Buffer Solutions :

(1) When acid and base are reacted in same amount (equivalent amount)
then both are limiting reagents which completely consumed to give salt and
water in this reaction we can find pH of solution by salt hydrolysis.
(2) When acid and base are reacted in unequal amount (un equivalent
amount) then one component (limiting reagent) will be finished and other
component (excess reagent) will be remained in the solution.
(3) When weak acid or weak base remaining in the solution along with their
strong counter part (salt) then such type of solution is known as Buffer
solution .
Weak acid + Strong base ————-> Salt + water
(excess) (limiting)

Acidic buffer

Weak base + Strong acid ————-> salt + water

(excess) (limiting)

Basic buffer

Consider One litre pure water whose pH is 7 at 298K temperature To this

suppose
(Q) if 0.365 gm HCl were added then find change in pH

[H+] = 0.365 x 1 = 0.01M pH = 2 change in pH = 7-2= 5

36.5 1

(Q) if 0.4gm NaOH were added then find change in pH

[HO-] = 0.4 x 1 =0.01M pOH = 2 pH = 14-2 = 12 change in pH = 12-7 =5
40 1
When pure water is present in a open vessel it absorbs CO2 gas from
atmosphere and it forms carbonic acid due to which [H+] ion concentration
increases and pH decreases
H2O(l)+CO2(g) <———-> H2CO3(aq)
H2CO3(aq) <———-> H+(aq) +HCO3-(aq)
HCO3-(aq)<————> H+(aq) +CO3-2(aq)
1)Buffer Solution : It is a solution whose pH does not change on addition of
small amount of acid (or) base (or) by dilution
Buffer solution contains both acidic and basic parts
2)Properties of Buffer solution :
(i) it has a constant pH
(ii) pH does not change (slightly change or practically negligible) by addition
small amount of acid or base
(iii) pH does not change on dilution
(iv) pH does not change on standing for long
3) Buffer range : it is a range of buffer solution over which it is effective (To
resist change in pH)
4) Buffer Action : Action of buffer solution on the addition of small amount of
acid or base by which it resist the change in pH is called buffer action
Types of Buffer Solutions : There are two types of buffer solutions
(1) Simple buffer : it contains one component.it is a salt of weak acid and
weak base Ex (1) CH3COONH4 (2) NH4CN

(2) Mixed buffer : It contains two components in which one is acidic and
other is basic . It is two types
Mixed Buffer Solution

Acidic buffer Basic buffer

It is a mixture of weak acid and it’s It is a mixture of weak base and it’s
Salt with strong base Salt with strong acid
It is a mixture of weak acid and it’s It is a mixture of weak base and it’s
Conjugate base Conjugate acid
Ex(1) CH3COOH+ CH3COONa Ex (1) NH4OH + NH4Cl
(Na+ ,K+ ,Ca+2 Ba+2) (Cl- ,Br- ,I- ,NO3-,SO4-2)
(2) HCOOH + HCOONa (2) Mg(OH)2 + MgCl2
(3) C6H5COOH + C6H5COONa (3) CH3NH2 + CH3NH3Cl
(4) Boric acid (H3BO3)+Borax (Na2B4O7) (4) Glycine + Glycine hydrogen
(5) H2S + NaHS Chloride
(6) NaHS + Na2S
(7) H3PO4 + H2PO4-
(8) H2PO4- + HPO4-2
(9) HPO4-2 +PO4-3
(Q) Which of the following will form acidic buffer ?
(1) CH3COOH + NaOH (1:1) (2) CH3COOH+ NaOH (2:1)
(3) H2S + NaOH (1:1) (4) H2S + NaOH (2:1)
(5) H2S + NaOH (2:3)
Formation of Buffer solution : There are two methods to prepare a buffer
solution
(1) Direct Method : In this method we can directly add weak acid and it’s
conjugate base (salt)
CH3COOH + CH3COONa
C1 mole/lit C2 mole/lit

(2) Indirect Method : In this method we can indirectly we can prepare buffer
solution as follows
(a) Addition of weak acid (excess reagent) and strong base (limiting reagent)
to give acidic buffer
CH3COOH + NaOH ————-> CH3COONa + H2O
(Excess) (Limiting)

Before M1V1 M2V2 -

After M1V1-M2V2 - M2V2

[CH3COOH] = M1V1-M2V2 [CH3COONa] = M2V2

V1+V2 V1+V2

NH4OH + HCl —————> NH4Cl + H2O

(Excess) (Limiting)

(b) Addition of salt of weak acid and strong base (excess) and Strong acid
(limiting) to give acidic buffer
CH3COONa + HCl ————-> CH3COOH + NaCl
(excess) (limiting)

NH4Cl + NaOH ———— > NH4OH + NaCl

(excess) (limiting)
Derivation of Expression for pH of Acidic Buffer Solution :
Consider a acidic buffer CH3COOH + CH3COONa
CH3COOH <————> CH3COO- + H+ (partial ionisation)

CH3COONa —————> CH3COO- + Na+ (Complete ionisation)

For weak acid Ka = [CH3COO-][H+] [H+] = Ka [CH3COOH]

[CH3COOH] [CH3COO-]
Applay logarithm on both sides

log[H+] = log Ka [CH3COOH]

[CH3COO-]

-log [H+] = -log Ka [CH3COOH]

[CH3COO-]

pH = -logKa - log [CH3COOH]

[CH3COO-]

pH = pKa + log [CH3COO-]

[CH3COOH]

Due to common ion effect of CH3COO- ionisation of weak acid CH3COOH

further decreases hence the concentration of CH3COO- ion taken as salt or
conjugate base concentration and concentration of CH3COOH at
equilibrium is taken as its initial concentration

pH = pKa + log [Salt]

[Acid]
This equation is known as Henderson - Hassalel balch equation or
Henderson equation for acidic buffer and it is applicable when

1 < [salt] < 10

10 [acid]
Buffer range : minimum pH [salt] = 1 pH = pKa - 1
[acid] 10

Maximum pH [salt] = 10 pH = pKa + 1

[acid] 1

There fore acidic buffer pH range = pKa + 1

Best buffer : A buffer whose resistance for change in pH is maximum is

known as best buffer
For a best acidic buffer [salt] = 1:1 pH = pKa
[acid]

Working Action of acidic buffer :

(1) When a small amount of a strong acid is added in the solution [H+]
increases which will combine with CH3COO– to form feebly ionised
CH3COOH which is also suppressed by common ion effect
CH3COO– + H+ (from acid) <————>CH3COOH (WeakAcid)
(2) when a small amount of a strong base is added in the solution [OH-]
increases which combine with CH3COOH to form feebly ionised H2O
molecules
CH3COOH +OH– (from base) <———-> CH3COO– + H2O
One can remember buffer action of acidic buffer with the help of following
figure
In acidic buffer [CH3COOH] = C1 [CH3COONa] = C2
Let suppose ‘a’moles of strong acid HCl is added to the above acidic buffer
then

CH3COONa + HCl ————-> CH3COOH + NaCl

C2 a (LR) C1
C2 - a - C1+a

pH = pKa + log [salt] pH = pKa + log [C2-a]

[acid] [C1+a]

pH slightly decreases hence change in pH is negligible

Let suppose ‘b’ moles of a strong base is added to the above acidic buffer
then
CH3COOH + NaOH ————-> CH3COONa + H2O
C1 b (LR) C2
C1- b - C2+ b
pH = pKa + log [salt] pH = pKa + log [C2+b]
[acid] [C1-b]

pH slightly increases hence change in pH is negligible

Derivation of Expression for pH of Basic Buffer Solution :

Consider a basic buffer NH4OH + NH4Cl

NH4OH <—————> NH4+ + HO- (partial ionisation)

NH4Cl ——————> NH4+ + Cl- (Complete ionisation)

For a weak base Kb = [NH4+][HO-] [HO-] = Kb [NH4OH]

[NH4OH] [NH4+]

log [OH-] = log Kb [NH4OH]

[NH4+]
 log [OH-] = log Kb + log [NH4OH]
[NH4+]

-log[OH-] = -log Kb - log [NH4OH]

[NH4+]

pOH = pKb + log [NH4+]

[NH4OH]

Due to common ion effect [NH4+] = [salt] and NH4OH ionisation decreases
so its equilibrium concentration is taken as initial concentration
[NH4OH] = [base]

pOH = pKb + log [salt] pH = 14 - pOH

[base]

This equation is called Henderson son - Hassel Balch

It is applicable when 1 < [salt] < 10

10 [base]
Buffer range :

Minimum pOH [salt] = 1 pOH = pKb - 1

[base] 10

Maximum pOH [salt] = 10 pOH = pKb + 1

[base]
There fore basic buffer pOH range = pKb + 1
Working Action of basic buffer :
(1) When a strong base NaOH is added to the basic buffer solution [HO-]
increase which will combine with NH4+ to form feebly ionised NH4OH
which is also suppressed by common ion effect

NH4+ + HO- (From base) <————> NH4OH (Weak base)

(2) when strong acid HCl is added to the basic buffer solution [H+]
concentration increases which will combined with un ionised base NH4OH
to form feebly ionised H2O molecules.
NH4OH + H+ (From acid) <———-> NH4+ + H2O
(3) One can remember the buffer action of basic buffer with the help of
following figure

Let consider in basic buffer [NH4OH] = C1 [NH4Cl] = C2

if ‘a’moles of acid is added

NH4OH + HCl ————> NH4Cl + H2O. pOH = pKb + log [C2+a]

C1 a (LR) C2. [C1-a]
C1-a - C2 +a
pOH slightly increases pH slightly decreases hence change in pH is
negligible
if ‘b’moles of a base is added

NH4Cl + NaOH ————-> NH4OH + NaCl

C2 b(LR) C1
C2 -b - C1+b
pOH = pKb + log [C2-b]
[C1+b]

pOH slightly decreases and pH slightly increases hence change in pH

negligible

Buffer Capacity ( O ) : Buffer capacity is number of moles of acid or base

added in one litre of buffer solution so as to change the pH by one unit.

O = No.of moles of acid (or) base added to 1L buffer solution

Change in pH value

Buffer capacity O = dx O = 2.303ab

d pH a+b

dx = amount of acid or base added

d pH = change in pH
a = concentration of weak acid or weak base
b = concentration of salt

For a best buffer O (or) d pH

max min
The Buffer capacity of an acid buffer is maximum if its pH value is equal to
pKa i.e [salt] = [acid]
The Buffer capacity of a basic buffer is maximum if its pOH value is equal to
the pKb i.e [salt] = [base]
Applications of Buffer solutions :
(1) The pH of blood stream maintained by proper balance of H2CO3 and
NaHCO3 concentration.
(2) In softening of hard water
(3) in biochemical reactions
(4) To control pH of solution in chemical analysis industrial synthesis and
enzyme catalysis reactions
(5) pH of human blood is maintained in between 7.36 - 7.42 by HCO3- and
H2CO3 buffer
(6) Sodium benzoate preserves James and Jellies by maintaining definite pH
(7) NH4OH + NH4Cl buffer is used for the analysis of Al+3 Fe+3 and Cr+3
cations of third group by qualitative analysis