1

IONIC EQUILIBRIUM

Different concepts have been put forth by different investigators to characterize acids and bases but
the following are the three important modern concepts of acids and bases:
1] Arrhenius concept:
According to Arrhenius concept, all substances which give H+ ions when dissolved in water are called
acids while those which ionize in water to furnish OH- ions are 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 + + Cl−
NaOH ⇌ Na+ + OH −
Some acids and bases ionize almost completely in solutions and are called strong acids and bases.
Others are dissociated to a limited extent in solutions and are termed weak acids and bases. HCl,
HNO3 , H2 SO4 , HClO4 ,etc., are examples of strong acids and NaOH, KOH, Ba(OH)2 are strong
bases. Every hydrogen compound cannot be regarded as an acid, e.g., CH 4 is not an acid. Similarly,
CH3 OH, C2 H5 OH, etc., have OH groups but they are not bases.
Actually free H + ions do not exist in water. They combine with solvent molecules/ i.e., have strong
tendency to get hydrated.
HX + H2 O ⇌ H3 O+ + X −
The reaction between an acid and a base is termed neutralization. According to Arrhenius, concept,
the neutralization in aqueous solution involves the reaction between H + and OH − ions or hydronium
and OH − ions. This can be represented as
H3 O+ + OH − ⇌ 2H2 O
Limitations:
i] The concept does not explain acidic and basic character of substances in non-aqueous solvents.
ii] 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.
iii] It could not explain the acidic character of certain salts such as AlCl3 in aqueous solution.
iv] It could not explain the basic nature of NH3 and metallic oxides and acidic nature of non-metal oxides.
2] Bronsted-Lowry concept:
Bronsted and Lowry independently proposed a concept of acids and bases. According to Bronsted-
Lowry concept an acid is a substance (molecule or ion) that can donate proton, i.e., a hydrogen ion,
OH + , to some other substance and a base is substance that can accept a proton from an acid. More
simply, an acid is a proton-donor and a base is a proton acceptor. Consider the reaction,
HCl + H2 O ⇌ H3 O+ + Cl−
In this reaction, HCl acts as an acid because it donates a proton to the water molecules/ Water, on the
other hand, behaves as a base by accepting a proton from the acid.

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The dissolution of ammonia in water may be represented as

NH3 + H2 O ⇌ NH4+ + OH −
In this reaction, H2 O acts as an acid as it donates a proton to NH3 molecules and NH3 molecule
behaves as a base as it accepts a proton.
When an acid loses a proton, the residual part of it has a tendency to regain a proton. Therefore, it
behaves as a base.
Acid ⇌ H + + base
The acid and base which differ by a proton are known to form a conjugate pair. Consider the following
reaction:
CH3 COOH + H2 O ⇌ H3 O+ + CH2 COO−
It involves two conjugate pairs. The acid-base pairs are
−𝐻+ +𝐻 +
𝐶𝐻3 𝐶𝑂𝑂𝐻 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− 𝐻2𝑂 ⇌ 𝐻3𝑂+
Acid +𝐻 + and
Base +
−𝐻
Base Acid
Such pairs of substances which can be formed from one another by loss or gain of a proton are known
as conjugate acid-base pairs.
If in the above reaction, the acid CH3 COOH is labeled acid1 and its conjugate base, CH3 COO− as
base 1. H2 Ois labeled as base 2 and its conjugate acid H3 O+ as acid2, the reaction can be written as
Acid1 + Base2 ⇌ BaSe1 + Acid2
Thus, any acid-base reaction involves two conjugate pairs, i.e., when an acid reacts with a base, another
acid and base are formed. Some more examples are given below:
Acid1 + Base2 ⇌ Acid2 + Base`1
H2 O + NH3 ⇌ NH4+ + OH −
HCN + H2 O ⇌ H3 O+ CN−
HF + CH3 COOH ⇌ CH3 COOH2+ + F −
CH3 COOH + NH3 ⇌ NH4+ + CH3 COO−
NH3 + NH3 ⇌ NH4+ + NH2−
H2 O + H2 O ⇌ H3 O+ + OH −
HCO− +
3 + H2 O ⇌ H3 O + CO3
2−

NH4+ + H2 O ⇌ H3 O+ + NH3
Thus, every acid has its conjugate base and every base has its conjugate acid. It is further observed that
strong acids have weak conjugate bases while weak acids have strong conjugate bases.
HCl ⟶ Cl− CH3 COOH ⟶ CH3 COO−
StrongWeak base Weak acidStrong base
There are certain molecules which have dual character of an acid and a base. These are called
amphiprotic or amphoteric.
Examples are NH3 , H2 O, CH3 COOH, etc.

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The strength of an acid depends upon its tendency to lose its proton and the strength of the depends
upon its tendency to gain the proton.
Acid- base chart containing some common conjugate acid-base pairs
(Acid) (Conjugate base)
−
HClO4 (Perchloric acid) ClO4 (Perchlorate ion)

------------------Increasing order of acid strength---------------------------

H2 SO4 (Sulphuric acid) H2 SO−
4
(Hydrogen sulphate ion)
HCl (Hydrogen chloride) Cl− (Chloride ion)

------------------- Increasing order of acid strength-----------------→

HNO3 (Nitric acid) NO−3
(Nitrate ion)
H3 O+ (Hydronium ion) H2 O (Water)
HSO− 4
Hydrogen sulphate ion) SO−2
4
(Sulphate ion)
H3 PO4 (Orthophosphoric acid) H2 PO4− (Dihydrogen phosphate ion)
CH3 COOH (Acetic acid) CH3 COO− (Acetate ion)
H2 CO3 (Carbonic acid) HCO− 3
(Hydrogen carbonate ion)
−
H2 S (Hydrogen sulphide) HS (Hydrosulphide ion)
NH4+ (Ammonium ion) NH3 (Ammonia)
HCN (Hydrogen cyanide) CN − (Cyanide ion)
C6 H5 OH (Phenol) C6 H5 O− (Phenoxide ion)
H2 O (Water) OH − (Hydroxide ion)

C2 H5 OH (Ethyl alcohol) C2 H5 O− (Ethoxide ion)

NH3 (Ammonia) NH2− (Amide ion)
_
CH4 (Methane) CH3− (Methide ion)

In acid-base strength series, all acids above H3 O+ in aqueous solution fall to the strength of H3 O+ .
Similarly the basic strength of bases below OH − fall to the strength of OH − in aqueous solution. This
is known as leveling effect.
The strength of an acid also depends upon the solvent. The acids HClO4 , H2 SO4 ,HCland
HNO3 which have nearly the same strength in water will be in order of HClO4 > H2 SO4 > 𝐻𝐶𝑙 >
𝐻𝑁O3 in acetic acid, since, the proton accepting tendency of acetic acid is much weaker than water.
So, the real strength of acids can be judged by solvents. On the basis of proton interaction, solvents
can be classified into four types.
i] Protophilic solvents:Solvents which have greater tendency to accept protons, i.e., water, alcohol.
Liquid ammonia, etc.
ii] Protogenic solvents: Solvents which have the tendency to produce protons, i.e., water, liquid hydrogen
chloride, glacial acetic acid, etc.
iii] Amphiprotic solvents: Solvents which act both as protophilic or protogenic, e.g., water, ammonia,
ethyl alcohol, etc.
iv] Aprotic solvents:Solvents which neither donate nor accept protons, e.g., benzene, carbon terachloride,
carbon disulphide, etc.
3] Lewis concept:
This concept was proposed by G.N. Lewis, in 1939. According to this concept, a base is defined as a
substance which can furnish a pair of electrons to form a coordinate bond whereas an acid is a
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substance which can accept a pair of electrons. The acid is also known as electron pair acceptor or
electrophile while the base is electron pair donor or nucleophile.
Some examples are
H3 N •• + BF3 = H3N → BF3
Base Acid
H+ + •
• NH3 = [H ← NH3 ]+
Acid Base
BF3 + [F]− = [F → BF3 ]+
Acid Base
Lewis concept is more general than the Bronsted Lowry concept.
According to Lewis concept, the following species can act as Lewis acids:
i] Molecules in which the central atom has incomplete octet: All compounds having central atom with
less than 8 electrons are Lewis acids e.g., BF3 , BCl3 , AlCl3 , BeCl2 , etc.
ii] Simple cations: All cations are expected to act as Lewis acids since they are deficient in electrons.
However, cations such as Na+ , K + , Ca2+ , etc, have a very little tendency to accept electrons,while
the cations like H + , Ag + Fe2+ , CO2+ , Mn2+ etc., have greater tendency to accept electrons and,
therefore, act as Lewis acids.
iii] Molecules in which the central atom has empty d-orbitals: The central atom of the halides such as
SiX4 , GeX4 , TiCl4 , SnX4 , PX3 , PF5 , SF4 , SeF4 , TeCl4 etc., have vacant d-orbitals. These can,
therefore, accept an electron pair and act as Lewis acids.
iv] Molecules having a multiple bond between atoms of dissimilar electro negativity: Typical examples
of molecules falling in this class of Lewis acids are CO2 , SO2 and SO2 . Under the influence of
attacking Lewis base, one 𝜋-electron pair will be shifted towards the more negative atom.

orHCO−
3
The following species can act as Lewis bases
i] Neutralspecies having at least one lone pair of electrons: For example, ammonia, amines, alcohols,
etc., act as Lewis bases because they contain a pair of electrons.
Ex:𝑁𝐻3 , 𝑅𝑁𝐻2 , 𝑅2 𝑁𝐻, 𝑅3 𝑁, 𝐻2 𝑂, 𝑅𝑂𝐻, 𝑅𝑂𝑅 etc.,
ii] Negatively charged species or anions: For example, chloride, cyanide, hydroxide ions, etc., act as
Lewis bases.
CN− , Cl− , Br − , I− , OH − etc.,
It may be noted that all Bronsted bases are also Lewis bases but all Bronsted acids are not Lewis acids.
iii] Molecles containing multiple bonds between atoms of same electronegativity
Ex: 𝐶𝐻2 = 𝐶𝐻2
Limitation: Since, the strength of the Lewis acids and base is found to depend on the type of reaction,
it is not possible to arrange them in any order of their relative strength.
HOME EXERCISE:
1] Which of the following is the strongest base?
a)C2 H5− b)C2 H5 COO− c)C2 H5 O− d)H2 PO−
4
2] The conjugate acid of NH3 is

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a) NH3 b)NH4+ c)N2 H4 d)NH2 OH

3] The conjugate base of H2 PO−
4 is
a) H3 PO4 b)P2 O5 c)PO3−
4 d)HPO2− 4
4] Water is well known amphiprotic solvent. In which chemical reaction wate is behaving as a base?
a)H2 SO4 + H2 O+ ⟶ H3 O+ + SO− 4 b)H2 O + H2 O ⟶ H 3+ + OH −
c)H2 O + NH2− ⟶ NH3 + OH − d)H2 O + HN3 +
4
⟶ NH + OH −
5] Which of the following is both Arthenius and Bronsted acid?
a)CO2 b) BF3 c)HNO3 d)AlCl3
6] The species which acts as a Lewis but not a Bronsted acid is
a)NH2− b)O2− c)BF3 d)OH −
NCERT Text Book Questions: 7.35, 7.36, 7.37, 7.38, 7.39, 7.40
Ostwalds’s Dilution Law:
According to Arrhenius theory of electrolytic dissociation, the molecules of an electrolyte in solution
are constantly splitting up into ions and the ions are constantly reuniting to form unionized molecules.
Therefore, a dynamic equilibrium exists between the ions and the unionized molecules of the
electrolyte in solution. It was pointed out by Ostwald that like chemical equilibrium, law of mass action
can be applied to such systems also.
Consider a binary electrolyte AB which dissociates into A+ andB − ions and the equilibrium state is
represented by

Initial conc.
Conc at equilibriumC − C ∝= C(1 − α) Cα Cα
Applying law of chemical equilibrium,
Cα × Cα Cα2
K= =
C(1 − α) (1 − α)
Where K is dissociation constant. Since weak electrolytes are feebly ionized, thus α is very small, then
1−𝛼 =1
K 1
∴ C α2 = Korα = √ and α ∝
C √C
Thus, the degree of dissociation of weak electrolyte is inversely proportional to the square root of the
molar concentration of the solution and it increases with increase in dilution For weak acids, ∞ =
K K
√ a & For weak base ,∞ − √ bwhere K a and K b are ionization constant weak acid and weak base.
C C
Ostwald’s dilution holds good for weak electrolytes only.
Degree of Dissociation or Ionisation:
It is the fraction of the molecules of an electrolyte present as ions. It is denoted by α
NO.of dissociated molecules
α=
Total no.of molecules
Depending on the degree of dissociation, the electrolytes are divided into two categories.
a] Strong Electrolyte: The substances which dissociates completely into ions in aqueous solution, and
hence are very good conductors of electricity are known as strong electrolyte e.g. HCl, NaOH, NaCl
etc.
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b] Weak Electrolyte: The electrolytes which ionize to a small extent in aqueous solution and hence
conduct electricity to a small extent, are called weakelectrolytes.
e.g. CH3 COOH, NH4 OH, (NH4 )2 CO3 ,etc.
The degree of dissociation depends on the following factors:
i] Nature of the solute: All ionic compounds i.e..strong electrolytes haveα ≈ 1
ii] Nature of the solvent: Polar solvents with high dielectric constant (like water) are more ionizing, and
hence the extent of ionization is more in these solvents.
iii] Concentration: Degree of ionization increases with dilution.
iv] Temperature: Degree of ionization is directly proportional to temperature.
v] Addition of other species: Addition of another solute having an ion common to that of weak electrolyte
results in the suppression of the degree of dissociation of weak electrolyte (common ion effect ).
Comparison of strengths of acids and bases:
Ka
According to the Ostwald’s dilution law, for a monobasic weak acid,α = √
C
+)
Here 𝛼 =Degree of ionization of the acid i.e. its proton (H releasing tendency. Thus, if represents
the strength of the acid
K a =Dissociation constant of the acid
C =Molar concentration of the acid solution,
For two acids, having the same molar concentration (C is constant )
𝛼1 𝐾𝛼1 𝑆𝑡𝑟𝑒𝑛𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝐻𝐴1 Kα1
=√ 𝑂𝑟 = =√
𝛼2 𝐾𝛼2 𝑆𝑡𝑟𝑒𝑛𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝐻𝐴2 Kα2
Thus the relative strengths of the two acids having same molar concentration can be compared in terms
of the square roots of their dissociation (or ionization) constants.
Similarly, for two bases having the same molar concentration (C is constant)
α1 Kα Strength of the base , (BOH)1 Kb
= √ 1 or =√ 1
α2 K α2 Strength of the base , (BOH)2 K b2
Remember
Kα
1] For a weak electrolyte.[H + ] = Cα = C × √ = √K α . C
C

2] Higher the K a value (or lesser the pK a value where pK a = − log Ka ) for an acid, stronger is the
acid. Higher the K b value (or lesser thepK b value, pK b = − log Kb ) for a base, stronger is the
base.
For a dibasic acid likeH2 SO4 , K a1 and K a2 represents the first and second ionization
constants. For tribasic acid like H3 PO4 , there are three ionization constants.For such acids
K a1 > K a2 > K a3 Similarly for polyacidic bases like Ca(OH)2 , K a1 > K a2
Ionic Product of water:
Pure water is a very weak electrolyte –
H2 O ⟶ H + + OH −
on applying the law of mass action at equilibrium ,
[H+ ][OH− ]
Then, K =
[H2 O]
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or [H + ][OH − ] = K[H2 O]
Since, ionization takes places to a very small extent, so the concentration of unionized water molecule
is regarded as constant. Thus the product of K[H2O] gives another constant Kw.
So, [H + ][OH − ] = K w
The product of concentration of H+ and OH- ion in water at a particular temperature is known as ionic
product of water.
The value of K w increases with the increase in temperature i.e. the ionization of water increases with
increase in temperature and finally the concentration of H + and OH − ions also increases.
The values of K w at various temperature are given below:

Temperature (°𝑪) Value of 𝑲𝒘

1) 0 0.11 × 10−14
2) 10 0.31 × 10−14
3) 20 – 35 or 25° (Room temp. ) 1 × 10−14
4) 60 2.9 × 10−14
5) 80 5.6 × 10−14
6) 100 7.50 × 10−14

The acidity and basicity depend upon the concentration of H+ and OH-ions .
If, [H + ] > [OH − ] = Acidic solution
[OH − ] > [H + ] = Basic solution
[OH − ] = [H + ] = Neutral solution
When an acid or a base is added to water, the ionic concentration product,[H + ][OH − ]remains constant,
i.e., equal to K w but concentrations of H + andOH − ions do not remain equal. The addition of acid
increases the hydrogen ion concentration while that of hydroxyl ion concentration decreases, i.e.,
[H + ] > [OH − ]; (Acidic solution)
Similarly, when a base is added, the OH − ion concentration increases while H + ion concentration
decrease, i.e., [OH − ] > [H + ]; (Alkaline or basic solution)
In neutral solution, [H + ] = [OH − ] = 1 × 10−7 M at 25°C
In acidic solution,[H + ] > [OH − ]
or[H + ] > 1 × 10−7 M
and[OH − ] < 1 × 10−7 M
In alkaline solution, [OH − ] > [H + ]
Or[OH − ] > 1 × 10−7 M
and[H + ] < 1 × 107 M
Thus, if the hydrogen ion concentration is more than 1 × 10−7 M., the solution will be acidic in nature
and if less than 1 × 10−7 M, the solution will be alkaline.
[H + ] = 10−0 10−1 10−2 10−3 10−4 10−5 10−6 (Acidic)
[H + ] = 10−7 (Neutral)
+
[H ] = 10 − 14 −13 −12 −11 −10 −9 −8
10 10 10 10 10 10 (Alkaline)
−
We shall have the following table if OH ion concentration is taken into account.
[OH − ] = 10−14 10−13 10−12 10−13 10−10 10−9 10−8 (Acidic)
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[OH − ] = 10−7 (Neutral)

[OH − ] = 10−0 10−1 10−2 10−3 10−4 10−5 10−6 (Alkaline)
It is, thus, concluded that every aqueous solution, whether acidic, neutral or alkaline contains both H −
and OH − ions. The product of their concentrations is always constant, equal to 1 × 10−14 at 25°C. If
one increases, the other decreases accordingly so that the product remains 1 × 10−14 at 25°C.
HOME EXERCISE
1] The degree of ionization of a compound depends
a) size of solute molecules b) nature of solute molecules
c) nature of vessel used d) quantity of electricity passed
2] Which one is strongest electrolyte in the following?
a) NaCl b) CH3 COOH c)NH4 OH d)C6 H12 O6
3] If 𝛼is the degree of ionization, C the concentration of a weak electrolyte and K a the acid ionization
constant then the correct relationship between α, C and K a is
Ka C Ka c
a)α2 = √ b)α2 = √ c)α = √ d)α = √
C Ka C Ka

4] A monoprotic acid in a 0.1 M solution ionizes to 0.001%Its ionization constant is

a)1 × 10−11 b)1 × 10−3 c)1 × 106 d) 1 × 10−8
5] pKa values of two acids A and B are 4 and 5. The strengths of these two acids are related as
a) strength of acid A: strength of acid B = 4.5
b) acid A is 3.3 times stronger that acid B
c) acid B is 10 times stronger than acid A
d) the strength of the two acids cannot be compared
6] The K a for CH3 COOH is1.7 × 10−5 and concentration of H + ions is3 × 10−4 . The
concentration of CH3 COOH is
a) 3.4 × 10−4 b)3.4 × 10−3 c)6.8 × 10−3 d)1.7 × 10−3
NCERT Text Book Questions: 7.43, 7.45, 7.53, 7.54

Hydrogen ion Concentration-pH Scale:

It is observed that when an acid or base is added to water, although the ionic product, [H+][OH-] ,
remains constant (equal to K w ),yet the concentration of H3 O+ andOH − ion changes. In order to
express the concentration of H3 O+ ion or H + ions in solution a new scale called pH scale was given
by Sorensen pH of a solution is defined as the negative logarithm of hydrogen ion (or hydronium ion
) concentration.
pH = − log[H3 O+ ]
Thus [H3 O+ ] = 10−pH mol L−1
Similarly, negative logarithm of hydroxyl ion concentration is called pOH.
pOH = − log[OH − ]
Also, K w = [H + ][OH− ]
−logK w = − log[H + ] − log[OH − ]
pK w = pH + POH

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For any acidic or basic solution, the sum of pH and pOH is equal to 14 and is referred to as pKw at 298
K. pH + pOH = pK w = 14
pHof a solution decreases with the increase in temperature , e.g. pH of boiling water is 6.5625,
although it is neutral.
For neutral solution; pH = pOH = 7 at 298K.
For acidic solution; pH < 7 𝐵𝑢𝑡 𝑝𝑂𝐻 > 7 𝑎𝑡 298 𝐾
For basic solution; pH > 7 𝐵𝑢𝑡 𝑝𝑂𝐻 < 7 298𝐾

[H + ] [OH − ] pH pOH Nature of solution

10° 10−14 0 14 Strongly acidic
−2 −12
10 10 2 12 Acidic
−5 −9 5 9 Weakly acidic
10 10
10−7 10−7 7 7 Neutral
10−9 10−5 9 5 Weakly basic
10−11 10−3 11 3 Basic
10 −14
10 0 14 0 Strongly basic
Note: Decrease in conc. of [𝐻 + ] by 10 times, pH increases by one unit.
The following table shows the pH range for a few common substances:
S.NO Substance 𝐩𝐇range S.NO Substance pH range
1 Gastric Contents 1.0 – 3.0 7 Milk (cow) 6.3 – 6.6
2 Soft drinks 2.0 – 4.0 8 Saliva (human) 6.5 – 7.5
3 Lemons 2.2 – 2.4 9 Blood plasma 7.3 – 7.5
4 Vinegar 2.4 – 3.4 10 (human) 10.5
5 Apples 2.9 – 3.3 11 Milk of magnesia 8.5
6 Urine (human) 4.8 – 8.4 Seawater

Importance of 𝒑𝑯 value:
i] pHhas a great importance in agriculture. Soil is often tested to determine whether acidic or basic
fertilizers are required for a particular crop.
ii] pHvalue plays important role in biological reactions such as digestion of food etc
iii] Human blood has pH value of 7.36 – 7.42 A change in pHby 0.2 units results in death.
iv] pHvalue plays an important role in qualitative analysis
v] Food preservation also requires a definite pH value.
Calculation of 𝒑𝑯 of Solutions:
Any method which can measure the concentration of H + ions or OH- ions in a solution can serve for
finding pH value.
i] Normality of strong acid = [H3 O+ ]
Normality of strong base= [OH − ]
∴ pH = − log[N] for strong acids
pOH = −log [N]for strong bases
ii] Sometimes, pH of acidto base becomes very close to that of 7. It shows that the solution is very dilute;
in such cases, H + or OH − contribution from water is also considered, e.g., in10−8 N HCl, [H + ]total =
[10−8 ]acid + [10−7 ]water = 11 × 10−8 M = 1.1 × 10−7 M
iii] pH of mixture: Let one litre of an acidic solution of pH2be mixed with two litre of other acidic solution
of pH 3. The resultant pH of the mixture can be evaluated in the following way
Sample-1 Sample-2

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pH = 2 pH = 3
+
[H ] = 10 M −2 [H + ] = 10−3 M
V = 1 litre V = 2 litre
M1 V1 + M2 V2 = MR (V1 + V2 )
10−2 × 1 + 10−3 × 2 = MR (1 + 2)
12×10−3
MR
3
−3
4 × 10 = MR (Here, MR = Resultant molarity)
pH = − log(4 × 10−3 )

N1 V1 −N2 V2 ∴ pH of mixture of acid base

N= V1 +V2
N will give [H + ] or [OH − ]depending on equivalents of acid or base
iv] 𝒑𝑯of weak acids and weak bases:
Weak acids and bases are not completely ionized. An equilibrium is found to have been established
between the ions and unionised molecules.
Let us consider a weak monobasic acid.

[H + ] = Cα; ∴ pH = − log10 [Cα]

Similarly, for weak base:
[OH − ] = Cα; ∴ pOH = log 10[Cα] and pH = 14 − pOH
v] 𝒑𝑯for the mixture of Weak Acid and Strong Acid
Let strong acid be HB whose conc. is C1 HB ⟶ H + + B−
HB ⟶ H + + B−
Conc 0 C1 C1
and weak acid whose conc. is C2 and degree of dissociation is α
HA ⟶ H + + A−
C2 (1 − α) C2 α C2 α
Cα
Total (H+) conc. = C1 + 2
Cα
pH = - log [C1 + 2 ]
[H + ][A− ] [C1 + C2 α][C2 α]
K a(HA) = =
[HA] [C2 (1 − α)]
vi) 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 andC2 ,α1 is the degree of dissociation of HA
in presence of HB (due to com1mon ion effect ) and α2 be degree of dissociation of HB in presence of
HA. In aqueous solution of HA and HB following equilibrium exists.
HA + H2 O(l) ⟶ H3 O+ + A− C1 α1 + C2 α2
conc. at equi. C1 (1 − α1 ) C1 α1 + C2 α2 C1 α1
HB + H2 O(l) ⟶ H3 O+ + B−
C2 (1 − α2 ) (𝐶1 𝛼1 + 𝐶2 𝛼2 ) 𝐶2 𝛼2
+ −
[H3 O ][A ] [C1 α1 + C1 α2 ][C1 α2 ]
K a(HA) = =
[HA] C1 (1 − α1 )

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[H3 O+ ][B − ] [C1 α1 + C1 α2 ][C1 α2 ]

K a(HB) = =
[HB] C1 (1 − α1 )
+
Total [H ] = C1 α1 + C2 α2
pH = − log[H + ] = − log[C1 α1 + C2 α2 ]
vii] pH of a dibasic Acids and Polyprotic Acid:
Let ‘s take the eg. of a dibasic acid H2 A. Assuming both dissociation areweak. Let the initial conc. of
H2 Abe C and 𝛼1 𝑎𝑛𝑑 𝛼2 be degree of dissociation for first and second dissociation.
H2 A ⟶ HA− + H+
[HA− ][H+ ]
C(1 − α1 )Cα1 (1 − α2 )𝐶𝛼1 + 𝐶𝛼1 𝛼2 Ka1 = [H2 A]
− + −−
HA ⟶ H + A
Cα1 (1 − α2 )Cα1 + Cα1 α2 Cα1 α2
[HA− ][H+ ]
Ka1 = [H2 A]
[Cα1 (1−α2 )][Cα1 α2 ]
Ka1 = C(1−α1 )
[H+ ][A− ] [Cα1 +Cα1 α2 ][Cα1 α2 ]
Ka2 = [HA− ]
= [Cα1 (1−α2 )]

After solving for α1 and α 2 . We can calculate the H+ conc.

[H + ] = Cα1 + Cα1 α2
pH = −log[Cα1 + Cα1 α2 ]
Solved Examples
Example-1:
What is the pH of the following solutions?
(a)10−3 MHCl (b) 0.0001 M NaOH (c) 0.0001 M H2 SO4
Solution:
a] HCl is a strong electrolyte and is completely ionised.
HCl ⇌ H + + Cl−
So, [H + ] = 10−3 M
pH = − log[H + ] = − log(103 ) = 3
b] NaOH is a strong electrolyte and is completely ionized.
NaOH ⇌ Na+ + OH −
So, [OH − ] = 0.0001M = 10−4 M
pOH = − log(10−4 ) = 4
As pH + pOH = 14 So, pH + 4 = 14 or pH = 10
c] H2 SO4 is a strong electrolyte and is ionized completely.
H2 SO4 ⇌ 2H + + SO2− 4
One molecule of H2 SO4 furnishes 2H + ions.
So,[H + ] = 2 × 10−4 M
pH = − log[H + ]
− log(2 × 10−4 ) = 3.70
Example 2:
Calculate the pH of the following solutions assuming complete dissociation:
a] 0.365 gL−1 HCl solution
b] 0.0001 MBa(OH)2solution

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Solution:
a] Mole mass of HCl = 36.5
0.365
Concentration of HCl = = 1.0 × 10−2 mol L−1
36.5
HCl is a strong electrolyte and is completely ionized
So, [H + ] = 1 × 10−2 mol L−1
pH = − log[H + ] = − log(1 × 10−2 ) = 2
b] Ba(OH)2is a strong electrolyte and is completely ionized
Ba(OH)2 ⇌ Ba+2 + 2OH −
One molecule on dissociation furnished2OH − ions.
So, [OH − ] = 2 × 10−4 M
pOH = − log[OH − ]
= − log(2 × 10−4 ) = 3.7
We know that, pH + pOH = 14
So,pH = (14 − 3.7) = 10.3
Example 3:
Find the pH of a 0.002 N acetic acid solution, if it is 2.3%ionized at a given dilution.
Solution:
2.3
Degree of dissociation,α = 100 = 0.023
Concentration of acetic acid, C = 0.002 M
The equilibrium is,
CH3 COOH ⇌ CH3 COO− + H +
𝐶(1 − 𝛼) 𝐶𝛼 Cα
So, [H ]Cα = 0.002 × 0.023; = 4.6 × 10−5 M
+

pH = − log[H + ] ; = − log(4.6 × 10−5 ) = 4.3372

Example 4:
Calculate the pH value of a solution obtained by mixing 50 mL of 0.2 N HCl with 50 mL of 0.1 N
NaOH.
Solution:
Number of milli-equivalents of the acid = 50 × 0.2 = 10
Number of milli-equivalents of the base = 50 × 0.1 = 5
Number of milli-equivalents of the acid left after the addition of base= (10 − 5) = 5
Total volume of the solution = 50 + 50 = 100 mL
Thus, 5 milli-equivalents of the acid are present in 100 mL of solution
Or 50 mili-equivalents of the acid are present in one litre of solution
Or 0.05 equivalents of the acid are present in one litre of solution
The acid is monobasic and completely ionized in solution.
0.05 N HCl = 0.05 M HCl
So,[H + ] = 0.05M
pH = − log[H + ] = − log[H + ] = −log5 × 10−2 = −log5.0 + log 10−2 = − [0.70 − 2] = 1.3
Example 5:
What will be the pH of a solution obtained by mixing 800 mL of 0.05 N sodium hydroxide and 200
mL of 0.1 N HCl, assuming the complete ionization of the acid and the base?
Solution:

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Number of milli-equivalents of NaOH = 800 x 0.05 = 40

Number of milli-equivalents of HCl = 200 x 0.1 = 20
Number of milli-equivalents of NaOH left after the addition of HCl
= (40-20) = 20
Total volume = (200 + 800) mL = 1000 mL = 1 litre
20 milli-equivalents or 0.02 equivalents of NaOH are present in one litre i.e.,
0.02 N NaOH = 0.02 M NaOH (Mono-acidic) and the base is completely ionized.
so, [OH − ] = 0.02 M
or[OH − ] = 2 × 10−2 𝑀
pOH = − log(2 × 10−2 ) = 1.7
We know that, pH + pOH = 14
So, pH = (14 – 1.7) = 12.3
Example 6:
What is the hydrogen ion concentration of solution (i) whose pH is 12.ii) whose pH is 5.6?
Solution:
i) pH = − log[H + ]
or log[H + ] = −pH = −12
[H + ] = 10−12 M
ii) pH = − log[H + ]
or Log[H + ] = −5.6 or [H + ] = 10−5.6 = 10−6 × 100.4 = 2.5 × 10−6 M
NCERT Text Book Questions: 7.41, 7.42, 7.47, 7.48, 7.49, 7.50, 7.51, 7.52, 7.55, 7.56, 7.57, 7.58, 7.59,
7.60, 7.62, 7.65, 7.66
Common ion Effect
Let AB be the weak electrolyte. Considering its dissociation,AB ⇌ A+ + B−
[A+ ][B− ]
And applying law of mass action, we have K = [AB]
The equilibrium constant, K, has a definite value at any given temperature. If now another electrolyte
furnishing the A+ and B − ions be added to the above solution, it will increase the concentration of either
A+ ions or B − ions(whichever has been added) and in order that K may remain constant, the
concentration AB must increase, i.e., the equilibrium will shift to the left hand side.
In other words, the degree of dissociation of an electrolyte (weak) is suppressed by the addition of
another electrolyte (strong) containing a common ion. This is termed as common ion effect. Acetic acid
is a weak electrolyte and its ionization is suppressed in presence of a strong acid (H + ion as common ion)
or a strong salt like sodium acetate (acetate ion as common ion). Similarly, the addition of NH4 Cl or
NaOH to NH4 OH solution will suppress the dissociation of NH4 OH due to common ion either
NH4+ or OH −
As a result of common ion effect, the concentration of the ion not in common in two electrolytes, is
decreased. The use of this phenomenon is made in qualitative analysis to adjust concentration S 2− ions
in second group and OH − ion concentration in third group of analysis.
Buffer Solutions:
A solution whose pH is not altered to any great extent by the addition of small quantities of either an
acid (H + ions) or a base (OH − ions) is called the buffer solution. It can also be defined as a solution of
reserve acidity or alkalinity which resists change of pH upon the addition of small amount of acid or
alkali.
General Characteristics of a Buffer Solution:
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i] It has a definite pH, i.e., it has reserve acidity or alkalinity

ii] Its pH does not change on standing for long.
iii] Its pH does not change on dilution
iv] Its pH is slightly changed by the addition small quantity of an acid or a base
Buffer solutions can be obtained:
i] by mixing a weak acid with its salt of a strong base (Acidic Buffer)
ex: a) CH3 COOH + CH3 COONa
b) Boric acid + Borax
c) Phthalic acid + Potassium acid phthalateii] by mixing a weak base with its salt of a strong
acid (Basic Buffer)
ex: a) NH4 OH + NH4 Cl
b) Glycine + Glycine hydrochloride
iii] by a solution of ampholyte. The ampholytes or amphoteric electrolytes are the substances which show
properties of both an acid and is base. Proteins and amino acids are the examples of such electrolytes.
iv] a) by a mixture of an acid salt and a normal salt of a polybasic acid, e.g,.Na2 HPO4 + Na3 PO4
b) A salt of weak acid and a weak base, such as CH3 COONH4 .
Explanation of Buffer Action
1] Neutral Buffer:
Let us see why CH3 COONH4 is a Buffer while NaCl is not. CH3 COONH4 exists almost entirely in form
of it’s ion CH3 COO− andNH4+ If an acid is added to that solution, the H + ion furnished by the acid
combine with CH3COO- ions to form feebly dissociated molecule of CH3 COOH.
CH3 COO− + H + ⟶ CH3 COOH
Since most of the H + ions added are taken up by CH3 COO− to form 𝐶𝐻3 𝐶𝑂𝑂𝐻which itself slightly
dissociated, the pH of CH3 COONH4 changes only slightly,
Now, suppose a base is added to CH3 COONH4 solution the OH − furnished by the base will be taken up
by NH4+ ion to form feebly dissociated NH4 OH.
NH4+ + OH − ⟶ NH4 OH
Since most of the OH − ions are taken up by NH4+ ions to form feebly dissociated NH4 OH. Due to this
very little change in the pH of CH3 COONH4 solution occurs.
Now let us see why a solution of NaCl is not a Buffer .In aqueous solution it is almost entirely
dissociated into Na+ and Cl− . If H + ions are added to this solution the H + combines with Cl− to form
HCl which completely dissociated due to strong electrolyte hence pH falls.
If OH − ions are added to the solution, it will combine with Na+ to form NaOH which will almost
completely dissociate. Hence pH will rise.
II] Acid Buffer:
A very common acidic buffer is prepared by mixing equimolar solutions of acetic acid and soldium
acetate. Acetic acid is very slightly dissociated while sodium acetate, being a salt, is almost completely
dissociated. The mixture thus contains CH3 COOH molecules as well as CH3 COO− and Na+ ions. Let us
consider the buffer action of this mixture.
Suppose a strong acid is added to the above mixture. The H + ions added will be taken up immediately
by CH3 COO− ions to from very slightly dissociated CH3 COOH:
H + + CH3 COO− ⟶ CH3 COOH
Addition of acid:

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Thus, the H + ions added are neutralized by the acetate ions present in the mixture. There is very little
change in the pH of the mixture.
If, on the other hand, a strong base is added, the OH − ions added are neutralized by the acetic acid
present in the mixture:
OH − + CH3 COOH ⟶ CH3 COO− + H2 O
Thus, there is very little change in the pH of the mixture.
Calculation of pH of Acidic Buffer
Acidic buffer: consists of a mixture of weak acid and its salt (strong electrolyte). The ionization of the
weak acid, HA, can be shown by the equation,
HA ⟶ H + + A−
[H+ ][A− ]
Applying law of mass action,K a = [HA]
….(i)
[HA]
Or[H + ] = K α [A−]
…(ii)
−
It can be assumed that concentration of A ions from complete ionization of the salt BA is too large to
be compared with concentration of A− ions from the acid HA.
BA ⟶ B+ + A−
Thus, [HA] = Initial concentration of the acid as it is feebly ionized in presence of common ion and
[𝐴− ] = Initial concentration of the salt as it is completely ionized.
[Acid]
So, [H + ] = K a
[Salt]
…(iii)
Taking logarithm and reversing sign,
[𝐴𝑐𝑖𝑑]
− log[𝐻 + ] = − log 𝐾𝑎 − log [𝑆𝑎𝑙𝑡]
[Salt]
or pH = log [Acid] = −logK a
[Salt]
or pH = pK a + log [Acid]
…..(iv)
This is known as Henderson’s equation
[Salt]
When[Acid] = 10, then
pH = 1 + pKa
[Salt] 1
and when [Acid] = 10, then
pH = pKa – 1
So, weak acid may be used for preparing buffer solutions having pH values lying within the ranges
𝑝𝐾𝑎 + 1𝑝 𝐾𝑎 − 1.

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III] Basic Buffer:

A very common basic buffer is prepared by mixing equimolar solutions of ammonium hydroxide and
its almost completely dissociated salt, ammonium chloride, constitutes. The solution will have
NH4 OHmolecule,NH4+ ions, Cl− ions and OH − ions
NH4 OH ⇌ NH4+ + OH − ( Feebly ionized)
NH4 Cl ⇌ NH4+ + Cl− (Completely ionized)
Addition of Strong Base:
When a drop of NaOH is added, the addedOH − ions combine with NH4+ ions to form feebly ionized
NH4 OH whose ionization is further suppressed due to common ion effect. Thus, pH is not disturbed
considerably.
NH4+ + OH − ⇌ NH4 OH
↑
(From strong base)
When a drop of HCl is added, the added H + ions combine with NH4 OH to form undissociated water
molecules.
NH4 OH + H + ⇌ NH4+ + H2 O

(From strong acid)
Thus, pH of the buffer is practically unaffected.
Calculation of pH of a Basic Buffer :
Basic Buffer consists ofa weak base and its salt with strong acid. Ionisation of a weak base, BOH, can
be represented by the equation,
BOH ⇌ B + + OH −
Applying law of mass action,
[B+ ][OH− ]
Kb = [BOH]
…….(i)
[BOH]
Or [OH − ] = K b [B+ ]
……..(ii)
As the salt is completely ionized, it can be assumed that whole of B + ion concentration comes from the
salt and contribution of weak base to B+ ions can be ignored.
BA ⇌ B+ + A− (Completely ionized)
[Base]
So, [OH − ] = Kb ……(iii)
[Salt]
[Salt]
Or pOH = log [Base] − log K b
[salt]
Or pOH = pK b + log [Base]….…(iv)
Knowing 𝑝𝑂𝐻, 𝑝𝐻 can be calculated by the application of the formula,
𝑝𝐻 + 𝑝𝑂𝐻 = 14
Buffer capacity:
The property of a buffer solution to resist alternation in its pH value is known as buffer capacity. It
[Salt ] [Salt]
has been found that if the ratio [Acid] or [Base]is unity, the pH of a particular buffer does not change at
all. Buffer capacity is defined quantitatively as number of moles of acid or base added in one litre of
solution as to change the pH by unity, i.e.,

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No.of moles of acid or base added to 1 litre

Buffer capacity(ϕ) = Change in pH
Buffer capacity is maximum
i] When [Salt] = [Acid], i.e., pH = pK afor acid buffer
ii] When [Salt] = [Base], i.e., pOH = pK b for base buffer under above conditions, the buffer is
called efficient.
Applications of Buffer Solutions:
Buffers are used:
i] To determine the pH with the help of indicators.
ii] For the removal of phosphate ion in the qualitative inorganic analysis after second group using
CH3 COOH + CH3 COONa buffer.
iii] For the precipitation of lead chromate quantitatively in gravimetric analysis, the buffer, CH3 COOH +
CH3 COONa, is used.
iv] For precipitation of hydroxides of third group if qualititative analysis, a buffer,
NH4 Cl + NH4 OH, is used.
v] A buffer solution of NH4 Cl, NH4 OH and (NH4 )2 CO3 is used for precipitation of carbonates of fifth
group in qualitative inorganic analysis.
vi] The pH of intracellular fluid, blood is naturally maintained. This maintenance of pH is essential to
sustain life because, enzyme catalysis is pH sensitive process. The normal pH of blood plasma is 7.4.
Following two buffers in the blood help to maintain pH (7,4):
a) Buffer of carbonic acid (H2 CO3 and NaHCO3 )
b) Buffer of phosphoric acid (H2 PO− 2−
4 , HPO4 )
Buffers are used in industrial processes such as manufacture of paper, dyes, inks, paints, drugs, etc.
Buffers are also employed in agriculture, dairy product and preservation of various types of foods and
fruits.
NCERT Text Book Question: 7.64
Salts are strong electrolytes. When dissolved in water, they dissociate almost completely into ions. In some
salts, cations are more reactive in comparison to anions and these react with water to produce H + ions. Thus,
the solution acquired acidic nature.
M + + H2 O ⇌ MOH + H +
Weak base
In other salts, anions may be more reactive in comparison to cations and these react with water to
produce OH- ions. Thus,
A− + H2 O ⟶ HA + OH −
Water acid
Salt hydrolysis:
The process of hydrolysis is actually the reverse of neutralization.
Salt + water ⟶ Acid + Base
If acid is stronger than base, the solution is acidic and in case base is stronger than acid, the solution
is alkaline. When both the acid and the base are equally strong, the solution is neutral in nature.
When both the acid and the base are weak, the solution is either acidic. Basic & neutral. This depends
upon the dissociation constant of the acid and base involved.
Types of Salts:
As the nature of the cation or the anion of the salt determines whether its solution will be acidic or
basic, it is proper to divide the salts into four categories.

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i] Salt of a strong acid and a weak base.

Examples:FeCl3 , CuCl2 , AlCl3 , NH4 Cl, CuSO4 , etc.
ii] Salt of strong base and a weak acid.
Examples:CH3 COONa, NaCN, NaHCO3 , Na2 CO3 , etc.
iii] Salt of a weak acid and a weak base.
Examples:CH3 COONH4 , (NH4 )2 CO3 , NH4 HCO3 etc.
iv] Salt of a strong acid and a strong base.
Examples:NaCl, K 2 SO4 , NaNO3 , NaBr, etc.
1] Salt of a strong acid and a weak base:
The solution of such a salt is acidic in nature. The cation of the salt which has come from weak base
is reactive. It reacts with water to form a weak base and H + ions. This is called cationic hydrolysis
B+ + H2 O ⟶ BOH + H +
Weak base
Consider, for example, NH4 Cl. It ionizes in water completely into NH4+ andCl− ions. NH4+ ions react with
water to form a weak base (NH4 OH) and H − ions.
NH4+ + H2 O ⇌ NH4 OH + H +
Thus, hydrogen ion concentration increases and the solution becomes acidic and pH < 7.
a] Hydrolysis constant. For the salt BA, the hydrolysis may be represented as
BA + H2 O ⇄ BOH + HA
Salt Weak Strong
↓ base ↓acid
Or B + A + H2 O ⟶ BOH + H + + A− or B+ + H2 O ⇄ BOH + H +
+ −

i.e., it is a case of cation hydrolysis.

[BOH][H+ ]
The hydrolysis constant K will be given by K = [B+ ][𝐻2 𝑂]
…(i)
For the weak base BOH, the dissociation equilibrium is:BOH ⇄ B + + OH −
The dissociation constant K b of the weak base BOH will be given by
[𝐵+ ][𝑂𝐻 − ]
𝐾𝑏 = [𝐵𝑂𝐻]
….(ii)
The ionic product of water, K w is given by K w = [H + ][OH − ] ……(iii)
Multiplying equation (i) with (ii) and dividing by (iii), we get
Kh Kb Kw
= 1orK h = ……(iv)
Kw Kb
b] Degree of Hydrolysis,suppose the original concentration of the salt in the solution is c mole / litre and
‘h’ is the degree of hydrolysis at this concentration. Then,
B+ + H2 O ⇌ BOH + H +
Initeal conc. C 0 0
Conc.At equi. C(1 – h) ch ch
The hydrolysis constant (K h )1 is given by,
[BOH][H+ ] ch.ch ch2
Kb = [B+ ]
= c(1−h) = 1−h
As .h, is very small, 1 – h = 1

kb Kb
∴ ch2 = K b or h2 = or h = √
c c

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K
Substituting the value of K h from equation (iv), we get K h = √ w ……(v)
K b
+ +
c] 𝐩𝐇. In this case we have B + H2 O ⇌ BOH + H
Original conc. c 0 0
Conc. at equi: c(1– h) ch ch
+]
i.e.,[H = ch
K Kw C K c 1/2
Substituting the value of h from equation (v) we get[H + ] = c√K wc = √ = ( Kw )
b Kb b
1/2
Kwc
∴ pH = − log[H + ] = − log ( )
Kb
1
orpH = − 2 [logK w − logK b + logc] …..(vi)
1
pH = [pK w − pK b − logc]
2
1
pH = 7 − 2 [pK b + logc]
2] Salt of a weak acid and a strong base
The solution of such a salt is basic in nature. The anion of the salt is reactive. It reacts with water to
form a weak acid and OH − ions.
A− + H2 O ⇌ HA + OH −
Weak acid
Consider, for example, the salt CH3 COONa. It ionizes in water completely to give 𝐶𝐻3 COO− and
Na+ ions. CH3 COO− ions react with water to form a weak acid, CH3 COOH and OH − ions.
CH3 COO− + H2 O ⟶ CH3 COOH + OH −
Thus, OH − ion concentration increases, the solution becomes alkalini and pH > 7
a] Hydrolysis constant: Representing the salt by BA as usual, the hydrolysis may be represented as
follows:
BA + H2 O ⇌ BOH + HA
Salt Strong Weak
↓ ↓
+ − + −
OrB + A + H2 O ⇌ B + OH + HA
− −
Or A + H2 O ⇌ OH + HA
i.e., it is a case of anion hydrolysis.
[OH− ][HA]
The hydrolysis constantKhfor the above reaction will be given byK h = [A− ]
..i)
For the weak acid HA, the dissociation equilibrium is:HA ⟶ H + + A−
[H+ ][A− ]
∴The dissociation constant K a of the acid HA will be given byK a = [HA]
…… ii)
Further, the ionic product of water,K w is given by K w = [H + ][OH − ] ….iii)
Multiplying equation (i) with (ii) and dividing by (iii), we get
Kh .Ka [OH− ][HA] [H+ ][A− ] 1 Kw
= [A− ]
× [HA]
× [H+][OH− or K h = …iv)
Kw ] Ka
b] Degree of Hydrolysis. Suppose the original concentration of the salt in the solution is c moles/litre
and h is its degree of hydrolysis at this concentration. Then we have
A− + H2 O ⟶ OH − + HA
Original molar conc. c 0 0
Molar conc. at equilibrium c(1-h) chch
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The hydrolysis constant (K h )will, therefore, be given by

[OH − ][HA] ch. ch ch2
Kh = Kh = = =
[A− ] c(1 − h) 1 − h
If h is very small as compared to 1, we can take 1-h = 1 so that the above expression becomes
Kh K
Ch2 = K h orh2 = or h = √ ch
c
K
Substituting the value of K h from equation (iv), we geth = √K w.c …….(v)
a

c] pH. In the present case, we have

A− + H2 O ⟶ OH − + HA
Original conc: c 0 0
Conc. at eqm.: c(1-h) chch
K K
i.e.[OH = ch ∴ [H + ] = [OHw−] = w
−]
ch
Substituting the value of h from equation (v), we get
Kw Kac Kw. Ka
[H + ] = =√ or [H + ] = √
c Kw c
1
KwKa Kw. Ka 2 1
∴ pH = − log[H + ] = −log√ = − log ( ) or pH = [log K w + log K a − logc]
c c 2
This equation may be rewritten as
1 1
pH = 2 [−log Kw – log Ka + log c]or pH = 2 [pKw + pKa + log c]
1
At 298 K, pK w = 14. Hence, at 298 K, we have pH = 7 + 2 [pK a + log c]
3] Salt of Weak acid and a weak base:
The solution of such a salt may be acidic, basic or neutral, depending upon the relative degree of
ionization of the weak acid and the weak base produced. Maximum hydrolysis occurs in these case as
both the cation and anion are reactive and react with water to produce H + and PH- ions. Consider the
example CH3 COONH4 . It gives CH3 COO− and NH4+ ions in solution. Both react with water
NH4+ + H2 O ⟶ NH4 OH + H +
CH3 COO− + H2 O CH3 COOH + OH − C
orCH3 COO− + NH4− + H2 O ⟶ CH3 COOH + NH4 OH
The resultant solution is neutral because the dissociation constant ofCH3 COOHand NH4 OHare equal.
When K a = K b , solution will be neutral when K a > K b solution will be slightly acidic and whenK b >
K a , solution will be slightly basic
a] Hydrolysis constant: Representing the slat by BA as before, we have
BA + H2 O ⟶ BOH + HA
Salt Weak Weak
↓
+
orB + A− + H2 O ⟶ BOH + HA
i.e., it involves both anion hydrolysis as well as cation hydrolysis. The equation for the hydrolysis
constant will be:
[BOH][HA]
Kh = [B+ ][A− ]
……(i)

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[H+ ][A− ]
For the weak acid, HA H + + A− , so thatK a = K a = [HA]
…….(ii)
[B+ ][OH+ ]
For the weak base,BOH B+ + OH − , so that K b = [BOH]
..……(iii)
Also, we know that Kw = [H + ][OH − ] …….. (iv)
Multiplying equations (i),(ii), (iii) and dividing by equation (iv), we get
Kh .Ka .Kb Kw
= 1 Kh = K …….(v)
Kw a Kb

b) Degree of Hydrolysis, In this case, we have

B+ + A− + H2 O ⟶ BOH + HA
Original c c 0 0
Conc. at.equ. c(1-h) c(1-h) ch ch
[BOH][HA] ch.ch h2
∴ Kh = [B+ ][A− ]
= c(1−h).c(1−h) = (1−h)2 ..….. (vi)
Here, the relationship between K h and h does not involve. Thus the degree of such a salt is independent
of the concentration of the solution.
If h is very small in comparison to 1, we can take 1 – h = 1 so that equation (vi) becomes
Kw
K h = h2 or h − √K h = √K ….… (vii)
a .Kb

c] pH
HA ⟶ H + + A−
[H + ][A− ] [HA] ch h
∴ Ka = or [H + ] = K a − = K a = Ka
[HA] [A ] c(1 − h) (1 − h)
h
But from equation (vi),1−h = √K h so that we have

Kw KaKw
[H + ] = K a √K h = K a √ =√
Ka. Kb Kb

+]
√K a K w K a K w 1/2
pH = − log[H = − log = − log ( )
Kb Kb
1
or pH = 2 [log K a + logK w − logK b ]
1
or this equation may be written as:pH = [pK w + pK a − pK b ]
2
or at 298 K, we have ph = 7
1
ph = 7 + 2 [pK a − pK b ]
For slats of weak acid and weak base, from the above expression.
a) If pK a < 𝑝K b , pH of the solution will be less than 7 and the solution will be acidic.
b) If pK a < 𝑝K b , pH of the solution will be greater than 7 and the solution will be basic.
c) If pK a < 𝑝K b , pH of the solution will be equal to 7 and the solution will be neutral.
4] Salt of a strong acid and a strong base:
The solution of such salt is neutral, as neither the cation nor the anion undergo hydrolysis
For example, Nacl. It gives Na+ and Cl− ions in solution. Both are not reactive.
NaCl + H2 O ⟶ NaOH + HCl
Or Na+ + Cl− + H2 O ⟶ Na+ + OH − + H + + Cl−
Or H2 O ⟶ H + + OH −
Thus it involves only ionization of water and no hydrolysis. In the resulting solution,

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[H + ] = [OH − ], so the solution is neutral.

NOTE:
Strong acids Weak acids Strong bases Weak bases
HCl CH3 COOH NaOH NH4 OH
H2 SO4 HCN KOH LiOH
HNO3 H2 CO3 RbOH Ca(OH)2
HClO4 H3 PO4 CsOH Be(OH)2
Hl H3 PO3 Ba(OH)2 Zn(OH)2
H2 SO3 HOCl Al (OH)3
COOH

COOH

Fe(OH)2
Fe(OH)3
RNH2

NCERT Text Book Questions: 7.63

Solved Examples:
Example 1:
Calculate the hydrolysis constant, degree of hydrolysis and pH of 0.10 M KCN solution at 25°C. For
HCN, K a = 6.2 × 10−10 .
Solutions:
Kw 10−14
Hydrolysis constant,K h = = 6.2×10−10 = 1.6 × 10−5
Ka

K 1.6×10−5
Degree of hydrolysis,h = √ ch = √ = 1.26 × 10−2
0.1

The hydrolysis reaction will be:

CN− + H2 O ⟶ HCN + OH −
Initial conc. c 0 0
At equ. 𝑐−𝑥 𝑥 𝑥(𝑥 = No. of moles of 𝐶N− reacted)
[𝐻𝐶𝑁][𝑂𝐻 − ] 𝑥 × 𝑥 𝑥 2
𝐾ℎ = = = 𝑜𝑟 𝑥 = √𝐾ℎ × 𝑐 = √(1.6 × 10−5 )(0.1) = 1.26 × 10−3
[𝐶𝑁 − ] 𝑐−𝑥 𝑐
i.e., [OH − ] = 1.26 × 10−3
+
Kw 10−14
∴ [H ] = = = 7.94 × 10−12
[OH − ] 1.26 × 10−3
𝑝𝐻 = − log[𝐻 + ] = − log(7.94 × 10−12 ) = 12 − 0.90 = 11.1
Alternatively, pH can be calculated directly by applying the formula,
1
pH = 7 + 2 [pK a + logC].
Example 2:
Calculate the pH of 0.10 M solution of NH4 Cl. The dissociation constant (K b ) of NH3 is 1.6 × 10−5
Solution:
As NH3 Cl is a salt of weak base and strong acid,
𝐾𝑤 10−14
𝐾ℎ = = 1.6×10−5 = 6.25 × 10−10
𝐾𝑏
The hydrolysis reaction will be NH4+ + H2 O ⟶ NH3 + H3 O+
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Or NH4+ ⟶ NH3 + H +
Initial conc. 𝑐
At equ. 𝑐−𝑥 𝑥 𝑥
+
[𝑁𝐻3 ][𝐻 ] 𝑥 × 𝑥 𝑥 2
𝐾ℎ = = = 𝑜𝑟 𝑥 = √𝐾ℎ × 𝑐 = √(6.25 × 10−10 ) × 0.1 = 7.9 × 10−6 𝑀
[𝑁𝐻4+ ] 𝑐−𝑥 𝑐
i.e.,[H + ] = 7.9 × 10−6 M
∴ pH = − log(7.9 × 10−6 ) = 6 − 0.90 = 5.10
Alternativel, applying the formula directly.
1 1
pH = 7 − [−logK b + logc] = 7 − [− log(1.6 × 10−5 ) + log 0.1]
2 2
1
= 7 − [(𝑟 − 0.02041) − 𝑎] = 5.10
2
Example 3:
The pK a of acetic acid and pK b of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate the
pH of ammonium acetate solution.
Solution:
As CH3 COONH4 is a salt of weak acid, weak base,
1 1
pH = 7 + [pK a − pK b ] = 7 + (4.76 − 4.35) = 7 + 0.005 = 7.005
2 2
Example 4:
What would be the pH of 0.1 M sodium acetate solution, given that the dissociation constant of acetic
acid is 1.8 × 10−5 .
Solution:
1 1
pH = 7 + [pK a + logc] = 7 + [−log 1.8 × 10−5 + log 0.1] = 8.87
2 2
Acid-Base Indicators:
Titration:
Titration is the measurement of the volume of a solution of one reactant that is required to react
completely with a measured amount of another reactant. As both the reactants are taken in the form of
solutions and the titration is the measurement of volume of one solution that must be added to another
solution till the reaction is complete, this method of quantitative analysis is, therefore, called
volumetric analysis. Usually the concentration of one of the solutions is known, (called standard
solution) and it is desired to find the concentration of other by titration. A known volume of the solution
is taken in the titration flask (with the help of a pipette) and the other solution is taken in the burette
which is graduated in cc’s and has a stop-clock at the bottom to control the amount of flow into the
flask. The solution to be titrated (taken in the flask) is called titrate and the solution with which the
titration is to be done (taken in the burette) is called the titrant. The point which the required volume
of one solution has been added to the other to exactly complete the reaction between the two is called
end point or equivalence point.
Types of titrations:
There are many types of titrations such as redox titrations (involving oxidation and reduction), acid-
base titrations(involving neutralization), precipitation titrations (e.g. NaClvsAgNO3 ), complexometric
titrations (involving formation of complexes) but here we shall take up a brief discussion of acid-base
titrations in aqueous solutions only.

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The substance usually added into the solution taken in the titration flask to detect the equivalent point
is called an indicator.
THEORY OF ACID-BASE INDICATORS (OSTWALD’S THEORY)
According to this theory:
1] Acid-base indicators are mostly complex organic molecules which are either weak acids or weak bases.
For example, phenolphthalein is a weak organic acid which may be represented in a simple way as
HPh and methyl orange is a weak organic base which may be represented as MeOH.
2] They dissociate in aqueous solution as follows:
Hph ⟶ H+ + ph− .. (i)
(Colourless) (Colourless) (Prink)
+
MeOH ⟶ Me + OH − .. (ii)
(Yellow) (Red) (Colourless)
The unioniozed from has one colour and the ions have different colour. For example, HPh is colourless
while ph ions have pink colour. Similarly, MeOH has yellow colour while 𝑀𝑒 + ions have red colour.
3] As the medium changes from acidic to basic or vice versa, the equilibrium shifts either towards right
or towards left and so the colour changes. For example, in acidic medium (i.e., in presence of excess
of H + ions), equilibrium
i] is towards left and the solution is colourless. While in basic medium,OH − ions will combine
with the H + ions to from unionized H2 O molecules, the equilibrium shifts towards right and
the solution has pink colour. Similarly, in case of methyl orange, in basic medium (i.e., in
present of excess of OH − ions) the equilibrium
ii] is towards left and the colour is yellow while in acidic medium, H + ions combine with the
OH − ions and the equilibrium (ii) shifts towards right and the colour is red.
Phenolphthalein cannot be used a indicator if the base is weak, e.g., NH4 OH. This is because
the OH − ions produced from the weak base are insufficient to shift the equilibrium (i) towards
right substantially,. Similarly, methyl orange is not a suitable indicator if the acid is weak like
acetic acid (CH3 COOH). This is because the H + ions produced are insufficient to combine with
the OH − ions and shift the equilibrium (ii) towards right significantly.
pH at the End-Point of Acid-Base Titrations:
One often assumes that the pH at the end point of an acid-base titration must be 7. However, we must
remember that what we have at the end point is an aqueous solution of a salt formed as a result of
neutralization of the acid by the base. If strong acid has been titrated with a strong base, the pH at the
end point is, of course, 7. But if a weak base is involved in the titration, pH at the end point depends
upon the hydrolysis of the slat formed. However, in any type of the acid-base titration, it is found that
there is a sudden change in the pH value at the end point.
As the titration proceeds, if the pH vales of the solution are measured (say with the help of a pH meter)
or calculated theoretically and then plotted against the volume of the solution added, the curve obtained
is called titration curve. The titration curves of strong acid against strong base (e.g., HCl versus NaOH),
weak acid against strong base (e.g.,CH3 COOH versus NaOH), weak base against strong acid (e.g.,
NH4 OH versus HCl) and weak acid against a weak base (e.g., CH2 COOHversus NH4 OH) are shown in
Fig. (a), (b) and(c) and (d) respectively. The point at which there is a sudden change in pH when a very
small amount of the titrant is added to the tirrate is called point of titration.
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a) b)

c) d)
To understand how pH changes during acid-base titration, let us consider the titration of 50.0 ml of 0.1
N HCl against 0.1 NaOH solution. The pH at different additions of NaOH solution may be calculated
theoretically as follows:
Initially, as the solution taken in the flask is 0.1 M HCl, [H + ] = 10−1 , pH = 1.0. After 10ml of 0.1 N
NaOH has been added, it will neutraluize 10 ml of 0.1 N HCl so that HCl left in the solution
= 40 ml of 0.1 N and total volume of solution = 60ml. To calculate normality of HCl in the final
solution, apply
N1 × V1 = N2 × V2 i. e 0.1 × 40 = N2 × 60 = N2 = 0.0667N or 0.0667M,
i.e., [H + ] = 6.67 × 10−2 M.
Hence, pH = 1.18.
Similarly, when 20,30 or ml etc. of NaOH solution have been added, the corresponding pH values can
be calculated as given in Table. Upto the addition of 49.09 ml of 0.1 N NaOH solution, the following
general formula can be used to calculate normality of HCl or [H + ]
50−v
Normality of HCl = (50+v) × 0.1 = [H + ] where v is the volume of 0.1 N NaOH solution added.
Titration of 50.0 ml of 0.1 N HCl with 0.1 N NaOH solution
Volume of 0.1 N NaOH pH
solution added
0.0 1.00
10.0 1.18
20.0 1.37
30.0 1.60
40.0 1.96
49.0 3.00
49.9 4.00
50.0 7.00
50.1 10.00
51.0 11.00
60.0 11.96
70.0 12.22

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When 50 ml of 0.1 N NaOH solution has been added, the end point of the titration is reached, All the
acid is neutralized. The solution contains NaCl only. Hence, pH = 7.0. Thus, pH of the solution has
suddenly increased from 4.0 to 7.0
Further, addition of even a very small amount of NaOH solution (say 0.1 ml) increases the pH of the
solution very rapidly. This may be seen as follows:
Now, volume of the solution = 50 + 50.1 = 100.1 ml
The volume of 0.1 N NaOH solution left unneutralized = 0. 1
To calculate normality of NaOH in the final solution, apply
N1 V1 = N2 V2 i. e 0.1 × 0.1 = N2 × 100.1 or N2 = 10−4 N or 10−4 M, i. e [OH − ] = 10−4 𝑀
Hence, [H + ] = 10−10 or pH = 10.0. similarly, [OH − ]and hence [H + ]or pH can be calculated when
more of NaOH solution is added In general, normality of NaOH solution and hence [OH − ] can be
calculated by applying the formula
v − 50
[NaOH] = [OH − ] = ( ) × 0.1M
50 + v
Thus, it may be seen that whereas the first 49.9 ml of NaOH solution added causes the pH change by
three units, the next 0.2 ml added causes a change of six units.
It may be noted that the steepness of the slope around the equivalence point is quite large in case of
titration of strong acid against strong base whereas it is less steep if the acid or the base is weak, Large
steepness means large change in pH on adding a very small volume of the solution.
Selection of a suitable indicator:
The indicator used should be such that it shows change in colour in the same pH range as required
around the equivalence point. A number of indicators are available for the entire pH range. These are
given in table.
Common acid-base indicators and their colour changes
Indicator pH-range Acidic colour Alkaline colour
Methyl violet 0-2 Yellow Violet
Methyl yellow 1.2-2.3 Red Yellow
Methyl orange 3.1-4.5 Red Yellow
Bromocresol green 3.8-4.6 Yellow Blue
Methyl red 4.2-6.2 Red Yellow
Litmus 4.5-8.3 Red Blue
Bromthymol blue 6.0-7.5 Ornage Blue
Phenol red 6.4-8.2 Yellow Red
Cresol red 7.2-8.8 Yellow Red
Thymol blue 8.0-9.6 Yellow Blue
Phenolpthalein 8.3-10.0 Colourless Red
Thymolpthalein 9.3-10.5 Colourless Blue
Alizarin yellow 10.1-12.0 Yellow Violet
Trinitrobenzene 12.0-14.0 Colourless Orange
.

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a) b)

c) d)
From the titration curves, it may be observed that
i] For titration of a strong acid against a strong base, any indicator out of methyl orange, methyl red,
phenolphthalein or bromthymol blue can be used to determine the end point.
ii] For titration of weak acid like acetic acid against a strong base like NaOH solution, only
phenolphthalein (or bromthymol blue) is a suitable indicator,
iii] For titration of weak base like NH4 OH against strong acid like HCl, methyl orange or methyl red or
bromothymol blue can be used as an indicator.
iv] For titration of weak acid with weak base, no indicator is found to function satisfactorily (except
bromthymol blue to some extent)
The colour changepK indicator = pH at the equivalence point
As already mentioned, acid-base indicators are weak organic acids or weak organic bases, Suppose we
consider an indicator which is a weak organic acid., Let it be represented by HIn. In aqueous solution,
it dissociates as:
HIn(aq) ⇄ H + (aq) + In − (aq)
HInandIn− have different colours. The equilibrium constant for the above reaction is
[H + ][In− ]
K In =
[HIn]
The exact point of the colour change will be at the pH when [HIn] = [In-]. Substituting this value, we
get K In = [H + ] or − log K In = − log[H + ] i. e pK ln = pH
Thus, for a particular, titration, the indicator selected should be such for whichpK In = pH of the
solution at the equivalence point. For example in the titration of HF with NaOH, pH at the equivalence
point is 8.1.pK In for cresol red is 8.1. Hence, cresol red should be used as indicator in this titration.
Explanation of the pH range of 2 units of indicators most of the indicators have a useful colour change
over a pH range of 2 units. For example the most common indicator, phenolphthalein, changes from
colorless to pink in the pH range from 8.3 to 10.0.
For the indicator HIn, HIn(aq) ⟶ H + (aq) + In− (aq)
[H+ ][In− ]
HInandIn− have different colours. The equilibrium constant isK In = [HIn]
Our eye can detect the change in colour if the concentration of one of the coloured form is at least 10
times greater than the concentration of the other. Thus,
[In− ] 1
To see the acidic colour, [HIn]
= 10

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[In− ] 10
And to see the alkaline colour. [HIn]
= 1
[HIn]
Rearranging eqn. (i) we get [H + ] = K In
[In− ]
 For acidic colour to be visible, [H + ] = 10K In
Or−logH + = log10 − logK In i. e pH = pK In + 1
Thus, for colour change of an indicator,pH = pK In ± 1
i.e., pH range for colour change is from pK In−1 pK In + 1, i.e., a pH range of 2 units.
Calculation of pK a or pK b values from pH of equivalence point
The pK a of a weak acid or weak base can be determined from the measurement of pH at the
equivalence point from the titration curve., For example, for a weak acid. HA,
HA ⇄ H + + A−
[H + ][A− ] [HA] [HA]
Ka = or [H + ] = − K a or − log[H + ] = −logK a − log −
[HA] [A ] [A ]
[HA]
i.e pH = pK a − log [A−]
i] Strong Acid vs. Strong Base:pH curve of strong acid (say HCl) and strong base (say NaOH) is vertical
over almost the pH range 4-10. So, the indicators phenolphthalein (pH range 8.3 to 10.5), methyl red
(pH range 4.4-6.5) and methyl orange (pH) range 3.2-4.5) are suitable for such a titration.
ii] Weak Acid vs. Strong Base:pH curve of weak acid (say CH3 COOH or oxalic acid)and strong base
(say NaOH) is vertical over the approximate pH range 7 to 11. So, phenolphthalein is the suitable
indicator for such a titration.
iii] Strong Acid vs. Weak Base: pH curve of strong acid (say HCl or H2 SO4 or HNO3 ) with a weak base
(say NH4 OH) is vertical over the pH range of 4 to 7. So, the indicators methyl red and methyl orange
are suitable for such a titration.
iv] WeakAcid vs. Weak Base: pH curve of weak acid and weak base indicates that there is no vertical
part and hence, no suitable indictor can be used for such a titration.
Solubility (s):
At a constant temperature, the mass of a solute or electrolyte dissolved in the 1 litre of solvent in its
saturated solution is called as solubility . Or number of gm mole of a solute dissolved in one litre of
solvent at constant temperature is called as solubility of that solute .
moles Solubility of solute in gm /litre
Solubility of a solute in =
litre molecular weight of the solute
Solubility Product (𝑲𝒔𝒑):
If to a given amount of solvent at a particular temperature, a electrolyteis added gradually in increasing
amounts, a stage is reached when some of the solute remains undissolved, no matter how long we wait
or how vigorously we stir. The solution is then said to be saturated. A solution which remains in contact
with undissolved solute is said to be saturated. At saturates stage, the quantity of the solute dissolved
is always constant for the given amount of a particular solvent at a definite temperature.
In case, the solute is an electrolyte, its ionization occurs in solution and degree of dissociation depends
on the concentration of dissolved electrolyte at a particular temperature. Thus, in a saturated solution
of an electrolyte two equilibria exist and can be represented as:
AB ↔ AB ↔ A+ + B −
Insoluble Unionised Ions
Solute (Saturated solution)

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[A+ ][B− ]
K1 =
[AB]
The concentration of AB remains almost constant,
K1 [AB] = Constant
K1 [AB] = [A+ ][B− ] = K sp
This K sp is called solubility product.
It is defiend as the product of the concentration ions in a saturated solution of an electrolyte at a given
temperature.
Consider, in general, the electrolyte of the type Ax By which is dissociated asAx By ⇄ xAy+ + yBx−
[Ay+ ]x [Bx− ]y
Applying law of mass action, [Ax By ]
=K

When the solution is saturate,[Ax By ] = K ′ (constant)

Or [Ay+ ]x [Bx− ]y = K[Ax By ] = KK ′ = K sp (constant)
Thus, solubility product is defined as the product ofmolarconcentrations of the ions raised to a power
equal to the number of times the ions occur in the equation representing the dissociation of the
electrolyte at a given temperature when the solution is saturated.
Difference between Solubility Product and Ionic Product:
Both ionic product and solubility product represent the product of the concentrations of the ions in the
solution, each raised to the power equals to the number of ions as represented by the dissociation of
one molecule of the substance. However, they differ in the following two aspects:
i] The term ionic product is applicable to all types of solutions, may be unsaturated or saturated.
On the other hand, the solubility product is applicable only to a saturated solution in which
there exists a dynamic equilibrium between the undissolved salt and the ions present in
solution. Thus, the solubility product is, in fact, the ionic product for a saturated solution.
Note:
At a certain temperature solubility product of a salt is constant.
Criteria of precipitation of an electrolyte:
Case I: When 𝐼𝑃 < K sp then solution is unsaturated in which more solute can be dissolved.
Case II:When𝐼𝑃 = 𝐾𝑠𝑝 , then solution is saturated in which no more solute can be dissolved.
Case III:When IP > K sp , then solution is supersaturated and precipitation takes place.
When the ionic product exceeds the solubility product, the equilibrium shifts towards left hand side,
i.e, increasing the concentration of unidssociated molecules of the electrolyte. As the solvent can hold
a fixed amount of electrolyte at a definite temperature, the excess of the electrolyte is thrown out from
the solution as precipitate.
For example, if equal volumes of 0.02 M AgNO3 solution and 0.02 M K 2 CrO4 solution are mixed, the
precipitation of Ag 2 CrO4 occurs as the ionic product exceeds the solubility product of Ag 2 CrO4 which
is 2 × 10−12 .
0.02
In the resulting solution, [Ag + ] = = 0.01 = 1 × 10−2 M
2
0.02
And [CrO2−
4 ] = = 0.001 = 1 × 10−2 M
2
Ionic product of Ag 2 CrO4 = [Ag + ]2 [CrO2−
4 ]
= (1 × 10 ) (1 × 10−2 ) = 1 × 10−6
−2 2

1 × 10−6 is higher than 2 × 10−12 and thus precipitation of Ag 2 CrO4 occurs.

Relationship between Solubility and Solubility Product:
The equilibrium for a saturated solution of a salt Ax By may be expressed as,Ax By ⇌ xAy+ + yBx−

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Thus, solubility product K sp = [Ay+ ]x [Bx− ]y

Let the solubility of the salt Ax By in water at a particular temperature be‘s’ moles per litrethen
⬚
Ax By → xAy+ + yBx−
xs ys
So, K sp = [xs]x [ys]y
K sp = X x , Y y (s)x+y
a] 1: 1 type salts or AB type of salts:
eg. AgCl, Agl, BaSO4 , PbSO4 , etc.
AB ⇄ A+ + B −
Let the solubility of AB be ‘s’ moles per litre.
So, K sp = [A+ ][B− ] = s × s = s 2
s = √K sp
b] 1: 2 or 2: 1 type of salts or 𝑨𝑩𝟐 𝒐𝒓 𝑨𝟐 𝑩 type of salts:
eg.Ag 2 CrO4 , pbl2 , Ag 2 CO3 , CaF2 , CaCl2 etc.
i] AB2 ⇄ A2+ + 2B−
s2s
Let the solubility of AB2 be ‘s’ moles per litre
So, K sp = [A2+ ][B− ]2 = s × (2s)2 = 4s3
Ksp
s = 3√ 4
ii] A2 B ⇆ 2A+ + B2−
Let the solubility of A2 Bbe ‘s’ moles per litre
K sp = [A+ ]2 [B −2 ]
= (2s)2 (s) = 4s3
Ksp
s = 3√ 4
c] 1: 3 type of salts or salts of 𝑨𝑩𝟑 or 𝑨𝟑 𝑩 type of salt:
AB3 = valence of A = 3 × valency of B
eg. FeCl3 , AlCl3 , Al(OH)3 , Fe(OH)3etc.
A3 B = 3 × valence of A = 3 × valency of B
eg. Na3 BO3 , Na3 PO4 etc.
i] AB3 ⇆ A3+ + 3B−
Let the solubility of A3 Bbe ‘s’𝑚𝑜𝑙𝑒/𝑙𝑖𝑡𝑟𝑒.
AB3 ⟶ A3+ + 3B −
s 3s
K ap = [A ][B ]3 = s × (3s)3 = 27s 4
3+ −

Ksp
s = 4√ 27
ii] A3 B ⇆ 3A+ + B−3
Let the solubility of A3 Bbe ‘s’ moles / litre.
A3 B ⇆ 3A+ + B−3 3s s
Ksp
𝐾𝑠𝑝 = [𝐴3+ ][𝐵 − ]3 = (3𝑠)3 × 27𝑠 4 s = 4√ 27
d] 2: 3 or 𝑨𝟐 𝑩𝟑 type of salts:
eg.Al2 (SO4 )3
A2 B2 ⟶ 2A+3 + 3B −2
Let the solubility of salt A2 B2 be ‘s’ moles/litre.
So, A2 B3 ⟶ 2A+3 + 3B−2

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K sp = [A+3 ][B−2 ]3
= (2s)2 × (3s)3
= 4s2 × 27s 3

K sp
K sp = 108s5 s = 5√
108
Effect of Common ion on Solubility:
As we saw that for a saturated solution product of concentration of ions should not exceed a constant
called solubility product. Now suppose, we some how added extra common ions to increase
concentration of ions it will tend product to exceed the constant but it cannot so ions will react to give
molecule and get precipitated e.g. let solubility of AB in water be s moles L−1. It is dissolved in solution
CB having a common ion B− letconcentration of CB be C.
AB ⇄ A+ + B −
s ss
K sp = s 2 = [A+ ][B− ]………..(1)
(Product should not exceed S 2 otherwise precipitation will start) Now. Let solubility of AB in CB be
CB ⟶ C+ + B−
C C C
AB ⇄ A+ + B −
𝑠1 𝑠1 𝑠1
+
[A ] = s1
[B− ] = s1 + C
K sp = (s1 )(s1 + C)
If 𝑠1 <<< 𝐶
K sp = s1 C = s2 from equation (1)
s2
OrS1 = C
’
So, solubility gets reduced.
Applications of 𝑲𝒔𝒑:
1] In purification of common salt: In a saturated solution of NaCl & impurities, by passing HCl
gasthrough it, increase the Cl− ion concentration which shifts the equilibrium
NaCl ⇆ Na+ + Cl− to left & causes the precipitation of NaCl .
2] In preparation of 𝑵𝒂𝑯𝑪𝑶𝟑 by Solvay method: Precipitation of NaHCO3 from its saturated solution
is done by addition of NH4 HCO3 ,HCO3− as common ion.
3] In prediction of precipitation in lonic reactions: Precipitation in an ionic reactions could be predicted
by comparing K sp to the ionic concentration product of ions.
4] Salting out action of Soap: When NaCl is added to saturated solution of soap (RCOONa)
concentration of Na+ increases & causes to precipitation of soap, it is due to
[Na+ ][RCOO− ] > K sp
5] In qualitative analysis: Qualitative analysis of mixtures is based on the principle of solubility product.
Some important applications are as follows –

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a]Precipitation of I group radicals: Group reagent is dilute HCl. In the presence of dilute HCl,
the ionic product of I group radicals as their chlorides becomes more than the solubility
product. Thus I group radicals get precipitated as their chlorides.
b] Precipitation of II group radicals: Group reagent is H2 S. In presence of dilute HCl, the
dissociation of H2 S is suppressed due to common ion (H + )and only ionic product of the
sulphides of II group radicals exceeds their solubility product and get precipitated .
c] Precipitation of III group radicals: Group reagent is NH4 OH in presence of NH4 Cl. The
presence of NH4 Clsuppresses the ionization of NH4 OH, NH4+ as common ion. Thus, the
ionic product of hydroxides of III group redials exceeds corresponding solubility products and
gets precipitated.
d] Precipitation of IV group radicals: Group reagent is H2S in presence of NH4OH. In the
presence of NH4 OH enhances the dissociation of H2 S. Thus, due to high ionization of H2 S the
concentration of S −2ions increases and ionic product of sulphides of IV group radicals
exceeds corresponding solubility product and get precipitated.
e] Precipitation of V group radicals: Group reagent is ammonium carbonate in presence of
NH4 Cl. Common ion NH4+ suppresses ionization of (NH4 )2 CO3 thus only V group carbonates
having low solubility product get precipitated.
NCERT Text Book Questions: 7.67, 7.68, 7.69, 7.70, 7.71, 7.72, 7.73

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