BUFFER SOLUTION

Buffer solution
• Adding as little as 0.1 mL of concentrated HCl to
a liter of H2O shifts the pH from 7.0 to 3.0.
• The same addition of HCl to a liter solution that is
0.1 M in both a weak acid and its conjugate weak
base, however, results in only a negligible change
in pH.
• Such solutions are called buffers, and their
buffering action is a consequence of the
relationship between pH and the relative
concentrations of the conjugate weak acid/weak
base pair.
 Buffer solution
• A solution containing a conjugate weak
acid/weak base pair that is resistant to a
change in pH when a strong acid or strong
base is added.
 Buffer solution
• A mixture of acetic acid and sodium acetate is one
example of an acid/base buffer.
• The equilibrium position of the buffer is governed
by the reaction
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO–(aq)…(1)
and its acid dissociation constant
 Buffer solution
• The relationship between the pH of an acid–base
buffer and the relative amounts of CH3COOH and
CH3COO– is derived by taking the negative log of
both sides of equation (1) and solving for the pH

(equation 2)
 Buffer solution
• Buffering occurs because of the logarithmic
relationship between pH and the ratio of the weak
base and weak acid concentrations.
• For example, if the equilibrium concentrations of
CH3COOH and CH3COO– are equal, the pH of the
buffer is 4.76.
• If sufficient strong acid is added such that 10% of
the acetate ion is converted to acetic acid, the
concentration ratio [CH3COO–]/[CH3COOH]
changes to 0.818, and the pH decreases to 4.67.
 Systematic Solution to Buffer
Problems
• Equation (2) is written in terms of the
concentrations of CH3COOH and CH3COO– at
equilibrium.
• A more useful relationship relates the buffer’s pH
to the initial concentrations of weak acid and weak
base.
• A general buffer equation can be derived by
considering the following reactions for a weak
acid, HA, and the salt of its conjugate weak base,
NaA.
 Systematic Solution to Buffer
Problems

Since the concentrations of Na+, A–, HA, H3O+, and OH– are
unknown, five equations are needed to uniquely define the
solution’s composition.
Two of these equations are given by the equilibrium constant
expressions
 Systematic Solution to Buffer
Problems

The remaining three equations are given by mass balance

equations on HA and Na+

Equation 3

Equation 4
 Systematic Solution to Buffer
Problems

Substituting equation (4) into the charge balance equation and

solving for [A–] gives
(5)
which is substituted into equation (3) to give the concentration of HA

Equation (6)
 Systematic Solution to Buffer
Problems
Finally, substituting equations 5 and 6 into the Ka
equation for HA and solving for pH gives the general
buffer equation

If the initial concentrations of weak acid and weak

base are greater than [H3O+] and [OH–], the general
equation simplifies to the Henderson–Hasselbalch
equation.
Henderson–Hasselbalch equation

Equation showing the relationship between a

buffer’s pH and the relative amounts of the buffer’s
conjugate weak acid and weak base.
 example
• Calculate the pH of a buffer that is 0.020 M
in NH3 and 0.030 M in NH4Cl.
• The acid dissociation constant for NH 4+ is
5.70 x 10–10
• What is the pH after adding 1.00 mL of 0.10
M NaOH to 0.10 L of this buffer?
 Solution
• The initial pH of the buffer is :

Adding NaOH converts a portion of the NH4+ to NH3 due to

the following reaction
NH4+(aq) + OH–(aq) NH3(aq) + H2O(l)
Since the equilibrium constant for this reaction is large, we
may treat the reaction as if it went to completion. The new
concentrations of NH4+ and NH3 are therefore
Solution