SOME APPLICATIONS OF

EQUILIBRIA IN
SOLUTION
BUFFER SYSTEMS
AND
SOLUBILITY OF SPARINGLY SOLUBLE SALTS
 BUFFER SYSTEMS
THE COMMON ION EFFECT
• Consider the dissolution of propanoic acid in water. Being a weak acid (CH3CH2COOH, Ka = 1.32 ×
10-5), the extent of dissociation is extremely small and can be represented as:

Equilibrium shifts in the

direction that consumes Added propanoate ion
added propanoate ion from sodium propanoate

• If propanoate ion, , from sodium propanoate is added to the solution of propanoic acid,

• According to the Le Chatelier Principle, the presence of propanoate ion from sodium propanoate
will suppress the dissociation in the equilibrium above such that any propanoate ion in solution
will be exclusively from the salt and not from the acid. This phenomenon is known as the
COMMON ION EFFECT
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.
• Calculate the [H+] and the percent dissociation of 0.1 M Propanoic acid. Also, calculate the [H +],
• and the percent dissociation of the same acid in the presence of 0.1 M Sodium propanoate
• The equilibrium process and the amount of species at equilibrium can be expressed thus:

• The dissociation constant Ka is

• Given that propanoic acid is a very weak acid, it can be assumed that . This
implies that

• And the percent dissociation becomes:

• In the presence of 0.10 M CH3CH2COONa;

• The acid dissociation constant, Ka

• Solving the above for x gives,

• And the percent dissociation becomes

• Compare these values for [H+] and percent dissociation of CH3CH2COOH with those for a 0.1 M
CH3CH2COOH solution, where [H+] = 1.15 × 10-3 M and the percent dissociation is 1.15%. The large
difference clearly shows that the presence of the CH 3CH2COO- ions from the dissolved CH3CH2COONa
greatly inhibits the dissociation of CH3CH2COOH. The position of the acid dissociation equilibrium has been
shifted to the left by the presence of CH3CH2COO- ions from CH3CH2COONa.
• One of the applications of this phenomenon of common ion effect is in BUFFERED SOLUTIONS
• A buffered solution is one that resist any change in the pH of solution when a small amount of an acid or a
base is added to it – ACID-BASE BUFFER
• The most important practical example of a buffered solution is human blood, which can absorb the acids and
bases produced by biological reactions without changing its pH.
A constant pH for blood is vital because cells can survive only in a very narrow pH range around 7.4 .

• A buffer usually consists of a weak acid and a conjugate base of the weak acid (usually from a salt) –
common ion effect.
A typical example of an acid buffer is a solution of acetic acid and acetate ion (from sodium acetate).
A base buffer is consists of a weak base and its salt (for example, NH3 and NH4Cl).

• By choosing the appropriate components, a solution can be buffered at virtually any pH.
• To illustrate how a buffered solution works, consider the question below:
• A buffered solution contains 0.10 M acetic acid (C2H3O2H, Ka = 1.8 × 10-5) and 0.10 M sodium acetate
(C2H3O2Na).
Calculate the pH of this solution
Calculate the change in pH that occurs when 0.010 mole of solid NaOH is added to 1.0 L of the buffered solution. Compare this pH
change with the change that occurs when 0.010 mole of solid NaOH is added to 1.0 L of water
• SOLUTION

• The concentrations are as shown below:

• The approximation in the equation above is valid (% dissociation = 1.34, <5%)

• The added NaOH will dissociate completely to furnish the solution with 0.010M OH -
• The reaction taking place is therefore:

• Such that, after the above reaction:

• The equilibrium now becomes:

• Hence,
• The change in pH as a result of the addition of 0.0010 M NaOH to the buffered solution is

• The pH has increased by 0.09 pH units

• For the unbuffered solution:

• Therefore the change in pH is

• When compared with the buffered solution, it can be seen that the change in pH is significantly high. The
buffered solution resisted change in pH compared with pure water
• Recall that for any weak acid, HA, the dissociation expression and the acid dissociation constant, Ka, is
given as:
• Re-arranging the equation above as:

• In a solution of a weak acid and its salt (with a common ion A-), all the [A-] is to a very close
approximation, from the salt. The expression for the pH above can then be written in terms of
the ratio of [Salt] to [Acid] as:

• This final expression is known as the Henderson-Hasselbalch equation for the determination of
the pH of a buffered solution consists of a weak acid and a salt of the weak acid.
• For the solution of a weak acid and a salt of the weak base such as a mixture of ammonia (NH 3)
and ammonium chloride (NH4Cl), the base dissociation expression can be written as:

• Rearranging this equilibrium constant expression as:

• In a solution of a weak base and its salt (with a common ion BH+), all the [BH+] is to a very close
approximation, from the salt. The expression for the pOH above can then be written in terms of
the ratio of [Salt] to [Base] as:
• This is the form of the Henderson-Hasselbalch equation of a base buffer (a solution consists of a
weak base and a salt of the weak base). The pH of the solution can be determined from: