociation constant can be given as—

[𝑯+ ][𝑨− ]
𝒌𝒂 = …………….①
[𝑯𝑨]
Let 1 mole of the acid is initially present in volume ‘V’ dm3 of the solution and the fraction
dissociated at equilibrium is ‘α’, where α is degree of dissociation of the acid. Then the
fraction of acid remain undissociated at equilibrium is (1-α)

∴ HA ⇌ H+(aq) + A- (aq)

Amount pr. at eqm. (1-α) α α

∴ concn at eqm. mol/dm3 (1-α)/V α/V α/V

On substituting the above values in equation ① it becomes

(𝜶⁄𝑽)(𝜶⁄𝑽)
𝒌𝒂 =
(𝟏 − 𝜶)⁄
𝑽
𝜶𝟐
∴ 𝒌𝒂 =
(𝟏 − 𝜶)𝑽
If ‘c’ is the initial concentration of an acid in mol/dm3 then, c=1/V. Hence, the above
equation becomes

𝜶𝟐 𝒄
∴ 𝒌𝒂 =
(𝟏 − 𝜶)
For weak acid α is very very small and therefore (1-α) ≌1

Hence,
∴ 𝒌𝒂 = 𝜶𝟐 𝒄

𝒌
i.e. 𝜶 = √𝒌𝒂 𝑽 𝑶𝑹 𝜶 = √ 𝒂 ⁄𝒄

This shows that degree of dissociation of weak acid is inversely proportional to square root of
its concentration or directly proportional to square root of volume in solution.
Ionization of weak base—

Consider a weak base of the type BOH that exist in solution partly as undissociated species
BOH and partly as B+ and OH- ions.

BOH ⇌ B+(aq) + OH- (aq)

The acid dissociation constant can be given as—

[𝑩+ ][𝑶𝑯− ]
𝒌𝒃 = …………….①
[𝑩𝑶𝑯]
Let 1 mole of the acid is initially present in volume ‘V’ dm3 of the solution and the fraction
dissociated at equilibrium is ‘α’, where α is degree of dissociation of the acid. Then the
fraction of acid remain undissociated at equilibrium is (1-α)

∴ BOH ⇌ B+(aq) + OH- (aq)

Amount pr. at eqm. (1-α) α α

∴ concn at eqm. mol/dm3 (1-α)/V α/V α/V

On substituting the above values in equation ① it becomes

(𝜶⁄𝑽)(𝜶⁄𝑽)
𝒌𝒃 =
(𝟏 − 𝜶)⁄
𝑽
𝜶𝟐
∴ 𝒌𝒃 =
(𝟏 − 𝜶)𝑽
If ‘c’ is the initial concentration of a base in mol/dm3 then, c=1/V. Hence, the above
equation becomes

𝜶𝟐 𝒄
∴ 𝒌𝒃 =
(𝟏 − 𝜶)
For weak base α is very very small and therefore (1-α) ≌1

Hence,
∴ 𝒌𝒃 = 𝜶𝟐 𝒄

𝒌
i.e. 𝜶 = √𝒌𝒃 𝑽 𝑶𝑹 𝜶 = √ 𝒃 ⁄𝒄

This shows that degree of dissociation of weak base is inversely proportional to square root
of its concentration or directly proportional to square root of volume in solution.
Polyprotic Acid—

These are the acids which have more than one ionisable (H +) hydrogen atom per molecule of
the acid.

i.e. they are capable of donating more than a single proton per molecule to a proton acceptor.

e.g. The acids which have 2 ionisable (H+) hydrogen atom per molecule of acid is called
diprotic acid. Like oxalic acid, malonic acid H2C3H2O4, hydrogen sulphide (H2S) etc.

Diprotic acid of the type H2A, dissociates in two steps as follows—

H2A⇌ H+(aq) + HA- (aq).............................. ka1

HA- ⇌ H+(aq) + A2- (aq).............................. ka2

The 1st ionisation constant can be given as—

[𝑯+ ][𝑯𝑨− ]
𝒌𝒂𝟏 =
[𝑯𝟐 𝑨]

and for 2nd ionisation constant –

[𝑯+ ][𝑨𝟐− ]
𝒌𝒂𝟐 =
[𝑯𝑨− ]

ka1 > ka2 since H+ released in second case is from –vely charged ion which is
difficult.

Similarly, triprotic acid, dissociates in three steps—

[𝑯+ ][𝑯𝟐 𝑨− ]
H3A⇌ H+(aq) + H2A- (aq) 𝒌𝒂𝟏 = [𝑯𝟑 𝑨]

[𝑯+ ][𝑯𝑨𝟐− ]
H2A- ⇌ H+(aq) + HA2- (aq) 𝒌𝒂𝟐 = [𝑯𝟐 𝑨− ]

[𝑯+ ][𝑨𝟑− ]
HA2- (aq) ⇌ H+(aq) + A3- (aq) 𝒌𝒂𝟑 = [𝑯𝑨𝟐− ]

and ka1 > ka2 > ka3

Common Ion Effect—

Common ion effect is used to describe the effect on an ionic equilibrium due to addition of a
strong electrolyte containing an ion that is a apart of the equilibrium.

e.g. When sodium acetate is added to an aqueous solution of acetic acid it will dissociates as
follows—

CH3COOH ⇌ CH3COO- + H+ ...........................①

CH3COONa ⇌ CH3COO- + Na+ ...........................②

i.e. on addition of CH3COONa which is a salt of weak acid and strong base dissociates
completely into aqueous solution as a result, additional CH 3COO- ions are forms in solution
and concentration of CH3COO- increases, due to which an equilibrium will be shifted to the
left in equation ①. Hence we can say ionization of acetic acid is decreased or ionization of
acetic acid is suppressed due to addition of common acetate ion.

Therefore, to a solution of a weak electrolyte when a strong electrolyte containing a common

ion is added, then the effect of added common ion is to suppress the dissociation of the weak
electrolyte.

This effect is known as common ion effect.

Application of Common Ion Effect—

1) In analysis of Group II, H2S gas is passed in acidic medium i.e. dil HCl solution.
Since H2S is diprotic acid, in presence of common H+ ion present in solution,
dissociation of H2S gas will be suppressed,. Hence, only those ions which have low
solubility product will gets precipitate.
2) In Group IIIA, to precipitate Fe(III), Cr(III), Zn(II) NH 4Cl is added in NH4OH
solution. Due to common ion NH4+ common ion, dissociation of NH4OH is
suppressed leading to low concentration of hydroxyl ions in solution.

pH (Pondus hydrogenii)—

In aqueous solution there is wide variation in hydrogen ion concentration. It can be change
from 100 i.e. 1 mole/dm3 in acid to 10-14 mol/dm3 in alkaline solution. Hence it becomes
difficult to calculate the concentration of hydrogen ion as negative exponents in fraction.

To avoid this, in 1909, Sorensen introduced a new scale known as Sorensen Scale or pH
scale.

It can be defined as the negative logarithm of hydrogen ion concentration to the base 10.

i.e. pH = - log 10[H+]

similarly, pOH = - log 10[OH-]

Show/ Prove that pH + pOH = 14—

We know that, in aqueous solution, the concentration of hydrogen ion and hydroxyl ion are
related with each other by the relation—

[H+] [OH-] = Kw = 10-14

Taking logarithm of both sides, it becomes

log 10[H+] + log 10[OH-] = log 10 10-14

on changing the sign of the above equation, we get-

– log 10[H+] – log 10[OH-] = –log 10 10-14 = – (–14 log 10 10)

But, pH = – log 10[H+] & pOH = – log 10[OH-]

∴ pH + pOH = 14 (∵log 10 10 = 1)

pH of the solution can be measured by using pH meter or pH – indicator or pH – paper.

Many pH indicators are large molecules derived from plants. They exist in conjugate acid-
base forms.

For e.g.

Indicator pH – range Acid Base

Litmus i.e. Azolitmin 5–8 Red Blue
Phenolphthalein 8∙3 – 10 Colourless Pink
Methyl orange 2∙9 – 4∙6 Pink Yellow
Bromophenol 2∙8 – 4∙6 Yellow Blue
Methyl red 4∙2 – 6∙3 Red Yellow

Calculation of pH for Strong and Weak electrolyte—

We know that, strong electrolytes like HCl, NaOH, H 2SO4, etc, dissociates completely in
their aqueous solution.

Their ionisation can be given as—

For acid HA⇌ H+(aq) + A- (aq)

For base BOH ⇌ B+(aq) + OH- (aq)

Hence, concentration of hydrogen ion or hydroxyl ions in solution is equalt to nothing but the
concentration of acid or base respectively.

Therefore, the pH & pOH can be calculated by using the formula—

pH = – log 10[H+] &

pOH = – log 10[OH-]

In case of weak electrolyte they do not dissociates completely in aqueous solution but
partially, instead an equilibrium is set up

i.e. HA⇌ H+(aq) + A- (aq)

BOH ⇌ B+(aq) + OH- (aq)

The strength of acid or base is measured quantitatively by knowing its dissociation constant
ka or kb.

[𝑯+ ][𝑨− ] [𝑩+ ][𝑶𝑯− ]

i.e. 𝒌𝒂 = [𝑯𝑨]
or 𝒌𝒃 = [𝑩𝑶𝑯]

∴ [𝑯+ ] = √𝒌𝒂 [𝑯𝑨] & [𝑶𝑯− ] = √𝒌𝒃 [𝑩𝑶𝑯]

∴ 𝒑𝑯 = − √𝒌𝒂 [𝑯𝑨] & 𝒑𝑶𝑯 = − √𝒌𝒃 [𝑩𝑶𝑯]

Buffer Solution—

The solution that resist change in pH on the addition of a small amount of acid or base or on
dilution or on preservation is known as buffer solution.

Buffer solution can maintain pH constant because it can react with externally added H+ or
OH- ions making them unavailable in solution.

Buffer solution has two components – one can take care of externally added H+ ions while
other removes externally added OH - ions.

There are three types of buffer solutions –

1) Acidic buffer solution

2) Basic buffer solution
3) Neutral buffer solution.

Acidic Buffer Solution—

When a weak acid and its salt with a strong base is used to prepare buffer then it is known as
acidic buffer. i.e. HA & BA

e.g. acetic acid + sodium acetate. (CH3COOH & CH3COONa)

Basic Buffer Solution—

When a weak base and its salt with strong acid is used to prepare buffer, then it is known as
basic buffer. i.e. BOH & BA

Neutral Buffer Solution—

When a salt of weak acid and weak base are used to prepare buffer solution then it is known
as neutral buffer. e.g. ammonium acetate.

Most of the biological fluids like blood are found to maintain their acidity or alkalinity within
a narrow range between 7∙35 - 7∙45. It does not change by more than 0.1 unit.

Buffer Action—

The resistance of a buffer solution to change in pH on addition of an acid or a base to it is

called the buffer action.

Mechanism of buffer action on Acidic Buffer—

The acidc buffer is prepared from weak acid HA and its salt with strong base BA.

The reversible dissociation of weak acid and dissociation of its salt can be given as follows—

Acid : HA⇌ H+(aq) + A- (aq) ...............①

Base : BA⇌ B+(aq) + A- (aq)................②

The dissociation of weak acid is suppressed because of common ion effect. Thus the solution
of acidic buffer contains large number of undissociated molecules of weak acid and equally
large numbers of A- ions obtained by complete dissociation of salt.

When small amount of an acid is added, the added H+ ions react with A- ions present in the
solution to produce weak acid HA which remains undissociated.

Similarly, when base is added OH- ions reacts with undissociated HA molecule converting
the OH- ions into the weak electrolyte H2O..

OH- + HA → H2O + A-
added weak electrolyte
+ -
Thus added H or OH ions are being removed and thereby maintaining the pH constant.

Henderson’s Equation for Acidic Buffer Solution—

Henderson’s equation gives the relation between pH of the solution and the concentration of
other species like acid or base or salt present in the solution.

Consider acidic buffer solution consisting of weak acid HA and its salt with strong base BA

The weak acid HA dissociates reversibly as-

HA⇌ H+(aq) + A- (aq) .............①

The dissociation constant of acid can be given by –

[𝑯+ ][𝑨− ]
𝒌𝒂 = ……………….②
[𝑯𝑨]
The term [HA] refers to the concentration of unionised acid, while [A -] refers to the
concentration of anion

Acid being weak, its ionisation is less and in presence of common anion A - ions it remains
practically undissociated

∴[HA] = [Acid] ................③

Where [Acid] represents total concentration of the acid in buffer solution.

Similarly, salt which is a strong electrolyte completely ionises, hence the entire concentration
of anion A- can be assumed to be obtained by dissociation of salt.

Hence, we have [A-] = [Salt]

On substituting these values of [A-] & [HA] in equation ②, we get—

[𝑯+ ][𝑺𝒂𝒍𝒕]
𝒌𝒂 =
[𝑨𝒄𝒊𝒅]
[𝑨𝒄𝒊𝒅]
or [𝑯+ ] = 𝒌𝒂
[𝑺𝒂𝒍𝒕]

Taking logarithm on both sides the above equation and changing the signs, it becomes-

[𝑨𝒄𝒊𝒅]
− 𝐥𝐨𝐠[𝑯+ ] = − 𝐥𝐨𝐠 𝒌𝒂 − 𝐥𝐨𝐠
[𝑺𝒂𝒍𝒕]
[𝑺𝒂𝒍𝒕]
∴ − 𝐥𝐨𝐠[𝑯+ ] = − 𝐥𝐨𝐠 𝒌𝒂 + 𝐥𝐨𝐠
[𝑨𝒄𝒊𝒅]
Substituting pH = -log[H+] & pka= -log ka, we get

[𝑺𝒂𝒍𝒕]
∴ 𝒑𝑯 = 𝒑𝒌𝒂 + 𝐥𝐨𝐠
[𝑨𝒄𝒊𝒅]
The above equation is known as Henderson’s equation for acidic buffer solution.

Numerical—

Find the pH of

i) 0.1M HNO3 &

ii) 0.05M NaOH solution
Solution—

i) HNO3(aq) → H+ + NO3-

0.01M 0.01M 0.01M

pH = – log 10[H ] = - log (0.01) = -(-1) = 1
+

ii) NaOH (aq) → Na+ + OH-

0.05M 0.05M 0.05M
pOH = – log 10[OH ] = -log (0.05) = -(-1.300)= 1.300
-

we know that,
pH + pOH = 14 = pH + 1.300
∴ pH = 14-1.300 = 12.699

Calculate the hydrogen ion concentration in moles per dm3 and the solution having pH
= 6.21.
pH = – log 10[H+]
i.e. pH = - (6.21) = – log 10[H+]
∴ antilog (-6.21) = [H+]
[H+] = 6.16 x 10-7 mol/dm3.
What will be the pH of the solution obtain by mixing 25 cm3 of 0.1MHCl with 25 cm3 of
0.05M KOH.
The number of milimoles of acid (0.1MHCl) in the solution = 25 x 0.1 = 2.5
The number of milimoles of base (0.05M KOH) in the solution = 25 x 0.05 = 1.25
∴ the number of milimoles of acid left in the solution after mixing with base is
2.5-1.25 = 1.25
∴1.25 m moles present in 50cm of solution. Hence number of moles present in 1000 cm3 of
3

solution will be—

1.25 : 50
𝟏.𝟐𝟓 ×𝟏𝟎𝟎𝟎
∴ = 𝟐𝟓 𝒎𝒎𝒐𝒍𝒆
𝟓𝟎
X : 1000
Hence 0.025mole
∴ [H+]= 0.025 mole dm-3
pH = – log 10[H+]
pH = -log (0.025) = - (-1.6021) = 1.6021
The dissociation constant of acetic acid is 1.8x10-5 at 298K. What will be the H+ ion
concentration and hence pH of 0.05M acid.
We know that, the dissociation constant for weak electrolyte
𝒌𝒂 = 𝜶𝟐 𝒄
𝒌 −𝟓
i.e. 𝜶 = √ 𝒂 ⁄𝒄 = √𝟏. 𝟖 × 𝟏𝟎 ⁄𝟎. 𝟎𝟓 = 𝟏. 𝟖𝟗𝟕 × 𝟏𝟎−𝟐
[H+] = αc = (1.897 x 10-2) (0.05) = 9.485 x 10-4 mol dm-3
pH =– log 10[H+] = - log (9.485 x 10-4) = -[0.9770 – 4.000] = 3.023
Basic Buffers:--
These buffers consist of a weak base and its salt of strong acid.

Consider a buffer solution is prepared by mixing a weak base BOH and its salt BA.

Then, in the solution, the equilibria which establishes can be given as –

Weak base : BOH ⇌ B+(aq) + OH- (aq)

Its salt of strong acid BA⇌ B+(aq) + A- (aq)

If a small quantity of a strong acid (H+ ions) are added to this buffer, the added H+ ions reacts
with BOH and form practically undissociable H2O.

H+ + BOH → H2O + B+

Similarly, when the base (OH- ions) are added, it reacts with the B+ ions present in the
solution (obtained from the dissociation of BA) to form weak base BOH

B+(aq) + OH- (aq) → BOH

Mechanism of buffer action on Basic Buffer—

Basic buffer consist of a mixture of a weak base BOH and its salt with a strong acid BA.

The reversible dissociation of weak base can be represented as

BOH ⇌ B+(aq) + OH- (aq)

The salt BA is a strong electrolyte which dissociates completely into the solution as

BA→ B+(aq) + A- (aq)

In presence of common ion B+, the dissociation of weak base is further suppressed so that it
remains practically undissociated. Thus a basic buffer solution contains a large amount of B+
ion from the salt and equally large number of undissociated molecules of the weak base.

When a small amount of acid is added, the added H+ ions combines with BOH to form weak
electrolyte

H+ + BOH → H2O + B+

Henderson’s Equation for Acidic Buffer Solution—

Basic buffer consist of a mixture of a weak base BOH and its salt with a strong acid BA.

The reversible dissociation of weak base can be represented as

BOH ⇌ B+(aq) + OH- (aq)

The dissociation constant k for the weak base can be given by—
b

kb 
B OH 
 

BOH 
The term [BOH] refers to the concentration of unionised base. But the base is weak and in

presence of common ion B+ which is obtained from the salt, its ionisation is further depressed

and remain practically constant.

Hence, [BOH] = [Base]

Where [Base] is the total concentration of base in buffer solution.

Similarly, the B+ ions are obtained almost entirely from the ionisation of Salt.

Hence [B+] = [Salt]

Hence, the dissociation constant k can also be written as—

b

kb 
OH Salt


or [OH- ]  kb
[ Base ]
[ Base ] [ Salt ]
Taking the common logarithm of both sides of above equation and on changing the signs of each

term we get- [ Base ]

 log[ OH  ]   log kb  log
[ Salt ]

[ Base ] [ Salt ]
 pOH  pkb  log or pOH  pkb  log
[ Salt ] [ Base ]
This equation is known as Henderson’s equation for basic buffer

Buffer Capacity:-

Buffer capacity is a measure of ability of a buffer solution to resist the pH change.

Defn.— It is defined as the amount of a strong acid or strong base (b) required to produce a pH

change of one unit in the buffer.

The amount ‘b’ is measured in ‘milli-equivalents’. It is obtained by using following equation –

 db

d ( pH )
When we plot a graph for buffer capacity as a function of pH, it shows that—

i) The buffer capacity is maximum at half neutralisation point of corresponding weak acid

or weak base.

ii) The maximum buffer capacity can be obtained by mixing salt and acid or base solution in

equimolar proportion.

iii) At pH + 1 unit of pk or pk the buffer capacity is very small.

a b

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