8.

4 Common
Ion Effect
Learning Outcomes

• Describe the common ion effect including buffer solutions.

Common Ion Effect

• An ion in common with one of the ions already present in equilibrium is called the
common ion. Ex: when sodium chloride is added to a solution of silver chloride, the
common ion is chloride ions.

Common ion effect is:

• The effect of reducing the degree of dissociation of a weak electrolyte when another
electrolyte with a common ion is added to it or,
• The effect of reducing the solubility of a sparingly soluble ionic compound when another
compound that contains an ion in common with it is added.
 Common Effect on Buffer Solution

• Consider the acid buffer obtained by adding sodium ethanoate to an aqueous

solution of ethanoic acid.
Ethanoic acid is a weak acid and only partially dissociates in water.

Sodium ethanoate is a salt, a strong electrolyte and is fully dissociated in aqueous

solution.

• When sodium ethanoate is added to ethanoic acid, the equilibrium position of

ethanoic acid shifts to the left in accordance with Le Chantelier’s principle.
• In other words, the degree of dissociation of ethanoic acid is decreased by the
addition of the common ion, the ethanoate ion. CH3COO-. This effect is called
common ion effect.

• Similarly, the dissociation of ethanoic acid is decreased by the addition of a small

amount of strong acid, such as dilute hydrochloric acid. In this case, the common
ion is the hydroxonium ion, H3O+.
 Solubility and Common Ion Effect

• The solubility of a substance is affected not only by temperature but also by other
factors, such as common ion effect and the formation of complex ions.

• The solubility of a sparingly soluble ionic compound decreases in the presence of a

strong electrolyte which provides a common ion. This effect is called the common ion
effect.

• If a saturated solution of silver chloride is prepared by mixing the solid with water, the
solution contains only silver and chloride ions in equilibrium with solid silver chloride.
• When sodium chloride (a strong electrolyte) is added to a saturated solution of silver
chloride (a sparingly soluble salt), the concentration of Cl- ions increases.

• According to Le Chatelier’s principle, the equilibrium shifts to the left to remove the
added Cl- ions. As a result, AgCl is precipitated and the concentration of Ag+
decreases. Thus, the solubility of AgCl decreases in the presence of the common ion,
Cl-.

• The common ion effect can also be explained based on solubility product concept.
For example:

At a constant temperature, Ksp is a constant.

• When calcium nitrate solution is added to a saturated solution of calcium fluoride, the
concentration of the common ion, Ca2+ (aq) will increase. This causes the ionic product,
[Ca2+][F-]^2 to increase and exceed Ksp. As a result, CaF2 is precipitated.

• The addition of a common ion, Ca2+ reduces the solubility of CaF2. The same effect is
produced if sodium fluoride is added. In this case, the common ion is the fluoride ion, F-.
Figure below shows the effect of sodium fluoride on the solubility of calcium fluoride.
 Precipitation of Soap

• In a saturated soap solution, the following equilibrium is established:

• In the manufacture of soap, the common salt (sodium chloride) is used to precipitate the
soap (sodium stearate) from the saturated soap solution. In this reaction, Na+ ion is the
common ion.

• This process is called salting out. Solid soap (sodium or potassium salt of stearic acid) is
removed (salted out) from the saturated soap solution by the addition of a concentration
solution of sodium chloride.
 Selective Precipitation of Sulphides

• The following results are obtained when H2S gas is passed into a mixture of Ni2+,
Zn2+ and Cu2+ ions in acidic =, neutral or alkaline solution.
• We can explain the results in the table as follows:
In an acidic solution, the concentration of S2- ions is very low due to common ion
effect.

Therefore, only metal sulphides with very low Ksp values will be precipitated.

• The Ksp values of CuS, ZnS and NiS are as follows:

Thus, when H2S is passed into an acidified solution od Cu2+, Zn2+ and Ni2+ ions, only
CuS is precipitated.
• In a neutral solution, the concentration of S2- ions is higher than the concentration
S2- ions in acidic solution. As a result, the value of the ionic product [metal ion][S2-]
becomes higher.

• CuS and ZnS have low Ksp and their ionic products become higher than the values of
their Ksp. Thus, they can be precipitate. However, NiS is not precipitated because
Ksp for NiS is very high and the ionic compound [Ni2+][S2-] cannot exceed Ksp.

• In solution made slightly alkaline with NH3 (aq), the equilibrium shifts to the right.
Therefore, the concentration of S2- is even higher. This enables all the three metal
sulphides to precipitate because their ionic products are higher than their Ksp
values.

• The concentration of S2- ions in H2S solution depends on the pH of the solution.
Thus, by controlling the pH of the solution containing Cu2+, Ni2+ and Zn2+ ions
before passing H2S into it, we can separate these metal ions present in the
solutions.
 Selective Precipitation of Hydroxides

• Most metal ions in aqueous solution will form a precipitate of insoluble hydroxide
with ammonia solution.

• However, only some metal ions such as Fe3+, Cr3+ and Al3+ will form a precipitate of
insoluble hydroxide with ammonia solution in the presence of ammonium chloride.
• Ammonia is a weak base. The concentration of OH- ions in aqueous ammonia is very low.

In the presence of NH4Cl the equilibrium will shift to the left, due to common ion effect of
NH4+.

The concentration of OH- ions in ammonia solution is further decreased. Thus, only metal
hydroxides with very low Ksp values, such as De9OH)3 and Al(OH)3 will be precipitate.
Solubility of Sparingly Soluble Salts of Weak Acids is
Strong Acid

• The salts of weak acids such as calcium phosphate, Ca3(PO4)2 or calcium

ethanedioate, CaC2O4 are sparingly soluble in water but dissolves readily in aqueous
solutions of strong acids.

• When solid calcium ethanedioate is added to water and allowed to reach chemical
equilibrium, a saturated solution is produced in which the concentration of Ca2+ and
C2O4^2- ions are very low.
• Pure water also dissociates but only to a very small extent, so that the
concentrations of H+ and OH- ions are also very low.

Under these conditions, very little combination of H+ and C2O4^2- ions take place even
though H2C2O4 is a very weak acid.

• When hydrochloric acid is added, it dissociates completely into ions. Consequently,

the concentration of H+ ions in the solution is raised to a high level.

This causes H+ and C2O4^2- ions to combine in large numbers to form the
undissociated H2C2O4 molecules. In the process, the concentration of C2O4^2- ions is
reduced considerably.
• As a result, the ionic product of calcium ethanedioate, [Ca2+][C2O4^2-] falls well below
its solubility product. When this happens, calcium ethanedioate will dissolved to
replenish the C2O4^2- ions removed.
 Solubility and Complex Ion Formation

• The graph beside shows the solubility of lead(II) chloride at constant

temperature in the presence of hydrochloric acid.

• Initially, lead(II) chloride is less soluble in hydrochloric acid than in water. This
is due to the common ion effect. The presence of the common ion, the Cl-
ion, decreases the solubility of PbCl2 in water.

• However, lead(II) chloride dissolves readily in concentrated hydrochloric acid

because of the formation of the complex ion PbCl4^2- (aq):
• Consequently, the concentration of Pb2+ (aq) is reduced to such a low level that the
ionic product is less than the solubility product of lead (II) chloride. This causes PbCl2 to
dissolve to replenish Pb2+ ions removed in complex formation.
Thank you