Acid-Base Equilibria

and Solubility Equilibria

 What a Buffer Is and How It Works: The
Common-Ion Effect
• a buffer is something that lessens the impact of an external force.
• An acid-base buffer is a solution that lessens the impact on its pH of the
addition of acid or base.
• Addition of strong acid or strong base to a buffered solution causes
only a minor change in pH.
• To withstand these additions, a buffer must have an acidic component
that reacts with the added OH− and a basic component that reacts
with the added H3O+.
• Most often, the components of a buffer are a conjugate acid-base
pair (weak acid and conjugate base or weak base and conjugate acid).
Presence of a Common Ion
Buffers work through the common-ion effect.
When you dissolve acetic acid in water, the acid dissociates slightly:

• What happens if you now introduce acetate ion by adding the soluble
salt sodium acetate?
• First, as a strong electrolyte, sodium acetate dissociates completely in
water:
• The sodium ion does not interact with water and thus is a spectator ion.
• From Le Châtelier’s principle, we know that adding CH3COO− ion will
shift the equilibrium position to the left; thus, [H3O+] decreases, in
effect lowering the extent of acid dissociation:

• We get the same result when we add acetic acid to a sodium acetate
solution instead of water.
• Acetate ion is called the common ion because it is “common” to both
the acetic acid and sodium acetate solutions.

The common-ion effect occurs when a given ion is added to an

equilibrium mixture that already contains that ion, and the position of
equilibrium shifts away from forming it.
Practice
• Determine the pH at 25°C of a solution prepared by adding 0.050
mole of sodium acetate to 1.0 L of 0.10 M acetic acid. (Assume that
the addition of sodium acetate does not change the volume of the
solution.) Ka = 1.8 × 10−5
• Determine the pH at 25°C of a solution prepared by dissolving 0.075
mole of sodium acetate in 1.0 L of 0.25 M acetic acid. (Assume that
the addition of sodium acetate does not change the volume of the
solution.)
• Determine the pH at 25°C of a solution prepared by dissolving 0.35
mole of ammonium chloride in 1.0 L of 0.25 M aqueous ammonia.
 Composition of Buffers
• A buffer resists changes in pH because it contains both an acid to
neutralize added OH- ions and a base to neutralize added H+ ions.
• pH resistance depends on roughly equal concentrations of both the
weak acid and its conjugate base such as CH3COOH>CH3COO- or NH4+ >
NH3.
• The acid and base that make up the buffer, however, must not
consume each other through a neutralization reaction.
There are two ways to make a buffer.
1. Mix a weak acid or a weak base with a salt of that acid or base.
For example, the CH3COOH > CH3COO- buffer can be prepared by adding
CH3COONa to a solution of CH3COOH.
Similarly, the NH4+ >NH3 buffer can be prepared by adding NH4Cl to a
solution of NH3.
2. Make the conjugate acid or base from a solution of weak base or acid by
the addition of a strong acid or base.
For example, to make the CH3COOH > CH3COO- buffer,
you could start with a solution of CH3COOH and add some NaOH to the
solution—enough to neutralize about half of CH3COOH according to the
reaction

Thus convert the strong base (OH-) to weak base CH3COO-. Addition of strong
base increase the pH of a solution, however, a buffer’s ability to convert
string base to week base minimize the effect of addition of pH
Neutralization reactions have very large equilibrium constants, and so
the amount of acetate formed will only be limited by the relative
amounts of the acid and strong base that are mixed.
Action of Buffers
• To understand how a buffer works, let’s consider one composed of a
weak acid HA and one of its salts MA, where M+ could be Na+, K+, or
any other cation that does not react with water.
• The acid-dissociation equilibrium in this buffered solution involves
both the acid and its conjugate base:

• The corresponding acid-dissociation-constant expression is

Solving this expression for [H+], we have

We see from this expression that [H+] and, thus, the pH are determined
by two factors:
1. the value of Ka for the weak-acid component of the buffer;
2. the ratio of the concentrations of the conjugate acid–base pair, [HA]/
[A-].
• If OH- ions are added to this buffered solution, they react with the
buffer acid component to produce water and A-

• This neutralization reaction causes [HA] to decrease and [A-] to

increase.
• As long as the amounts of HA and A- in the buffer are large relative to
the amount of OH- added, the ratio [HA]/ [A-] does not change much
and, thus, the change in pH is small.
• If H+ ions are added, they react with the base component of the
buffer:

• This reaction can also be represented using H3O+

• Using either equation, we see that this reaction causes [A-] to decrease
and [HA] to increase.
• As long as the change in the ratio [HA] / [A-] is small, the change in pH will
be small.
An example of an HA/A- buffer is the HF>F- buffered solution shown in
The buffer consists of equal concentrations of hydrofluoric acid (HF) and
fluoride ion (F- )
• The addition of OH- reduces [HF] and slightly increases [F- ] whereas
the addition of H+ reduces [F-] and slightly increases [HF].
• It is possible to overwhelm a buffer by adding too much strong acid or
strong base.
Calculating the pH of a Buffer : Henderson–Hasselbalch equation
 Practice
• Starting with 1.00 L of a buffer that is 1.00 M in acetic acid and 1.00 M in
sodium acetate, calculate the pH after the addition of 0.100 mole of NaOH.
(Assume that the addition does not change the volume of the solution.)
Ka= 1.8 x 10-5

• the pH of 1 L of a buffer that is 1.0 M in acetic acid and 1.0 M in sodium

acetate after the addition of 0.25 mole of NaOH.
Exercise
• Select an appropriate weak acid from the table given bellow and
describe how you would prepare a buffer with a pH of 9.50

• Select an appropriate acid from Table below and describe how you
would prepare a buffer with pH = 4.5.
• How much HCl must be added to a liter of buffer that is 1.5 M in
acetic acid and 0.75 M in sodium acetate to result in a buffer pH of
4.10?
Addition of Strong Acids or Bases to Buffers
To calculate how the pH of the buffer responds to the addition of a
strong acid or a strong base

1. Consider the acid–base neutralization reaction and determine its

effect on [HA] and [A-]. This step is a limiting reactant stoichiometry
calculation.
2. Use the calculated values of [HA] and [A- ] along with Ka to calculate
[H+]. This step is an equilibrium calculation and is most easily done using
the Henderson–Hasselbalch equation (if the concentrations of the weak
acid–base pair are very large compared to Ka for the acid).
• Select an appropriate weak acid from the table in the margin, and
describe how you would prepare a buffer with a pH of 9.50.