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Review: Solubility Rules

Salts are generally more soluble in HOT


water
Alkali Metal salts are very soluble in water.
Ammonium salts are very soluble in water.
Salts containing the nitrate ion, NO
3
-
, are
very soluble in water.
Most salts of Cl
-
, Br
-
and I
-
are very soluble in
water - exceptions are salts containing Ag
+

and Pb
2+
.
Dissolving a salt...
At first, the only
process occurring
is the dissolving
of the salt - the
dissociation of
the salt into its
ions.


However, soon the ions
floating in the water
begin to collide with the
salt crystal and are
pulled back in to the
salt. (precipitation)

Eventually the rate of
dissociation is equal to
the rate of precipitation.
The solution is now
saturated. It has
reached equilibrium.
There is no change in amount of
solid precipitate at the bottom of
the beaker.
Concentration of the solution is
constant.
The rate at which the salt is
dissolving into solution equals the
rate of precipitation.

Saturated Solution
Example: BaSO
4,
in water
When barium sulfate dissolves, it dissociates into
ions. When the solution is saturated, the following
equilibrium exists:

BaSO
4
(s) Ba
2+
(aq)

+ SO
4
2-
(aq)

Since this is an equilibrium, we can write an
equilibrium expression for the reaction:

K = [Ba
2+
][SO
4
2-
]

Since K is always calculated by just multiplying
concentrations, it is called a solubility product
constant, Ksp
Example
For each salt below, write a balanced
equation showing its dissociation in water.
Then write the Ksp expression for the salt.

1. Iron (III) hydroxide, Fe(OH)
3

2. Nickel sulfide, NiS
3. Silver chromate, Ag
2
CrO
4

4. Zinc carbonate, ZnCO
3

5. Calcium fluoride, CaF
2

Some Ksp

Values
Note:
These are experimentally determined, and may
be slightly different on a different Ksp table.
Solubility vs Ksp
Solubility Ksp
Quantity of solute that
dissolves to form a
saturated solution
g/L or mol/L
Changes with changes of
concentration
Equilibrium constant for
equilibrium between an
ionic solid and its
saturated solution
Unitless
One value for a given
solute at any specific
temperature
Solubility and Ksp
Generally, it is fair to say that salts
with very small solubility product
constants (Ksp) are only sparingly
soluble in water.
When comparing the solubilities of two
salts, however, you can sometimes
simply compare the relative sizes of
their Ksp values.
This works only if the salts have the
same formula type!



Example
CuI has Ksp = 5.0 x 10
-12
and CaSO
4

has Ksp = 6.1 x 10
-5
. Which is more
soluble in water?

Calcium sulfate is more soluble.


But be careful...
Salt Ksp
Solubility
(mol/L)
CuS 8.5 x 10
-45
9.2 x 10
-23
Ag
2
S 1.6 x 10
-49
3.4 x 10
-17
Bi
2
S
3
1.1 x 10
-73
1.0 x 10
-15
Example
A saturated solution of silver chromate,
Ag
2
CrO
4
, has [Ag
+
] = 1.3 x 10
-4
M. What
is the Ksp for Ag
2
CrO
4
?
Example
The Ksp of NiCO
3
is 1.4 x 10
-7
at 25C.
Calculate its molar solubility. What
mass of NiCO
3
is needed to prepare
500 mL of saturated solution?

Calculate the pH of a saturated solution
of silver hydroxide, AgOH.
Ksp = 2.0 x 10
-8


Example
The Common Ion Effect on
Solubility
The solubility of MgF
2
in pure water is 2.6
x 10
-4
mol/L. What happens to the
solubility if we dissolve the MgF
2
in a
solution of NaF, instead of pure water?

The Common Ion Effect on Solubility
The presence of a common ion in a solution will
lower the solubility of a salt.

LeChateliers Principle:

The addition of the common ion will shift the
solubility equilibrium backwards. This means
that there is more solid salt in the solution
and therefore the solubility is lower!

Example
Calculate the solubility of MgF
2
(K
sp
= 7.4 x
10
-11
) in a solution of 0.080 M NaF.
Criteria for Precipitation or
Dissolution
Solubility equilibria can be achieved
starting from either side
When precipitating from the ions, one can
calculate for Q (ion product) at any moment
in precipitation process
If Q > Ksp, precipitation occurs until Q=Ksp
If Q = Ksp, equilibrium (saturated solution)
If Q < Ksp, solid dissolves until Q = Ksp
Example
Will a precipitate form if 10.0 mL of 0.010
M AgNO
3
and 10.0 mL of 0.00010 M
NaCl are mixed? Assume final volume of
solution is 20.0 mL.
Ksp AgCl = 1.7 x 10
-10

Example
Assume that 0.10 M NaF solution is added
slowly, with stirring, to a solution that
contains 0.10 M Cr(NO
3
)
3
and 0.10 M
Ca(NO
3
)
2
. Which salt precipitates first?
Ksp, CaF
2
= 5.3 x 10
-9

Ksp, CrF
3
= 6.6 x 10
-11

Example
The solubility product for gadolinium
hydroxide, Gd(OH)
3
is 1.8 x 10
-23
. If a
solution is 0.010 M in Gd
3+
ion and the
pH of the solution is slowly increased, at
what pH will Gd(OH)
3
begin to
precipitate?
Solubility and pH
Solubility of any substance whose anion
is basic will be affected by pH
Example:
Mg(OH)
2(s)
Mg
2+
(aq)
+ 2OH
-
(aq)

In acidic buffers, S increases
Rule: The solubility of slightly soluble
salts containing basic anions, increases
as [H
+
] increases.