I

O
N
I
C
E
Q
U
I
L
I
B
R
I
U
M
I
N
S
O
L
U
T
I
O
N
S
Michael Faraday(1824) classified Substances into
Electrolytes and non-Electrolytes on the basis of
Conductivity behavior of their aqueous solutions. The
substances which conduct electricity in their aqueous
solutions were termed as Electrolytes. Examples NaCl,
H2SO4
Those substances which do not conduct electricity in their
aqueous solutions are termed as Non-Electrolytes.
Examples:- Sugar, Urea etc.
• SVANTE ARRHENIUS (1880) explained that Electrolyte,
when dissolved in water split into charged particles
called IONS. This process is called Ionization or
Dissociation.
• Certain Electrolytes , such as NaCl, KCl, HCl are almost
completely ionized in solutions whereas electrolytes
such as NH4OH, CH3COOH are weakly ionized .

• The Electrolytes which are almost completely ionized in

solutions are called STRONG Electrolytes. On the other
hand , the electrolytes weakly ionized in their solutions
are called WEAK Electrolytes.
• In case of weak electrolytes, the ions produced by
dissociation of electrolytes are in equilibrium with
undissociated molecules of the Electrolyte.
Dissociation of Strong Electrolytes given by NaCl
(aq) Na+ (aq) + Cl- (aq)
NH4Cl (aq) NH4 +(aq) + Cl – (aq)
• Dissociation of Weak Electrolytes are written with
double arrows (⇌ )
 CH3COOH(aq) + H2O (l) ⇌ CH3COO – (aq)+ H3O + (aq)

This type of equilibrium involving ions in aqueous solution

is called Ionic Equilibrium.
Electrolytes may be Acids, bases or Salts.

Acids are Sour in taste. Vinegar contains Acetic acid

whereas Citrous fruits such as Orange, lemon etc contain
Citric acid. Tamarind contains Tartaric acid. Acids turn blue
litmus paper Red.

Bases are bitter in taste. They turn Red litmus paper Blue.
Caustic Soda (NaOH), Washing Soda (Na2CO3.10 H2O ) and
aqueous Ammonia are commonly used Bases.

Salts are made up of oppositely charged ions. In Solid

state they are held by strong electrostatic forces of
 attraction. When a Salt is dissolved in water the attractive
forces between the ions are highly weakened
• This is due to the reason that the electrostatic forces are
inversely proportional to the Dielectric constant of the
medium and water has high Dielectric constant of 80 .
And this facilitates the free movement of ions in the
solutions. The ions, in solution are further stabilised by their
Solvation with water molecules. Water molecules being
polar molecules can have ion-dipole interactions with ions
of the salt. Thus ionic compounds get dissociated when
dissolved in water.
• Substances like polar molecules HCl, CH3COOH , HCN
etc. When dissolved in water ionize due to dipole-dipole
interaction between molecules of water and the polar
molecules of the substance.
• The term Dissociation refers to the process of separation
of ions in water in case of Ionic compounds
• Whereas the term Ionization is used in cases where a
molecule splits into ions when dissolved in water.
 IONIZATION OF WEAK ELECTROLYTES

Weak Electrolytes are ionized only partially. The ions

produced as a result of dissociation of weak electrolytes
are present in Dynamic equilibrium with the undissociated
molecules .

The fraction of total total number of molecules of

electrolyte dissolved, that ionizes at equilibrium is called
degree of ionization or dissociation.

3
 ARRHENIUS CONCEPT OF ACIDS & BASES
According to Arrhenius concept ,
An Acid is a substance which can furnish hydrogen ions in
its aqueous solution.
A Base is a substance which can furnish hydroxyl ions in its
aqueous solution.
For example, substances such as HNO3 , HCl, CH3COOH
are Acids whereas NaOH, KOH NH4OH are Bases,
According to this concept,
HNO3 (aq) ⇌ H+(aq) + NO3 – (aq)
HCl (aq) ⇌ H+ (aq) + Cl – (aq)
CH3COOH (aq) ⇌ H+ (aq) + CH3COO – (aq) NaOH
(aq) ⇌ Na + (aq) + OH – (aq)
KOH (aq) ⇌ K + (aq) + OH – (aq)
NH4OH (aq) ⇌ NH4 + (aq) + OH – (aq)
 ARRHENIUS CONCEPT OF ACIDS & BASES
Acids such as HNO3, HCl which are almost completely
ionised in aqueous solution are termed as Strong Acids
whereas acids such as CH3COOH which are weakly ionised
and are called weak acids. Similarly , Bases which are almost
completely ionised in aqueous solution are termed as Strong
Bases, for example NaOH, KOH. whereas Bases such as
NH4OH which are weakly ionised and are called weak
bases.
According to Arrhenius theory, Neutralisation of Acids and
bases is basically a reaction between H + and OH – ions in
solutions.
H+ (aq) + OH – (aq) ⇌ H2O (l)
 Nature of Hydrogen ion & Hydroxyl ion in Aq. Solution
Hydrogen atom contains one proton and one electron. H+ ion
is formed by loss of this electron. Hence H+ ion is simply
proton. Charge density of this unshielded proton is very
high. Therefore, it is not likely to exist independently as H +
ion . In an aqueous solution H+ ion is considered
present in hydrated form in combination with a water
molecule as H3O + .
H+ + H2O 🡪 H3O + .

H3O + ion is called Hydronium ion.

BRONSTED – LOWRY CONCEPT OF
ACIDS & BASES
proposed new definitions for Acids and Bases. They proposed that :
An Acid is a substance that can donate a proton. In 1923, a Danish
Chemist J.H.Bronsted and an English chemist T.M. Lowry
independently
 A Base is a substance that can accept a proton.
These definitions are more general because , even ions can behave
as acids and bases ,according to these definitions.
Moreover, these definitions are not restricted to reactions taking place
in aqueous solution only. Consider some examples.

HCl (aq) + H2O (l) ⇌ H3O + (aq) +

Cl – (aq)

NH4 + (aq) + H2O (l) ⇌ H3O + (aq) + NH 3 (aq)

H2O (l) + NH3 (aq) ⇌ NH 4 + (aq) + OH- (aq)

H2O (l) + CO 3 -2 (aq) ⇌ HCO3 – (aq) + OH – (aq)
Acid Base
From the above equations, it is obvious that acid base reactions
involve transfer of proton from the Acid to Base . A substance
can act as an Acid only if another substance capable of accepting
a proton, is present.

Conjugate acid – base pairs :

 An Acid after losing a proton becomes a Base whereas
Base after accepting the proton becomes an Acid.
Let us consider an example , the reaction between Water &
Ammonia represented by the following equilibrium :
H2O (l) + NH3(aq) ⇌ NH4 + (aq) + OH - (aq)
Acid 1 Base 2 Acid 2 Base 1
In the forward reaction , water donates a proton to Ammonia
(Base ) and acts as an Acid. In the reverse reaction , NH4 + ions
donate a proton to the OH – ions (Base) and acts as an Acid.
A Base formed by the loss of proton by an acid is called
Conjugate Base of the acid whereas an Acid formed by gain of a
proton by the base is called Conjugate Acid of the Base.
In the above example , OH – is the Conjugate Base of H2O and
NH4 + is conjugate acid of NH3 .

Acid-Base pairs such as H2O / OH – and NH4 + / NH3 which

are formed by loss or gain of proton are called

Conjugate Acid-Base Pairs. A strong Acid would have large
tendency to donate a proton . Thus , Conjugate base of a strong
Acid would be a weak base. Similarly , Conjugate base of a
weak Acid would be a Strong Base. Some more examples :
CH3COOH (aq) + H2O (l) ⇌ H3O + (aq) + CH3COO - (aq)
H2O (l) + CO3 -2 (aq) ⇌ HCO3 –(aq) + OH – (aq)
It may be noticed that H2O is behaving as a Base and an Acid
in the above reactions . Such substances which can act as
Acid s as well as Bases are called AMPHOTERC substances.
LEWIS ACIDS AND BASES
Although Bronsted –Lowry theory was more general than
Arrhenius theory of Acids and Bases but it failed to explain the
acid base reactions which do not involve transfer of proton.
For example it fails to explain how acidic oxides such as
anhydrides CO2 , SO2 , SO3 etc ., neutralise basic oxides such
as CaO , BaO etc., even in the absence of Solvent.
G.N.LEWIS (1923) proposed broader and more general
definitions of acids and bases , which do not require the
presence of protons to explain the acid base behaviour.
According to Lewis Concept ,
An Acid is a substance which can accept a pair of electrons.
A Base is a substance which can donate a pair of electrons.
Acid- Base reactions according to this concept involve
donation of electron pair by a Base to an Acid to form a Co-
ordinate bond. Lewis bases can be neutral molecules

such as :NHunshared pairs of electrons , or anions such

as CN3 , CH3O:H , H2O: etc ., having one or more - , OH
-
, Cl - etc.,

Lewis acids are the species having vacant orbitals in the

valence shell of one of its atoms. The following species
can act as Lewis acids.
 • Molecules having an atom with incomplete Octet . For eg.
BF3 , AlCl3
H3N : + BF3 🡪 H3N : BF3 Cl -
+ AlCl 3 🡪 Cl : AlCl3 (or ) (AlCl 4 )-
* Simple cations : For example, H + , Ag + , etc., H2O:
+H+ 🡪 [H3O ] +
* Molecules in which central atom has vacant orbitals and
may acquire more than an OCTET of valence electrons.
For example SiF4
SiF4 + 2 F - ______. [Si F6] -2

Molecules containing multiple bonds . For example CO+2 + [O]2- +

CO2 🡪 [Ca]+2 [CO3]2- 2SO2
[Ca]
et
LIMITATIONS OF LEWIS CONCEPT :

1. It is too general and includes all the Coordination compounds and

co-ordination reactions.

2. It does not help to assign the relative strengths of Acids

and bases.
3. It does not explain the behavior of protonic acids such as
HCl , H2SO4 etc, which do not form co-ordinate bond with
bases which is the primary requirement of this theory.
4. Normally, formation of Co-ordination compounds is
slow. Therefore Acid-Base reactions should also be slow,
but in actual practice , acid- Base reactions are
extremely fast.

5. The Catalytic activity of many acids is due to H +(aq)

ions .

Since a Lewis Acid need not contain Hydrogen , many

Lewis acids will not possess Catalytic property.
 IONIZATION OF ACIDS AND BASES
According to Arrhenius theory strong acids and Strong
+
Bases are able to completely dissociate and produce H &
OH – ions respectively in the medium .
According to Bronsted - Lowry concept of Acids and Bases
, the strength of an acid is measured in terms of its tendency
to lose proton whereas strength of a Base is measured in
terms of its tendency to accept proton. The conjugate base
of a strong Acid is a weak Base.
HCl (aq) + H2O (l) 🡪 H3O + (aq) + Cl – (aq)
Strong Acid Weak Base

CH3COOH (aq) + H2O (l) 🡪 H3O + (aq) + CH3COO – (aq)

Weak Acid Strong Base
A Base is considered as Strong if it has great tendency to
accept a proton. Therefore , Conjugate acid of strong base
has little tendency to lose proton and hence is a weak
Acid.
CH3COOH (aq) + OH – (aq) ⇌ H 2O (l)+ + CH3COO – (aq)
strong Base weak acid
On the other hand , Conjugate acid of a weak base is a
Strong Acid.
HCl (aq) + H 2O ( l) ⇌ H3O + (aq) + Cl – (aq)
Weak Base strong Acid
The strength of acids or Bases is experimentally
measured by determining its Ionization constants or
dissociation constants.
IONIZATION CONSTANTS OF WATER
Some substances like water are unique in their ability
of acting both as an acid and a base. In the presence of
an Acid, HA it accepts a proton and acts as the base
while in the presence of a Base, B- it acts as an Acid
 by donating a proton. In pure Water , one H2O molecule
donates proton and acts as an Acid and another water
molecule accepts a proton and acts as a Base at the
same time.
The following equilibrium exists :
H2O(l) + H2O(l) ⇌ H3O + (aq) + OH – (aq)
Acid Base C.A C.B
The dissociation constant is represented by
K = [H3O +] [OH – ] / [H2O]
The concentration of water is omitted from the denominator as
water is a pure liquid and its concentration remains constant.
[H O] is incorporated within the equilibrium constant to give a
2

new constant . KW which is called the IONIC PRODUCT OF

WATER.
KW = [ H+] [ OH-]
The concentration of H+ has been found to be experimentally
1.0 X 10 -7 M at 298 K. And , as dissociation of water produces
equal number of H+ and OH- ions , the concentration of
[OH-] = [ H+] = 1.0 X 10 -7 M . Thus , the value of KW at 298 K
,
KW = [H3O + ] [ OH-] = (1.0 X 10 -7 ) 2 M 2
The value of KW is temperature dependent as it is an
equilibrium constant. The density of pure water is 1000 g/L
and its molar mass is 18 g/mol. From this the molarity of water
can be given as [H 2O ] = (1000g/L)(1mol/18 g) = 55.55 M
Therefore, the ratio of dissociated water to that of
un dissociated water can be given as :
10 -7 / (55.55) = 1.8 x 10 -9 (or) 2 x 10 -9 ,
( Thus equilibrium lies mainly towards un dissociated
water)
 We can distinguish Acidic, neutral and Basic aqueous
solutions by the relative values of the [H3O + ] & [ OH-]
concentrations:

Acidic : [H3O + ] > [ OH-]

neutral : [H3O + ] = [ OH-]
Basic : [H3O + ] < [ OH-]
THE PH SCALE
Hydronium ion Concentration in Molarity is more
conveniently expressed on a logarithmic scale known as
pH scale. It is defined as the negative logarithm to base of
10 of the activity (aH+)of Hydrogen ion.
In dilute solutions(,0.01M), activity of H + ion is equal in
magnitude to Molarity represented by [H + ] . It should be
noted that activity has no units and is defined as :
(a H+) = [H + ] / mol l-
 From the above definition of pH , the following can be
written , pH = - log a H+ = - log {[H + ] / mol l- }
Thus in acidic solution of HCl [ 10 -2 M] will have pH=2.
Similarly, a basic solution of NaOH having [ OH- ]= 10-4 M
pure water has a concentration of Hydrogen ions , [H and
[ H3O +] = 10 -10 M will have a pH of 10. At 25 0 C , +] =
10 -7 M.
Hence pH of pure water is given as : pH = -log (10 -7 )= 7
Acidic solutions possess a concentration of Hydrogen ions
[H+] > 10 -7 M , while Basic solutions possess a
concentration of Hydrogen ions [H+] < 10 -7 M. Thus we
can summarise that
Acidic solution has PH < 7
neutral solutions has pH = 7
Basic solution has PH > 7
Ionic product of Water, Kw = - log {[ H3O +] [ OH- ]}
 = - log [ H3O +] - log [ OH- ] = -log 10 -14 pKw
= pH + pOH = 14
Although Kw may change with temperature the variations
in pH with temperature are so small that we often ignore it.
 APPLICATION OF PH :
The pH scale is logarithmic, a change in pH by just one
unit also means change in [H+] by a factor of 10, similarly
, when the hydrogen ion concentration, [H +] a factor of
100, the value of pH changes by 2 units.
Measurement of pH of a solution is very essential as its
value should be known when dealing with Biological and
Cosmetic applications. The pH of a solution can be found
roughly with the help of pH paper that has different colour
in solutions of different pH. Now -a-days pH paper is
available with four strips on it. The different strips have
different colours at the same pH. The pH in the range of
1-14 can be determined with an accuracy of 0.5(approx)
using pH paper.

For great accuracy pH meters are used. pH meter is a

device that measures the pH-dependent electrical
potential of the test solution within 0.001 precision. pH
meters of the size of a writing pen are now available in
the market.
 IONISATION CONSTANT OF WEAK Acids
The ionisation of weak acidHX can be represented by the
equation : HX (aq) + H2O (l) ===== H3O +(aq) + X–(aq)
Ionisation constant of acid HX can be represented as :
Ka = [H+] [X-] / [HX]
At a given temperature T, Ka is a measure of the strength of
the acid HX i.e., larger the value of Ka , the stronger is the acid.

K
a is a dimensionless quantity with the understanding that

the standard state concentration of all species is 1 M.

pKa = - log (K a )
Knowing the K a value of an acid and its initial concentration, c It
is possible to calculate the equilibrium concentration of all the
species and also the degree of dissociation of the acid and the
pH of the solution.
Ionisation constant of weak base
The ionisation of weak base MOH can be represented by
the equation : MOH (aq) ⇌ M +(aq) + OH–(aq)
In a weak Base there is partial ionisation of MOH into M +
& OH– , the cse is similar to that of acid- dissociation
equilibrium. This equilibrium constant for base ionisation is
called Base ionisation constant and is represented by Kb. It
can be represented in terms of concentration in Molarity of
various species in equilibrium by the following equation :
K b = [ M + ] [ OH– ] / [MOH ] , Alternatively if c = initial
concentration of base and @ = degree of ionization of base
.
when equilibrium is reached , the equilibrium constant can
be written as : K b = (c @)2/ c (1-@) = C@2/(1-@ )
Many organic compounds like Amines are weak bases.
Amines are derivatives of Ammonia in which one or more
hydrogen atoms are replaced by another group. For
example , Methylamine , Codeine, quinine and Nicotine all
behave as very weak bases due to their small Kb value.

Ammonia produces OH – in aqueous solution :

NH3 (aq) + H2O (l) ⇌ NH4 + (aq) + OH – (aq)

The pH scale for the Hydrogen ion concentration has been
extended to get : p K b = - log (K b )
RELATION BETWEEN K a & Kb
K a & Kb represent the strength of an acid & base
respectively. In case of a conjugate Acid-base pair , they
are related in a simple manner so that if one is known, the
other can be deduced. Considering the example of NH 4 +
 and NH3
NH4 + (aq) + H2O (l) ⇌ H3O + (aq) + NH3(aq)
K a = [H3O +] [ NH3 ]/ [NH4+ ] [H2O] = 5.6 X 10 -10
NH3(aq) + H2O (l) ⇌ NH4 + (aq) + OH –(aq)
Kb = [NH4+ ] [ OH – ]/ [NH3] [ H2O] = 1.8 X 10 -5
Net : 2 H2O (l) ⇌ H3O + (aq) + OH –(aq)
Kw = [H3O + ][ OH –] = 1.0 X 10 -14 M
Where Kw represents the strength of NH4 + as an acid and

Kb represents the strength of NH3 as a base.

It can be seen that the net reaction that the equilibrium
constant is equal to the product of equilibrium constants
K a & Kb for the reactions added. Thus ,
K a X Kb = [H3O +] [ NH3 ]/ [NH4+ ] X [NH4+ ] [ OH – ]/ [NH3]
 = [H3O + ][ OH –] = Kw
=(5.6 X 10 -10 ) X (1.8 X 10 -5 ) = 1.0 X 10 -14 M This
can be extended to make a generalization.
“ The equilibrium constant for a net reaction obtained after
adding two (or more) reactions equals the product of the
equilibrium constants for individual reactions :
K NET = K1 X K2 X………
Similarly in case of a conjugate acid-base pair :
K a X K b = Kw , p K
a + p Kb = Kw = 14

DI- and Polybasic acids and Di- Polyacidic bases

Some of the acids like Oxalic acid, Sulphuric acid and

Phosphoric acids have more than one ionisable proton per
molecule of the acid. Such acids are known as Polybasic or
polyprotic acids. The ionisation reactions for example for a
dibasic acid H2X are represented by the equations :
 H2X(aq) ⇌ H + (aq) +H X- (aq)
H X- (aq) ⇌ H + (aq) + X- (aq)
And the corresponding equilibrium constants are :
Ka1 = [H + ][H X- ] / [H2X ]
Ka2 = [H + ] [X- ]/ [ H X- ]

&K
Where Ka1 a2 are called first and second ionisation
constants respectively of the acid H2X. For the tribasic acid
Like H3PO4 we have three ionisation constants.
It can be seen that higher order ionisation constants
(Ka2 & Ka3 ) are smaller than the lower order ionisation
constant(Ka1 ) of a polyprotic acid . Because it is more difficult
to remove a positively charged proton from a negative ion
Due to electrostatic forces. One more example is H2CO3 .

FACTORS AFFECTING ACID STRENGTH

 Broadly speaking the extent of dissociation of an acid
depends upon the Strength and Polarity of the H-A bond.

In general, when strength of H-A bond decreases, i.e ., the

energy required to break the bond decreases. HA becomes
a Stronger acid. Also when the H-A bond becomes more
polar i.e., the electronegativity difference between the atoms
H and A increases and there is marked charge separation,
cleavage of the bond becomes easier thereby increasing the
acidity.
But It should be noted that while comparing elements in
the same group of the periodic table , H-A bond strength is
more important factor in determining acidity than its polar
nature. As the size of A increases down the group , H-A
bond strength decreases and so the acid strength
increases. For eg.,
Size increases
-----------------------------🡪
HF << HCl << HBr << HI
 -------------------------------🡪
Acid strength increases

Similarly , H2S is stronger than H2O .As the

electronegativity of A increases , the strength of the acid
also increases.
Electronegativity of A increases
--------------------------------------🡪
CH4 < NH3 < H2O < HF
------------------------------------🡪
Acid strength increases
COMMON ION EFFECT IN THE IONISATION OF
ACIDS & BASES
• Consider an example of Acetic acid dissociation equilibrium
represented as :
CH3COOH (aq) ⇌ H +(aq) + CH3COO –(aq)
or H Ac (aq) ⇌ H +(aq) + Ac -(aq) K a = [H
+] [Ac - ]/ [H Ac ]
Addition of of acetate ions to an Acetic acid solution results in
decreasing the concentration of Hydrogen ions , [H +] . Also , if
H + ions are added from an external source then the equilibrium
moves in the direction of undissociated Acetic acid i.e ., in a
direction of reducing the concentration of H + ions.

This phenomenon is an example of Common ion Effect . It

can be defined as a shift in equilibrium on adding a substance
that provides more of an ionic species already present in the
dissociation equilibrium. This is based on the Le Chatelier’s
principle.
HYDROLYSIS OF SALTS & The PH of their solutions
Salts are formed by the reactions between acids and
bases in definite proportions , undergo ionization in water.
The cations/ anions formed on ionisation of salts either
exist as hydrated ions in aqueous solutions or interact with
water to reform corresponding acids/bases.
 The process of interaction between water and cations/
anions or both os salts is called Hydrolysis. The pH of the
solution gets affected by the interaction. The Cations of
Strong bases (eg., Na +,K+, Ca+2 , Ba +2 etc ) and Anions
(eg., Cl-,Br -, NO3- ,ClO4 – etc ) of Strong acids simply get
hydrated but do not hydrolyse, and therefore the solutions
of salts formed Strong acids and bases are neutral. i.e their
pH is 7.
Consider the hydrolysis of salts of the following types :

1. Salts of Weak acid and strong base e.g., CH3COONa In the first
case, Strong base NaOH gets completely ionised in aqueous
solution. Acetate ion thus formed undergo hydrolysis in water to
give Acetic acid and OH- ions .

CH3COONa (aq) ----------🡪 CH3COO - (aq) + Na + (aq)

CH3COO - (aq) + H2O (l) ⇌ CH3COOH(aq) + OH- (aq)
2. Salts of Strong acid and Weak base e.g., NH4Cl
Acetic acid being a weak acid remains mainly unionised in solution.
This results in increase of OH- ion concentration in solution making it
Alkaline. Hence pH of the solution is > 7
NH4Cl (aq) -----🡪 NH4 +(aq) + Cl -(aq)
Ammonium ion undergo hydrolysis in water to form NH4OH & H +
NH4 +(aq) + H2O (l) ⇌ NH4OH (aq) + H + (aq)
3. Salts of Weak acid and Weak base
e.g., CH3COONH4
Similarly NH4Cl in which strong acid HCl ,in water dissociates
Completely

Ammonium hydroxide being weak base ,hence remains almost

unionised in solution. This results in increased H + ion concentration
making the solution acidic. Thus the pH of NH4Cl solution in water
becomes < 7.

Consider the hydrolysis of CH3COONH4 , the ions formed undergo

hydrolysis as follows :
CH3COO - + NH4 + + H2O ⇌ CH3COOH + NH4OH
Both the products above ,also remain into partially dissociated form :
CH3COOH ⇌ CH3COO - + H +
NH4OH ⇌ NH4 + + OH -
H
2O ⇌ H + + OH -

Degree of hydrolysis is independent of concentration of solution, and

pH of such solutions is determined by their pK values : pH = 7 + ½
(pKa –pKb ).
The pH >7 if the difference is positive and it will be < 7 if the difference
is negative.
BUFFER SOLUTIONS
• Many body fluids e.g., blood or urine have definite pH
and any deviation in their pH indicates malfunctioning of
the body.
• The control of pH is also very important in many chemical
and Biochemical processes. Many chemical and cosmetic
formulations require that these be kept and administered
 at a particular pH. “ The solutions which resist change
in pH on dilution or with the addition of small
amounts of acid or alkali are called BUFFER Solutions
”. Buffer solutions of known pH can be prepared from the
knowledge of pKa of the acid or pKb of the base and by
controlling the ratio of the salt
• And acid or salt and base. A mixture of Acetic acid and
Sodiumacetate (pH = 4.75) acts as Buffer solution while a
mixture of NH4Cl & NH4OH acts as a buffer (pH= 9.25).
SOLUBILITY EQUILIBRIA OF SPARINGLY
SOLUBLE SALTS

The solubility of Ionic solids in water varies a great deal. For

e.g., Calcium Chloride ,so soluble that they are hygroscopic in
nature and even absorb water from atmosphere. Lithium
fluoride have so little solubility that they are commonly termed
as insoluble . The solubility depends on a number of factors in
which Lattice enthalpy of the salt and Solvation enthalpy of the
ions in a solution. For a salt to dissolve in a solvent the strong
forces of attraction between its ions (Lattice Enthalpy) must be
overcome by the ion- solvent interactions.
SOLUBILITY EQUILIBRIA OF SPARINGLY
SOLUBLE SALTS
The solvation enthalpy of ions is referred to in terms of
solvation which is always negative. This depends upon the
nature of the solvent. In case of a non-polar solvent, solvation
enthalpy is small and hence , not sufficient to overcome
Lattice Enthalpy of the salt. Consequently , the salt does not
dissolve in non-polar solvent. As a general rule, for a salt to be
dissolved in a particular solvent , its solvation enthalpy must
be greater than its Lattice Enthalpy. Each salt has its
characteristic solubility which depends on temperature. Salts
are classified on the basis of solubility into three categories :
namely Soluble, Slightly soluble & sparingly soluble where
Solublity values are 0.1 M ,
• 0.01 M < Solubility <0.1 M , < 0.01 M respectively.
SOLUBILITY PRODUCT
• Consider Solid like Barium Sulphate in contact with
its saturated aqueous solution . The equilibrium
between
• The undisolved solid and the ions in a saturated
solution can be represented by the equation :
Ba SO4 (s) ⇌ Ba+2(aq) + SO4 -2 (aq)
• The equilibrium constant is given by the equation :
K = {[Ba+2 ] [SO4 -2 ]} / [Ba SO4 ]
• For a pure solid substance the concentration
remains constant and we can write
K sp = K [Ba SO4 ] = [Ba+2 ] [SO4 -2 ] ,

where K
sp the Solubility Product Constant or simply solubility
product

• The experimental value of K sp at 298 K is 1.1 x 10 -

10

• For Solid BaSO4 , in equilibrium with its saturated

solution, the product of the concentrations of
Barium and sulphate ions is equal to its Solubility
Constant. The concentrations of the two ions will be
equal to the Molar Solubility of BaSO4
• If Molar solubility is S , then 1.1 x 10 -10 = (s) (s) = S
2

• or S = 1.05 X 10 -5
• A salt may give on dissociation two or more than
two anions and cations carrying different charges.
For example Zirconium Phosphate [ Zr +4]3[PO4 -3]4
. It dissociates into 3 Zirconium cations of charge
+4 and 4 phosphate anions of charge -3. If the
 Molar solubility of Zirconium Phosphate is S. Then
it can be seen from the
Stoichiometry of the compound that [ Zr +4] = 3 S and
[PO4 -3] = 4 S
• and K sp = (3s)3 x (4S)4 = 6912 S 7
• S = {K sp / { 3 3 X 4 4} 1/7 = {K sp / 6912} 1/7
• A Solid salt of the general formula Mx+p X y –q with
Molar solubility S in equilibrium with its saturated
solution may be represented by the equation :

MxXy ⇌ x M p+ + yX q- where x(p+) = y(q-)

And its Solubility product constant is given by
Ksp = [M p+]x [X q-]y = (xS)x (yS)y = X x .Yy . S (x+y)
S (x+y) = Ksp / X x .Yy

The term Ksp is given by Q sp

 Under equilibrium conditions , Ksp = Q sp but otherwise it
gives the direction of the processes of precipitation or
dissolution.
COMMON ION EFFECT
It is expected from le-Chatelier’s principle that if we increase
the concentration of any one of the ions , it should combine
with the ion of its opposite charge and some of the salt will be
precipitated till once again Ksp = Q sp .Similarly , if the
concentration of one of the ions is decreased , more salt will
dissolve to increase the concentration of both the ions till once
again Ksp = Q sp .

This is applicable even to soluble salts like Sodium Chloride

except that due to higher concentrations of the ions , we use
their activities instead of their Molarities in the expression for
Ksp .
 COMMON ION EFFECT
Thus if we take a saturated solution of NaCl and pass HCl gas
through it , then NaCl is precipitated due to increased
concentration of chloride ion available from the dissociation of
HCl. Sodium chloride thus obtained is of very high purity and
we can get rid of impurities like Sodium and Magnesium
Sulphates.

The common ion effect is also useful for almost complete

precipitation of a particular ion as its sparingly soluble salt
with a very low value of solubility product for gravimetric
estimation. Thus we can precipitate Silver ion as Silver
Chloride, Ferric ion as its hydroxide and Barium ion as its
sulphate for quantitative estimations.