CHEMICAL EQUILIBRIUM

Chemical reactions can be classified into two types as 1) irreversible

reactions and 2) reversible reactions.
The reactions in which the products will never give back the original reactants
under any circumstances are called unidirectional reactions or irreversible
reactions.
Eg: 1. Decomposition of hydrogen peroxide 2H2O → 2H2O + O2
2. Decomposition of mercuric nitrate 2HgO → 2Hg + O2
3. Decomposition of ammonium nitrate NH4NO3 → N2O +2H2O
4. Charring of sugar C12H22O11 concH 2 SO4 12C + 11H2O
5. Dehydration of oxalic acid COOH ⎯⎯⎯⎯→ CO + CO2 +H2O
1COOH concH 2 so4

Burning of fules, wood and paper and radioactive decay:

Reversible reactions: The reactions in which the products formed will give
back the original reactants under favourable circumstances are called
reversible reactions.
1. All reversible reactions occur only in closed system.
2. All reactions which are carried out in a closed system need not be
reversible.
Examples for reversible reactions:
1. Decomposition of calcium carbonate or lime stone.
CaCO3 CaO + CO2
2. Decomposition of magnetic carbonate MgCO3 MgO + CO2
3. Synthesis of ammonia N2 + 3H2 2NH3
4. Synthesis of sulphur trioxide 2SO2 + O2 2SO3
5. Synthesis of hydrogen iodide H2 + I2 2HI
6. Dissociation of phosphorus pentachloride PCl5 PCl3 + Cl2

In a reversible reaction, the reaction which takes place from left to

right is called forward reaction and the reaction which proceeds from right to
left is called backward reaction. The rate of forward reaction slowly decreases
and the rate of backward reaction slowly increases. When the rate of forward
reaction becomes equal to the rate of backward reaction, then the reaction is
said to be at equilibrium. Thus the state at which the rate of forward reaction
is equal to the rate of backward reaction is called “Equilibrium state”.

Characteristics of chemical equilibrium:

1. Equilibrium is established only in reversible reactions in a closed system.
2. At equilibrium state the rate of forward reaction is equal to the rate of
backward reaction.
3. Equilibrium can be attained from the reactants side or from the products
side.
4. Chemical equilibrium is dynamic in nature.
5. At equilibrium the molar concentrations of the reactants and the products
are constant.

1
6. At equilibrium the molar concentrations of the reactants need not be
equal to the concentrations of the products.
7. The partial pressures of the gaseous components are constant.
8. The colour intensity of the coloured component is constant.
9. At equilibrium the entropy of the system is maximum and the free energy
is minimum.
10. The free energy change (G) is zero.

LAW OF MASS ACTION :-

Law of mass action states that, the rate of a chemical reaction is
directly proportional to the product of active masses of reacting substances.
Consider a reaction A + B ⎯⎯ → C+D
According to the law of mass action, the rate of forward reaction depends
upon the concentration of A or B or both. Therefore
rate   A  B ; rate = k  A  B 
Concentration of species is indicated in square brackets
LAW OF CHEMICAL EQUILIBRIUM :- It states that, at a given
temperature, the ratio of the product concentrations of the products raised to
their stoichiometric coefficients in the balanced equation to the product of
concentrations of the reactants raised to their stoichiometric coefficients. It
has a constant value.
Consider a general reversible reaction
aA + bB cC + dD
Applying of law of mass action to the forward reaction
Vf  [A]a [B]b or Vf = kf [A]a [B]b
Where Vf is the rate of forward reaction and kf is the rate constant of
forward reaction

Similarly applying law of mass action to the backward reaction

Vb  [C]c [D]d or Vb = kb [C]c [D]d
Where Vb is the rate of backward reaction and kb is the rate constant of
backward reaction

At equilibrium Vf = Vb

Therefore kf [A]a [B]b = kb [C]c [D]d

OR
kf
=
C c D d or K c =
C c Dd Kc =
kf
Where Kc = Equilibrium constant.
kc Aa B b Aa Bb kc

Equilibrium constant expressed in terms of molar concentrations is denoted

by KC.

The units of Kc are (conc) n where n is the difference in the number of

moles of gaseous products and gaseous reactants.

2
Homogeneous equilibrium: If all the reactants and products are in the
same phase in equilibrium system is called homogeneous equilibrium.

Eg: H2(g) + I2(g) 2HI(g) ; 2SO2(g) + O2(g) 2SO3(g)

N2(g) + 3H2(g) 2NH3(g) ; PCl3(g) + Cl2(g) PCl5(g)
N2(g) + O2(g) 2NO(g) ;
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l)+ H2O(l)
The equilibrium constant for the reactions involving gases is expressed
in terms of pressure (Kp) because pressure is directly proportional to the
concentration.
2SO2(g) + O2(g) 2SO3(g)
( PSO3 )
2

Kp =
( PSO2 ) ( O2 )
2

Consider a general reversible reaction

aA + bB cC + dD
The equilibrium constant in terms of concentration (Kc) for the reaction is
C c Dd ( PC ) ( PD )
c d

Kc = and in terms pressure (Kp) is Kp =

Aa Bb ( PA) ( PB )
a b

The ideal gas equation is PV = nRT, since n/V = c, therefore

P = cRT
[C ]c ( RT )c [D]d ( RT ) d [C ]c [D]d ( RT ) c +d
Hence K p = or K =
[A]a [B]b ( RT ) a +b
p
[A]a ( RT ) a [B]b ( RT )b
[C ]c [D]d (c + d) −(a + b) [C ]c [D]d
Kp = a b
(RT) or K p = a b
(RT) n
[A] [B] [A] [B]
[C ]c [D]d
since = Kc
[A]a [B]b
Therefore K p = Kc ( RT )n
The units of KP are (atm)n
The equilibrium constants KP and Kc are related by KP = Kc(RT)n.
1. If n = 0, then KP = KC
Eg: H2(g) + I2(g) 2HI(g) ; N2(g) + O2(g) 2NO(g)
2. If n is positive the KP>KC
Eg: PCl5(g) PCl3(g) + Cl2(g) ; 2NH3(g) N2(g)+ 3H2(g)
3. If n is negative the KP<KC.
Eg: N2(g) + 3H2(g) 2NH3(g) ; PCl3(g)+ Cl2(g) PCl5(g)
2SO2(g) + O2(g) 2SO3(g) .

Heterogeneous equilibrium : If all the reactants and the products are

in different phases in equilibrium system is called heterogeneous equilibrium.

Eg: CaCO3(s) CaO(s) + CO2(g) ; 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g).

NH4HS(s) NH3(g) + H2S(g) ; C(c) + S2(g) CS2(s)

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 In a reaction at equilibrium if only some of the reactants and products
are in the gaseous state equilibrium constant expressed in terms of partial
pressures KP is called condensed equilibrium constant.
For the reactions CaCO3(s) CaO(s) + CO2(g) ; KP = PCO2

NH4HS(s) NH3(g) + H2S(g); K p = PNH3. PH2 S

PROBLEMS :-
1. The following concentrations were obtained for the formation of NH 3 from
N2 and H2 at equilibrium at 500 K. [N2] = 1.5 x 10-2 M , [H2] =
3.0 x 10-2 M and [NH3] = 1.2 x 10-2 M. Find the equilibrium constant ?.
N 2 (g) + 3 H2 (g) 2 NH3(g)

Kc =
 NH 3 
2

; Kc =
(1.2 x 10 ) −2 2

 N2   H 2  (1.5 x 10 ) (3.0 x 10 )
3 −2 −2 3

1.44 x 10−4 1.44

Kc = −8
= x 104 = 0.0355 x 104 = 3.55 x 102
1.5 x 27 x 10 40.5
2. At equilibrium, the concentrations of N2= 3 x 10-3 M , O2 = 4.2 x 10-3 M
and NO = 2.8 x 10-3 M in a sealed vessel at 800K. What will be Kc for the
reaction
N 2 (g) + O2 (g) 2 NO(g)

Kc =
 NO
2

; Kc =
( 2.8 x 10 ) −3 2

,K =
7.84 x 10−6
= 0.622
 N 2  O2  (3 x 10 ) ( 4.2 x 10 )
−3 −3 c
12.6 x 10−6

3. PCl5, PCl3 and Cl2 are at equilibrium at 500K and having concentration as
PCl5 = 1.41 M, PCl3 = 1.59 M and Cl2 = 1.59 M. Find Kc for the reaction
PCl5 (g) PCl3 (g) + Cl2(g)

Kc =
 PCl3  Cl2  ; Kc =
(1.59 )
2

= 1.79
 PCl5  1.41
4. For the equilibrium, 2 NOCl (g) 2 NO(g) + Cl2(g) , the value of Kc is
3.75x10-6 at 1069K. Calculate Kp for the reaction at this temperature ?
K p = K c ( RT ) , for the above reaction n = 3-2=1,
n

K p = 3.75 x 10−6 x 0.0831 x 1069 = 0.033

5. The value of Kc is 4.24 at 88K for the reaction
CO( g ) + H2O( g ) CO2 (g) + H2 (g)
Calculate the equilibrium concentrations of CO2, H2, CO and H2O at 800K
if only CO and H2O are present initially at concentrations of 0.1 M each ?.
Initial concentration of CO and H2O is 0.1 M. Let ‘x’ mole per litre of
each of the reactant reacted, and ‘x’ mole per litre of each of products
formed at equilibrium, then at equilibrium

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 CO( g ) + H2O( g ) CO2 (g) + H2 (g)
Initial concentration 0.1 0.1 0 0
At equilibrium 0.1-x 0.1-x x x

Kc =
( CO2 ) ( H 2 ) ; 4.24 =
x2
( CO ) ( H 2O ) ( 0.1 − x )
2

x2 = 4.24 ( 0.1 − x ) x 2 = 4.24 ( 0.01 + x 2 − 0.2 x )

2
;

x2 = 0.0424 + 4.24x 2 − 0.848x ; 3.24x2 − 0.848x + 0.0424 = 0

−b  b2 − 4ac
It is like quadratic equation i.e ax + bx + c = 0 , x =
2

2a
a = 3.24, b = -0.848, c = 0.0424
0.848  0.8482 − 4 x3.24 x0.0424 0.848  0.719104 − 0.549504
x= ; x=
2 x3.24 6.48
0.848  0.1696 0.848  0.411825
x= ; x=
6.48 6.48
0.848 + 0.411825 1.25985
x= ; x= = 0.194
6.48 6.48
0.848 − 0.411825 0.436575
x= ; x= = 0.067
6.48 6.48
Since the value 0.194 is more than initial concentration i.e 0.1, therefore
x=0.067.
Hence the equilibrium concentrations are
[CO2] = [H2] = 0.067 M and [CO] = [H2O] = 1- 0.067 = 0.033M
Characteristics of Equilibrium Constant :-
1. Expression for equilibrium constant is applicable only when
concentrations of the reactants and products have attained constant
value at equilibrium.
2. The value of equilibrium constant is independent of initial
concentrations of reactants and products.
3. Equilibrium constant is constant for a given reaction at a given
temperature and changes with temperature.
4. If ‘x’ is the equilibrium constant for forward reaction then it will be 1/x
for the backward reaction.
5. Equilibrium constant depends on stoichiometry of the reaction.
Applications of Equilibrium constant :-
1. Predicting the extent of a reaction:-
The numerical value of equilibrium constant indicates the extent
of reaction. Higher the value of equilibrium constant (K) greater is the
extent of forward reaction and vice versa .
A. If Kc > 103, then the concentration of products is more
B. If Kc < 10-3, then the concentration of reactants is more.
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 2. Predicting the direction of the reaction :-
The equilibrium constant helps in predicting the direction in which
a given reaction will proceed. For this purpose we need “Reaction
Quotient” (Q). It is the ratio of product of concentration of products to
the product of concentration of reactants. The concentration of
reactants and products are not necessarily equilibrium values.
1. If Q > K, then the reaction will proceed in the direction of reactants.
2. If Q < K, then the reaction will proceed in the direction of products.
3. If Q = K, then the reaction is at equilibrium.
Factors affecting equilibrium :
One of the important fact in industrial preparation of compounds is that
to maximise the yield of product with minimum expenditure of energy. It is
possible by altering the conditions particularly in reversible reactions which
are at equilibrium. The effect of external conditions on the position of
equilibrium was given by Le-Chatlier.

Le – Chatelier’s principle: It states that, when a system at equilibrium is

subjected to change or stress in factors like concentration, temperature,
pressure that govern the equilibrium, then the equilibrium shifts in the
direction in which the change is reduced or nullified.

1. EFFECT OF CONCENTRATION :-
When the concentration of the reactants is increased or the
concentration of products decreased then the equilibrium shifts to the right
side (products side). Similarly, when the concentration of the products is
increased and the concentration of reactants is decreased then the
equilibrium shifts towards the left side (reactant side).
2. EFFECT OF TEMPERATURE :-
When temperature is increased endothermic reaction is favoured and
the equilibrium shifts in the direction in which heat is absorbed and when
temperature is decreased then the equilibrium shifts in the direction in which
heat is released.
3. EFFECT OF PRESSURE :-

When pressure is increased, then the equilibrium shifts in the direction

in which volume decreases and when pressure is decreased then the
equilibrium shifts in the direction in which volume increases.
If the total volume of the reactants is equal to the total volume of the
products, change of pressure has no effect on equilibrium.

4. EFFECT OF CATALYST :-
Catalyst is a substance generally it increases the rate of reaction in
such a way that it takes the reaction in a path of lower activation energy. It
increases the rate of both forward and backward reactions to the same
extent, therefore it has no effect on the equilibrium.

Le-Chatelier’s principle is applicable to physical and chemical equilibrium.

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Application Le-Chatlier’s principle.

1. Synthesis of ammonia : ( By Haber’s Process):

Ammonia in this process is prepared from nitrogen and hydrogen

N2 (g) + 3 H2 (g) 2 NH3 (g) ; H = - 46 kJmole−1

Formation of ammonia is reversible and exothermic in nature.

Therefore low temperature is favourable for the formation of ammonia.
However, the reaction doesn’t takes place at very low temperature,
therefore an optimum temperature 725K – 775K is maintained. Since the
rate of reaction is slow at this temperature and the rate is increased by
using finely divided iron powder as catalyst with molybdenum as
promoter.
Since the formation of ammonia is accompanying with decrease in
number of moles, therefore high pressure is favourable for the formation
of ammonia. A pressure of 200 – 500 atm. is maintained.
The optimum conditions for the better yield of NH3 are :
1. Temperature :- 725K – 775K
2. Pressure : - 200 to 500 atmospheres.
3. Catalyst : - Finely divided iron powder with molybdenum as promoter.

2. Synthesis of sulphuric acid ( By Contact Process ): The important

step in this process is oxidation of sulphur dioxide to sulpur trioxide.
2 SO2 (g) + O2 (g) 2 SO3 (g) ; H = - 189 kJmole−1
Formation of sulphur trioxide is reversible and exothermic in nature.
Therefore low temperature is favourable for the formation of SO 3
However, the reaction doesn’t takes place at very low temperature,
therefore an optimum temperature 673K – 723K is maintained. Since the
rate of reaction is slow at this temperature and the rate is increased by
using V2O5 ( Vanadium pentoxide )as catalyst.
Since the formation of SO3 is accompanying with decrease in number
of moles, therefore high pressure is favourable for the formation of SO3,
however SO3 being acidic in nature, it corrodes the reaction vessel at high
pressure. Therefore an optimum pressure of 1 – 2 atm. is maintained.
The optimum conditions for the better yield of NH3 are :
1. Temperature :- 673K – 723K
2. Pressure : - 1 – 2 atmospheres.
3. Catalyst : - V2O5.

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 ACIDS & BASES
Acids are the substances which are sour to taste, turn blue litmus to
red, liberate hydrogen on reacting with some metals, neutralize bases etc.
Similarly, bases are the substances which are bitter to taste, turn red
litmus to blue, soapy to touch, neutralize acids etc.
ARRHENIUS THEORY OF ACIDS AND BASES :- According to this theory,
Acids:- Substances that dissociates in aqueous solutions to give hydrogen
ions (H+) are called “Acids”.
Ex : HCl, H2SO4, HNO3, H2CO3, HNO2, HCOOH, CH3–COOH.
Bases:- Substances that produce hydroxyl ions (OH-) in aqueous solutions
are called “Bases”.
Ex : NaOH, KOH, Ca(OH)2 etc.
The ionization of an acid HX in aqueous solutions can be represented as
→ H(+aq ) + X(−aq )
HX ( aq ) ⎯⎯
The H+ ion (proton) in aqueous solution is very reactive and it forms a bond with
water to give hydronium ion (H3O+).
→ H3O(+aq) + X(−aq)
HX ( aq ) + H2O( aq) ⎯⎯
Similarly, the ionization of base say MOH is represented as
→ M(+aq ) + OH(−aq )
MOH( aq ) ⎯⎯
Salt:- Substances that neither give H+ ions nor OH- ions in aqueous solutions
are called salts. Ex NaCl, KNO3, CaCl2 etc.
Neutralisation:- The process in which H+ ion of acid and OH- ion base combine
to give water is called Neutralisation.
Strong Acids : Acids that dissociates to give more number of H+ ions in
aqueous solution are called strong acids.
Ex : HCl, H2SO4, HBr, HI, HNO3, HClO4.
Weak Acids :- Acids that dissociates to give less number of H+ ions in aqueous
solution are called weak acids.
Ex: HCN, H2CO3, HNO2, H2SO3, HCOOH, H2C2O4, CH3–COOH, C6H5COOH.
Strong Bases: Bases that produce more number of OH- ions in aqueous
solution are called strong bases.
Ex : NaOH, KOH, Ba(OH)2 etc.
Weak Bases :- Bases that produce less number of OH- ions in aqueous solution
are called strong weak bases.
Ex: NH4OH, Zn(OH)2 etc.
Drawbacks of Arrhenius theory :
1. This concept is limited to aqueous solution only.
2. It failed to account for the basic properties of substances like NH3 and
PH3.
3. It failed to account for the acidic properties of substances like CO2.

BRONSTED – LOWRY THEORY: According to this theory

Acids:- Substances that are capable of donating a hydrogen ion (proton,H+)
are called “Acids”. That means proton donor is an acid.
Ex : HCl, H2SO4, HNO3, H2CO3, HNO2, HCOOH, CH3–COOH.
Bases:- Substances that are capable of accepting a hydrogen ion (proton,H+)
are called “Bases”. That means proton acceptor is a base.
Ex : OH- , Cl- , etc.
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 Consider the dissolution of hydrochloric acid in water
HCl + H 2O H3O + + Cl−
HCl in this reaction donated a proton to water and water accepted a proton
from HCl, and are thus, called Bronsted Lowry acid and base respectively. In
reverse reaction H3O+ acts as proton donor and is a Bronsted acid and Cl- acts
as proton acceptor and is a Bronsted base.
Consider the dissolution of ammonia in water
NH 3 + H 2O NH 4+ + OH −
NH3 in this reaction accepted a proton from water and water donated a proton
to NH3 , and are thus, called Bronsted Lowry base and acid respectively. In
reverse reaction NH 4+ acts as proton donor and is a Bronsted acid and OH- acts
as proton acceptor and is a Bronsted base.
From the above two equations it is clear that, water plays dual role, i.e it
acts proton donor and proton acceptor.
Conjugate acid – base pair : The acid – base pair that differs only by one
proton is called “ Conjugate acid – base pair. Thus Cl- is conjugate base of HCl
and H3O+ is conjugate acid of H2O.

If acid is strong, then its conjugate base is weak base and vice versa.
Strong acids weak conjugate bases
HCl  Cl-
HNO3  NO3-
HClO4  ClO4-
H2SO4  HSO4-
Weak acids Strong conjugate bases
HCN  CN-
H2 S  HS-
H2CO3  HCO3-
HCOOH  HCOO-
CH3COOH  CH3COO-.
Similarly, if base is strong, then its conjugate acid is weak acid and vice versa.
Strong bases weak conjugate acids
OH-  H2O
CN -  HCN
Weak Base Strong conjugate acids
Cl -  HCl
HSO4 -  H2SO4

9
LIMITATIONS TO BRONSTED – LOWRY THEORY:

1. It failed to explain acidic and baisic properties of compounds in their

native state.
2. It failed to explain the acidic properties of non metal oxides and basic
properties of metal oxides
3. It failed to explain the acidic properties of substances like BF3, BCl3, AlF3,
FeCl3, SnCl2, SnCl4.
4. There is no term like salt in this concept.

LEWIS THEORY (OR) ELECTRONIC CONCEPT: According to this theory

Acids:- Substances that are capable of accepting a pair of electrons are
called “Acids”. That means electron pair acceptor is an acid.
Bases:- Substances that are capable of donating a pair of electrons are
called “Bases”. That means electron pair donor is a base.
Classification of Acids : Acids are classified as
1. All cations : H+,Na+, Mg2+, Al3+, Fe+2, Fe+3, Cu+2etc.
2. Molecules whose central atom having vacant orbitals. E.g: BF3, BCl3,
AlF3, AlCl3 etc.
3. Molecules whose central atom having vacant ‘d’ orbitals.
E.g: FeCl3, FeBr3, SnCl2, SnCl4 etc
4. Molecules having multiple bonds between dissimilar atoms. Ex CO2.
Classification of Bases : Bases are classified as
1. All anions are Lewis bases. Cl-, Br-, I-, NO3-, SO42-, CO32-, etc.,
2. Molecules having one or more lone pairs of electrons are Lewis bases.
E.g: H2O, ROH, R2O, NH3, RNH2, R2NH, R3N, etc.,
3. Molecules having multiple bonds between similar atoms are Lewis bases.
Ex: Ethylene ( CH2=CH2).

All Lewis bases are Bronsted bases but all Lewis acids are not
Bronsted acids because, as the base provide lone pair of electrons in
both the cases. For example NH3 it accepts proton as well as donate
electron pair. However, many Lewis acids do not have proton. For
example HCl is a Bronsted acid as it donates proton but it is not a Lewis
acid as it doesn’t have lone pair.
IONIC PRODUCT OF WATER ( Kw) :
The product of the molar concentrations of hydrogen ions and hydroxide
ions in pure water is constant at constant temperature which is called ionic
product of water.
H 2O H + + OH −
[ H + ] [OH − ]
K= or K[H 2O] = [ H + ] [OH − ]
[ H 2O]
Since water is weak electrolyte and its dissociation is less, therefore the
concentration of water is taken as constant. Thus
Kw = [H+] [OH-] , where Kw is called Ionic product of water.

10
 OR
H 2O + H 2O H3O + + OH −
[ H 3O + ] [OH − ]
K= or K[H 2O]2 = [ H 3O + ] [OH − ] ; Kw = [H3O+] [OH-]
[ H 2O]2
The value of Kw at 250 C is 1.0 x 10-14(Moles/litre)2. It varies with
temperature because the dissociation of water varies with temperature.
As water dissociate to give equal number of H+ ions and OH- ions, therefore
In neutral solution [H+] = [OH-] = 1.0 x 10-7 M
In acidic solutions [H+] > [OH-] i.e > 1.0 x 10-7 M
In basic solution [H+] < [OH-] i.e <1.0 x 10-7M.

PH Scale :- The H+ ion concentration is in molarity can easily be expressed in

terms of pH. The pH of a solution is defined as the negative logarithm to base
10 of the H+ ion concentration. Mathematically it is represented as

PH = - log [H+ ]

Let us find the pH of 1 x 10-2 M HCl solution.

PH = – log [H+] = – log 1 x 10-2 = 2
The PH of pure water is 7 at 250C.
For acidic solutions PH < 7 ; For basic solutions PH > 7 ; and for neutral
solutions PH = 7.
PH scale is applicable only for dilute solutions.
Solutions having higher concentration of OH- ions are basic in nature
and POH is calculated first by using equation POH = –log [OH-]. However the
nature of solution is also expressed only in terms of PH for basic solutions.
Consider the equation Kw = [H+] [OH-], applying negative logarithm on
both sides,
− log K w = − log([H+ ] [OH − ] ; − log K w = − log[H + ] − log[OH− ]
−14
P H + POH = 14 ;
− log K w = − log 1 x 10 Kw
= 14 ; P = P + P H OH

Therefore, for basic solutions PH = 14 – POH .

Universal Indicator :- A mixture of all know indicators which gives different
colours at different PH values is called “Universal Indicator”.
The formulae PH = –log [H+] and POH = –log [OH-] are used for strong
acids and strong bases respectively but not for weak acids and weak bases.
Problems :-
1. The concentration of H+ ion in a sample of soft drink is 3.8 x 10-3M.
Find the PH of the soft drink.
PH = –log [H+] ; PH = –log 3.8 x 10-3
P =3 –log 3.8 ;
H PH =3 – 0.58 = 2.42.
2. Calculate the PH of 0.001 M HCl solution ? Ans : 3.
3. Find the P of 0.005 M H2SO4 solution ?
H Ans : 2.
4. Find the PH of 0.05 M NaOH solution ? Ans : 12.6990.

11
 5. Calculate the PH of 1 x 10-8M HCl solution ?
1 x 10-8M HCl solution is very dilute solution. Therefore the
concentration of H+ ion of water is to be considered along with given
acid concentration. Therefore,
P H = - log  H + 
Total
i.e (
P H = - log  H + 
H 2O
+  H + 
HCl )
P H = - log (1x 10−8 + 1 x 10−7 ) ; P H = - log ( 0.1 x 10−7 + 1 x 10−7 )
P H = - log (1.1 x 10−7 ) ; P H = 7 - log 1.1 ; P H = 7 - 0. 02 = 6.98
PH of weak acids : Weak acids are the substances that do not undergo
complete dissociation. Consider a weak acid HA with initial concentration of
‘c’ moles per litre,  is its degree of dissociation, then
HA H+ + A −
Initial concentration c 0 0
At equilibrium c(1 -  ) c c

 H +   A−  c . c c 2
Therefore K a = ; Ka = =
 HA c (1 −  ) (1 −  )
Ka is dissociation constant of acid.

− log cK a
 H +  = c K a ; PH =
2
Ka
For weak acids, degree of dissociation(  ) is less and  =
c
Problem: The ionization constant of HF is 3.2 x 10 . Calculate the degree of
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dissociation of HF in its 0.02 M solution and also calculate the concentration

of all species.
Ka = 3.2 x 10-4 and c = 0.02
HF H+ + F−
Initial concentration 0.02 0 0
At equilibrium 0.02(1-  ) 0.02  0.02 
Ka 3.2 x10−4
= ; = = 0.12
c 0.02
 HF  = 0.02(1- ) = 0.02 - 0.02x0.12 = 0.02 - 0.0024= 0.0176
 H +  =  F −  = 0.02 = 0.02 x 0.12 = 0.0024
PH of weak bases :
− log cKb
OH −  = c K b ; POH = PH = 14 – POH.
2
Where Kb = Degree of dissociation of base.
Kb
For weak bases, degree of dissociation(  ) is less and  =
c
Relation between Ka and Kb : Ka x Kb = Kw.
Strength of acids and bases : Strength of acids and bases mainly depends
on their Ka and Kb or PKa and PKb values. Higher the value of Ka or lower the
value of PKa stronger is the acid. Similarly Higher the value of Kb or lower the
value of PKb stronger is the base.

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Hydrolysis of salts :- Aqueous solution salts may be neutral or acidic or
basic in nature because the cations and anions or both of salts may undergo
hydrolysis. Thus “The phenomenon of interaction of cation or anion or both of
salt with water to give acidic or basic or neutral nature to the solution is
called Salt hydrolysis”.
1. Nature of aqueous solution of salts of strong acid and strong base : The
aqueous solution of salt of strong acid and strong base is neutral
because neither the cation nor the anion undergoes hydrolysis. The PH
solution remains 7.
Ex : Aqueous solution of NaCl, KCl, NaNO3, KNO3, BaCl2 etc.
2. Nature of aqueous solution of salts of weak acid and strong base : The
aqueous solution of salt of weak acid and strong base is basic/alkaline
in nature due to anionic hydrolysis. The PH solution is >7.
Ex : Aqueous solution of CH3COONa, Na2CO3, KCN, HCOONa etc

3. Nature of aqueous solution of salts of strong acid and weak base : The
aqueous solution of salt of strong acid and weak base is acidic in
nature due to cationic hydrolysis. The PH solution is <7.
Ex : NH4Cl, (NH4)2SO4, AlCl3, FeCl3, CuSO4, FeSO4, AgNO3 etc.

4. Nature of aqueous solution of salts of weak acid and weak base : The
aqueous solution of salt of weak acid and weak base may be acidic or
basic or neutral in nature that depends on Ka and Kb values.

The PH of aqueous solution of weak acid and weak base is

calculated from the equation P H = 7 + 1/2 [P Ka - P Kb ] .
For example : Calculate the PH of solution of acetic acid (PKa = 4.76)
and ammonium hydroxide (PKb = 4.75 ).
P H = 7 + 1/2 [P Ka - P Kb ] ; P H = 7 + 1/2 [4.76 - 4.75] = 7.005

Buffer Solutions :- Solutions which resist to change in PH upon dilution of

small amount of strong acid or strong base are called “Buffer solutions”.
Buffers are two types
A) Acidic Buffer : A mixture of weak acid and salt with strong base is
called acidic buffer. Ex : CH3COOH + CH3COONa

B) Basic Buffer : A mixture of weak base and its salt with strong acid is
called basic buffer. Ex : NH4OH + NH4Cl.

Consider acidic buffer with a weak acid (HA) and its slat with
strong base. Weak acid ionizes in water as

HA + H 2O H 3O + + A − . For which equilibrium constant K a is

[H3O + ] [A − ]
Ka = water is in large excess & its concentration is neglected
[ HA]

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 On rearranging the equation we get
[ HA] [ HA]
-log [H 3O + ] = -log K a - log −
or P H = P Ka - log or
[A ] [A − ]
[A − ]
P H = P Ka + log A − represents salt and HA represesents acid
[ HA]
[salt]
Therefore P H = P Ka + log . This is called Hinderson-Hasselbalch
[Acid]
equation.

Solubility product (Ksp):- Majority of salts are highly soluble in water,

however there are certain salts like BaSO4, AgCl etc which are sparingly
(less) soluble in water and are called “Sparingly soluble salts”.
Consider a sparingly soluble binary salt (MX). It ionizes in water as
MA M + + A − . The equilibrium constant K is given as
[M + ] [A − ]
K= ; K [MA] = [M + ] [A − ]
[MA]
Since the salt is sparingly soluble salt, hence its concentration is constant,
therefore, K SP = [M + ] [A − ] where KSP is solubility product.
Let ‘S’ moles/lit is the concentration of each of M+ and A- at
equilibrium, then K SP = S x S or K SP = S2 and S = K SP
K SP
For ternary salts like M2A or MA2 : K SP = S x (2S)2 or K SP = 4S3 and S = 3
4
Higher the value of solubility product more is the solubility of the
compound. The solubility of salt increases with increase of concentration of
H+ ion or decrease of PH.

Common ion effect :- The phenomenon of suppression of ionization of a

weak electrolyte in water by the addition of another electrolyte which has an
ion common with the electrolyte is called “Common ion effect”.
For example : Acetic acid a weak acid ionizes in aqueous solution as
CH 3COOH CH 3COO − + H +
Addition of acetate ions ( CH3COO- in the form of CH3COONa) a
common ion suppresses the dissociation of acetic acid. This is because of
increase of acetate ion concentration shifts the equilibrium to the left side.
If we pass HCl gas through saturated NaCl solution, then NaCl
precipitated out due to common ion effect and is called Salting out. NaCl thus
obtained is very pure.
Applications of common ion effect :
1. Common ion effect is used in controlling the H+ ion concentration in
buffer solution.
2. The concentration of S2- in the 2nd group or OH- in 3rd group in
qualitative analysis is controlled by HCl and NH4OH on the basis of
common ion effect.

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