• Equilibrium is the state of process, in which the e.g.

, AgNO 3 + NaCl ---+ AgCl j, + NaNO 3

concentration of reactants and products becomes SnC12 + 2FeC13 ---+ SnC14 + 2FeCl2
constant until the conditions of temperature and • State of equilibrium : Chemical equilibrium is that
pressure are changed. At equilibrium state both the state of a reaction at which the rate of forward reaction
forward and backward reactions move with equal becomes equal to rate of backward reaction.
speed.
Characteristics of chemical equilibrium
PHYSICAL EQUILIBRIUM • Equilibrium state is attained only when reaction is
• It is the process which involves physical changes carried out in a closed vessel.
only, like equilibrium between different states of • At equilibrium, concentration of all reactants and
substances at a particular temperature. products becomes constant.
> Solid � liquid : ice � water at 0 ° C • Equilibrium is dynamic in nature i.e., reaction seems
rate of melting = rate of freezing to be static but actually takes place in both the
> Liquid � gas (vapour) : water � water at 100°C directions with same speed.
(vapours) • Chemical equilibrium can be attained from either
rate of evaporation = rate of condensation direction i.e., from the side of reactants or products.
> Solid � gas (vapour) : CO2 (solid) � CO2 (vapours) • At the stage of equilibrium free energy change is zero
rate of sublimation = rate of condensation i.e., 6.G = 0.
> Solid � saturated solution of solid in liquid
rate of dissolution = rate of precipitation

i
> Gas � saturated solution of gas in liquid
always exothermic and spontaneous
a Freezing point / melting point : The temperature at
which the solid-liquid equilibrium is reached for a
pure substance under one atmospheric pressure is
called normal melting point or normal freezing point
of the substance.
Boiling point : The temperature at which liquid-gas
Time�
•
Variation of reaction rates offmward and backward
equilibrium is attained for a pure substance under reaction with time.
normal atmospheric pressure (1 atrn) is called nmmal
boiling point of the substance.
• Law of chemical equilibrium
For a given reversible reaction,
CHEMICAL EQUILIBRIUM aA + bB � cC + dD
• If the process involves only chemical change, the Rate of forward reaction (R1) = [A] a [B] h (law of mass
equilibrium is called chemical equilibrium. action)
= k1 [A] 0 [Bj h
• Reversible reaction : A reaction in which the reactants Rate of backward reaction (Rb) oc [C] c [D] d = kb [C]"[D] d
are formed back by the reaction of products with .each At equilibrium, Rr = Rb ; k1 [A] a [BJ b = kb[C] 0 [Dt
other at the given conditions of the reaction. These
reactions if carried out in a closed vessel do not go kr - [cnnt
to completion. -;;- [At[Bl
e.g., CH3 COOH + C2H5 OH � CH3 COOC2H5 + H2 O k
N2(gl + 3H2(g) � 2NH3 (g) _l_ = Kc = equilibrium constant
Irreversible reaction : These are the reactions in
• kb
which products do not react back to give the reactants, [C] c [Dt
i.e., reaction can not be retraced at any point. [Af[Bt
Equilibrium

• The given equation is known as law of chemical ([ C]RT t ([D]RT t

K = -'-----'---'- [ Ct [Dt x (R T ) (c+d) (a+b)
equilibrium. Law of chemical equilibrium is for a ----'-,- -
reversible reaction at equilibrium, the ratio of the P ([A]RT t ([B]RT / [A] 0 [Bl . .
product of the concentrations of the products and if (c + d) - (a + h) = An
the product of the concentrations of the reactants is
constant at cons tant temp erature when each KP = KfiT""
concentration term is raised to the power equal to the An (number of moles of gaseous product) - (number
=

corresp onding stoichi ometric coefficient in th e of moles of gaseous reactants)

balanced chemical equation. The ratio is known as • Units of equilibrium constant (Kc) = (mol/L)""
equilibrium constant. (Kp) = (atm)"''
Eq uilibrium Constant
• For a reaction,
CH3 COOH + H2 O � CH3 COO- + H3 O+ ; K1 = 1 .8 x 1 0-5
aA + bB � cC + dD
2H2 O � H3 O+ + OH- ; K2 = 1 X 1 0 - 14
[ CflDt Calculate equilibrium constant for
Equilibrium constant, Kc = b
[At [B] CH3 COOH + OH- � CH3 Coo- + H20
For a homogeneous gas phas e reaction, the molar Soln. : It is given that
CH3 COOH + H2 O � CH3 COO- + H3 O+
Ill
concentration of a substance is directly proportional
to its partial pressure p at constant temperature. Then K1 = 1 .8 x 1 0-5 . . . (i)
equilibrium is denoted by Kr +
2 H 2 0 � H 3 0 + OH- , K2 = l x l 0- 14 . . . (ii)
K = (pc )" x (pD t :. For reaction,
p (PA Y X (PB i CH 3 COOH+ OH- � CH 3 COO- + H 2 0 . . . (iii)
• Relation between KP and Kc
K = � = 1 .8 x 1 0-
. 5
P = !!:_RT = CRT = 1 .8 1 09
K2 l x l 0-1 4
X

• Characteristics of equilibrium constant

If for a reation, A + B � C + D, equilibrium constant, K = i����;

If reaction is reversed. A + B � C+D K' = 1/K
1 1 1 1 K' = efK
If reaction is divided by -A + - B :;,= - C + -D
factor n. n n 11 11

If reaction is multiplied by nA + nB � nC + nD
factor n.
If reaction is written in n A + B .!S:..
� X + }' ; X + Y .5.:,.
..,.:... P + Q . . . . C+D
number of steps.

Illustration 2 Pco = 2p = 2 x 0.3 = 0.6 atm

A vessel at 1 000 K contains carbon dioxide at a pressure 2 ( 2
of 0.5 atm. Some of the carbon dioxide is converted to =;, K = Pco = � = 1 . 8 atm
carbon monoxide on addition of graphite. Calculate tlw Pco2 (0.2)
value of K, if the total pressure at equilibrium is 0 .8 atm. Factors affecting equilibrium constant : Equilibrium
Soln.: CO 2 + C(graphiteJ � 2CO constant is only affected by temperature.
Let the decrease in pressure of CO2 after reaction = )- In exothe1mic reversible reactions, as temperature
p atm increases, K increases .
Then, increase in pressure due to CO after reaction = )- In endothermic reversible reaction s , as
2p atm temperature increases, K decreases .
Final total pressure = (0.5 - p) + 2p = 0.8 atm van't Hoff equation
=;, p = 0.3 atm
j
@

I K2 - Mi [ Tz - 1i
o
Thus after reaction, Pco2 = 0.5 - 0.3 = 0.2 atm
og Ki - 2 . 3 0 3 R T;T2
 K1 and K2 are equilibrium constants at temperature T1 • Effect of change in temperature: In a reaction at
and T2, Mf0 = enthalpy of reaction. equilibrium if temperature is increased, reaction will
• Reaction quotient : Ratio at any stage of reaction proceed in the direction in which some heat can be
other than the equilibrium is called reaction quotient destroyed i. e. , absorbed so that temperature of the
or concentration quotient. It is represented as Q0 or system remains cons tant . It mean s increase in
Qp or simply Q. Thus, for the reaction, temperature supports the endothermic reaction where
aA + bB � xX + yY heat is absorbed. Decrease in temperature favours
exothermic reaction in which heat is liberated.
[XJ" [Y]Y
Q = --- • Effect of change in press ure : In a reaction at
[Ar [nt equilibrium if pressure is increased, then according to
Few important results can be drawn from reaction Le Chatelier's principle, the equilibrium will _shift in a
quotient (Q) direction in which the pressure decreases. Tiris implies
• If Q = K, the reaction is in equilibrium. that equilibrium will shift in a direction which produces
• If Q < K, the reaction proceeds in forward direction smaller number of moles, since pressure is directly
(i. e. , from left to right). proportional to the number of moles.
• If Q > K, the reaction proceeds in backward direction
(i. e., from right to left).
• Effect of catalyst : It does not effect the equilibrium
position. It only helps in attaining the equilibrium state
LE CHATELIER'S PRINCIPLE quickly.
• The law states that if any kind of change in • Effect of adding inert gas
concentration, temperature or pressure is imposed on > If inert gas is added at constant volume to the
the system in equilibrium, then equilibrium shifts in reaction at equilibrium, the equilibrium will not be
a direction that tends to undo the effect of the change changed/disturbed, because at constant volume
imposed. addition of an inert gas will not change the molar
• Effect of change in concentration : In a reaction at concentration of the reactants and products.
equilibrium, if concentration of any reactant or > If inert gas is added at constant pressure to the
product is increased, the equilibrium shifts in a reaction at equilibrium, the volume of reaction
direction where it will be consumed. The increase in mixture increases and equilibrium will shift in
concentration of reactant or decrease in concentration the direction in which there is increase in the
of products shifts the equilibrium in forward direction number of moles of the gas. If number of moles
whereas increase in concentration of products and on either side of equilibrium are same, there will
decrease in concentration of reactants shifts the be no effect of adding an inert gas on the state
equilibrium in backward direction. of equilibrium.

Summary of factors affecti ng equi libriu m

Favour/Effect Exothermic Higher number of moles Production of that species No effect No effect

I Temperature Pressure Concentration Addition of Addition of

l
Inert gas Catalyst

I Favour/Effect I
l
Endothermic Lower number
of moles
l
Consumption of
that species
=,., "'e
<1 � 1
0 "'

p.

Leads to higher
number of moles
l
No effect

I l l u stration 3 2S0 2(g) + 02{g) � 2S03 (gl

For the exothermic formation of sulphur trioxide from KP 40.5 atm- 1 at 900 K and t:,.)f = -1 98 kJ mol- 1
=

sulphur dioxide and oxygen in the gas phase: (i) Write the expression for the equilibrium constant for
the reaction.
Equilibrium

(n) At room temperature ("" 300 K) will KP be greater than, (ii) Na 2 C0 3 (aq) : Base according to Bronsted-Lowry
less than or equal to KP at 900 K. concept
(iii) How will the equilibrium be affected if the volume of
the vessel containing the three gases is reduced, Na 2 C0 3 � 2Na+ + cot
keeping the temperature constant. What happens? co�- + H � HC0 3
+
(proton acceptor)
(iv) What is the effect of adding 1 mole of He(g) to a fl.ask (iii) C0 2 (gJ : Acid according to Lewis concept.
containing S02 , 02 and S0 3 at equilibrium at constant
volume?
In case of CO2 (0 C = =
0), double bond exists
Soln.: (i) The equilibrium constant for this reaction is between carbon and oxygen. Since oxygen is more
written in tenns of the partial pressure of the reactants electronegative than carbon, a slight positive charge
and products. So, is induced on carbon and hence it can accept an
Pso3 (g)
2
electron pair.
K =
(iv) H2 0 : Both acid and base i.e. , amphoteric according
Pso2 (g} x Po2 (g)
p 2
to Arrhenius concept and Bronsted-Lowry concept
(ii) This reaction is exothermic. So, its equilibrium
constant should increase with the lowering of H3 0
+
;;:::::===== H2 0 ;:::::::::===:=::!:
proton donor
H
+
+ OH­
temp erature proton acceptor
(d lnK/dT := b., H°IR'f'l.) . Therefore, the value of KP at (v) NH! : Acid according to Arrhenius, Bronsted­
300 K will be greater than the value at 900 K Lowry and Lewis concept.
(in) When the volume of the vess el is reduced, the
volume of the reaction mixture will decrease. As a NH! � NH3 + H (proton donor and electron deficient)
+

result, pressure of the gaseous mixture will increase.

According to the Le Chatelier's principle, the system
El ectrolytes
will move in a direction to undo the effect of the • When an ionic compound is dissolved in water or
pressure increase. The system therefore will move in melted, it gets split into its ions. The process is known
a direction so as to decrease the number of moles of as ionization or dissociation. Since the ions have
the gaseous substances in the system. The number either pos itive or negative charge, the aqueous
of moles decrease in going from reactants to the solution of such compounds can conduct electricity.
product side. Therefore, a decrease in the volume of • A compound whos e aqueous solution or melt
the reacting system will shift the equilibrium to the
right. That is, more S0 3 (g) will be formed from the conducts electricity is known as electrolyte, whereas
reactants . non-electrolyte is the compound who s e neither
(iv) Addition of helium to the reaction mixture at aqueous solution nor melt conducts electricity.
equilibrium under constant volume has no effect on • Strong and weak electrolytes : Electrolytes which
the equilibrium. diss ociate almost completely into ions in aqueous
IONIC E Q U I LIBRIUM solution are known as strong electrolytes, e. g. > NaCl,
HCl, NaOH, H 2 S0 4 , etc. They are very good
Acids and Bases
c onductors of electricity. Th ey have degree of
dissociation nearly one i. e. , a "' 1 .
• A rr h e n i u s A substance which A substance which Whereas those electrolytes which dis sociate only
c o n c e p t gives H+ ion when gives OH- ims when partially into ions in aqueous solution are known as
(1 884) dissolved in water. dissol'6:I. in wata: weak electrolytes, e.g. , CH3 COOH, NH40H, etc.
e. g . , HCl, H2 S0 4 , e.g. , KOH, NaOH, They have conductivity smaller than that of strong
HN03 Ca(Olf1 electrolytes . Their value of degree of dissociation is
• Brons ted- Proton donors Proton acceptors much smaller than one i. e. , a << 1. An equilibrium is
1.owiy concept e. g. , CH 3 C O OH, e.g. , NH3 , c1-, cot- set up in case of partially ionized weak electrolytes
HCl, HN0 3 between ions and unionized electrolyte.
(1923)
• Lewis concept Electron acceptor Electron donor e.g. NH 4 OH � NH 1( aq) + OH�aq )
(1939) e.g. , H+ , S03 , S02, e.g., 02-, NH3 , H2� { aq )

A1Cl3 , Ag+ • Degree of ionisation (a) : The fraction of total number

of molecules dis sociated into ions at a particular
RJOtOEiMII temperature is known as degree of ionisation or degree
Classify the following as acid or base and also mention
the concept on the basis of which these are so. of dissociation. It is denoted by a.
(i) HC�aq) (ii) Na2C03(uq) (iii) C02(g-} Number of moles dissociated
a � ----------
(iv) H20 (v) NH!" Total number of moles
Soln.: (i)HCl (aqJ : Acid according to Arrhenius concept and
Bronsted-Lowry concept D egree of ionisation depends on temperature and
(proton donor) increases with increase in temperature.
HCl � H + + Cl-
• Ostwald's dilution law : It is applicable only to weak
electrolytes , not to strong electrolytes . Consider a So, Ka = a 2 C => a=�
weak electrolyte AB with initial concentration ' C'
(moles L- 1 ) and degree of dissociation 'a' . Then, [H3 O + ] = Ca = C� = �Ka C
AB ___,_ A + + B- • Ionisation of a base BOH
BOH + H2 0 � s+ + OH-
( aq) � ( aq} ( aq}

Initial concentration C O 0
At equilibrium C(l - a) Ca Ca Initial C excess O 0
Applying law of equilibrium to the above equilibrium At equilibrium C(l - a) Ca Ca
• Ionisation constant of a base (Kb) :
K = [A ] [B-] = Ca x Ca = Ca
+ 2

[AB] C (l - a) (1 - a) [B + ] [OH- J Ca x Ca:

Kb =
C(l - a)
Where, K is known as dissociation constant. [BOH]
As a is very small for weak electrolytes (a << 1) then Ca. 2
(1 - a) "" 1 , Ca2 = K Kb = - -
1-a

a=� or a= Jc If a is small, Kb = o:2 C

a = f¥ "" JKb V
Thus, degree of dissociation of weak electrolyte is V = volume of solution containing 1 mole.
inversely prop ortional to the square root of molar
concentration of its solution. If V is the volume of [OH- ] = Ca = JKb C
solution in litres containing 1 mole of the electrolyte, • Ionisation of polybasic acids and polyacidic bases :
then Acids which have more than one ionisable proton
per molecule of the acid are known as polybasic or
C ,,,, _l polyprotic acids. For example oxalic acid ((COOH)i),
V
sulphuric acid (H2 SO 4) , phosphoric acid (H3 PO 4) ,
a= ffe or a = Jv carbonic acid (H2 CO3 ), etc.
i. e. , we can say that degree of dissociation of weak Consider any dibasic acid,
electrolyte is directly proportional to the square root Ka1 , +
of volume of solution containing one mole of the H2 A (aq) H + HA-
solute. Kaz ,
Thus it can be said that degree of dissociation of HA- H+ + A2-
weak electrolytes increases with dilution. The ionization constants Ka 1 and Ka2 are given as
[H + ] [HA- ] K = [H ] [A - ]
111 tm tffl 1M rll
+ 2
""
Kai ----- a2
A solution of organic acid (K0 = l 0--8) dissociates 0. 1 %. [H2A] [HA- ]
What is the concentration of the acid solution? It has been found that K0 1 > Ka2
For example,
Soln.: a = 0. 1 % = _QJ__ = 1 0-3 , K = Ca2
1 00 H3PO 4 � H + H 2 PO 4 ; Ka 1 = 7.52 x 1 0-3
+

K 1 0-8 ,.--- H + HPO 4- ,· K"2 = 6 •23 x 1 0

H 2 po-4 __,_
= = 1 0-2 i.e. , 0.0 1 M
+ 2 -&

C=2 a 3
(1 0- ) 2
,.--- H + po 4- '· K"3 = 4 . so x 1 0-13
HPO 24- __,_ + 3

• Ionisation of an acid R4 It is observed that Ka l > Ka2 > Ka3 .

HA + H2O � H3 O+ + A- The reason for decrease in the dissociation constant
n excess 0 0 of successive stages is that in the first dissociation,
n - na na na a neutral molecule gives a proton (H+), while in the
(a = degree of ionisation) second stage of dissociation, the proton is coming
• Ionisation constant of acid (Ka) : from a negatively charged molecule and in the third
na na step of dissociation, a doubly negatively charged
x molecule is giving a proton which in tum is more
K = [H 3O ] [A] _ V V
+
a
[HA] n(l - a) difficult than first two dissociations .
Similarly, polyacidic bases also ionise in steps with
respective ionisation constants like Kh 1 , Kho , etc.
V
(Ca)(Ca) .
(": - = concentrat10n = C) For any polyacidic base, Kb1 > Kb2 > Kb3 and so on.
n
(1 - a)C V
STRENGTH OF ACIDS AND BASES
a.2
K = -- C • Strength of acid is measured in terms of H+ produced
a (l - a) i. e. , greater the number of H+ produced in aqueous
If a is very small then 1 - a '°' 1 solution, stronger is the acid. Whereas strength of
Equilibrium

base is measured in terms of OH- produced i.e. , greater 1

the number of OH- produced in aqueous solution, Thus ' pH = - log[H ] = log-+- or [H ] = l O -pH
+ +
[H ]
stronger is the base.
Likewise, pOH of a solution
HA + water � H7aq) + �--;,q) 1
Acid pOH = -log[OH - ] = log--
[OH- ]
K.. = [W][OH- J
where, Ka is the dissociation constant of acid HA . = ionic product of water = 1 0- 1 4 (mol/L)2
Similarly for a base, Kb = [OH-J where Kb i s the pKw = -logKW
dissociation constant of a base BOH. pKw = pH + pOH = 14
Relationship between [W], [OH-] and pH value of the
• Relative strength of acids and bases : According to
@

solution is
Ostwald's dilution law, for weak acids,
[H+ ] rn-0 w - 1 2 1 0 -" 1 0·· 1 •

t"'
Hf' 10--1 1 0--1 10·' 10"" 10-5 lo-' 1 0--1 1 0--' 10--1 0 1 0--1 1
Ka = Ca..2 a = {K; or a = "I](
Ve 1
'-- a

For two weak acids of equimolar concentration,

,
[Ofr] 10-- 1 4 1 0-- " 10-- 1 2 1 0- 1 1 1 0 10 ! ()"' 1o-< 1 0-7 1 ,r" 1 0-' 1 0 -< 1 0--1 1 0-1 1 0 - 1 1 0•

pH O 2 3 4 5 6 7 8 9 10 11 12 13 14
--------D, --------->
'2 = Acidic Basic
Neutral
ctz Ka2
Degree of dissociation is considered as measure of l@tt®iMiM
strength of an acid How much KOH should be dissolved in one litre of solution
to prepare a solution having a pH of 1 2 at 25 ° C?
Strength of acid 1 (HA1 ) Ka Soln.: KOH is a strong alkali and is completely dissociated
=� 1
Strength of acid 2 (HA2 ) Ka.2 into the constituent ions,
Similarly, for equimolar weak bases, KOH + H20 (excess) � K\,qJ + OH-(aq)
In a s olution having pH = 1 2 , the hydrogen 10n
Strength of base 1 (B10H) jE;;,, concentration is given by the equation
Strength ofbase 2 (B2 OH) = �K½ pH = -log[H+]
Relative strength of some of the acids are as follows: 1 2 = -log[W]
HC1O4 > HBr > HCl > HNO 3 > H2 SO4 > H3 O+ > H2 SO3 or [H+] = 1 0-12 mol L- 1
> H2C0 3 > CH3COOH Since, the ionic product in water should have a fixed
HC1O4 > HC103 > HClO2 > HCIO
value, hence at 25 ° C
Relative strength of some of the bases are as follows:
KOH > NaOH > Ca(OH)2 > NfiiOH Kw = 1 .0 X I 0-14
NH3 > NH2 ·NH2 > NH2OH So, 1 .0 x 1 0- 14 = [W] [OH-J
.
I otttMtiMll\i This gives, [OH- ] = 1 0 x l�-J = l .0 x 10-2 mo! C 1
4

Compare the strength of HCN (Ka = 4.9 x 10--10) with O.Gl M 1 0-

Since KOH is completely dissociated, hence
aqueous solution of formic acid in which it is 1 4. 5 %
dis sociated . [KOH] = [OH-] = 1 .0 x 1 0-2 mol L- 1
Molar mass of KOH = (39 + 1 6 + 1) g mol- 1
Soln. : Applying,
= 56 g moI- 1
Strength of fom1ic acid Ka (formic acid) Then, cone. of KOH = LO x 1 0-2 mol L 1- x 56 g mo1-1
Strength of HCN Ka (HCN) = 0.56 g L-1
Degree of dissociation of HCOOH (a) = 1 4.5 % Thus, 0.56 g of KOH should be dissolved per litre of
14 5 the solution to obtain a solution of pH 12.
= - = 0. 1 45
1 00 • pK. and pKb
Ka (HCOOH) = Ca2 = 0.0 1 x (0. 145)2 = 2. 1 x 1 0 4- pKa = - logKa
pKb = - 1ogKb
Strength of fonnic acid 2.1 X 1 0-4 Ka X Kb = [ff] [OH-J
Thus, --- - --- = = 6,5 X 1 02
Strength of HCN 4 . 9 X 1 0-! 0 So, K. X Kb = Kw or pKw = pKa + pKb
i. e. , Formic acid is 6 . 5 x 1 02 times stronger than HYDROLYSIS OF SALTS
HCN or we can s ay that HCN is 6 . 5 x 1 0 2 times
weaker than formic acid. @ Salt hydrolysis is a process in which a salt reacts
with water to give acid and the base.
HYDROGEN ION CONCENTRATION AN D pH SCALE
BA + H 2 O -f HA + BOH
• Sorensen (1 909) defined pH of a solution as negative Salt Water Acid Base
logarithm of the hydrogen ion concentration of the solution. Hydrolysis is the reverse of neutralization.
• Salts of strong acid and strong base
Hydrolysi s constant, Kh = Kw
Example : KCI, NaCl, K2 S04 , Na2 S04 , KN0 3 , NaN0 3 , Ka x Kb
etc.
where, Kw = ionic product of water
Consider the hydrolysis of NaCl,
Ka = dissociation constant of weak acid
NaCl + H 2 0 ----? NaOH + HCl
Kb = dissociation constant of weak base
or, Na + + Cl- + H 2 0 Na + OH- + H + ci­
+ +

v�
-;'I>

or, H 2 0 ----t H + + OH - Degree of hydrolysis, h = jK;, or h - �

Thus such salts only ionize and do not hydrolyse. 1
pKb ] .
It is obvious from the above reactions that
[W] = [OH-J i. e. , solution is neutral.
and pH =
2 [pKw + pK0 -

• Salts of weak acid and strong base

IOtttl®Mii•i
Calculate the hydrolysis constant of the salt containing
Example : CH3 COONa, Na3 P04, K2 C0 3 , Na2 C0 3 , etc.
Consider the hydrolysis of CH3COONa, NOz ions (Given K., for HN02 = 4.5 X 1 0-1 °}.
CH3 C00Na + H 2 0 � CH 3 COOH + NaOH Soln.: N0 2 comes from weak acid.
or, CH3 COO- + Na+ + H2 0 � CH3 COOH + Na+ + OH-
Thus, for salts of weak acid, Kh = Kw
i. e. , CH ; coo- + H 2 0 � CH 3 COOH + OH- Ka
Such salts undergo anionic hydrolysis since anion Kw = 1 0-14
reacts with water to give basic solution. 1 0-1 4
Kh = ---- = 2.2 x 1 0-5
Hydrolysis constant, Kh = Kw 4.5 X 1 0-JQ
Ka BUFFER SOLUTIONS
where, Kw is ionic product of water and Ka i s
dissociation constant of weak acid. • Buffer solution is defined as a solution which resists
the change in its pH value when small amount of acid
Degree of hydrolysis, h = {K;;" or h = �

1
vc v� or base is added to it or when the solution is diluted.
Buffer solution has a definite pH value at specific
temperature and it , does not change on keeping fur a
and pH = + log C] .
2 [pKw + pK0 long time.
• Salt of strong acid and weak base • Types of buffer solutions
Example : N�Cl, CuS04, CaCl2, A1Cl3, etc.
BA + H 2 0 � BOH + HA
Salt Weak base Strong acid Acidic buffers (pH < 7)
(mixture of weak acid + its
or B + + A- + H 2 0 � BOH + H + A­
+
salt with a strong base)
i. e. , B + + H 2 0 � BOH + H+ e.g., �COOH + aI3COONa [Salt)
pH = pKa + log --
These salts undergo cationic hydrolysis since cation (pH = 4.7) [ Acid]
reacts with water to give acidic solution. fliNCH2 COOH
+ Cl H3NCH2 COOH
- +

Hydrolysis constant, Kh = Kw (pH = 2 .4)

Kb
where Kw i s i onic product of water and Kb is
dissociation constant of weak base. Basic buffers (pH > 7)
(mixture of weak base and
Degree of hydrolysis h = Pi or its salt with strong acid)
e.g., H3 B0 3 + Na2B40 7 pH = pKw - pKb + log--
( [Salt] )
1 (pH = 8.0)
and pH = - log CJ .
2 [pKw - pKb
[Base]

Na2HP04 + Na:,P04
• Salts of weak acid and weak base (pH = 1 1 . 5)
Example : CH3 COONH4, AlP04 , (N�)2C03 , etc.
BA + H 2 0 � BOH + HA • Buffer capacity : The number of equivalents of a
strong acid (or a strong base) required to change the
Salt Weak base Weak acid
or, B + A- + H 2 0 � BOH + HA
+
pH of one litre of a buffer solution by one unit keeping
The s e s alts involve both cationic and anionic
hydrolysis to give alm ost neutral solution since both the total amount of the acid and the salt in the buffer
acid and base produced are weak. constant, is called buffer capacity.
Equilibrium

No. of moles of acids or base added shifted to th e right, according to Le Chatelier 's
principle and ionization of NH4OH is suppressed.
per litre of buffer
Buffer capacity = ------------­
Change in pH ;;::=:'" !NH: j+ Off
The range of pH over which the buffer s olutions
remain effective is called buffer range. ----1'- lNH: J + ci-
Buffer Buffer range in pH
Acidic pKa ± l Common ion
Basic (pKw - pKb) ± 1 Thus , degree of dis s ociation of an electrolyte
Example : pKa of acetic acid is 4.74, then the range decreases by common ion effect but dissociation
of buffer solution of acetic acid is constant of that electrolyte remains constant.
pl-I = 4.74 ± 1 , i. e., 3 .74 to 5 .74 • Applications of solubility product
IW!ffi®MIU l> Predicting precipitate formation:
Calculate tl;ie amount ofNH3 and NH4Cl required to prepare if ionic product > K,p precipitation takes place
a buffer solution of pH = 9.0 when total concentration of if ionic product < K'P no precipitation takes place
buffering reagents is 0.6 mol litre-1 . (pKb for NH3 = 4.7, log ,. Predicting solubility of sparingly soluble salt:
2 = 0.30). Solubility of a sparingly soluble salt can be calculated
from its solubility product at a given temperature.
. [ Salt]
Soln. : Applymg, pOH = pKb + log -­ )(Y � x + + y-
[ Base]
pOH = 1 4 - pH = 14 - 9 = 5 .0 Let solubility is s s s
[Salt] [Salt}
5.0 = 4.7 + log -� log �- = 5 .0 - 4.7 = 0.3
K,p = [J. '"] [Y-J = (s) (s) =
'"
s1 , s = Jx;;
[Base] ' [ Base } Type of salt Solubility product
Taking antilog, AB type K,r = s2
[Salt] AB2 or A2B type Ksp = 4s
3
�- = 2 , [Salt] = 2 x [Base] AB3 or A� Ksp = 27s4
[Base]
AB4 or A 4B K,p = 256s 5
But it is given that [Salt] + [Base] = 0. 6 M where, s = solubility (mole/litre)
On solving two above equations Precipitation of common salt : When HCl gas is
[Base] = 0.2 mol litre- 1 pas s ed through saturated s olution of impure
[Salt] = 0.4 mol litre- 1 common salt, the concentration of er- increases
so1..mm1n PROD UCT due to ionization of HCL
• Solubility product of a sparingly soluble salt at a given NaCl � Na + + Cl - , HCl � H + CT
+

temperature is defined as the product of molar concentration Thus ionic product [Na+] [CI-] exceeds solubility
of its ions in a saturated solution, with each concentration product and pure NaCl precipitates out.
t=i raised to the power equal to number of ions present Qualitative Analysis : Various basic radicals are
in the chenrical equation representing the equilibrium of identified and s eparated by the principle of
dissociation of one molecule of the salt. It is represented solubility product and common ion effect.
as K,p . l)m1ffl'l!jlll®!ll"q·
®
lll'l fi 1':'l1J
j,jllll,m
�jl.li
AxBy � xAY+ + yBx - Predict whether a precipitate will be formed or not on mixing
equal volumes of 2 x 104 M BaCl2 solution and 2 x 1 0 5- M
Solubility product (K,p ) = [A Y + l" [Bx - y Na2SO4 solution if solubility product of BaSO4 is l x 10-1 0.
For example, Soln. : Ba So 4 � Ba-) + + S o?- 4 ,
AgCl � Ag+ + Cl- , K,p = [Ag ] [C l - ] BaC1 2 � Ba 2 + 2cr
+ +

Al(O H h � Ai + 3O H - , Ksp = [Al ] [O H - ] Na 2 SO 4 � 2Na + + SO�-

J+ 3+ 3

Common Ion Effect Since equal volumes of BaC12 and Na2 SO4 are mixed,
11 Common ion effect is defined as the suppression of concentration of Ba2+ and SO�- after mixing would be
ionization of weak electrolytes by addition of strong
+ [ BaC 12 ] = 2 x 1 -4 = l
electrolytes having an ion common to the weak [B a 2 ] = 0 0 -4 M
electrolyte. 2 2
For example weak base NH4 OH ionizes to a small 5
extent [SO � - ] = [Na 2 4] : 2 >< 1 0 - = 1 0 _5 M
SO

2 2
NH 4 OH � NH; + OH- Ionic product of BaSO 4
4 5
When a strong electrolyte like NH4 Cl or NaOH is = [Ba ] [SO�- ] = [10- ] [1 0- ] = 1 0 - 9 M
® 2+

added to this solution, a common ion NH; and OH­ Ionic product 0 0- M) > K,p ( 1 X 1 0- 10)
9

respectively is furnished so that the equilibrium is Hence, precipitation will take place.
 CONCEPT MAP

CHEMI CAL EQll lLIBRIUM

For a reversible reaction at

e quilibrium , the ratio of the
Change in concentration :
product of concentration of the
p roducts to the product of Homogen eous Heterogeneous If cone. of any reactant or
concentrations of the reactants equilibrium : When equilibrium : When product is increased, the
is constant. all the reactants and reactants and e quilibrium shifts in a
products are in the products are present direction where it is being
same phase. in two or more
Equilibrium constant, Kc different phases
conswned.
The c onstant of ratio of
concentrations of products and Change in temperature :
reactants. If temp erature is increased
reaction will proceed in the
direction where heat is
absorbed.
Does not change Tincreases , Kc increases
Chan ges with
with • Stoichiometry
(F or endothermic reactions) Change in pressure : If
• Concentration • Direction of pressure is increased , then
• Catalyst reaction Tincreases , Kc decreases e quilibrium will shift in a
• Temp erature (For exothermic reactions) direction where number of
moles reduces.

Addition of inert gas

At constant At constant pressure

volume Equilibrium will shift
No change in towards greater
equilibrium number of moles