7.

EQUILIBRIUM
Reversible and irreversible reactions
A reaction that takes place in only one direction is called an irreversible reaction.
e.g. Reaction between NaOH and HCI
NaOH + HCI -> NaCl + H20
Reversible reactions are those which take place in both directions. i.e. here reactants
combined to form products and the products recombine to form reactants.
E.g. Haber process for the preparation of ammonia
N2(g) + JH2(g) 2NH.i(g)
The process by which reactants are converted to products is called forward reaction and the
process by which products recombine to form reactants is called backward reaction. After
sometimes, the rate of forward reaction becomes equal to the rate of backward reaction and
the reaction attains equilibrium.
v'Equilibrium is a state at which the concentration of reactants and products do not change
with time.
& quilibrium is a state at which the rates of forward and backward reactions are equal.
'7 Equilibrium is dynamic in nature. i.e. at equilibrium the reaction does not stop. The reactant
' molecules collide to form products and the product molecules collide to form the reactants
and the rates of these reactions are equa9
Physical equilibrium: Equilibrium set up in physical process is called physical equilibrium.
a) solid liquid
HiO (s) H20 (I)
At equilibrium : Rate of melting= Rate of freezing

The temperature at which the solid and the liquid phases are at equilibrium at atmospheric
pressure is called freezing point or melting point.

b) liquid gas

H20 (I) HiO (g)

At equilibrium : Rate of evaporation = Rate of condensation

The pressure exerted by the vapours in equilibrium with the liquid at a particular temperature
is called vapour pressure of the liquid.

c) solid gas

h(s) h(vapour)

d)Equilibrium involving dissolution of solids in liquids

1
 Sugar ( in solution) sugar (solid)
At equilibrium : Rate of dissolution of sugar = Rate of crystallisation of sugar

e)Equilibrium involving dissolution of gases in liquids

COi(g) C02(in solution)

__
_....:;_ law. ' ...
The solubility ofa gas in a liquid depends on pressure and is given by Henry's

( It states that the mass of a gas dissolved in a given mass of solvent al a particular
temperature is proportional to the pressure of the gas above the solvent.
m oc p ~ ~ 'C

m = kp ~ ~ S I \ ~(f ,w
·1· f . 1· "dd .h. . p) er(J ~ ,
The so Iub11ty o a gas m a 1qm ecreases wit mcrease m temperatur~
Chemical Equilibrium
Equilibrium associated with chemical reactions is called chemical eguilibrilll!l- At
equilibrium, the,concentrations of reactants and products are constant.
Consider a hypothetical reaction, A + B ....,-- C + D
As the reaction proceeds, the concentration of the reactants decreases and that of the products
increases. After sometimes, the two reactions occur at the same rates and an equilibrium state
is reached. This can be illustrated by the following graph.

Reaction coordinates .

After the equilibrium is attained, the concentration of the reactants and products become
constant.
At equilibrium, the rate of forward reaction (rr) = the rate of backward reaction (n,).
Law of mass action ?
(it states that the rate of a chemical reaction is directly proportional to the product of the
molar concentration of the reactants at constant temperature at any given time.)
The molar concentration is also called active mass.
A+ B - - - products
Rate of the reaction, r oc [AJ[B]
t = k[AJ[BO k is called rate constant.

2
 aA+bB _ __. products

Rate of the reaction , r oc [A)"[B]h

r = k[A) 0 (B] b

Law of Chemical Equilibrium and Equilibrium Constant

A+B C+D
According to law of mass action
Rate of forward reaction, rr = kr[A)[B]

Rate of backward reaction, fb = kb[C](D]

At equilibrium, the rate of forward reaction (rr) = the rate of backward reaction (rb).

kr[A](B] = kb[C][D]
kr [C][D]
kb [AJ(B]

Kc = [C]ID]
[AJ[B]

Where Kc is called the equilibrium constant.

For a general reaction,
aA + bB cC + dD,
Kc= [C]c[Dt
]

r, Law of Chemical Equilibriu~ states that at constant temperature, the product of

concentration of the products to that of the reactants, in which each concentration tenns is
raised to a power which is equal to the stoichiometric coefficients in the balanced chemical
equation, has a constant value.
__,__
For the reaction H2 + h -- 2HI;
Kc= [Hl] 2

[H2][h]

For the reaction N2 + 3H2 2NH3;

Kc= [NH3)2
[N2][H2] 3

3
 Equilibrium constant for the reverse reaction is the inverse of that for the forward reaction.
i.e. if the equilibrium constant for the reaction H2+ Ii 2HI is Kc, then that for the
reverse reaction
21-0 H2 + Ii IS

r •c = I/Kc-]

Equilibrium constant for gaseous reactions

For a reaction involving gase~the concentration tenns are replaced by partial pressures.
aA +bB cC + dD
Kp = (pc) 0 (Po)d
(PA)"(p9)6

For example, H2(g) + h(g) 2HI(g);

Kp= Pttt
PH2.P12
Where Kp is called equilibriwn constant in tenns of partial pressure, PH1, PH2 and P12 are the
partial pressures of HI, H2 and Ii respectively.

Relation between Kc and Kp

___,._
Consider a general reaction, aA + bB .....-- cC + dD
The equilibriwn constant in terms of concentration for this reaction is
Kc = [C]c[D]d
1AJ"[Bf~-... ... (1)
And the equilibriwn constant in terms of partial pressures is
Kp= Pc0 .Pod
PA".Ps 6 .. .. .. .. .... (2)
From ideal gas equation, PV = nRT, P = nRTN = CRT (since nN = C, the concentration)
Therefore, PA= CART, Ps = CsRT, Pc= CcRT and Po= CoRT
Substitute these values in equation (2), we get

Kp = [CcRT]0 .[CoRT]d
[CART]"[CsRT]h
Or Kp= Cc0.Cod {RTf'd
CA".Csb (RT)a+b
Or, Kp = Cc0 .Cod [RT](c+d)-(a+b)

-
 Or, Kp = Kc.(RT)"'", where Kc = Ccc·cod

~P'° kc.CE---d'h] ~kt

And An is the change in no. of moles of gaseous species. i.e.

An = no. of moles of gaseous products - no. of moles of gaseous reactants.

Special cases:
vi) If An= 0, then Kp = Kc
vii) If An > 0, then Kp > Kc and
v" iii) If An < 0, then Kp < Kc

and heterogeneous equilibria S ""-X~u.& •

An equilibrium reaction in which all the reactants and products are in the same phase is
called homogeneous equilibrium.
e.g. N2(g) + 3H2(g) 2NHi(g)
2S02(g) + 02(g) 2S03(g)
Equilibrium reaction in which the reactants and products are in different phases is called
heterogeneous equilibrium.
e.g. CaC03(s) CaO(s) + C02(g)
HiO (s) ......- H20(l)
~baracteristics of Equilibrium constant
The important characteristics of equilibrium constant are:
l. Equilibrium constant is applicable only when the concentrations of the reactants and
products have attained their equilibrium state.
2. The value of equilibrium constant is independent of the initial concentrations of reactants
and products.
3. The value of equilibrium constant depends on temperature.
4. The equilibrium constant for the reverse reaction is the reciprocal of that of the forward
reaction.
5. If for the reaction A B, the value of equilibrium constant is K, then for the
reaction nA nB, its value is K". u. 1<''==- k.., (t\. ~-to
of equilibrium constant
The important applications of equilibrium constant are:
1. Prediction of the extent ofa reaction
Greater the value of equilibrium constant, greater will be the concentration of products. In
general,

5
 va) If Kc> I03 (i.e. Kc is very large), the reaction proceeds nearly to completion
"'°b) If Kc< 10·3 (i.e. if Kc is very small), the reaction proceeds rarely .
.,c) If the value of Kc is in be~ween I03 and 10·3 appreciable concentrations of both reactants f)
and products are present. u. kc. V CPv-, rP9t,uL.cl- lJ'2.c.-,fi.-_.!J
2. Predic~ion of the direction of the reaction r"J" t r ~ w,,;f' I.e._ •
By knowmg the values of Kc and Qc, we can predict the direction of a reaction.
The reaction quotient(Qc) is defined in the same way as the equilibrium constant (Kc)
except that the concentrations in Qc are not necessarily the equilibrium values.
For a general reaction, aA + bB cC + dD,
the reaction quotient, Qc = fC)C(Djd t) \. 1)
[Aj•[Bjb l"\--"7
IfQc > Kc, the reaction will proceed in the direction ofreactants (backward direction). ";Z'
'2u,;-.r,::.t
IfQc < Kc, the reaction will proceed in the direction of products (forward direction). '4 -fo ,._,J3,
IfQc = Kc, the reaction mixture is at equilibrium.(!'~ '\ 7'.Aci,,J
3. Calculation of equilibrium concentrations / i'\
By knowing the value of equilibrium constant, we can calculate the equilibrium ~.)I
concentrations of reactants and products.
Relationship between equilibrium constant (Kc), reaction quotient (Oc) and Gibbs
energy (AG)
The Gibb's energy change of a reaction is related to the reaction quotient (Qc) by the
equation:
dG = dG0 + RT lnQc
where, dG0 is standard Gibbs energy.
At equilibrium, dG = 0 and Qc = Kc, so the equation becomes,
0
O=dG + RT lnKc ___ f.~ i, ~.,,JJ:l
P""'1f
J
Or, dG0 =-RT lnKc _ _ _ _ _ _ _.,..~
On changing the base, we getFG =- 2.303RT logKc N
0

We know that for a spontaneous process d G should be negative. So the value of Kc should
be positive.
7
Factors affecting equilibrium .c.~ k ~c,, ~'''-" i J ~ --
The important factors affecting equilibrium are temperature, pressure, concentration and
catalyst. The effect of these factors on equilibrium state can be explained by using
vLe Chatelier's Principle. V!
It states that whenever there is a change in concentration, pressure or temperature of a system
at equilibrium, the system will try to readjust in such a way so as to cancel the effect of that
change.
1.Effectofconcentrationchange [~Jt-[f~).,l,, iv~
[r)1' [ ~ ] J BR,
6
 Ifwe change the concentration of reactants or products in an equilibrium process, then
according to Le Chatlier's principle, the system will try to reduce the effect of that change.
For this the rate of either forward or backward reaction changes.
{j_n general, an increase in concentration of reactants increases the rate of forward
reaction (i.e. the equilibrium is shifted to the forward direction) and an increase in
concentration of products increase the rate of backward reaction rate (i.e. the
equilibrium is shifted to the backward direction))
For example in the reaction 2S02(g) + 02(g) 2S03(g), ifwe increase the
concentration ofS02 or 02, the system will try to reduce the concentration by shifting the
reaction to forward direction.
Ifwe remove SOJ from the reaction mixture, its concentration decreases. Here also to
increase the concentration, the system will shift to the forward direction.
In Haber process for the re aration of ammonia he amount of ammonia formed can be
increased by increasing the concentration ofN2 o H2 or by removing NHJ from the reactio.n
mixture. N,.+-~H:a_
2. Effect of temperature change
According to Le Chatlier's principle~crease in temperature favours endothermic
process and decrease in temperature favours exothermic proces~n a reversible reaction,
if the forward reaction is endothermic, the backward reaction will be exothermic.
Eg. N2(g) + 3.Hi(g) 2 NHJ(g); .ill= - 92.38kJ/mol •Uj trl -lFR.
)Cl)
trl SR.~
Here since .ill is negative, the forward reaction is exothermic. So to increase the production p~
ofNHJ, temperature should decrease. At higher temperature, the rate of backward reaction fi.
increases. i.e.the ammonia formed is decomposed to N2 and H2.

3. Effect of pressure change / .. h. o-.J. f,tc,,1\

Pressure has its role only in gaseous reactions:-:' V"""r .-.f
In general an increase in pressure shifts the equilibrium in the direction of lesser
number of gaseous and vice versa.
Thus in the reaction, N2(g) + 3H2(g) 2 NHJ(g), when the pressure increases, the
system will try to reduce the pressure. This can be achieved by shifting the reaction into the
direction in which no. of moles decreases (since pressure is directly proportional to the
number of moles). So in this reaction, the equilibrium will shift to the forward direction.
If the volume of the reaction mixture is halved, the concentration and the partial pressure
become doubled. So the reaction is shifted to the direction in which the number of moles or
volume decreases.
4. Effect of catalyst
In an equilibrium reaction, a catalyst increases the rate of both forward and backward
reactions simultaneously and helps to attain the equilibrium faster. Jeers the activation

--'-.r.o '
7
 energy for the forward and backward reactions by exactly the same amount. It docs not affect
the eq_uilibrium composition of the reaction mixture) .
Thus in Haber process for the manufacture of ammonia, iron (Fe) acts as the catalyst.
In contact process for the manufacture of sulphuric acid, V2Os (Vanadium pentoxide) is used
as the catalyst for the conversion ofSO2 to SOJ.

5. Effect of inert gas addition

!fan inert gas (which does not take part in the1eaction) is added to an equilibrium mixture at
constant volume there is no change to the e~u:nzlt is because the addition of inert gas
at constant volume does not change the partial pres(u;.e or the concentration of the reactants
and the products.
Ionic equilibrium in solution
Equilibrium involving ions is called ionic equilibrium.
E.g. dissociation of acetic acid in water.
CH.JCOOH + H2O CHJcoo- + H.JO+
Electrolytes and non-electrolytes
Based on the ability to conduct electricity, Michael Faraday divided substances into two -
electrolytes and non-electrolytes.
Electrolytes are substances w~ch conduct electricity in molten state or in solution state.
e.g. All acids, bases and almost all salts.
Non- electrolytes are substances which do not conduct electricity in molten state or in_
s£!!!tion stl!le.
e.g. sugar, urea etc.
/t>r; ~t...J ,,o• ..... ,,_..,, ,sC..,4-'8
~'7:T ~-
Electrolytes are further classified into two - strong electrolytes and weak electrolytes.
~v
L.

Stron electrolytes are electrolytes which dissociate almost com Ietel into ions in aqueous

solution.
E.g. strong acids like HCI, HNOJ, H2SO4 etc., strong bases like NaOH, KOH etc. and salts
like NaCl, KC!, Na2SO4, K2SO4, KNOJ, NaNOJ etc.
Electrolytes which ioniseto a small extent in aqueous solution are called weak electrolytes.
E.g. CH.JCOOH, HCOOH, NH4OH , (NH4)2C03 etc
A weak electrolyte dissociates only partially in aqueous solution and so an equilibrium is
formed between the ions and the unionised molecules. This type of equilibrium involving
ions in aqueous solution is called ionic equilibrium.
Acids, Bases and Salts
Acid - base concepts:
1. Arrhenius concept: According to this concept acids are substances which give hydrogen
ion (W) or hydronium ion CH.JO+) in aqueous solution and bases are substances which give
hydroxyl ion (OH--) in aqueous solution.
e.g. HCI is an acid since it produces H3O+ in aqueous solution.
HCl(I) + HiO(I) -> H.JO +(aq) + c1- (aq)

8
e.g. for base NaOH
NaOH(s) + 1-!iO(I) -+ Na+(aq) + OH- (aq)
Note: W ions exist in water as hydronium ions (f-'3O+)
H+ + fuO HJO+
Limitations: This concept is applicable only to aqueous solutions. Also it could not account
for the basicity of substances like NH.J which do not possess OH· ion.
2. The Bronsted - Lowry concept:
Accordmg to this concept acids are proton {W) donors and bases are (W) acceptors.
For example in the reaction NHJ(I) + H2O(I)

donates an Wion to fonn OH·.

NI-Li +(aq) + OH·(aq)
Here NHJ is a ~ase since it accepts an H+ ion to fonn NI-Li +and H2O is an acid since it
/ ~- b
5)
.3; '.; 7 38t2' "·
Q, 1 1
In the reverse reaction, NH/ is an acid and OH· is a base. \...:_'D ·
The acid base pair that differs by only one proton is called a conjugate acid - base pair.
An acid fonned from a base is called conjugate acid and a base fonned from an acid is called
conjugate base.

NH/(aq) + OH·(aq)
base acid conj. acid conj. base
In general, Acid - W-+ Conjugate base
Base+ W -+ Conjugate acid
HCI + HiO ff.JO+ + CI·
Acid base conj. acid conj. Base
If the acid is strong, its conjugate base is weak and vice versa. So in the above example c1- is
a weak conjugate base of the strong acid HCI.
Water can act both as acid and base. So it is an amphoteric substance.
e.g. NH3 + H2O NI-Li++ OH" (H2O as an acid)
HNO3 + H2O ff.JO++ NOJ- ( H2O as a Base)
3.Lewisconcept: ~ ' J , ~4-b~ V ~ ~oP.U W> Ti .. 1iI.
According to this concept acids are electron pair accept8rs and bases are electron pair donors.
Substances which donate electron pair are called Lewis bases and substances which accept
electron pair are called Lewis acids.
Example for Lewis acids are BFJ, AICb, W, Co 3+, Mg2+etc. f-1-~ b
Example for Lewis bases are Nfu, H2O, OH-, Cl-, Br- etc.
For a substance to act as Lewis acid, it should contain vacant orbitals and for a substance to
act as Lewis base, it should contain lone pairs of electrons.
e.g. BFJ + Nfu-+ BF3<-Nfu
All cations are Lewis acids and all anions are Lewis bases.
The ionization constant of water (The ionic product of water)
Water is a weak electrolyte and hence it ionizes only partially as:

9
 HiO
Or, HiO + H20 1-bO+ + OH-
The dissociation constant, K = [H'J[OH-J or, K = [1-bO+][oH·]
[H20] [H20] [HiO]
Or, Kw= [H+][oH-J or, Kw= [HJO+][oH·J
Where Kw is called ionization constant of water or ionic product of water.
It is defined as the product of the molar concentration of hydrogen ion (hydronium ion) and
hydroxyl ion in water or in any aqueous solution.
For pure water at 298K, [H+] = [OH"] = 10-7M.
ThereforeJ Kw= [H+][OH·] = I Q·7x Io· 7 = Io· 14 M2]
The value of Kw is temperature
By knowing the concentrations of HJO+ and OH· ions, we can predict the nature of an
aqueous solution.

t
lf [HJO+] > [OH"], the solution is acidic
If [1-bO+] < [OH"], the solution is basic
If [1-bO+] = [OH"], the solution is neutral
The pH scale
pH is defined as the negative logarithm of the hydrogen ion or hydronium ion concentration
in oles er litre .
i.e pH = - log[W] or pH = - log[l-bO+]
Negative logarithm ofhydioxy 10n concentration in mol/L is called pOH.
i.e. pOH = -log[OH"]
For pure water, at 298K, [W] = 10-1. Therefore pH of pure water is 7.
If the pH is less than 7, the solution is acidic
If the pH is greater than 7, the solution is basic
If the pH is 7, the solution is neutral.
If the pH is 0, I, 2 etc., the solution is a strongly acidic and ifit is 12, 13, 14 etc, it is strongly
basic.
The pH of our blood is1.:1.Jmd that of our saliva is g So blood is slightly basic and saliva
is slightly acidic.
1/.'. elation between H and OH
We know that Kw= [H+][OH"] = 10- 14 at 298K
Taking negative logarithm on both sides:
-logKw = -log[H+] + -log[OH"] = -log I 0- 14
Or, pKw =pH+ pOH = 14
Thus by knowing the pH, we can calculate pOH as pOH = 14 - pH

Ionisation constant of weak acids

Consider a weak acid HX, which ionizes only partially as:

10
 HA+H2O
Let 'c' be the initial concentration of HA and ' a' is the degree (extent) of dissociation. (It is
the ratio of the number of moles of the electrolyte dissociated to the total number of moles).
Then, HA(aq) + H2O(I) --. H30-' (aq) + A···(aq)
Initial concn. c O o
Change in concn ca ca ca
Eqm. concn. c(l-a) ca ca
The dissociation constant, Ka= [HJO+][A·]
[HA]
Where Ka is the dissociation constant of the weak acid.
Or, Ka = ca x ca ca2
c(l-a) Tix
1-a = 1 as is a is very small for weak acid.

Ka=ca2 /

a=Fc
Larger the value of Ka, stronger is the acid. O
The negative logarithm of Ka is called pKa. kt:(, 1' f> l<,.q J,,
i.e. pKa = -logKa. \/""
Greater the value of Ka, smaller will be the value ofpKa and stronger will be the acid. -~

Ionisation constant of weak bases

Consider a weak base Bo'H, which ionizes partially as:
BOH B+ + OH"
Let 'c' be the initial concentration ofBOH and 'a' is the degree of dissociation.

Then,
+ oH-(aq)
BOH(aq)
0
Initial concn. C
ca ca
Change in concn ca
ca
Eqm. concn. c(l-a) ca
The dissociation constant of weak base, Kb= [B+][OH"]
[BOH]

Or, Kb = ca x ca ca2 V
c(l-a) T-a

1-a = 1 as is a is very small for weak base.

Kb =ca2

11
 a=JKb/c V
Also, -logKb = pKb /
As the value of Kb increases, pKb decreases and the basic strength increases.

Relation between Ka, Kb and K,.

For conjugate acid- base pair Ka and Kb are related as: Ka x Kb= Kw
This can be deduced as follows:
NH4 + + H2O :::;;== N1-IJ + I-LO+
Ka = [NI-h][HJO+]
[NH.t+]

Nl-b + H2O :::;;== + + OH-

Kb = [NH.t+][OH-]
[NI-h]
Net reaction : 2HiO

Kw= (H3O+l[OH-]

Ka x Kb= [NI-h][I-hO+] x [NH.t+][OH·] = [I-hO+][OH-] = Kw

[NHt+1 [NI-h]
i.e. Ka X Kb= Kw= 10· 14
or, pKa + pKb = pKw = 14 , _ __,,~ <t)~
Po yprotic acids
Acids which can donate more than one proton are called poly protic acids.
HiX :::;;== HX·· + W
Kat = [HX··][H+]
[HiX]

HX- W + x2-
Ka2 = [H+][X2-]
[HX-J
Kat> Ka2
It is more difficult to remove a positively charged proton from a negatively charged ion due
k.
to electrostatic force of attraction.~ 'l -a..,
\/Factors affectine acid strength -_;
*Strength ofH-A bond decreases the energy required to break the bond decreases and H+ is
easily released and acidic strength increases.

12
 *Polarity ofH-A bond increases, there is significant charge separation and acidic strength
increases
*In the same group H-A bond strength is more important and acidic strength increases as the
size of anion increases.
HF<HCl<HBr<HI
In the same period H-A bond polarity becomes the deciding factor for acidic strength.
CH4<NH3<1-liO<HF
'@ C~mmon Ion E~ect . . .
i..At 1s the suppression of the d1ssoc1at1on of a weak electrolyte by the addition of a strong
electrolyte containing a common ion.
For e.g. consider the dissociation of acetic acid (a weak electrolyte).
ClliCOOH(aq) ClliCOO-(aq) + W (aq)
Ifwe add some sodium acetate (CH3COONa) to the above equilibrium reaction, the
concentration of acetate ion increases. Then according to Le-Chatlier's principle, the
equilibrium will shift towards left or, the rate of forward reaction decreases. i.e. the
dissociation rate of acetic acid decreases. This is known as common ion effect.
Another example is the dissociation of the weak base ammonium hydroxide
NI-LiOH NI-Li+(aq) + oH-(aq)
If we add some NI-LiCI to the above equilibrium process, the concentration of NI-Li + increases
and hence the equilibrium shifted to the left. i.e. the dissociation rate ofNI-LiOH decreases.
Common ion effect is applicable in salting out of soap and in precipitation of group ill
cations.
Hydrolysis of salts
The interaction of anion or cation of the salt with water to produce an acidic or basic solution
is termed as hydrolysis of salt.
There are four types of salts _ 1
1. Salt of strong acid and strong base l'"lft.._ . .Aw":._J 4- g(,..~ ~ - _. N&lAIJ/
Eg: NaCl ( salt ofHCI and NaOH) ,-, - ~Q
NaCl+ H20 NaOH + HCI
Na+ + CJ· + H20 _ ____. Na++ OH-+ W + c1-
H20 - - + W + OH-
The salts of strong acid and strong base do not undergo hydrolysis and the resulting solution
is neutral.

2.Salt of strong acid and weak base SI+ o.-J U. rtf (. -:J-
Eg: Nl-LiCI( salt ofHCl and NI-LiOH)
NI-LiCl - NI-Li+ + c1-
NI-Li+ + HzO - Nl-LiOH + H+
The hydrolysis of salt of strong acid and weak base gives acidic solution due the presence of
free W ions.( cationic hydrolysis)

13
 'u
3. Salt of weak acid and strong base
Eg: CH.JCOONa ( salt of CH.JCOOH and NaOH )

CH.JCOONa - CH.JCOO- + Na+

CH.JCOO- + HiO :;==: CH3COOH + 01-1-
The hydrolysis of salt of weak acid and strong base gives basic solution due the presence of
01-1- ions.(anion hydrolysis)
4. Salt of weak acid and weak base
Eg: CH.JCOONHi (salt ofCH.JCOOH and NH40H)
CH.JCOONH4 - - - - . CH3Coo- + Nfu +
CH.JCOO- + NHi + + I-bO :;==: CHJCOOH + NH40H
Here both the cation and anion undergo hydrolysis .The resulting solution may be neutral,
acidic or basic depending upon the relative strengths of acids and bases.
The pH of these solutions can be calculated using the equation

jPH = 7+ i(pKa - pKb ) j

~uffer Solutions
Solution which resists the change in pH on dilution or with the addition of small amount of
acid or base is called Buffer solution.
There are two types of buffer solutions - acidic buffer and basic buffer.
l./4cidic buffer solution contains equimolar quantities of a weak acid and its salt with a strong
base.
Eg: A mixture of acetic acid and sodium acetate acts as an acidic buffer around pH 4.75.
\/Basic buffer solution contains equimolar quantities of a weak base and its salt with a strong
acid.
. Eg: A mixture ofNlliOH and NlliCI acts as a basic buffer around pH 9.25.
pH of a Buffer solution - Henderson-Hasselbalch Equation
pH of a Acidic Buffer:
Consider an acidic buffer prepared by mixing a weak acid HA and its conjugate bas A- The
weak acid HA ionises in water as:
HA + I-bO :;==:

The dissociation constant of weak acid, Ka= [HJO+][A-]

[HA]
Taking -ve logarithm on both sides:
-log Ka= -Iog[HJO+] + - log[A-] - -log[HA]
Or, -log[HJO+] = -logKa + Iog[A-]- log[HA]
Or,fH = pKa + Jog !:~l )
1

14
 This equation is known as ' rson-Hasselbalch equation. The equation can be written in
general form as pH = pKa + log [Salt) 0. " .. ' CA...t
[Acid]
Buffer action: e ability of the but er so ution to resist the changes in pH value on the
addition of small amount of an acid or base is called buffer action.

Buffer action of acidic buffer :

Consider an acidic buffer of Cl-bCOOH and Cl-bCOONa.The solution contains Cl-bCOO- ,
Na+ and undissociated Cl-bCOOH.
• If a small amount of HCI is added to this buffer solution, HCI ionise to produce W
ions and are combined with Cl-bCOO- to form undissociated CH3COOH and there
will be no change in its pH value.
Cl-bCOO- + W _ ___. Cl-bCOOH
• If a small amount ofNaOH is added to this buffer solution, OH-ions get neutralised
by CH3COOH and pH remains unchanged.combine with W
oH-+ ClliCOOH _ __. CH3Coo- + H20
pH of a Basic Buffer:
BOH(aq) + OW(aq)
Kb= [B+][Off]
[BOH]

Taking -ve logarithm on both sides:

-log Kb = -log[B+] + - Iog[OR] - -log[BOH]
Or, -Iog[OW] = -IogKb + Iog[B+] - log[BOH]
(B+]
pOH = pKb + log [BOHJ

(Salt]
pOH = pKb + log - -""as:::.e]"'----
18

(Salt]
or pH= 14 -(pKb + log----'--..:..--)
_ (Base]

"13uffer action of basic buffer :

Consider a basic buffer of NThOH and NH4CJ. The solution contains NTh+ ions, CJ- ions
and undissociated NThOH.

• When a few drops ofHCI are added, H+ ions formed are neutralised by OH- ions
and there will be no change in its pH value.

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 • When a few drops of NaOH are added , Ol-1- ions fonned are neutralised by NH4 '
ions and there will be no change in its pH value.

NH/ + 01-1- - NH40H

P-olubility Equilibrium
V The solubility of a salt in solvent mainly depends on the lattice enthalpy and solvation
enthalpy. As a general rule, for a salt to be able to dissolve in a particular solvent its
solvation enthalpy must be greater than its lattice enthalpy.
Each salt has its characteristic solubility which depends on temperature. We can classify salts
on the basis of their solubility in the following three categories.
Category I Soluble - Solubility> 0.IM
Category II Slightly Soluble - Solubility in between 0.0IM and 0.IM
Category III Sparingly Soluble - Solubility< 0.0IM

.,/Solubility Product Constant

Consider the dissociation of a sparingly soluble salt in water. Since it dissolves only partially,
there exists an equilibrium between the undissolved solid and the ions.
e.g. Solution of barium sulphate (BaS04)
2
BaS04 (s) Ba2+ (aq) + S04 -(aq)

2
The equilibrium constant, Kc= [Ba +][SO/-]
[BaS04]
For a pure solid, the concentration remains constant.

Therefore, Kc[BaS04] = [Ba2+J[SO/- ]

Or, Ksp = [Ba2+J[SO/-]

Where Ksp is called the solubility product constant or simply the solubility product. It is
defined as the product of the molar concentration of ions of a sparingly soluble salt in a
saturated solution.
2
IfS is the molar solubility ofBaS04, then Ksp = S x S = S
For a general salt AxBy, its dissociation can be denoted as:
AxBy(s) xAy+ (aq) + yBx• (aq);
Ksp = [Ay+]•[B•-JY

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 If the concentration in the above equation is not the equilibrium concentration, then Ksp is
given by Qsp( ionic produt).
At equilibrium, Ksp = Qsp.
vlfKsp > Qsp, the dissolution process occurs and ifKsp < Qsp, the precipitation of the salt
occurs.
Solubility product and common ion effect found application in the purification ofNaCI. Ifwe
V take a saturated solution of NaCl and pass HCI gas through it, then NaCl gets precipitated
due to the increased concentration of Cl· ions. NaCl thus obtained has very high purity.

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