CHEMICAL EQUILIBRIUM

(I) Types of chemical reactions:

Irreversible reactions Reversible reactions
The reactions which move in one direction and The chemical reactions which
reach to completion are called irreversible take place in both forward &
reactions or unidirectional reactions. backward directions and do not
Examples: reach to completion are called
(i) Acid-base neutralisation reactions: reversible reactions. Examples:
HCl + NaOH → NaCl + H 2O (i) 2 N2 ( g ) + 3H 2 ( g ) ƒ 2 NH3 ( g )
(ii) Precipitaiton reactions: (ii) 2SO2 ( g ) + O2 ( g ) ƒ 2SO3 ( g )
AgNO3 (aq) + NaCl (aq) → AgCl (s) + NaNO3 (aq) (iii) N2 ( g ) + O2 ( g ) ƒ 2 NO( g )
BaCl2 (aq) + H 2 SO4 (aq) → BaSO4 (s) + 2HCl (aq)
(iv) CaCO3 (s) ƒ CaO(s) + CO2 ( g )
(iii) Decomposition reactions:
 {In a closed vessel}
CaCO3 (s) ⎯⎯⎯⎯⎯
In an open → CaO(s) + CO ( g )
vessel
2
(v)
NH 4 HS ( s) ƒ NH 3 ( g ) + H 2 S ( g )
(iv) Redox and combustion reactions:
SnCl2 + 2 FeCl3 → SnCl4 + 2 FeCl2
2Mg + O2 → 2MgO
State of chemical equilibrium:
When the reactants in a closed vessel at a particular temperature react to give
products, the concentrations of the reactants keep on decreasing, while those of
products keep on increasing for some time after which there is no change in the
concentrations of either of the reactants or products. This stage of the system is the
dynamic equilibrium or equilibrium state and the rates of the forward and
reverse reactions become equal. The mixture of reactants and products in the
equilibrium state is called an equilibrium mixture.

(II) Equilibrium in physical processes:

1

Physical Process;
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Example
1 It exists in closed vessel at its fixed melting point and one
atm (1.013 bar) pressure. If there is no exchange of heat
Solid Liquid ;
with the surroundings, the mass of the two phases remains
H2O(s) H2O(l ) constant.
 2 It exists in closed vessel at its fixed boiling point and one
Liquid Vapour; atm (1.013 bar) pressure. Vapour pressure of system is
H2O(l ) H 2O(g) constant at given temperature.
3 Solid Vapour ; It exists in closed vessel at its sublimation temperature.
I2 (s) I2 (vapour) NH 4Cl (s) NH4Cl (vapour)
Camphor(s) Camphor(V)

4 Solute (s) Solute In a saturated solution of solid in liquid, dynamic

(Solution); equilibrium present between undissolved solute and
Aq
Sugar(s) Sugar(aq) dissolved solute. Concentration of solute in solution is
constant at a given temperature.
5 For dissolution of gas in liquid, the concentration of gas
in liquid is proportional to the pressure of the gas over the
liquid. Henry’s law states that the mass of a gas
dissolved in a given mass of a solvent at any
temperature is proportional to the pressure of the gas
Solute(g) Solute above the solvent. m p  m = kp
(Solution) ;
Aq. Where, K is Henry’s law constant and depends upon the
CO2 (g) CO2 (aq) temperature. Thus, the amount of dissolved gas decreases
with increase of temperature.

(III) General characteristics of equilibrium:

(i) Equilibrium is possible only in a closed system at a given temperature.
(ii) Equilibrium is dynamic in nature, i.e., both the opposing processes (forward
and backward) occur at the same rate. (iii) At equilibrium, all the measurable
properties of the system remain constant. (iv) Equilibrium can be attained by either
of the side.
(v) When equilibrium is attained for a physical process, it is characterized by
equilibrium constant. (vi) The magnitude of equilibrium constant represents the
extent to which the reaction has proceeded before reaching equilibrium.

(IV) Types of chemical equilibria:

(A) Homogenous equilibria: If the physical states of the participating substances
i.e., reactants and products are same then the equilibria is called homogenous
equilibria. e.g.(i) N2(g)+3H2(g) 2NH3(g) (ii) H 2 ( g ) + I 2 ( g ) ƒ 2HI ( g )
2

(iii) 2SO2 ( g ) + O2 ( g ) ƒ 2SO3 ( g )

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(iv) CH3COOC2H5(aq) + H2O(l) CH3COOH(aq) + C2H5OH(aq)

(B) Heterogenous equilibria: If the physical states of the participating substances
i.e., reactants and products are not same, then the equilibria is called homogenous
equilibria.
Examples: (i) CaCO3 (s) ƒ CaO(s) + CO2 ( g ) (ii) NH 4 HS (s) ƒ NH3 ( g ) + H 2 S ( g )
(iii) The equilibrium between water vapour and liquid water in a closed
container. H2O(l) H2O(g)

(V) Law of chemical equilibrium and equilibrium constant (Application of law

of mass action):
Law of mass action states that “at constant temperature, the rate of a chemical
reaction at any instant is directly proportional to the product of molar
concentrations (or active masses) of the reacting species with each concentration
term raised to the power of stoichiometric co-efficient of that species in the
chemical equation”
The equilibrium equation is also known as the law of mass action because in the
early days of chemistry, concentration was called “active mass”.
This law is applicable to all reactions occurring in the gas phase or in the liquid
phase.
Active mass of a dilute solution is its molar concentration (can be molality or
molefraction). Active mass of a gas is its partial pressure. Active mass of a pure
solid and pure liquid is taken as unity.
For a general elementary reaction, a A + b B ƒ c C + d D
According to law of mass action,
Rate of forward reaction  [ A]a [ B ]b  Rate of forward reaction = K f [ A]a [ B]b
Where, Kf = rate constant or velocity constant for forward reaction.
Rate of backward reaction  [C]c [D]d  Rate of backward reaction = Kb [C]c [D]d
Where, Kb = rate constant or velocity constant for backward reaction.
At equilibrium, rate of forward reaction = rate of backward reaction
K f [C]c [D]d [C]c [D]d
 K f [ A]a [ B]b = Kb [C]c [D]d  =  K c =
Kb [A]a[B]b [A]a[B]b
Where, Kc is the equilibrium constant and the expression on the right side is
called the equilibrium constant expression.

Factors not affecting the equilibrium constant: Equilibrium constant is

applicable only when concentrations of the reactants and products have attained
their equilibrium state. The value of equilibrium constant is independent of the
following factors.
(i) Initial concentrations of the reactants and products involved. (ii) The direction
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from which the equilibrium has been attained. (iii) The presence of catalyst (iv) The
rate of reaction. (v) The presence of inert materials.

Factors affecting the equilibrium constant:

(1) Effect of temperature: Equilibrium constant is temperature dependent.
(a) For reactions with H = 0 (i.e., neither heat is evolved nor absorbed), the
equilibrium constant value remains same at all temperatures.)
(b) For exothermic reactions (H = −Ve i.e., heat is released), as temperature
increases equilibrium constant value decreases.
(c) For endothermic reactions (H = +Ve i.e., heat is absorbed), as temperature
increases equilibrium constant value increases.
The variation of equilibrium constant with temperature is given by Vant Hoff’s
equation,
K  m H  1 1 
log  2  =  −  Where, K1 and K2 are equilibrium constants of a reaction
 1
K 2.303 R  T1 T2 
at temperatures T1 and T2; ∆mH= Molar enthalpy of reaction.
(2) Mode of representation of the reaction (3) Stoichiometric representation of
the chemical equation:
Relations between equilibrium constants for a general reaction and its multiples:
Sl. Chemical reaction Equilibrium
No. constant
(i) A + B ƒ C + D Kc
(ii) C + D ƒ A + B (the above reaction-i is reversed) K' =
1
c
Kc
(iii) nA + nB ƒ nC + nD (reaction-i is multiplied with n), e.g., K = Knc
''
c

1 1 1 1 K''c = K1c 2 (or) Kc

(a) A + B ƒ C + D (If n = 1/2)
2 2 2 2
(b) 2A + 2 B ƒ 2C + 2D (If n = 2) K''c = Kc2
(iv) 2A + 2 B ƒ 2C + 2D (reaction-i is reversed and multiplied K' '' = 1
c n
with n), e.g., Kc
1 1 1 1 1 1
(a) C + D ƒ A + B (If n = 1/2) K'c'' = 1/ 2 (or)
2 2 2 2 Kc Kc
(b) 2C + 2D ƒ 2A + 2 B (If n = 2) 1
K'c'' =
Kc2
(v) If reversible reaction occurs in two steps and each Kc = K1.K2
step has its own equilibrium constant, then
Equilibrium constant in gaseous systems & Relation between Kc and Kp:
[C]c [D]d
For a general elementary reaction, aA + bB ƒ c C + dD; Kc =
[A]a[B]b
(pC )c (pD )d [C]c [D]d (RT)(c+d) [C]c [D]d
(RT)(c+d)−(a +b) = Kc (RT)n
4

Kp = = (a+b)
=
(pA )a (pB )b a b a b
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[A] [B] (RT) [A] [B]

Where, ∆n=(no. of moles of gaseous products)–(no. of moles of gaseous
reactants)= nP(g) − nR(g) (RT >1 when T > 12.18 K which is normal condition)
If ∆n = 0 then, Kp = Kc; If ∆n = +ve then, Kp > Kc; If ∆n = -ve then, Kp < Kc
Equilibrium constant in terms mole fraction: For a general reaction,
a A + bB c C + dD
( C )c ( D )d
The equilibrium constant, K = Relationship between K p and Kχ :
(  A )a ( B )b
Kp = K  Pn
Units of equilibrium constant: Kc = (mo es / it )n
n
KP = ( atm) (or) (bar)n (or) (Pasca )n

Equilibrium constant expressions and units for some reactions:

It must be remembered that in heterogeneous equilibrium pure solids or liquids
must be present (however small it may be) for the equilibrium to exist, but their
concentrations or partial pressure do not appear in the expression of the equilibrium
constant.
2
[ HI ]2 PHI
(1) H2(g)+ I2(g) 2HI(g); K c = and Kp = ; n = (2) − (2) = 0 ; 
[ H 2 ][ I 2 ] PH 2 .PI2
K p = Kc
Units: Kc and Kp have no unit since n = 0
2
[ NH 3 ]2 PNH
(2) N2 ( g ) + 3H 2 ( g ) ƒ 2 NH 3 ( g ); Kc = and K p = 3
[N2 ][H2 ]3 PN2 .PH32
n = (2) − (4) = −2 ;  K p = Kc ( RT )−2 (or ) K p  Kc
Units: n = −2 ; Kc has units ( moles / lit )−2 and Kp has units (bar )−2 (or ) (atm)−2
2
[ SO3 ]2 PSO
(3) 2SO2 ( g ) + O2 ( g ) ƒ 2SO3 ( g ); Kc = and K p = 3
[ SO2 ]2 [O2 ] 2
PSO .P
2 O2
n = (2) − (3) = −1 ;  K p = Kc ( RT )−1 (or ) K p  Kc
Units: n = −1 ; Kc has units ( moles / lit )−1 and Kp has units (bar )−1 (or ) (atm)−1
2
[NO2 ]2 pNO
(4) N2O4(g) 2NO2 (g); Kc = and K p = 2
[ N 2O4 ] pN2O4
n = (2) − (1) = 1 ;  K p = Kc ( RT )1 (or ) K p  Kc
Units: n = +1 ; Kc has unit mol/L and Kp has unit bar or atm.
[PCl3 ][Cl2 ] pPCl3 . pCl2
(5) PCl5 (g) ƒ PCl3 ( g ) + Cl2 ( g ); Kc = and K p =
[ PCl5 ] pPCl5
5

n = (2) − (1) = 1 ;  K p = Kc ( RT )1 (or ) K p  Kc

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Units: n = +1 ; Kc has unit mol/L and Kp has unit bar or atm.

(6) CaCO3 (s) ƒ CaO(s) + CO2 ( g );
The active mass of a solid is unity whatever may be its mass.
 [CaCO3 ( s)] = 1 and [CaO( s)] = 1  K c = [CO2 ] and K p = pCO2
n = (1) − (0) = 1 ;  K p = Kc ( RT )1 (or ) K p  Kc
Units: n = +1 ; Kc has unit mol/L and Kp has unit bar or atm.
(7) NH 4 HS (s) ƒ NH3 (g) + H 2 S ( g )
The active mass of a solid is unity whatever may be its mass.  [ NH 4 HS (s)] = 1
 Kc = [ NH3 ][ H 2 S ] and K p = pNH3 . pH2S
n = (2) − (0) = 2 ;  K p = Kc ( RT )2 (or ) K p  Kc
Units: n = +2 ; Kc has units ( moles / lit )2 and Kp has units (bar )2 (or ) (atm)2

(VI) Applications of equilibrium constant:

(1) Predict the extent of a reaction:
(a) If Kc > 103, products predominate over reactants, i.e., if Kc is very large, the
reaction proceeds nearly to completion. (b)If Kc < 10–3, reactants predominate over
products, i.e., if Kc is very small, the reaction proceeds rarely. (c) If Kc is in the
range of 10– 3 to 103, appreciable concentrations of both reactants and products are
present.
(2) Predict the direction of the reaction:
[C]ct [D]Dt
Reaction quotient, Q c = {The concentrations are at time, t and not at
[A]at [B]bt
equilibrium}. Then, (a) If Qc > Kc, the reaction will proceed in the direction of
reactants (reverse reaction i.e., from right to left). (b) If Qc < Kc, the reaction will
proceed in the direction of the products (forward reaction i.e., from left to right).
(c) If Qc = Kc, the reaction mixture is already at equilibrium. i.e., no net reaction
occurs.

(VII) Relationship between equilibrium constant ‘K’ and reaction quotient ‘Q’
and Gibbs energy ‘G’:
As per thermodynamics, ∆G = ∆G0 + RT lnQ
Where, ∆G is Gibbs energy change and ∆G0 is standard Gibbs energy change
At equilibrium, ∆G = 0 and Q = KC, the equation becomes ∆G = ∆G0 + RT ln K = 0
– G0
– G0
G = −RT n K  n K =
0
Taking antilog, we get K = e RT
RT
– G0
– G0 2.303 RT
G = −2.303RT l og K  l og K =
0
Taking antilog, we get K = e
2.303RT
6

Where KC or Keq or K is a dimensionless quantity at standard conditions as RHS

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cannot have any unit.

0
Case-1: If ∆G0 < 0, then –∆G0/RT is positive, and e– G RT  1 , making K >1, which
implies a spontaneous reaction or the reaction which proceeds in the forward
direction to such an extent that the products are present predominantly.
 0
(ii) If ∆G0 > 0, then –∆ G0/RT is negative, and e– G RT  1 , making K < 1, which
implies a non-spontaneous reaction or a reaction which proceeds in the forward
direction to such a small degree that only a very minute quantity of product is
formed.

(VIII) Factors affecting equilibria - Le Chatelier’s principle:

It states that “a change in any of the factors that govern (or determine or direct or
control) the equilibrium conditions of a system will cause the system to change in
such a manner so as to reduce or to counteract (oppose) the effect of the change.
Le Chatelier’s principle is applicable to all physical and chemical equilibria.
(1) Effect of concentration change:
(i) Increase in the concentration of reactants (or decrease in the concentration of
products) favours the shift of equilibrium position towards products side i.e.,
favours forward reaction.
(ii) Increase in the concentration of the products (or decrease in the concentration
of reactants) favours the shift of equilibrium position towards the reactant side i.e.,
favours backward reaction.
(iii) Addition of reactants to the system (or removal of products from the system) at
the equilibrium will cause a shift in the equilibrium position of the reaction in the
direction of formation of products i.e., favours forward reaction.
(iv) Addition of products to the system (or removal of reactants from the system) at
the equilibrium will cause a shift in the equilibrium position of the reaction in the
direction of formation of reactants i.e., favours backward reaction.
(2) Effect of pressure change:
(i) Pressure does not show any marked effect on equilibrium reactions taking place
in the solution phase or in the solid phase.
(ii) Pressure has no effect on equilibrium where np = nR, that means n = 0 .
Example: H2 (g) + I2 (g) 2HI(g) {pressure has no effect}
(iii) Pressure has effect on equilibrium where np  nR, that means n  0 .
(a) Increase the external pressure on the reaction at equilibrium favours the reaction
in the direction in which the volume or number of moles or molecules decreases.
Examples:
N2 (g)+3
144444 H 2 ( g43) ƒ 2 NH 3 ( g ) {Increase the pressure of the system favours forward
42 44444 14442 4443
4 Volume 2 Volume

reaction}
7

CaCO3 (s) ƒ CaO (s) + CO2 ( g43) {Increase the pressure of the system favours backward
14442 4443 144444442 444444
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0 Volume 1 Volume

reaction}
(b) Decrease the external pressure on the reaction at equilibrium favours the
reaction in the direction in which the volume or number of moles or molecules
increases.
(3) Effect of temperature change:
(i) Increase in the temperature of the reaction mixture at equilibrium favours
endothermic reaction or the reaction in the direction in which heat is absorbed.
(ii) Decrease in the temperature of the reaction mixture at equilibrium favours
exothermic reaction or the reaction in the direction in which heat is liberated.
(4) Effect of inert gas addition:
(i) If we add inert gas at constant volume, the total pressure of the system is
increased. But, the partial pressure of each reactant and product remains the same
and the molar concentration of the substance involved in the reaction also remains
the same. Hence, inert gas addition has no effect on the state of equilibrium.
The reaction quotient changes only if the added gas is a reactant or product
involved in the reaction.
(ii) If we add inert gas at constant pressure, the total volume is increased, the
number of moles per unit volume of each reactant and product is decreased. Hence
equilibrium will shift to the side where number of moles are increased.
(5) Effect of a catalyst:
It increases the rate of forward and reverse reactions that pass through the same
transition state and does not affect equilibrium.
Catalyst lowers the activation energy for the forward and reverse reactions by
exactly the same amount. So equilibrium attains quickly. Catalyst does not affect
the equilibrium composition of a reaction mixture.
(6) Effect of change in volume: If volume of the reaction mixture at equilibrium
increases then, the pressure inside the container decreases. Now, the system will
try to increase the pressure by shifting equilibrium towards increase in number of
moles side.
Application of Le chatelier’s principle for industrial synthesis of ammonia and
sulphur trioxide:
(1) Industrial synthesis of ammonia by Haber’s process:
[NH3 ]2
N2 (g)+3
14444 H2 (g3) ƒ 2NH3 (g); H = −92.2 kJ; Kc =
42 44444 = 3.6 ×108 at 250 C
14442 4443 [N2 ][H2 ]3
4 Volume 2 Volume

The optimum conditions used in Haber’s process are:

Pressure: 200 – 500 atm; Temperature: 725 – 775 K; Catalyst: Fe; Promoter: Mo
(2) Industrial synthesis of SO3:
[SO3 ]2
SO2 (g) +444444
214444442 O2 (g3) ƒ 2SO3 (g); H = −189 kJ; Kc = = 1.7 ×1026 at 250 C
1442 443 2
[SO2 ] [O2 ]
3 Volume 2 Volume
8

Optimum conditions used in the synthesis of sulphur trioxide:

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Pressure: 1 to 2 atm; Temperature: 673 K – 723 K;

Catalyst: Vanadium pentoxide (V2O5 ) or Platinised asbestos

Applications to physical equilibria:

(i) Effect of pressure on melting of ice. Ice ƒ Water; H = + ve
An increase in pressure favours the forward reaction because Vice > Vwater. Thus,
more and more ice melts into water on increasing pressure. Also at higher
temperature more water is formed as it absorbs heat. (Water has more entropy than
ice. ∆G = ∆H – T ∆S, after increase of pressure, ∆H and T
(ii) Effect of pressure on boiling point: Water ƒ Vapour; H = +ve
An increase in pressure favours backward reaction because Vvapour > Vwater. Thus
boiling point of water increases with increase in pressure.
(iii) Effect of temperature on the solubility of solids:
If the dissolution of solute is endothermic (e.g., urea, glucose, NaCl etc.) an
increase in temperature favours the forward reaction i.e., dissolution.
Sol ubil ity  Temperature
Solute +Solvent Solution; H = +ve
If the dissolution of solute is exothermic (e.g., Ca(OH )2 ) an increase in temperature
favours the backward reaction i.e., solubility decreases with rise in temperature.
1
Solute + Solvent Solution; H = −ve ; Sol ubil ity 
Temperature
(iv) Effect of pressure on solubility of gases:
When a gas dissolves in a liquid (say water), there is a decrease in volume and
dissolution process is of exothermic nature.
Gas+ liquid Dissolved gas; H = −ve
High pressure will favour the dissolution process i.e., the forward process because
it will result in decrease of volume. Thus, the solubility of a gas in a liquid always
increases with the increase in pressure according to Henry’s law.
The solubility decreases with the increase in temperature because the backward or
endothermic process will be favoured when the temperature is increased.

IONIC EQUILIBRIUM (or) ACIDS-BASES & SALTS

(I) Acids, Bases and Salts:
(1) Arrhenius concept of acids and bases:
(a) Acids: All substances that dissociates in water to give hydrogen ions, H+(aq)
are called acids.
Examples: HCl, CH3COOH, H3PO4, etc.,
9

Bases: All substances that dissociates in water to give hydroxyl ions, OH–(aq) are
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called bases. Examples: NaOH, Ca(OH)2, etc.,

(b) Strength of acids and bases: Acids and bases which are almost completely
ionized in aqueous solution are termed as strong acids & strong bases respectively
where as acids and bases which are weakly ionized in aqueous solution are called
weak acids & weak bases respectively.
(c) Neutralisation: According to Arrhenius concept, neutralization of acids and
bases is basically a reaction between H+ and OH– ions in solutions. H+ (aq) + OH–
(aq) ⎯⎯ → H2O (l)
(d) Limitations: This theory is applicable only to aqueous solutions. That means
dry HCl shall not act as an acid. So, HCl acts as an acid in water only and not in
any other solvent.

(2) Bronsted-Lowry theory of acids and bases: (1923)

(a) Acid: A substance or a chemical species which can donate proton is known as
an acid i.e., a proton donar is an acid.
Base: A substance or a chemical species which can accept proton is known as a
base i.e., a proton acceptor is a base.
Example-1: HCl and H 3O + are proton donars. So, they are Bronsted - Lowry acids.
HC + H2O H3O+ + C −
Acid−1 Base − 2 Acid− 2 Base−1
−
H2O and Cl are proton acceptors. So, they are Bronsted - Lowry bases.
Example-2:
NH3 + H2O NH+4 + OH
Base−1 Acid-2 Acid-1 Base-2

(b) Types of Bronsted-Lowry acids:

Molecular Acids: HClO4, HCl, H2SO4, HNO3, H3PO4, H3PO3, H2CO3, H2O, H2S,
HCN, HCOOH, CH3COOH, etc.,
Cationic acids: NH+4 , H3O+ , N2H5+ , C 2H5NH3+ ,..
Anionic acids: HSO−4 , H2PO4− , HPO42− , H2PO3− , HCO3− , OH− , HS− ,..
Types of Bronsted-Lowry bases:
Molecular bases: NH3, N2H4, C2H5NH2, C6H5NH2, H2O, C2H5OH,..
Cationic bases: [Al(H2O)5 OH]++ , [Cu(H2O)3 OH]+ ,..
Anionic bases: C O−4 , C − , HSO−4 , SO24− , NO3− , H2PO−4 , HPO24− , PO34− , H2PO3− , HPO32− ,
HCO3− , CO32− , OH− , O 2− , HS − , S 2− , CN− , HCOO− , CH3COO− ,..
It may be noted that “all Bronsted bases are also Lewis bases but all Lewis acids
are not Bronsted acids”.
(c) Neutralisation: The transfer of proton from an acid to the base is called
neutralization or protolysis.
10

(d) Conjugate acid-base pair:

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(i) A pair of acid-base which differs by a single proton is called conjugate acid-base
pair.
(ii) The removal of a proton from a Bronsted-Lowry acid gives its conjugate base.
The addition of proton to a Bronsted-Lowry base gives its conjugate acid.
(iii) Relative strength of conjugate acid-base pair:
Strong acid gives weak conjugate base and weak acid gives strong conjugate base.
Strong base gives weak conjugate acid and weak base gives strong conjugate acid.

(3) Lewis acid-base theory:

(a) Lewis acid: A substance or a chemical species that can accept a pair of
electrons to form a co-ordinate covalent bond is called Lewis acid. Simply, Lewis
acid is an electron pair acceptor.
Lewis base: A substance or a chemical species that can donate a pair of electrons
to form a dative bond is called Lewis base. Simply, Lewis base is an electron pair
donor.
(b) Types of Lewis acids:
(i) Atoms with electron sextet. e.g., O, S, Se, Te, etc.,
(ii) Molecules with incomplete octet in the valence shell of central atom.
e.g., BF3, BCl3, AlCl3, BeF2, FeCl3, etc.,
(iii) Molecules in which central atom can expand its octet using vacant d-orbitals
present in its valence shell. e.g., SiF4 , SnC 4 , SF4 , TeF4 , FeC 3 , etc.,
(iv) Molecules having multiple bonds between atoms of dissimilar electro
negativities.
e.g., CO2, SO2, SO3, NO2, Cl2O7, P4O10, etc.,
(v) All simple cations. e.g., H+, Ag+, Fe3+, Cu2+,Ni2+, Fe2+, etc.,
+ +
(vi) Carbonium ions. e.g., CH3 , CH3 CH2 , etc., (In organic chemistry Lewis acids are
called electrophiles. Electrophile means electron seeking species or electron
deficient species.)
Types of Lewis bases:
(i) Molecules having one or more lone pairs of electrons on the central atom and all
the atoms present on central atom are not electronegative.
•• •• •• •• •• ••
e.g., Nitrogen nuc eophi es : NH3 , R NH2 , R 2 NH, R3 N, NH2 − NH2 , etc.,
•• •• ••
Oxygen nuc eophi es : H2 O, R OH, R − O − R, etc.,
•• •• ••

(ii) All anions.

− − − − − − − − − − − − − − − − −
e.g., H, C , Br, I , OH, OR(OCH3 , OC 2H5 ), SH, SR, HS O3 , CN, (SCN) − , NH2 , NHR, NR 2 , HCOO, RCOO , etc.,
(iii) Carbanions. e.g., CH3 , CH3CH2 , etc.,
11

(iv) Molecules having carbon-carbon multiple bonds or molecules having multiple

bonds between atoms of similar electronegative atoms.
Page

e.g., A kenes (H2C = CH2 ..), a kynes(HC  CH...), benzene, CO, NO, etc.,
(v) In complex compounds all ligands are Lewis bases. (In organic chemistry Lewis
bases are called necleophiles. Nucleophile means nucleus seeking species or
election rich species.)
(c) Neutralization: According to Lewis theory, the formation of co-ordinate
covalent bond is known as Neutralization process. Example: BF3 + :NH3 →
BF3:NH3
(d) Drawbacks: Lewis theory could not explain the strength of acids and bases.
Note: All Lewis Bases are Bronsted-Lowry bases and similarly all Bronsted-Lowry
bases are Lewis bases. All Lewis acids are not Bronsted-Lowry acids and similarly
all Bronsted-Lowry acids are not Lewis acids.

(II) Ionic product of water: “The product of the concentration of hydrogen ions or
hydronium ions and hydroxide ions at any temperature in pure water or in any
aqueous solution is known as the ionic product of water”. It is represented by Kw.
The concentration of H+ ion found experimentally as 1.0 × 10–7 M at 298 K. And,
as dissociation of water produces equal number of H+ and OH– ions, the
concentration of hydroxyl ions, [OH–] = [H+] = 1.0 × 10–7 M. Thus, the value of Kw
at 298K,
Kw = [H3O+][OH–] = (1 × 10–7)2 = 1 × 10–14 M2
The value of Kw is temperature dependent as it is an equilibrium constant. As
temperature increases, the ionization of water increases and hence KW value
increases.
Density 1000 g /Lit
(ii) Molarity of pure water, M = = = 55.55 mo / Lit
GMW 18 g / mo
Therefore, the ratio of dissociated water to that of undissociated water can be given
as,
10 –7
= 1.8 × 10–9 or ~ 2 in 10–9 (thus, equilibrium lies mainly towards
55.55
undissociated water)
(iii) We can distinguish acidic, neutral and basic aqueous solutions by the relative
values of the H3O+ and OH– concentrations:
Neutral: [H3O+] = [OH– ] = 1×10-7 mol/lit at 25 0C.
Acidic: [H3O+] > [OH– ] (or) OH −  < 1×10-7M
Basic: [H3O+] < [OH–] (or) [H+] < 1×10-7 M

(III) The pH Scale: The pH of a solution is defined as the “negative logarithm to

base 10 of the activity ( aH ) of hydrogen ion”.
+

pH = – log a H = – log {[H+] / mol L–1}  [H+ ] = 10−pH mol L-1

12

Acidic solution has pH < 7 (For a strong acid pH value is very low)
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Basic solution has pH > 7 (For a strong base pH value is very high)
Neutral solution has pH = 7
We know, Kw = [H3O+] [OH–] = 10–14 at 298 K
Taking negative logarithm on both sides of equation, we obtain
− og KW = − og{[H3O+ ][OH − ]}
= − og[H3O+ ] − og[OH − ] = − og10−7 − og10−7 = 7 + 7 = 14
 pKW = pH + pOH = 14 at 250 C
For any aqueous solution, the sum of pH and pOH depends on the ionic product of
water. i.e., pH + pOH = pKw
At 25 0C, for any aqueous solution, pH+ pOH =14
For pure water or neutral solution, pH= pOH =7.
Like pH, we also define: pOH = - log [OH-]
pKW= - log Kw pKa = -log Ka pKb= -log Kb
Applications of pH:
(1) Calculation of pH of concentration of strong acids or strong bases:
(i) When H+ or OH- ion concentration is known, then
pH = − log[H+ ] or [H+ ] = 10−pH
pOH = − log[OH − ] or [OH − ] = 10−pOH
(ii) When the acid or the base is completely ionized in aqueous solution indicates
strong acid or strong base.
For any strong acid, [H+] = normality of the solution (or) [H+] = molarity of the
acid × basicity of the acid.
For any strong base, [OH − ] = normality of the solution (or) [OH − ] = molarity of the
base × acidity of the base.
(iii) When the pH of a solution is known and to calculate [ H + ] of solution we follow
a process.
e.g., Calculate the hydrogen ion concentration in a solution of pH = 3.75.
Solution: pH = - log [ H + ] = 3.75
−
 log [ H + ] = - 3.75 = -4.0000 + 0.2500 or 4.2500
−
 [ H + ] = antilog [4.2500] = antilog 0.25 × 10−4
 [ H + ] = 1.8
× 10−4 M
(2) Calculation of pH of strong acids or strong bases in dilution:
(i) If the aqueous solution of an acid is diluted by,
a) Ten times, the pH of the solution increases by one unit.
b) Hundred times, the pH of the solution increases by two units.
c) Thousand times, the pH of the solution increases by three units.
If the aqueous solution of a base is diluted by,
13

a) Ten times, the pH of the solution decreases by one unit.

Page

b) Hundred times, the pH of the solution decreases by two units.

c) Thousand times, the pH of the solution decreases by three units.
But, the pH of acid is always less than 7 and base is always more than 7.
(ii) If the aqueous solution of an acid is diluted with water its pH value increases.
V2
After dilution, pH = initial pH + log
V1
Where, V1 = initial volume of the solution, V2 = volume of solution after dilution
If the aqueous solution of a base is diluted with water its pH value decreases. After
V2
dilution, pH = initial pH - log
V1
Where, V1 = initial volume of the solution, V2 = volume of solution after dilution
# Whatever the volume of water added, the pH of acid is always less than 7 and
base is always more than 7
# If a very dilute acid is added to a concentrated acid the very dilute acid is treated
as water for the purpose of calculating the pH value of the mixture.
# If a very dilute base is added to a concentrated base, the very dilute base is
treated as water for the purpose of calculating the pH value of the mixture.
(3) Calculation of pH of a mixture of strong acids or strong bases:
(i) If two strong acids with known concentration and volume are mixed first we
calculate the concentration of mixture of two strong acids and then calculate pH.
N1V1 + N2 V2
H+  = Nmix =
mix V1 + V2
If two strong bases with known concentration and volume are mixed first we
calculate the concentration of mixture of two strong bases and then calculate pOH
and pH.
N1V1 + N2 V2
OH−  = Nmix =
mix V1 + V2
(ii)When a strong acid and a strong base are mixed and it is partial neutralization,
to calculate the pH of a mixed solution,
(a) If NaVa > NbVb indicates, the resultant solution is acidic and
Na Va − Nb Vb
[H+ ] = Nmix =
Va + Vb
(a) If N b Vb > N a Va indicates, the resultant solution is basic and
Nb Vb − Na Va
[OH− ] = Nmix =
Va + Vb
(iii) When two acidic solutions with known pH values and different volumes are
mixed first we calculate the concentration of the mixture and then calculate pH.
14

(IV) Ionization constants of weak acids:

Formulae for any weak acid: Formulae for any weak base:
Page

(i) Ionization constant of acid, Ka = (i) Ionization constant of base, Kb =

c 2 c 2
(1 −  ) (1 −  )
(ii) K a = c 2 (ii) K b = c 2
 α = degree of ionization of acid α = degree of ionization of base
c = molar concentration of acid c = molar concentration of base
(iii)  = Ka / C (iii)  = K b / C
(iv) For two weak acids with (iv) For two weak bases with
dissociation constants Ka1 and Ka2 at dissociation constants Kb1 and Kb2 at the
the same concentration ‘c’ same concentration ‘c’
1 Ka1 Strength of acid HA1
= = 1 Kb Strength of base B1OH
2 Ka2 Strength of acid HA 2 = = 1

2 Kb Strength of base B2OH

(v)  H +  = c
2

(v) [OH] = c
(vi)  H +  = Ka  c (vi) OH  = K b  c
1
(vii) pH = 2 ( pK a − log c ) (vii) pOH =
1
( pK b − log c )
2
(viii) pKa = − log Ka pH = 14 − pOH
(ix) For a polybasic acid, Ka1  Ka2  Ka3 (viii) pKb = − log Kb
(ix) For a polyacidic base, Kb1  Kb2  Kb3
For a conjugate acid-base pair, Ka  Kb = Kw
pKa + pKb = pKw = 14 at 298K

(VI) Hydrolysis of salts and the pH of their solutions:

The reaction between the cation or anion or both of a salt with water giving either
acidic solution or basic solution or even neutral solution is known as salt
hydrolysis.
The hydrolysis reaction is a reversible reaction.
The equilibrium constant for the hydrolysis reaction is known as hydrolysis
constant. It is represented by Kh. Various salts can be divided into four types.
(i) Salts of strong acid and strong base: Examples: NaCl, NaBr, NaNO3, Na2SO4,
KCl, KBr, KNO3, K2SO4, KI, CsCl, CaCl2, Ca(NO3)2, BaCl2, etc.,
The cations (Ex: Na+, K+, Ca2+, Ba2+, etc.) of strong bases and anions (Ex: Cl–, Br–,
NO3–, ClO4–, etc.) of strong acids simply get hydrated but do not hydrolyze, and
therefore the solutions of salts formed from strong acids and bases are neutral i.e.,
their pH is 7.
(ii) Salts of weak acid and strong base: Examples: CH3COONa, CH3COOK,
Na2CO3, K2CO3, NaHCO3, KHCO3, NaCN, KCN, Na2S, K2S, NaClO, HCOOK,
15

Na2B4O7, etc.,
Page

The pH of such a solution is more than 7 due to anionic hydrolysis. The aqueous
−
solution of the salt turns red litmus to blue. A (aq) + H2O( ) HA(aq) + OH− (aq)
(iii) Salts of strong acid and weak base: Examples: NH4Cl, MgCl2, AlCl3,
Al2(SO4)3, Al(NO3)3, FeCl3, FeSO4, CuCl2, CuSO4, ZnCl2, ZnSO4, Zn(NO3)2,
AgNO3, etc.,
The pH of such solution is less than 7 due to cationic hydrolysis. The aqueous
+ +
solution of the salt turns blue litmus to red. M (aq) + H2O( ) MOH(aq) + H (aq)
(iv) Salts of weak acid and weak base: Examples: CH3COONH4, (NH4)2CO3,
NH4HCO3.
The aqueous solution of the salt is acidic or basic or neutral due to both cationic
and anionic hydrolysis. (a) Neutral, if Ka of acid is equal to Kb of base. (b) Acidic,
if Ka of acid is greater than Kb of the base. (c) Basic, if Ka of acid is less than Kb of
base.
Salt hydrolysis at a glance:
Salt Nature of Hydroly Degree of pH
solution sis hydrolysis
constan
t
(i) NaCl Neutral due to - No 7
(Strong acid + no hydrolysis hydrolysis
Strong base)
(ii) Basic due to K = K W Kw 1
p H = 7 + (pKa + log C)
h
Ka h = 2
CH3COONa anionic Ka .C
(Weak acid + hydrolysis K C
[OH− ] = ch = W
Strong base) Ka
(iii) NH 4Cl Acidic due to K = Kw Kw 1
pH = 7 − (pKb + log C)
h h=
(Strong acid + cationic Kb Kb .C 2
Weak base) hydrolysis K C
[H+ ] = ch = W
Kb
(iv) Neutral or K = Kw Kw 1
pH = 7 + (pKa − pKb )
h
Ka .Kb h= 2
CH 3COONH 4 acidic or basic Ka .Kb
(Weak acid + due to both
Weak base) cationic and
anionic
hydrolysis
16

(IX) Buffer solutions: The solutions which resist change in pH on dilution or with
the addition of small amounts of acid or alkali are called buffer solutions.
Page

Types of buffer solutions:

(A) Salt buffer (or) Solutions of single substances: The solution of salt of weak
acid and weak base. e.g., Ammonium cyanide (NH4CN), ammonium acetate
(CH 3COONH 4 ) , ammonium benzoate (C6 H5COONH 4 ) acts as buffer.
(B) Solutions of mixtures:
(a) Acidic buffer solutions: It contains a mixture of weak acid and its salt formed
from strong base. Examples: (1) CH3COOH + CH3COONa (pH around 4.75)
(2) CH3COOH + CH3COOK (3) C6H5COOH + C6H5COONa
(4) Phthalic acid + potassium hydrogen phthalate (5) H2CO3 +NaHCO3
(6) Citric acid+ sodium citrate(7) HCN + NaCN (8) HCN + KCN
(9) HCN + Ca(CN)2 (10) H3PO4 + NaH2PO4 (11) H3PO4 + Na2HPO4
(12) H3PO4 + Na3PO4 (13) NaH2PO4 + Na2HPO4 (14) NaH2PO4 + Na3PO4
(15) H3PO3 + NaH2PO3 (16) H3PO3 + Na2HPO3 (17) NaH2PO3 + Na2HPO3

(18) H3PO2 + NaH2PO2 (19) H3BO3 + NaH2BO3 (20) H3BO3 + Na2B4O7

(Borax)
(b) Basic buffer solutions: It contains a mixture of weak base and its salt formed
from strong acid. Examples: (1) NH4OH + NH4Cl (pH around 9.25) (2) NH4OH +
NH4NO3
(3) NH4OH + NH4(SO4)2 (4) NH4OH + NH4ClO4
(5) Pyridine + Pyridine hydrochloride (6) Piperidine + Piperidinium hydrochloride
(7) Quinoline + Quinolinium hydrochloride
(8) CH3 NH 2 (Methyl amine) + CH 3 NH 3+Cl − (Methyl ammonium chloride)
(9) C6 H 5 NH 2 (Phenyl amine) + C6 H 5 NH 3+Cl − (Phenyl ammonium chloride)
Henderson–Hasselbalch equation to calculate pH of acid buffer and basic buffer
solution:
(1) For acid buffer solution,
[Conjugate base, A − ] [Sa t] [N .V ]
pH = pKa + og (or) pH = pKa + og (or) pH = pKa + og Sa t Sa t
[Weak acid, HA] [Acid] [NAcid.VAcid ]
(2) For basic buffer solution,
[Conjugate acid, B + ] [Conjugate acid, B + ]
pOH = pKb + og (or) pH = 14 − pKb − og
[Weak base, BOH] [Weak base, BOH]
[Sa t] [N .V ]
(or) pOH = pKb + og (or) pH = 14 − pKb − og Sa t Sa t
[Base] [NBase .VBase ]
Buffer capacity (β):
The number of moles of acid or base that must be added to one liter of a buffer
solution to change its pH value by one unit is known as the buffer capacity or
buffer value or buffer index or buffer efficiency of the buffer solution.
17

Number of mo es of acid or base 

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added to a itre of so ution 

Buffer capacity (  ) =   = dn
Change in pH va ue d(pH)
Where, dn = infinitesimally small number of moles of acid or base added.
A good buffer will have high buffer capacity.
The buffer capacity of an acid buffer is very high if its pH value is equal to pK a of
acid present in it, i.e., [Salt] = [Acid]. The pH range in which an acid buffer works
effectively is pKa ± 1.
The buffer capacity of a basic buffer is very high if its pOH value is equal to the
pKb of base present in it, i.e., [Salt] = [Base]. The pOH range in which a basic
buffer works effectively is pKb ± 1.

(X) Solubility: The number of grams of solute that can be dissolved in 100 grams of
solvent at a particular temperature is called solubility.
Weight of so ute
So ubi ity= 100
Weight of so vent
We classify salts on the basis of their solubility in the following three categories.
Category I Soluble Solubility > 0.1M
Category II Slightly soluble 0.01M < Solubility < 0.1M
Category III Sparingly soluble Solubility < 0.01M
Solubility product constant: In saturated solution, equilibrium state is established
between un-dissolved solute and dissolved solute. Equilibrium between the un-
dissolved solid and the ions in a saturated solution can be represented by the
equation:
xM p + (aq) + yBq − (aq)
Saturated so ution
Mx X y (s) + Aq
in water
“The product of the concentration of ions in a saturated solution of an electrolyte at
a given temperature is called solubility product constant or solubility constant”.
Solubility product of a salt, MxXy is given by: KSP = [Mp+ ]x [Xq− ]y Where x.p+ = y.q−
If ‘S’ is the solubility of the electrolyte, then KSP = [Mp+ ]x [Xq− ]y = xSx ySy = xx .yy .S(x+y)
1
K  K  x+y
 S( x + y ) = x SP y  S =  x SP y 
x .y  x .y 
KSP values for different types of electrolytes:
(i) Electrolyte of the type AB (1:1 type binary electrolyte):
AB(s) A x + (aq) + B y − (aq)
S S S
KSP = [A x + ][By − ] = (S)(S) = S2 (mo / Lit) 2 (or) M2
 So ubi ity of AB type of e ectro yte, S = KSP mo / Lit
18

Examples :
Ag + (aq) + C − (aq)
Page

AgC (s)
2–
BaSO4 (s) Ba2+ (aq) + SO4 (aq)
2–
PbSO4 (s) Pb 2+ (aq) + SO4 (aq)
(ii) Electrolyte of the type AB2 or A2B (1:2 or 2:1 type ternary electrolyte):
AB2 (s) A 2+ (aq) + 2B− (aq)
Examples :
S S 2S CaF2 (s) Ca2+ (aq) + 2F− (aq)
2+ − 2
KSP = [A ][B ] = (S)(2S) = 4S (mo / Lit) (or) M
2 3 3 3
Ag 2CrO4 (s) 2Ag + (aq) + CrO42− (aq)
KSP Ag CO (s) 2Ag + (aq) + CO32− (aq)
 So ubi ity of AB2 type of e ectro yte, S = 3 mo / Lit 2 3
4 H2 S(s) 2H+ (aq) + S 2− (aq)
(iii) Electrolyte of the type AB3 or A3B (1:3 or 3:1 type quarternary
electrolyte):
AB3 (s) A 3+ (aq) + 3B− (aq) Examples :
S S 3S 3+
A (OH)3 (s) A (aq) + 3OH− (aq)
3+ − 3
KSP = [A ][B ] = (S)(3S) = 27S (mo / Lit) (or) M
3 4 4 4

Cr(OH)3 (s) Cr 3+ (aq) + 3OH− (aq)

1
K 
 So ubi ity of AB3 type of e ectro yte, S =  SP  mo / Lit
4
Fe(OH)3 (s) Fe3+ (aq) + 3OH− (aq)
 27 
Ionic product (QSP): The product of concentrations of all the ions in the solution,
each raised to the power equal to the number of ions as represented by the
dissociation of one molecule of the substance is called ionic product.
The concept of solubility product helps the formation of a precipitate.
(a) If ionic product > KSP, a precipitate formed indicates super saturated solution.
(b) If ionic product < KSP, no precipitate formed indicates unsaturated solution.
(c) If ionic product = KSP, indicates saturated solution.

(X) Common ion effect: It can be defined as “The suppression of the dissociation
of a weak electrolyte by the addition of strong electrolyte having common ion is
called common ion effect”.
Common ion effect on solubility of salts:
From Lechatlier’s principle, if concentration of any one of the ions is increased it
should combine with the ion of its opposite charge and some of the salt will be
precipitated till KSP = QSP.
Similarly, if concentration of one of the ions is decreased, more salt will dissolve to
increase the concentration of both the ions till once again KSP = QSP.
This is applicable even to soluble salts such as NaCl except that due to higher
concentration of the ions, instead of their molarities, their activities are used in
the expression for QSP.
Calculation of solubility of salts under various conditions:
(i) Solubility of AgCl in 0.1M NaCl solution: Solubility of AgCl decreases in
19

presence of NaCl due to common chloride ion.

Ag + (aq) + C − (aq)
Page

AgC (s)
So ubi ity in water at equi ibrium : − S S
So ubi ity in 0.1M NaC at equi ibrium : − S '
S + 0.1
'

KSP = [Ag + ][C − ]Tota = S' (S' + 0.1) ( Where, S  S )

'
(ii) Simultaneous solubility: When two sparingly soluble salts are present in water
with at least a common ion, then solubility of both salts decrease. Examples: AgCl
and AgBr, SrSO4 and BaSO4.
For example, calculation of simultaneous solubility of AgCl and AgBr in the
solution:
AgC (s) Ag + (aq) + C − (aq) AgBr(s) Ag + (aq) + Br − (aq)
At equi ibrium : − S1 + S2 S1 − S1 + S2 S2
KSP1 (AgC ) = [Ag + ]Tota [C − ] KSP2 (AgBr) = [Ag + ]Tota [Br − ]
 KSP1 = (S1 + S2 ) S1  KSP2 = (S1 + S2 ) S2
KSP1 (S1 + S2 ) S1
=
KSP2 (S1 + S2 ) S2

20
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