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SOLUBILITY OF SPARINGLY From;

[𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
SOLUBLE SUBSTANCES Kc = [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
Kc[AmBn] = [An+]m[Bm-]n
SPARINGLY SOLUBLE SUBSTANCES Remember
Are substances which dissolve only partially AmBn is a solid and sparingly soluble
in water to give free ions. They are therefore its concentration is constant.
considered as if insoluble in water since very [AmBn] = constant
small portion of them dissolve in water. Then;
But in actual sense no substance which is Kc[AmBn] gives another constant (ksp)
absolutely 100% insoluble in water even if Kc[AmBn] = Ksp
they dissolve in very small extent which can Thus,
not be noted. Kc[AmBn] = [An+]m[Bm-]n
These substances are AgCl, AgBr, CaCl2, ksp = [An+]m[Bm-]n
CaCO3, BaCl2, BaSO4. They dissolve in water ksp = [An+]m[Bm-]n
to give free ions which exist in equilibrium Where,
with solid phase as shown below. Ksp → Solubility constant
AgCl(s) Ag(aq)+ + Cl(aq)- Definition
At equilibrium amount of solid dissociated Solubility constant is the product of the molar
into ions(x) will give the same proportions concentration of the ions in its saturated
amount of ions produced in solution(x) solution each raised to the power equal to the
stoichiometric coefficient of the species in the
AgCl(s) Ag(aq)+ + Cl(aq)-
chemical equations.
x x x
Its unit depends on the nature of substance or
Where;
amount of free ions released.
x→ Amount of AgCl(s) dissociated into its Eg.
ions (solubility)
1) Al2S3(s) 2Al3+(aq) + 3S(aq)2-
SOLUBILITY OF SPARINGLY Let “x” be molar solubility of Al2S3 (amount
SOLUBLE SUBSTANCES of moles of Al2S3 dissolved in water to form
Is the ability of a substance to dissolve in a free ions (moldm-3))
given solvent which is given as the amount of Now;
the substance dissolved in one litre of Al2S3(s) 2Al3+ + 3S(aq)2-
saturated solution. x 2x 3x
It is expressed in gdm-3. 3+
[Al ] = 2xmoldm -3

[S2-] = 3xmoldm-3
SOLUBILITY PRODUCT - Ksp Then;
Suppose AmBn is asparingly soluble Ksp (Al2S3) = [Al3+]2[S2-]3
substance which dissolves in water to form = (2x)2(3x)= 4x2.27x3
free ions existing in equilibrium with solid Ksp = 108x5mol5dm-15
phase as shown below.
AmBn(s) mA(aq)n+ + nB(aq)m-
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b) CaF2 if its ksp at this temperature is

2) Mg(OH)2(s) Mg2+ + 2OH(aq)-
2.66x10-11mol3dm-9.
Let “x” be molar solubility of Mg(OH)2
(moldm-3) at equilibrium. Example 43
Mg(OH)2(s) Mg2+ + 2OH(aq)- a) Which carbonate has lower solubility,
xx 2x Ag2CO3 (ksp = 8.2 x10-12) or CuCO3(ksp =
Now, 2.5x10-10)?
[Mg2+] = x, [OH-] = 2x b) The solubility product of Ag2CrO4 and
Ksp = [Mg2+][OH-]2 AgBr are 1.1x10-12 and 5.0x10-13respectively.
= x.(2x)2= 4x3 Calculate the ratio of the molarities of their
Ksp = 4x3mol3dm-9 saturated solution.

COMMON IONIC EFFECT

Ksp does not depend on concentration of ions
Is the decrease in solubility of sparingly
present in saturated solution. It depends on
soluble substance when solution containing
temperature like other equilibrium constant.
one of its ion is added into it.
Ksp is useful to compare solubility of similar
In order to have outstanding knowledge on
composition or ratio sparingly soluble
this concept, consider addition of HCl into the
substances such as AgCl and ZnCl or CaCl2
saturated solution of AgCl.
and PbCl2 etc.
“The greater the value of ksp the greater the Before addition of HCl, AgCl dissolves
solubility of the substance and vice versa” slightly in aqueous solution to form saturated
Note that solution in which free ions of Ag+ and Cl–
Ksp cannot be used to compare the solubility exist in equilibrium as shown.
of substances or salts with different formulae
such as ZnS and CaCl2. They can be AgCl(s) Ag+(aq) + Cl-(aq)
compared by calculating their solubility Addition of HCl into the saturated solution
“The greater the value of solubility the more above, increases concentration of Cl- as
soluble substance becomes and vice versa” shown by dissociation of HCl below

Example 41 HCl(aq) → H+(aq) + Cl-(aq)(Common ion)

Calculate the solubility product at 25c of
Increase in concentration of Cl- disturbs the
a) Al2S3 if its solubility at 25c is 0.0051gdm-
3
equilibrium reaction
.
b) Al(OH)3 if its solubility at 25c is AgCl(s) Ag+(aq) + Cl-(aq), therefore
0.000135gdm-3. the position of equilibrium will shift to the
left by forming AgCl(s) as shown
Example 42
AgCl(s)↽Ag+(aq) + Cl-(aq)Hence, due
Calculate the solubility in gdm-3 of
to this reverse reaction to form AgCl(s) the
a) Mg(OH)2 if its ksp at this temperature is
solubility of the AgCl(s) is decreased.
1.82x10-11 mol3dm-9

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Note that complex is formed hence the precipitates

Solubility of AgCl refers to the ability of appear to dissolve and disappear in the
AgCl to dissolve in solution to form free ions. solution.
Thus, common ion effect hinders this ability Ag+ + 2Cl-→ [AgCl2]-
by reverse reaction leading to decrease in The formation of this complex demands more
solubility of AgCl. Ag+ therefore precipitate dissolves to give out
Ag+ which combine with excess Cl- to form
This effect of decreasing solubility of
complex until all precipitates disappear.
sparingly soluble substances can be shown
numerically. Hence;
The knowledge of common ion effect is very
Example 44
useful to explain the following questions in
Calculate the solubility of Mg(OH)2 in
terms of complex compound formation.
i) water
ii) 0.01M NaOH Example 46
iii) Comment in the difference in solubility of With the aid of equation where necessary
Mg(OH)2 in (i) and (ii) above. account on the following phenomenon
Given that Ksp (Mg(OH)2) is 2.4x10-11 a) White precipitate was observed when
mol3dm-9. NaOH is passed through the solution
containing Al3+, the precipitates disappeared
Example 45
when NaOH was added in excess.
Calculate the solubility of CaF2 in moldm-3 i)
In water b) Lead (II) chloride is slightly soluble in
ii) In 1M HFGiven that Ka of HF = 5.6x10- dilute HCl but highly soluble in concentrated
4
moldm-3, Ksp of CaF2 = 4x10-11mol3dm-9 HCl.
c) When HCl is added slowly into AgCl,
Don’t dare to forget
white precipitate was observed, the
The phenomenon of decrease in solubility of
precipitates disappeared when HCl was added
sparingly soluble substances depends upon
in excess.
the amount of solution added to the saturated
solution of sparingly soluble substances. If IONIC PRODUCT, QSP
small amount of solution containing one of Unlike solubility product (ksp), Ionic product
the ions of sparingly soluble substance added (Qsp) is applied in the solution which is not
into saturated solution of sparingly soluble necessary to be saturated or in equilibrium. It
substance, then reverse reaction to form is obtained as the product of ions in the
precipitates of the substance occurs. solution obtained by mixing two sparingly
( i.e addition of HCl slowly into AgCl leads to soluble substances which form the 3rd
reverse reaction to form AgCl(s)). sparingly soluble substance. For example:
AgCl(s)↽Ag+(aq) + Cl-(aq) Mixture of Na2CO3 and CaCl2 gives the CO32-
White ppt and Ca2+ in solution which lead to obtain
CaCO3 as the 3rd sparingly soluble substance.
If the solution (say HCl) is added in excess to
the saturated solution of AgCl, then the

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Now contain less amount of ions than the

CaCO3(s) Ca2+(aq)+ CO32-(aq) maximum amount at a given temperature. The
The product of concentration of Ca2+ and sparingly soluble substances continue to
CO32- in the solution mixture is called ionic dissolve therefore no formation of precipitate
product (Qsp). (ppt).AgCl(s)→ Ag+(aq) + Cl-(aq)
Definition
Ionic product (Qsp) is the product of o If Qsp = ksp, then
concentration of ions of sparingly soluble The solution is said to be saturated
substance, each raised to the power of their Definition
stoichiometric coefficients in the balanced Saturated solution is the solution which
equation at any concentration of the solution contain maximum amount of ions that
(mixture). sparingly soluble substances can dissolve at a
given temperature. The concentration of ions
Eg. CaCO3(s) Ca2+(aq) + CO32-(aq)
can be said as either minimum concentration
Qsp = [Ca2+] [CO32-] for precipitate to be formed or maximum
concentration of ions without forming the
Generally, precipitate. No formation of precipitate (ppt).
For any sparingly soluble substance AmBn, AgCl(s) Ag+(aq) + Cl-(aq)
Qsp can be expressed as shown below.
AmBn(s) mAn+(aq) + nBm-(aq) o If Qsp > ksp, then
The solution is said to be super saturated
Qsp = [An+]m[Bm-]n
Definition
Where;
Super saturated solution is the solution which
Qsp is the product of concentration of ions
contain more than the maximum amount of
not necessary to be that of saturated solution
ions that sparingly soluble substances can
in equilibrium.
dissolve at a given [Link] formation
Don’t forget of precipitate occurs.
AgCl(s)↽ Ag+(aq) + Cl-(aq).
Ksp = [An+]m[Bm-]nWhere;
Ksp is the product of concentration of ions Difference between Qsp and Ksp
when the solution is saturated at a given Apart from their definitions, they can be
temperature ( at equilibrium). differentiated as follows.
i) The value of Qsp depends on concentration
Ionic product is very useful to determine of ions while the value of ksp depends on
whether the solution mixture of substances is temperature.
saturated (in equilibrium) or not by ii) Qsp is applicable for solution at any
comparing its value to the solubility product. concentration (saturated, unsaturated and
o If Qsp < ksp, then supper saturated solution) while ksp is
applicable for saturated solution only.
The solution is said to be unsaturated
Definition
Unsaturated solution is the solution which

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Factors affecting solubility of sparingly decreases when dissolved in solution with

soluble substances high temperature and vice versa.

1) Common ion effect Example 47

The solubility of sparingly soluble substances A solutions is prepared by mixing 50cm3 of
is found to decrease if there is common ion 0.005M CaCl2 solution and 80cm3 of 0.006M
effect as explained earlier. ZnF2 solution at 25c.
Eg. When AgCl is added in dilute HCl, the i) Calculate the concentration of calcium and
solubility of AgCl will be decreased due to fluoride ions in the mixed solution
reverse reaction of equation below leading to
eliminate Cl- from dilute HCl. ii) Find the reaction quotient, Q for this
reaction.
AgCl(s) Ag+(aq) + Cl-(aq) iii) Given that the solubility product CaF2, ksp
= 3.95x10-11, state with reasons whether or
This decrease in solubility is associated by
not precipitation will occur.
formation of precipitate (ppt).
Example 48
2) Complex formation
Calculate the concentration of calcium
It occurs when common ions are added in
carbonate precipitated in gdm-3 if 0.1M
large amount (concentrated or excess) to
calcium chloride was added to 0.1M sodium
sparingly soluble substances. Formation of
carbonate solution. The solubility product of
soluble complex lead to increase in solubility
calcium carbonate is 1.69x10-6mol2dm-8.
of sparingly soluble substances hence the
precipitate is disappeared at the end point. Eg. Example 49
When mixture in factor one above is added in How many grames of AgCl will be
concentrated HCl, formation of [AgCl2]- precipitated if 5.85g of NaCl are dissolved in
occurs which lead to dissolve ppt of AgCl saturated solution of AgCl, given that ksp of
hence increasing solubility. AgCl is 1.69x10-10moldm-3.

Ag+ + 2Cl-→ [AgCl2]- (soluble complex) then; Example 50

An aqueous solution of Na2S is gradually
AgCl(s) Ag+ + Cl-
added to a solution containing Ca2+, Cu2+and
3) Temperature Ag+each at concentration of 50-3M.
It can be explained in similar ways as position Determine [S2-] at which precipitation of each
of equilibrium or equilibrium constant. cation occurs. Given that;
Ksp of CaS = 1x10-28mol2dm-6
For endothermic process Ksp of CuS = 1x10-36mol2dm-6
Dissolving sparingly soluble substances in Ksp of Ag2S = 1x10-50mol3dm-9
solution with high temperature increases the Hence give the order of precipitation of given
solubility and vice versa. compounds.
For exothermic process
Solubility of sparingly soluble substances

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