Buffers

Definition: A buffer solution is one which resists changes in pH when small quantities of an acid
or an alkali are added to it.

Acid Buffers:

An acidic buffer solution is simply one which has a pH less than 7. Acidic buffer solutions are
commonly made from a weak acid and one of its salts - often a sodium salt. Eg. Ethanoic acid
and Sodium ethanoate

How does an acid buffer work?

(1)

CH3COONa(aq) CH3COO- (aq) + Na+(aq) (2)

The solution will therefore contain these important things:

 Lots of un-ionised ethanoic acid since the acid is weak and the equilibrium naturally lies
to the left. This is needed to replace Hydrogen ions that are used up by base. Since hardly
any of the acid dissociates the concentration of unionized acid can be assumed to be the
original concentration of the acid.;
 Lots of ethanoate ions from the sodium ethanoate, since it is a soluble salt and all
dissolves. This is needed to help remove excess Hydrogen ions by bonding with it and
forming unionized ethanoic acid. Since all the salt dissolves and the mole ratio between
Sodium ethanoate and the ethanoate ion is 1:1, we can safely assume that the
concentration of the ethanoate ion in the buffer is the same as the original concentration
of the salt.;
 Enough hydrogen ions to make the solution acidic.
 On addition of small amount of H+(aq).

The concentration of the H+ ion increases . The above equilibrium(1), shifts Left removing the
excess H+ , by bonding with the ethanoate ions from the salt forming more unionized ethanoic
acid, and maintaining pH. In the process the concentration of the acid increases and the
concentration of the salt decreases.

 On addition of small amount of OH-(aq).

The OH- reacts with the H+ ion to form H2O.
OH-(aq) + H+(aq)  H2O(l)
This removes H+ ions from the above equilibrium causing it to shift Right, replacing the
removed H+ ions and maintaining pH. In the process the concentration of the acid decreases
and the concentration of the salt increases since when ethanoic acid ionized it not only
produces Hydrogen ions but also ethanoate ions.

Calculating the pH of an Acidic buffer.

Ka for ethanoic acid is 1.74 x 10-5 mol dm-3. Calculate the pH of a buffer solution containing 0.10
mol dm-3 of ethanoic acid and 0.20 mol dm-3 of sodium ethanoate.

In any solution containing a weak acid, there is an equilibrium between the un-ionised acid and
its ions. So for ethanoic acid, you have the equilibrium:

That means that you can write the equilibrium constant, Ka, for it:
Then all you have to do is to find the pH using the expression
pH = -log10 [H+]

Basic Buffers:

An alkaline buffer solution has a pH greater than 7. Alkaline buffer solutions are commonly
made from a weak base and one of its salts. Eg. Ammonium hydroxide and ammonium chloride.

How does a Basic Buffer work.

(1)
NH4Cl(aq) NH4+(aq) + Cl-(aq) (2)
The solution will therefore contain these important things:

 lots of unreacted ammonia since the base is weak and the equilibrium naturally lies to the
left. This is needed to replace Hydroxide ions that are used up by acid. Since hardly any
of the base dissociates the concentration of unionized base can be assumed to be the
original concentration of the base.;

 lots of ammonium ions from the ammonium chloride since it is a soluble salt and all
dissolves. This is needed to help remove excess Hydroxide ions by bonding with it and
forming unionized aqueous ammonia. Since all the salt dissolves and the mole ratio
between ammonium chloride and the ammonium ion is 1:1, we can safely assume that the
concentration of the ammonium ion in the buffer is the same as the original concentration
of the salt.;

 enough hydroxide ions to make the solution alkaline.

 On addition of small amount of H+(aq).

The OH- reacts with the H+ ion to form H2O.
OH-(aq) + H+(aq)  H2O(l)

This removes OH- ions from the above equilibrium causing it to shift Right, replacing the
removed OH- ions and maintaining pH. In the process the concentration of the base decreases
and the concentration of the salt increases

 On addition of small amount of OH-(aq).

The concentration of the OH- ion increases . The above equilibrium(1), shifts Left removing the
excess OH- and maintaining pH. In the process the concentration of the base increases and the
concentration of the salt decreases.

Calculating the pH of a Basic Buffer

Find the pH of a solution containing 0.100 mol dm-3 of ammonia and 0.0500 mol dm-3 of
ammonium chloride?
You can write a Ka expression for the ammonium ion, and make the same sort of assumptions as
we did in the previous case:

The value for Ka for the ammonium ion is 5.62 x 10-10 mol dm-3.

Calculating change in pH.

Calculate the change in pH when 1cm3 of 1.0 mol dm-3 NaOH(0.001 moles of OH-) is added to
1dm3 of buffer of 0.01 moldm-3 ethanoic acid and 0.04 moldm-3 sodium ethanoate.
Original pH is 5.37. Ka of ethanoic acid= 1.7 x 10-5 mol dm-3.
Remember when we add base to an acid buffer the concentration of the acid decreases and the
concentration of the salt increases. Therefore the new concentrations are:
Substuting into the expression:

Biological buffers

1.
H2CO3/HCO3-

2. H2PO4-/HPO42-

3. Proteins and amino acids.