You are on page 1of 6

SOLUBILTY PRODUCT (K

sp
)

When a sparingly soluble salt is mixed with water a dynamic equilibrium is established in
which salt is constantly dissolving and crystallising at the same rate when the solution is
saturated, and the maximum constant concentration is achieved.
e.g. for calcium sulphate: CaSO
4(s)
+ aq Ca
2+
(aq)
+ SO
4
2-
(aq)

o the equilibrium expression is:



However, since the concentration of water and the solid is effectively constant the equilibrium
expression is simplified to:
K
sp
= [Ca
2+
(aq)
] [SO
4
2-
(aq)
]
Generally for a sparingly soluble salt,
A
a
B
b(s)
+ aq aA
n+
(aq)
+ bB
m-
(aq)



o K
sp
is called the solubility product of the ions concerned and is constant at constant
temperature for a saturated solution i.e. when no more will dissolve.
The solubility product(K
sp
) for a sparingly soluble strong electrolyte is defined as the
product of the concentration of the ions raised to their appropriate powers in a saturated
solution at a specific temperature.
Solubility is the amount of a substance that can be dissolved in 1dm
3
of solution, i.e.,
the molarity of a saturated solution.
N.B.: solubility product and solubility are different things!
o At the saturation solution point, controlled by the K
sp
expression, it doesn't matter how
much solid you add, no more can dissolve.
o The solubility of the sparingly soluble salt is governed by the K
sp
expression, i.e.
whatever ion concentrations are present of the compound, then the expression must be
obeyed. (see common ion effect below).
o If on mixing solutions containing the two constituent ions the K
sp
expression is
exceeded, precipitation will take place until the product of the ion concentrations equals
the K
sp
value. If the Ksp expression is not exceeded, no precipitation will take place.
Other solubility product expressions
o Note: In the K
sp
expression, the ion concentrations are raised to powers equal to
their molar ratio in the compound:
This is analogous to the molar ratio from the equations for K
c
or K
p
expressions,
and similarly, watch the units!
o silver chloride : AgCl
(s)
+ aq Ag
+
(aq)
+ Cl
-
(aq)

K
sp
= [Ag
+
(aq)
] [Cl
-
(aq)
]
o calcium carbonate: CaCO
3(s)
+ aq Ca
2+
(aq)
+ CO
3
2-
(aq)
(H slightly -ve)
K
sp
= [Ca
2+
(aq)
] [CO
3
2-
(aq)
]
Sea shells are mainly made of calcium carbonate which is a tough mineral and
will not dissolve appreciably in water.
However, when the sea creatures die and the remains sink to great depth in the
oceans, the shells will then dissolve because of changes in the position of two
equilibria. At great depths the pressure is much higher and the temperature
K
sp
= [A
n+
(aq)
]
a
[B
m-
(aq)
]
b

lower, both factors favouring more CO
2
dissolving, therefore the following forward
reaction is promoted,
CaCO
3(aq)
+ CO
2(aq)
+ H
2
O(l) Ca
2+
(aq) + 2HCO
3
-
(aq)

and secondly, the lower temperature favours a higher K
sp
value because the
dissolving process is slightly exothermic, so more of the calcium carbonate
will dissolve. There are no shells lying at the bottom of the oceans! The limestone
cliffs you see in the landscape were formed in warm shallow tropical seas.
o magnesium hydroxide : Mg(OH)
2(s)
+ aq Mg
2+
(aq)
+ 2OH
-
(aq)

K
sp
= [Mg
2+
(aq)
] [OH
-
(aq)
]
2
= 1.1 x 10
-11
mol
3
dm
-9

The Common Ion Effect
o If a 2nd soluble substance is added to the saturated solution of a salt, that has an ion in
common with the salt, this will cause precipitation of the salt. This is because the K
sp

expression is initially exceeded, causing precipitation until the new concentrations
satisfy the K
sp
expression Le Chatelier again!). This precipitation is known as the
'common ion effect' and happens irrespective of the solubility of the substances e.g.
If you add some concentrated hydrochloric acid to a saturated sodium chloride
('salt' is very soluble) solution ('brine') sodium chloride is precipitated.
NaCl
(s)
Na
+
(aq)
+ Cl
-
(aq)

[Na
+
(aq)
] x [Cl
-
(aq)
] is ~constant for a saturated solution of sodium chloride
at constant temperature. If you increase one ion concentration, the other
must decrease to maintain equilibrium, and the only way this can happen
is by precipitation of the salt.
Applying Le Chatelier's Principle, the conc. HCl
(aq)
increases the chloride
ion Cl
-
(aq)
concentration so the reaction 'net change' must initially move to
the left to restore equilibrium i.e. NaCl is precipitated.
Similarly if you add dilute sulphuric acid OR saturated calcium chloride solution to
saturated calcium sulphate (sparingly soluble) solution then calcium sulphate
appears as a faint precipitate.
CaSO
4(s)
Ca
2+
(aq)
+ SO
4
2-
(aq)

[Ca
2+
(aq)
] x [SO
4
2-
(aq)
] is ~constant for a saturated solution of calcium
sulfate at constant temperature.
The sulphuric acid increases the sulfate ion SO
4
2-
(aq)
concentration OR
calcium chloride increases the calcium ion Ca
2+
(aq)
concentration. Either
way, increasing one of the concentrations of the salts constituent ions will
cause precipitation of calcium sulfate according to Le Chatelier's Principle.
Calculating K
sp

Question:
The concentration of a saturated solution of BaSO
4
is 3.90 10
-5
M. Calculate K
sp
for
barium sulfate at 25C
Answer:
Always begin problems involving K
sp
by writing a balanced equation:
BaSO
4 (s)
Ba
2+
(aq)
+ SO
4
2-
(aq)

Mole ratio is 1:1:1 [BaSO
4
] =[Ba
2+
] = [SO
4
2-
] = 3.90 10
-5
M
K
sp
= [Ba
2+
][SO
4
2-
]

= (3.90 10
-5
)(3.90 10
-5
)
K
sp
= 1.52 10
-9





Question:
The concentration of lead ions in a saturated solution of PbI
2
at 25C is 1.3 10
-3
M.
What is its K
sp
?
Answer:
PbI
2 (s)
Pb
2+
(aq)
+ 2 I
-
(aq)


Mole ratio is 1:1:2 [PbI
2
] =[Pb
2+
] = 1.30 10
-3
M
[I
-
] = 2 1.30 10
-3
= 2.60 10
-3


K
sp
= [Pb
2+
][I
-
]
2



= (1.30 10
-3
)(2.60 10
-3
)
2



= (1.30 10
-3
)(6.76 10
-6
)
K
sp
= 8.79 10
-9
M

Question:
Given that the solubility of Ca
3
(PO
4
)
2
= 2.5 x 10
-6
M. Calculate K
sp
for Ca
3
(PO
4
)
2.
Answer:
Ca
3
(PO
4
)
2(s)
3Ca
2+
+


[Ca
3
(PO
4
)
2
] = 2.5 x 10
-6
M
[Ca
2+
] = 3(2.5 x 10
-6
) =7.5 x 10
-6

] =2(2.5 x 10
-6
) =5.0 x 10
-6

K
sp
= [Ca
2+
]
3

]
2

=(7.5 x 10
-6
)
3
(5.0 x 10
-6
)
2

= 1.1 x 10
-26
Calculating Ion Concentrations (Solubility)
Question:
What is the molarity of calcium carbonate in a saturated solution at 298K?
K
sp
(CaCO
3
) = 5.0 x 10
-10
mol
2
dm
-6

Answer: CaCO
3(s)
+ aq Ca
2+
(aq)
+ CO
3
2-
(aq)

Since mole ratio of Ca
2+
:CaCO
3
:CO
3
2-
is a 1:1:1 ratio, so [Ca
2+
(aq)
] = [CO
3
2-
(aq)
] = [CaCO
3(aq)
]
K
sp
= [Ca
2+
(aq)
] [CO
3
2-
(aq)
]
[Ca
2+
(aq)
] = [CO
3
2-
(aq)
] = [CaCO
3(aq)
] = x
K
sp
= x
2
= 5.0 x 10
-10
mol
2
dm
-6

x = (5.0 x 10
-10
)
= 2.24 x 10
-5
mol dm
-3

Question:
K
sp
for MgCO
3
at 25C is 2.0 10
-8
. What are the ion concentrations in a saturated
solution at this temperature?
Answer:
MgCO
3(s)
Mg
2+
(aq)
+ CO
3
2-
(aq)

K
sp
= [Mg
2+
][CO
3
2-
]
Mole ratio is 1:1:1 [Mg
2+
] = [CO
3
2-
]
let our unknown ion concentrations equal x
2.0 10
-8
= (x) (x) = x
2

x
2
= 2.0 10
-8

x = 2.0 10
-8
find the square root of 2.0 10
-8

= 1.4 10
-4
M
x = [Mg
2+
] = 1.4 10
-4
M
AND x = [CO
3
2-
] = 1.4 10
-4
M
Question:
(b) What is the solubility of calcium carbonate in 0.1 mol dm
-3
sodium carbonate
solution?
[K
sp
(CaCO
3
) = 5.0 x 10
-10
mol
2
dm
-6
]
Answer:
The tiny contribution of carbonate from the dissolved calcium carbonate can be ignored, so
effectively the carbonate concentration is that of the sodium carbonate itself.
K
sp
= [Ca
2+
(aq)
] [CO
3
2-
(aq)
] = 5.0 x 10
-10
= [Ca
2+
(aq)
] x 0.1
[Ca
2+
(aq)
] = [CaCO
3(aq)
]
= 5.0 x 10
-10
/0.1
= 5.0 x 10
-9
mol dm
-3

Question:
If equal volumes of aqueous 0.01 mol dm
-3
sodium chloride and 0.005 mol dm
-3
silver nitrate solution
are mixed, show by calculation whether or not a precipitate of silver chloride forms?
[K
sp(AgCl)
= 1.8 x 10
-10
mol
2
dm
-6
]
Answer:
K
sp(AgCl)
= [Ag
+
(aq)
] [Cl
-
(aq)
] = 1.8 x 10
-10
mol
2
dm
-6

[NaCl
(aq)
] = [Cl
-
(aq)
] = 0.01 / 2 = 0.005 mol dm
-3

(both original concentrations are halved because of mixing equal volumes i.e. diluted by a
factor of 2)
[AgNO
3(aq)
] = [Ag
+
(aq)
] = 0.005 / 2 = 0.0025 mol dm
-3

The ionic product = [Ag
+
(aq)
] x [Cl
-
(aq)
] = 0.005 x 0.0025 = 1.25 x 10
-5
mol
2
dm
-6

The ionic product on mixing exceeds the K
sp
value so precipitation takes place.


Question:
For the equilibrium: CaSO
4(s)
+ aq Ca
2+
(aq)
+ SO
4
2-
(aq)

K
sp
= [Ca
2+
(aq)
] [SO
4
2-
(aq)
] = 2.0 x 10
-5
mol
2
dm
-6

(a) What is the solubility of calcium sulphate in a saturated solution of the salt in g cm
-3
?
(b) Assuming equal volumes of solutions are mixed, what is the minimum concentration of
sodium sulphate (Na
2
SO
4
) solution that when added to a 1.0 x 10
-4
mol dm
-3
solution of
calcium sulphate, will just begin to cause precipitation of calcium sulphate?
Answer:
(a) [Ca
2+
(aq)
] = [CaSO
4(aq)
] = (2.0 x 10
-5
) = 4.47 x 10
-3
mol dm
-3

A
r
's: Ca = 40, S = 32, O = 16, M
r
(CaSO
4
) = 136, 1 dm
3
= 10
6
cm
3

solubility = 4.47 x 10
-3
x 136 = 0.608 g dm
-3
, so scaling down to 100 cm
3

solubility = 0.608 x 100/10
6
= 6.1 x 10
-5
g/100 cm
3
(b)Let [Na
2
SO
4(aq)
] = [SO
4
2-
(aq)
] = the theoretical concentration of sodium sulphate at the point of
precipitation.
This is ignoring the tiny contribution from the calcium sulphate solution.
On mixing the equal volumes of solutions, the calcium sulphate concentration is halved.
Therefore on substituting into the K
sp
expression on the point of precipitation...
2.0 x 10
-5
= ((1.0 x 10
-4
)/2) x [Na
2
SO
4(aq)
]
therefore [Na
a
SO
4(aq)
] = 2.0 x 10
-5
/0.5 x 10
-4
= 0.4 mol dm
-3

However, on mixing, the sodium sulphate solution concentration must also be halved,
therefore the original sodium sulphate solution must be at least 0.8 mol dm
-3

Question:
o Equal volumes of 0.025 mol dm
-3
potassium bromide (KBr) and 0.005 mol dm
-3
lead(II)
nitrate (Pb(NO
3
)
2
)solutions were mixed.
K
sp(PbBr2)
= 7.9 x 10
-5
mol
3
dm
-9

o (a) Write out (i) the K
sp
expression for lead(II) bromide and (ii) the ionic equation for its
precipitation.
Answer: (i) K
sp(PbBr2)
= [Pb
2+
(aq)
] [Br
-
(aq)
]
2
, (ii) Pb
2+
(aq)
+ 2Br
-
(aq)
==> PbBr
2(s)

o (b) Show by calculation if lead(II) bromide precipitates after mixing the solutions.
Answer:
[Br
-
(aq)
] = [KBr
(aq)
] = 0.025 / 2 = 1.25 x 10
-2
mol dm
-3

[Pb
2+
(aq)
] = [Pb(NO
3
)
2(aq)
] = 0.005 / 2 = 2.5 x 10
-3
mol dm
-3

The ionic product = [Pb
2+
(aq)
] [Br
-
(aq)
]
2
= 2.5 x 10
-3
x (1.25 x 10
-2
)
2
= 3.91 x 10
-7
mol
3

dm
-9

The K
sp
value of 7.9 x 10
-5
is NOT exceeded, so no precipitation takes place


Caculations (Common Ion Effect)
Question:
Calculate the solubility of PbSO
4
in 0.100 M Na
2
SO
4
. Ksp
(PbSO4)
= 1.96 10
-8

Answer:
Ksp = [Pb
2+
] [SO4
2-
]
Common ion: SO4
2-

[PbSO
4
(dissolved)] Pb
2+
(aq) + SO4
2-
(aq)

x x 0.100 + x

Since x is very small compared to 0.100,
0.100 + x is very nearly equal to 0.100.

[Pb
2+
] [SO4
2-
] = x 0.100 = 1.96 10
-8

x = = 1.96 10
-7
M
Molar solubility of PbSO4 in 0.100 M Na2SO4 = 1.96 10
-7

You might also like