Ionic Equilibrium

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IONIC EQUILIBRIUM
Total Sessions – 11
SESSION – 1
AIM - To introduce the Concept of Acids and Bases
THEORY
In chemical equilibrium we studied reaction involving molecules only but in ionic
equilibrium we will study reversible reactions involving formation of ions in water.
When solute is polar covalent compound then it reacts with water to form ions.
Electrical conductors
Substances, which allow electric current to pass through them, are known as
conductors or electrical conductors.
Conductors can be divided into two types,
(1) Conductors which conduct electricity without undergoing any chemical
change are known as metallic or electronic conductors.
(2) Conductors which undergo decomposition (a chemical change) when an
electric current is passed through them are known as electrolytic conductors or
electrolytes.
Electrolytes, divided into two types on the basis of their strengths,
(i) Substances which almost completely ionize into ions in their aqueous solution
are called strong electrolytes.
Degree of ionization for this type of electrolyte is one i.e., α ≈ 1.
For example : HCl, H2SO4, NaCl, HNO3 , KOH, NaOH, HNO3 , AgNO3 , CuSO4 etc. means all
strong acids, bases and all types of salts.
(ii) Substances which ionize to a small extent in their aqueous solution are
known as weak electrolytes.
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Degree of ionization for this type of electrolytes is α <<< 1.
For example: H2O, CH3COOH, NH4OH, HCN, Liq. SO2 , HCOOH etc. means all
weak acids and bases.
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.
Exp- HCl, HNO3 , H2 SO4 , HClO4 ,etc., are strong acids
NaOH, KOH, Ba(OH)2 are strong bases.
• Others are dissociated to a limited extent in solutions and are termed weak
acids and bases.
Note- Every hydrogen compound cannot be regarded as an acid,
e.g., CH4 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:
• The concept does not explain acidic and basic character of substances in
non-aqueous solvents.
• It could not explain the basic nature of NH3 and metallic oxides and acidic
nature of non-metal oxides.
• It could not explain the behaviour of acids/bases in non aqueous solutions.
• It could not explain the neutralization reaction giving salt in absence of a
solvent.
• It could not explain the acid character of certain salts like AlCl3, BF3
etc. in aqueous solution.
• It could not explain the existence of H+ in water.
2. Bronsted-Lowry concept:
According to Bronsted-Lowry concept an acid is a substance (molecule or
ion) that can donate proton, i.e., a hydrogen ion H+ , to some other
substance.
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−
Here, 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.
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
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 + Base +
Base −H Acid
and
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 base1. H2 O is labeled as base2 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−
Strong acid Weak base Weak acid Strong base
There are certain molecules which have dual character of an acid and a
base are called as amphiprotic or amphoteric.
Examples are NH3 , H2 O, CH3 COOH, etc.
The strength of an acid depends upon its tendency to lose its proton and
the strength of the base depends upon its tendency to gain the proton.
Acid- base chart containing some common conjugate acid-base pairs

(Acid) (Conjugate base)
------------------Increasing order of acid strength-------------------------

HClO4 (Perchloric acid) ClO−4 (Perchlorate ion)
H2 SO−
------------------- Increasing order of acid strength-----------------→

H2 SO4 (Sulphuric acid) 4 (Hydrogen sulphate ion)
HCl (Hydrogen chloride) Cl− (Chloride ion)
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.
Note- The strength of an acid also depends upon the solvent. The acids
HClO4 , H2 SO4 ,HCl and 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. protic solvents: Solvents which neither donate nor accept protons, e.g.,
benzene, carbon terachloride, carbon disulphide, etc.
Limitations
* Failed to explain the acidic nature of BF3
* Failed to explain the basic nature of MgO, Cao etc
3. Lewis concept:- 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 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.
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:
• 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.
• 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.
• 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.
• 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.
or HCO−3
The following species can act as Lewis bases
• Neutralspecies having at least one lone pair of electrons:
Exp-ammonia, amines, alcohols, etc., act as Lewis bases because they contain
a pair of electrons. NH3 , RNH2 , R 2 NH, R 3 N, H2 O, ROH, ROR etc.,
• Negatively charged species or anions: For example, chloride, cyanide,
hydroxide ions, etc., act as Lewis bases. CN− , Cl− , Br − , I− , OH− etc.,
Note- It may be noted that all Bronsted bases are also Lewis bases but all
Bronsted acids are not Lewis acids.
• 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.
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SESSION–2
AIM- To introduce Ostwald Dilution Law
To introduce Ionic Product of Water
Ostwalds’s Dilution Law:
According to Arrhenius theory, 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.
This law deals with the application of the law of mass action to the equilibrium
between the ions and unionized molecules in aqueous solutions of weak binary
electrolytes such as acetic acid, propionic acid, HCN, NH4OH, etc.
Consider a dilute solution of a weak binary electrolyte AB containing
c moles in 1litre. At any given temperature, there will be equilibrium between
the unionized molecules of AB and the ions A+ and B−. Let ‘’ be the degree
of dissociation of AB at equilibrium.
AB A+ + B−
Initial conc. c 0 0
Conc. at. equilb. c(1−) c c
Then according to the law of mass action, the equilibrium constant Keq will be given
[A+ ] [B− ] cα × cα α2 c
by Keq = [AB]
=
c(1 − α)
=
1 − α
𝛼2 𝑐
This expression “Keq = 1 − 𝛼” is called Ostwald’s dilution law.
Keq is called the dissociation (or ionization) constant of the weak electrolyte.
1 𝛼2
If 1 mole is present in ‘V’ litres of solution, c = V .  Keq = . This is
𝑉(1−𝛼)
another expression for Ostwald’s dilution law.
 has a very small value for a weak electrolyte and is therefore negligible in
comparison with unity.
 1 −   1.
 Keq = 2c
Keq
 =√ c
 α = √K eq × V
This law is valid only for weak electrolytes that too in dilute solutions. It is
not applicable for strong electrolytes.
Degree of Dissociation(): The fraction of the total electrolyte that undergoes

dissociation at equilibrium is known as degree of dissociation.
NO.of dissociated molecules
α=
Total no.of molecules
The variation of ‘’ of an electrolyte is governed by:
(i) Nature of solute: All ionic compounds i.e. strong electrolytes have   1 at
normal dilution. Most of the polar covalent compounds i.e. weak electrolytes
have  << 1
(ii) Nature of Solvent: Higher the dielectric constant of a solvent more is
its ionising power. Water is the most powerful ionising solvent as its
dielectric constant is highest.
(iii) Dilution: The extent of dissociation of an electrolyte increases with dilution of
solution.
𝟏 𝟏
𝛂 ∝
Con. of solution
∝
wt. of solution
∝ Dilution of solution ∝ Amount of solvent
(iv) Temperature: The extent of dissociation of an electrolyte also increases with
an increase in temperature.
(v) Addition of other species with commom ion: Addition of another solute having
an ion common to that of weak electrolyte shows a decrease in degree of
dissociation of weak electrolyte.
i.e., The degree of ionisation of an electrolyte decreases in the

presence of a strong electrolyte having a common ion.
1. The smaller the value of Ka, the weaker the acid.
2. The criteria for making approximation 1−   1 is decided by first solving
the problem by assuming 1−=1. After solving for , if a  5 percent or
0.05, rework the problem using the quadratic formula.
3. for strong electrolytes Ka approaches to infinity since  approaches unity from
equation (1)
Comparison of strengths of acids and bases: According to the Ostwald’s dilution
K
law, for a monobasic weak acid,α = √ Ca
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 HA Kα1
= √K Or = Strenght of the acid HA1 = √K
α2 α2 2 α2
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
K
• For a weak electrolyte.[H+ ] = Cα = C × √ Cα = √K α . C
• 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 the pK b value,
pK b = − log Kb ) for a base, stronger is the base.
• For a dibasic acid like H2 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 = or [H+ ][OH− ] = K[H2 O]
[H 2 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 𝐊 𝐰

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 + and OH − 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 10−13 10−12 10−11 10−10 10−9 10−8 (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)
[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.

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SESSION – 3AND 4
AIM - To introduce pH scale
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
For any acidic or basic solution, the sum of pH and pOH is equal to 14 and
is referred to as pKw at 298K. pH + pOH = pK w = 14
pH of 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 at 298K
[H + ] [OH − ] pH pOH Nature of solution

10° 10−14 0 14 Strongly acidic
10−2 10−12 2 12 Acidic
10−5 10−9 5 9 Weakly acidic
10−7 10−7 7 7 Neutral
10−9 10−5 9 5 Weakly basic
10−11 10−3 11 3 Basic
10−14 100 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:
• pH has a great importance in agriculture. Soil is often tested to determine
whether acidic or basic fertilizers are required for a particular crop.
• pHvalue plays important role in biological reactions such as digestion of food
etc
• Human blood has pH value of 7.36 – 7.42 A change in pH by 0.2units
results in death.
• pH value plays an important role in qualitative analysis
• 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.
1. Normality of strong acid = [H3 O+ ]
Normality of strong base = [OH − ]
∴ pH = − log[N] for strong acids pOH = − log[N] for strong bases
2. 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., In 10−8N HCl, [H+ ]total = [10−8 ]acid + [10−7 ]water
= 11 × 10−8 M = 1.1 × 10−7 M
3. pH of mixture: Let one litre of an acidic solution of pH2 be 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
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
4 × 10−3 = MR (Here, MR = Resultant molarity)
pH = − log(4 × 10−3 )
N V −N V
N = 1 1 2 2 is pH of mixture of acid base
V1 +V2
N will give [H + ] or [OH − ]depending on equivalents of acid or base
4. 𝐩𝐇 of 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
5. 𝐩𝐇 for 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
Total (H+) conc. = C1 + C2 α
pH = - log [C1 + C2 α]
[H + ][A− ] [C1 + C2 α][C2 α]
K a(HA) = =
[HA] [C2 (1 − α)]
6. pH calculation of solution of a mixture of two weak Acids in water
Let two weak acids be HA and HB and their conc. are C1 and C2 ,α1 is the
degree of dissociation of HA in presence of HB (due to common 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 )
+ −
[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 ]
7. pH of a dibasic Acids and Polyprotic Acid:

Let‘s take the eg. of a dibasic acid H2 A. Assuming both dissociation are
weak. Let the initial conc. of H2 A be C and α1 and α2 be degree of
dissociation for first and second dissociation.
H2 A ⟶ HA− + H+
C(1 − α1 )Cα1 (1 − α2 )Cα1 + Cα1 α2
[HA− ][H+ ]
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 α2 . 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 M HCl (b) 0.0001M NaOH (c) 0.0001M 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
Solution:
a. Mole mass of HCl = 36.5
Concentration of HCl = 0.365
36.5
= 1.0 × 10−2 mol L−1
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)2 is a strong electrolyte and is completely ionized?
Ba(OH)2 ⇌ Ba+2 + 2OH −
One molecule on dissociation furnished 2OH − 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 0.002N acetic acid solution, if it is 2.3%ionized

at a given dilution.
2.3
Solution: Degree of dissociation,𝛼 = 100 = 0.023
Concentration of acetic acid, C = 0.002M
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 50mL of

0.2N HCl with 50mL of 0.1N NaOH.
Solution:- Number of milli-equivalents of the acid = 50 × 0.2 = 10
Number of milli-equivalents of the base = 50 × 0.1 = 5
No, 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, 5milli-equivalents of the acid are present in 100mL of solution
Or 50mili-equivalents of the acid are present in one litre of solution
Or 0.05equivalents of the acid are present in one litre of solution
The acid is monobasic and completely ionized in solution.
0.05N HCl = 0.05M 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 800mL of

0.05N sodium hydroxide and 200mL of 0.1N HCl, assuming the complete ionization
of the acid and the base?
Solution:
Number of milli-equivalents of NaOH = 800 x 0.05 = 40
Number of milli-equivalents of HCl = 200 x 0.1 = 20
No, of milli-equivalents of NaOH left after addition of HCl= (40-20) = 20
Total volume = (200 + 800)mL = 1000mL = 1litre
20milli-equivalents or 0.02equivalents of NaOH are present in one litre i.e.,
0.02N NaOH = 0.02M 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
SESSION –5 AND 6
AIM
✓ To introduce common ion effect
✓ To introduce Buffer Solutions
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 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:
• It has a definite pH, i.e., it has reserve acidity or alkalinity
• Its pH does not change on standing for long.
• Its pH does not change on dilution
• Its pH is slightly changed by the addition small quantity of acid or base.
Buffer solutions can be obtained:
1. 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 phthalate
2. By mixing a weak base with its salt of a strong acid (Basic Buffer)
ex: a) NH4 OH + NH4 Cl
b) Glycine + Glycine hydrochloride
3. By a solution of ampholyte. The ampholytes or amphoteric electrolytes are
the substances which show properties of both an acid and is base.
Ex- Proteins and amino acids.
4. 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− and NH4+ 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 COOH which 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.
2. 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:
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, Ka = [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
…(iii) [Salt]
Taking logarithm and reversing sign,

[Acid]
− log[H + ] = − log K a − log [Salt]
[Salt]
or pH = log
[Acid]
= −logK a
[Salt]
or pH = pK a + log [Acid] This is known as Henderson’s equation
….. (iv)
[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 pK a + 1p Ka − 1.
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 OH molecule, 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 added OH− 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
…….. (ii)
[B+ ]
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)
So, [OH− ] = Kb [Base]
[Salt]
……(iii)
[Salt]
Or pOH = log [Base] − log K b
….…(iv)
[salt]
Or pOH = pK b + log
[Base]
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 has been found that if the ratio
[𝑆𝑎𝑙𝑡 ] [𝑆𝑎𝑙𝑡 ]
[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.,
𝑁𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑜𝑟 𝑏𝑎𝑠𝑒 𝑎𝑑𝑑𝑒𝑑 𝑡𝑜 1 𝑙𝑖𝑡𝑟𝑒
Buffer capacity(𝜙) = 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑝𝐻
Buffer capacity is maximum
• When [Salt] = [Acid], i.e., pH = pK a for acid buffer
• 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−4 , HPO2−
4 )
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.
SESSION–7 AND 8
AIM- To Introduce Salt Hydrolysis
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.
1. Salt of a strong acid and a weak base.
Examples:FeCl3 , CuCl2 , AlCl3 , NH4 Cl, CuSO4, etc.
2. Salt of strong base and a weak acid.

Examples:CH3 COONa, NaCN, NaHCO3 , Na2 CO3 , etc.
3. Salt of a weak acid and a weak base.
Examples:CH3 COONH4 , (NH4 )2 CO3 , NH4 HCO3 etc.
4. 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+ and Cl− 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 + ]
= = 1−ℎ
𝑐 (1−ℎ)
As .h, is very small, 1 – ℎ = 1
kb Kb
∴ ch2 = K b or h2 = or h = √
c c
Kw
Substituting the value of 𝐾ℎ from equation(iv), we get Kh = √
Kb
……(v)
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
Substituting the value of h from equation (v) we get

Kw KwC K w c 1/2
[H + ] = c√ =√ =( )
Kbc Kb Kb
+]
K w c 1/2
∴ pH = − log[H = − log ( )
Kb
1
Or pH = − [logK w − logK b + logc] …..(vi)
2
1
pH = [pK w − pK b − logc]
2
1
pH = 7 − [pK b + logc]
2
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 concen, 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
↓ ↓
Or B + + A− + H2 O ⇌ B + + OH− + HA
Or A− + H2 O ⇌ OH− + HA
i.e., it is a case of anion hydrolysis.
The hydrolysis constantKhfor the above reaction will be given by

[OH− ][HA]
Kh = [A− ]
..(i)
For the weak acid HA, the dissociation equilibrium is:HA ⟶ H+ + A−
∴The dissociation constant 𝐾𝑎 of the acid HA will be given by
[H+ ][A− ]
Ka = [HA]
…… ii)
Further, the ionic product of water, Kw 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) ch ch
The hydrolysis constant (Kh )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 Kh
Ch2 = K h or h2 = or h = √
c c
Substituting the value of 𝐾ℎ from equation (iv), we get h=√

Kw
Ka .c
….(v)
c]pH. In the present case, we have

A− + H2 O ⟶ OH − + HA
Original conc: c 0 0
Conc. at eqm.: c(1-h) ch ch
K Kw
i.e.[OH− ] = ch ∴ [H + ] = [OHw− ] =
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
∴ pH = − log[H + ] = −log√ = − log ( ) or pH
c c
1
= [log K w + log K a − logc]
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 298K, pK w = 14. Hence, at 298K, we havepH = 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
Or CH3 COO− + NH4− + H2 O ⟶ CH3 COOH + NH4 OH
The resultant solution is neutral because the dissociation constant of
CH3 COOHand NH4 OHare equal. When K a = K b , solution will be neutral when
K a > K b solution will be slightly acidic and when K 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
↓
Or B + + 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)
[𝐻+ ][𝐴− ]
For the weak acid, HA H +
+ A −
, so that 𝐾𝑎 = 𝐾𝑎 =
[𝐻𝐴]
…….(ii)
[B+ ][OH+ ]
For the weak base,BOH B+ + OH− , so that Kb = [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− ]
= = (1−h)2 ..….. (vi)
c(1−h).c(1−h)
Here, the relationship between 𝐾ℎ 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 = √ ….… (vii)
Ka .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 = √𝐾ℎ 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 = [log K a + logK w − logK b ]
2
1
or this equation may be written as: pH = [pK w + pK a − pK b ]
2
or at 298K, we have ph = 7
1
ph = 7 + [pK a − pK b ]
2
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,
[H + ] = [OH − ], so the solution is neutral.

Each topic contains

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SESSION – 9
AIM
✓ To solve some numericals on (a)hydrolysis constant and (2)degree of
hydrolysis
✓ To introduce indicators
Solved Examples:
Example 1:
Calculate the hydrolysis constant, degree of hydrolysis and pH of 0.10M
KCN solution at 25°C. For HCN, K a = 6.2 × 10−10 .
Kw 10−14
Solutions: Hydrolysis constant,K h = = = 1.6 × 10−5
Ka 6.2×10−10
Kh 1.6×10−5
Degree of hydrolysis, h=√ =√ = 1.26 × 10−2
c 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 = √K h × c = √(1.6 × 10−5 )(0.1)
[CN − ] c−x c
= 1.26 × 10−3
i.e., [OH − ] = 1.26 × 10−3
+
Kw 10−14
∴ [H ] = −
= −3
= 7.94 × 10−12
[OH ] 1.26 × 10
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 + [pK a + logC].
2
Example 2: Calculate the pH of 0.10M 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 = = = 6.25 × 10−10
Kb 1.6×10−5
The hydrolysis reaction will be NH4+ + H2 O ⟶ NH3 + H3 O+
Or NH4+ ⟶ NH3 + H +
Initial conc. 𝑐
At equ. 𝑐−𝑥 𝑥 𝑥
[NH3 ][H + ] x × x x 2
Kh = = = or x = √K h × c = √(6.25 × 10−10 ) × 0.1
[NH4+ ] c−x c
= 7.9 × 10−6 M
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:pH = 7 + 12 [pK a + logc] = 7 + 12 [−log 1.8 × 10−5 + log 0.1] = 8.87
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. NaClvs 𝐴𝑔𝑁𝑂3 ), complexometric titrations
(involving formation of complexes) but here we shall take up a brief
discussion of acid-base titrations in aqueous solutions only.
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) (Pink)
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 presence of excess 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.
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
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
.
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 change𝑝𝐾𝑖𝑛𝑑𝑖𝑐𝑎𝑡𝑜𝑟 = 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− ]
𝐾𝐼𝑛 =
[𝐻𝐼𝑛]
The exact point of the colour change will be at the pH when [HIn] = [In-].
Substituting this value, we get 𝐾𝐼𝑛 = [𝐻+ ] 𝑜𝑟 − 𝑙𝑜𝑔 𝐾𝐼𝑛 =
− 𝑙𝑜𝑔[𝐻+ ] 𝑖. 𝑒 𝑝𝐾𝑙𝑛 = 𝑝𝐻
Thus, for a particular, titration, the indicator selected should be such for
which𝑝𝐾𝐼𝑛 = 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.𝑝𝐾𝐼𝑛 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)
𝐻𝐼𝑛 and 𝐼𝑛− have different colours. The equilibrium constant is 𝐾𝐼𝑛 =
[𝐻 + ][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
[𝐼𝑛− ] 10
And to see the alkaline colour. [𝐻𝐼𝑛]
= 1
[𝐻𝐼𝑛]
Rearranging eqn. (i) we get [𝐻 + ] =
[𝐼𝑛− ]
𝐾𝐼𝑛
 For acidic colour to be visible, [𝐻+ ] = 10𝐾𝐼𝑛
Or−𝑙𝑜𝑔𝐻 + = 𝑙𝑜𝑔10 − 𝑙𝑜𝑔𝐾𝐼𝑛 𝑖. 𝑒 𝑝𝐻 = 𝑝𝐾𝐼𝑛 + 1
Thus, for colour change of an indicator,𝑝𝐻 = 𝑝𝐾𝐼𝑛 ± 1
i.e., 𝑝𝐻 range for colour change is from 𝑝𝐾𝐼𝑛−1 𝑝𝐾𝐼𝑛 + 1, i.e., a 𝑝𝐻
range of 2 units.
Calculation of 𝑝𝐾𝑎 𝑜𝑟 𝑝𝐾𝑏 values from 𝑝𝐻 of equivalence point
The 𝑝𝐾𝑎 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.

Each topic contains

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SESSION–10 AND 11
AIM
✓ To introduce Solubility and Solubility product
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)
[A+ ][B − ]
K1 =
[AB]
The concentration of AB remains almost constant,

K1 [AB] = Constant
K1 [AB] = [A+ ][B − ] = K sp
This K spis 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
as Ax By ⇄ xAy+ + yB x−
[𝐴 𝑦+ ]𝑥 [𝐵𝑥− ]𝑦
Applying law of mass action, [𝐴𝑥 𝐵𝑦 ]
=𝐾
When the solution is saturate,[Ax By ] = K ′ (constant)
Or [Ay+ ]x [B x− ]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 = K sp , 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
𝐾2 𝐶𝑟𝑂4 solution are mixed, the precipitation of 𝐴𝑔2 𝐶𝑟𝑂4 occurs as the
ionic product exceeds the solubility product of 𝐴𝑔2 𝐶𝑟𝑂4 which is
2 × 10−12 .
In the resulting solution, [Ag + ] = 0.02
2
= 0.01 = 1 × 10−2 M
0.02
And [CrO2− 4 ] = 2 = 0.001 = 1 × 10 M
−2
Ionic product of Ag 2 CrO4 = [Ag + ]2 [CrO2−4 ]

= (1 × 10−2 )2 (1 × 10−2 ) = 1 × 10−6
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+ + yB x−
Thus, solubility product K sp = [Ay+ ]x [B x− ]y
Let the solubility of the salt 𝐴𝑥 𝐵𝑦 in water at a particular temperature
be‘s’ moles per litrethen
Ax By → xAy+ + yB x−
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 = s2
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 , CaCl2etc.
i] AB2 ⇄ A2+ + 2B −
s2s
Let the solubility of AB2be ‘s’ moles per litre
So, K sp = [A2+ ][B − ]2 = s × (2s)2 = 4s3
Ksp
s = 3√
4
ii] A2 B ⇆ 2A+ + B 2−
Let the solubility of 𝐴2 𝐵be ‘s’ moles per litre
K sp = [A+ ]2 [B −2 ] = (2s)2 (s) = 4s 3
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)3 etc.
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
K sp = [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
𝐾𝑠𝑝 = [𝐴+3 ][𝐵−2 ]3
= (2𝑠)2 × (3𝑠)3
= 4𝑠 2 × 27𝑠 3
𝐾𝑠𝑝
𝐾𝑠𝑝 = 108𝑠 5 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 s s
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 = s 2 from equation (1)
s2
Or S1 = 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 NaHCO3from
its saturated solution is done by addition of NH4 HCO3 ,HCO−3 as common ion.
3] In prediction of precipitation in lonic reactions: Precipitation in an ionic

reactions could be predicted by comparing 𝐾𝑠𝑝 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 –
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 −2 ions
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.

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Ionic Equilibrium

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ACTIVE SITE EDUTECH - 9844532971

Degree of ionization for this type of electrolytes is α <<< 1.

Consider the reaction,

Acid- base chart containing some common conjugate acid-base pairs

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

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

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

- In acid-base strength series, all acids above H3 O+ in aqueous solution fall

solvents. On the basis of proton interaction, solvents can be classified into

3. Lewis concept:- According to this concept, a base is defined as a substance

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Degree of Dissociation(): The fraction of the total electrolyte that undergoes

i.e., The degree of ionisation of an electrolyte decreases in the

Ionic Product of water:

Temperature (°𝐂) Value of 𝐊 𝐰

[H + ] = 10−0 10−1 10−2 10−3 10−4 10−5 10−6 (Acidic)

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For neutral solution; pH = pOH = 7 at 298K.

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

Calculation of 𝐩𝐇 of Solutions: - Any method which can measure the concentration

2. Sometimes, pH of acidto base becomes very close to that of 7. It shows that

[H + ] = Cα; ∴ pH = − log10 [Cα]

5. 𝐩𝐇 for the mixture of Weak Acid and Strong Acid

7. pH of a dibasic Acids and Polyprotic Acid:

After solving for α1 and α2 . We can calculate the H+ conc.

One molecule of H2 SO4 furnishes 2H + ions.

Example 2: Calculate the pH of the following solutions assuming complete

Example 3:- Find the pH of a 0.002N acetic acid solution, if it is 2.3%ionized

Example 4:- Calculate the pH value of a solution obtained by mixing 50mL of

Example 5:- What will be the pH of a solution obtained by mixing 800mL of

Example 6:- What is the hydrogen ion concentration of solution

The equilibrium constant, K, has a definite value at any given temperature.

Explanation of Buffer Action

Calculation of pH of Acidic Buffer

Taking logarithm and reversing sign,

Calculation of pH of a Basic Buffer :

As the salt is completely ionized, it can be assumed that whole of B + ion

Knowing pOH, pH can be calculated by the application of the formula,

Applications of Buffer Solutions:

Buffers are used in industrial processes such as manufacture of paper, dyes,

2. Salt of strong base and a weak acid.

1] Salt of a strong acid and a weak base:

b] Degree of Hydrolysis, suppose the original concentration of the salt in the

c] 𝐩𝐇. In this case we have B + + H2 O ⇌ BOH + H+

Substituting the value of h from equation (v) we get

2] Salt of a weak acid and a strong base

The hydrolysis constantKhfor the above reaction will be given by

b]Degree of Hydrolysis. Suppose the original concentration of the salt in the

Substituting the value of 𝐾ℎ from equation (iv), we get h=√

c]pH. In the present case, we have

Substituting the value of h from equation (v), we get

3] Salt of Weak acid and a weak base:

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

4] Salt of a strong acid and a strong base:

Or Na+ + Cl− + H2 O ⟶ Na+ + OH− + H+ + Cl−

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The hydrolysis reaction will be:

Alternatively, pH can be calculated directly by applying the formula,

Example 2: Calculate the pH of 0.10M solution of NH4 Cl . The dissociation

THEORY OF ACID-BASE INDICATORS (OSTWALD’S THEORY)