BUFFER SOLUTION

Generally, pH of an aqueous solution decreases on addition of a small amount of HCl

because of increase in the concentration of H+ ions. On the other hand, if a small amount
NaOH is added, the pH of the solution increases. However, there are some solutions which
resist the change in pH on addition of small amount of strong acid or alkali. Such solutions
are called buffer solutions. For example, solution of ammonium acetate, blood, an equimolar
mixture of NH4OH + NH4Cl, CH3COOH + CH3COONa, etc. Thus buffer solution is defined
as that solution which resists the change in hydrogen ion concentration on the addition
of small amount of acid or base.
Buffer solutions are of two types.
(a) Acidic buffer: It is obtained by mixing equimolar quantities of a weak acid and its
salt with strong base. e.g.,
(i) CH3COOH + CH3COONa (ii) HCOOH + HCOOK
The pH value of acidic buffers is usually less than 7.
(b) Basic buffer: It contains equaimolar quantities of weak base and its salt with
strong acid. e.g.,
(i) NH4OH + NH4Cl (ii) C6H5NH2 + C6H5NH3
The pH value of basic buffers is usually more than 7.
Examples of some common buffer solution with their pH values are listed below.
Buffer solution Range of pH value
CH3COOH + CH3COONa 4.74
HCOOH + HCOOK 3.70 + 5.6
Citric acid + sodium citrate 1.0-5.0
Phthalic acid + Pot. Hydrogen phthalate 2.2-3.8
KH2PO4 + K2HPO4 5.8+8.0
NH4OH + NH4Cl 9.25
H3BO3 + Na2B4O7 (Borax) 9.2-11.0
H2CO3 + NaHCO3 7.4

Buffer action: The ability of buffer solution to resist the change in its pH value on
addition of small amount strong acid or strong base is called buffer action.
Let us consider an acidic buffer containing equimolar amounts of CH 3COOH and
CH3COONa to understand the buffer action. Buffer solution has large concentration of
species namely CH3COO-, Na+, and unionized CH3COOH.
CH 3COOH    CH 3COO   H 

 CH 3COO   Na 
CH 3COONa 
When few drops of HCl are added to this buffer solution, the H + ions of HCl immediately
combine with CH3COO- ions to form undissociated acetic acid molecules.
 CH 3COO  (aq)  H  (aq)    CH 3COOH

Thus there will be no appreciable change in its pH value.

Likewise, if few drops of NaOH are added to buffer solution, the OH - ions (provided by
NaOH) will combine with H+ ions present in buffer solution to form unionized water
molecules. Thus, additional OH- ions are neutralized by acetic acid and the pH of the solution
remains almost constant.
CH 3COOH    CH 3COO   H 

H   OH     H 2 O

Similarly, a basic buffer solution consisting of equimolar amounts of NH 4OH and NH4Cl has
large concentration of NH4+ ions, Cl- ions and unionized NH4OH.
 NH 4   Cl
NH 4 Cl 

 NH 4   OH 
NH 4 OH 
When few drops of HCl are added to it, the H+ ions of HCl are neutralized by OH- ions of
weakly ionized NH4OH i.e. the pH of the solution is almost restored.
 NH 4  (aq)  OH  (aq)
NH 4OH (aq) 

OH  (aq)  H  (aq) 
 H 2O

On the other hand, if few drops of NaOH are added to the buffer solution, the OH - ions
provided by NaOH combine with NH4+ to form weakly ionized NH4OH. Thus, the pH of the
solution is almost constant.
Buffer capacity: It is defined as the number of moles of acid (or base) required by one litre
of buffer solution for changing its pH by 1 unit.
Number of moles of acid or base added per litre
Buffer capacity =
Change in pH
Thus higher the amount of acid or base used to produce a definite change of pH in a buffer
solution, higher will be its buffer capacity. In general, the buffer capacity of a solution is
maximum when both the components of buffer solution are present in equivalent amounts
(i.e. when the molar ratio of salt and acid is 1).
Calculation of pH of buffer solution
The pH of buffer solutions can be calculated applying Henderson’s equation.
For pH of acidic buffer solution

pH = pK a  log
 Salt 
 Acid 
where pK a   log K a
For pH of a basic buffer solution

pOH = pK b  log
 Salt 
 Base
pH  14  pK a  log
 Salt 
 Base
where pK b   log K b
pH  pOH  14