8.

8 Buffers
• Buffers are mixtures of weak acid and its conjugate base or
weak base and its conjugate acid.

• These conjugate pairs will allow a solution to resist changes

in pH when small amounts of acids and/or bases are added.

• Usually buffers have common ions in them that act as a

reservoir and help maintain a relatively constant pH.

• Le Chatelier’s Principle explains the changes (See Figure 3

on Page 560)
• Suppose a buffer contains relatively large quantities of a
weak acid, HA(aq), and its conjugate base, A -(aq):

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

• When hydroxide ions are added to the solution, the non-

ionized weak acid molecules react with the hydroxide ions,
removing the hydroxide ions from the solution

HA(aq) + OH-(aq) A-(aq) + H2O(l)

• The net result of this reaction is that when a base is added,

OH-(aq) ions are not allowed to accumulate but are replaced
by A-(aq) ions (equilibrium shifts to the right to produce
more product).
• However, when hydrogen ions are added to the
solution, they push the ionization equilibrium to the
left, removing the hydrogen ions from the solution
and increasing the concentration of the acid
molecules

HA(aq)  H3O+(aq) + A-(aq)

• The essence of buffering is that [HA(aq)] and [A -(aq)]

are large compared with the amount of OH-(aq) or H+
(aq) added. A high initial concentration of the
buffering entities is very important for them to
function effectively.
 Weak acids and bases with their conjugate-salt:

• Buffers are solutions of weak acids or bases and

their respective soluble salts

• This is why buffer problems should be treated as

common ion problems.
 Buffers in Action
• Living organisms are very sensitive to pH changes as
enzymes carry out their function optimally over a small
pH range.

• Human blood plasma has a pH of about 7.4 maintained

by the hydrogen carbonate- carbonate buffer system.

• Any change in pH of more than 0.2 induced by

poisoning or disease is life-threatening. If blood was
not buffered, the acid absorbed from a glass of orange
juice would be fatal.
 Ex. acetic acid- acetate ion buffer
• When base is added:

CH3COOH + OH-CH3COO- + H2O(l)

• When acid is added:

CH3COO- + H3O+CH3COOH + H2O (l)

• Therefore adding acid or base has no effect on pH since

OH- or H3O+ are removed by one component of buffer
solution.
• Eventually if enough acid or base is
added a considerable pH change will
occur.

• The amount of acid or base that can

be added is considered the buffer
capacity. The buffer capacity is
determined by the concentrations
of its conjugate acid-base pairs.

• The highest buffer capacity is when

at a point half-way to the
equivalence point where pH=pKa.
(pKa)
 Calculating the pH of a Buffer:
Ex.1 Calculate the pH of a buffer that contains 0.20
M acetic acid and 0.20 M sodium acetate.

+
I 0.2 0.2 0
C -x +x +x
E 0.2- x 0.2 + x 0+x

Check Assumption: = 1.8 × 10−5

˃ 100, YES! We can assume
Ka expression:

• Ka= [CH3COO- ] [H3O+]

[CH3COOH]

Solve for x:
Solve for pH:

ka= (0.2 + x) (x) X = [H3O+]

(0.2-x)
pH= -log (1.8 × 10−5 )
1.8 × 10−5 = 0.2x
0.2
1.8 × 10−5 = x pH= 4.7
Example 2:
• Calculate the pH of a buffer solution containing
0.15 mol/L ammonia (kb= 1.8 × 10−5 ) and 0.04
mol/L ammonium chloride.

• Entities:
NH3, NH4Cl (NH4+, Cl-), H2O

Equation:
NH3 (aq) + H2O(l) ↔ NH4+ (aq) + OH-(aq)
 NH3 (aq) + H2O(l) ↔ NH4+ (aq) + OH-(aq)
I 0.15 0.04 0
C -x +x +x
E__0.15 -x____________________0.04 + x_______x_____

Kb= [NH4+ (aq)][OH-(aq)] Check Assumption:

[NH3 (aq)] ˃ 100, Yes!
Solve for pOH:
kb= (0.04 + x) (x)
(0.15-x) X = [OH-]
pOH= -log (6.75 × 10−5 )
1.8 × 10−5 = 0.04x
0.15 pOH= 4.17
2.7 × 10−6 = 0.04x
pH = 14- 4.17
6.75 × 10 = x
−5
pH= 9.83
Henderson-Hasselbach Equation:
Example 3: Calculate the pH of a buffer containing 0.33 M of
ammonia and 0.33 M of ammonium chloride

Using the Henderson-Hasselbach equation:

Kb for NH3 = 1.8 x 10-5

pKb = -log(1.8 x 10-5 )

=4.74
pH = 14.00 – 4.74
pOH = pKb + log [NH4+] = 9.26
[NH3]
= 4.74 + log (0.33 M)
(0.33M)
= 4.74