The Solubility Product Principle

Solubility Product Constants

Silver chloride, AgCl,is rather insoluble in
water.
Careful experiments show that if solid AgCl is
placed in pure water and vigorously stirred, a
small amount of the AgCl dissolves in the
water
-10 -
sp
10 1.8 ] ][Cl [Ag K = =
+
K
sp
= solubility product constant
Solubility Product Constants
In general, the dissolution of a slightly soluble
compound and its solubility product expression
are represented as:
( )
| | | |
M Y r M s Y
K M Y
r s s
H O
s r
100%
sp
s
r
r
s
2

+
=
+
~
+
Solubility Product Constants
The same rules apply for compounds that have
more than two kinds of ions.
One example of a compound that has more than
two kinds of ions is calcium ammonium
phosphate.
( ) ( ) ( ) ( )
| || || |
+ +
+ +
=
+ +

3
4 4
2
sp
3
aq 4
1
aq 4
2
aq s 4 4
PO NH Ca K
PO NH Ca PO CaNH
Determination of Solubility Product
Constants
Example: One liter of saturated silver chloride
solution contains 0.00192 g of dissolved AgCl at
25
o
C. Calculate the molar solubility of, and K
sp

for, AgCl.
The molar solubility can be easily calculated from
the data:
L
AgCl mol
10 34 . 1
AgCl g 143
AgCl mol 1
L
AgCl g 00192 . 0
L
AgCl mol ?
5
=
=
Determination of Solubility Product
Constants
The equation for the dissociation of silver
chloride, the appropriate molar concentrations,
and the solubility product expression are:
( )
| || |
AgCl Ag Cl
1.34 10 1.34 10
K Ag Cl
s
-5 -5
sp

+

=
+
+
M M
Determination of Solubility Product
Constants
Substitution of the molar concentrations into the
solubility product expression gives:
| || |
| || |
K Ag Cl
sp
=
=
=
+

134 10 134 10
18 10
5 5
10
. .
.
Determination of Solubility Product
Constants
Example 2: One liter of saturated calcium
fluoride solution contains 0.0167 gram of CaF
2

at 25
o
C. Calculate the molar solubility of, and
K
sp
for, CaF
2
.
1. Calculate the molar solubility of CaF
2
.
L
CaF mol
10 14 . 2
g 78.1
mol 1
L 1.0
CaF g 0167 . 0
L
CaF mol ?
2
4
2 2

=
=
Determination of Solubility Product
Constants
From the molar solubility, we can find the ion
concentrations in saturated CaF
2
. Then use
those values to calculate the K
sp
.
Note: You are most likely to leave out the factor of 2 for
the concentration of the fluoride ion!
( ) ( )
| || |
( )( )
11
2
4 4
2
2
sp
4 4 4
- 1
aq
2
aq 2
10 92 . 3
10 28 . 4 10 14 . 2
F Ca K
) 10 14 . 2 2( 10 14 . 2 10 14 . 2
F 2 Ca CaF

+

+
=
=
=

+

M M M
Uses of Solubility Product
Constants
The solubility product constant can be used to
calculate the solubility of a compound at 25
o
C.
Calculate the molar solubility of barium sulfate,
BaSO
4
, in pure water and the concentration of
barium and sulfate ions in saturated barium sulfate
at 25
o
C. For barium sulfate, K
sp
= 1.1 x 10
-10
.
Uses of Solubility
Product Constants
Make the algebraic substitution of xs into
solubility product expression and solve for x,
giving the ion concentrations.
( )( )
| | | | M
M x
x x
10 0 . 1 SO Ba
10 0 . 1
10 1 . 1
5 2
4
2
5
10
+

= =
=
=
Uses of Solubility
Product Constants
Finally, to calculate the mass of BaSO
4
in 1.00 L
of saturated solution, use the definition of
molarity.
L
BaSO g
10 3 . 2
mol
g 234
L
mol 10 1.0
L
BaSO g ?
4
3
5
4

=
Uses of Solubility Product Constants
The solubility product constant for magnesium
hydroxide, Mg(OH)
2
, is 1.5 x 10
-11
. Calculate the
molar solubility of magnesium hydroxide and the pH
of a saturated magnesium hydroxide solution at
25
o
C.
Uses of Solubility
Product Constants
Substitute the algebraic expressions into the
solubility product expression.
( )( )
x x
x
x
x
2 15 10
4 15 10
375 10
16 10
2
11
3 11
3 12
4
=
=
=
= =

.
.
.
. molar solubility
Uses of Solubility
Product Constants
Solve for the pOH and pH.
( )( )
| |
x x
x
x
x
M M
2 15 10
4 15 10
375 10
16 10
2 32 10
2
11
3 11
3 12
4
4
=
=
=
= =
= =
= =

.
.
.
.
.
molar solubility
OH
pOH 3.49 pH 10.51
-
The Common Ion Effect in Solubility
Calculations
Calculate the molar solubility of barium
sulfate, BaSO
4
, in 0.010 M sodium
sulfate, Na
2
SO
4
, solution at 25
o
C.
Compare this to the solubility of BaSO
4
in pure water.
1. Write equations to represent the equilibria.
The Common Ion Effect in Solubility
Calculations
2. Substitute the algebraic representations of the
concentrations into the K
sp
expression and solve for x.
| || |
( )( )
( )
4
8
10 -
10 2
4
2
sp
BaSO of solubility molar 10 1 . 1
10 1.1 = 0.010
0.010 0.010
applied. be can assumption g simplifyin The
010 . 0
10 1 . 1 SO Ba K
= =

~ +
+ =
= =

+
x
x
x
x x
The Common Ion Effect in Solubility
Calculations
The molar solubility of BaSO
4
in 0.010 M Na
2
SO
4
solution
is 1.1 x 10
-8
M.
The molar solubility of BaSO
4
in pure water is 1.0 x 10
-5

M.
BaSO
4
is 900 times more soluble in pure water than in
0.010 M sodium sulfate!
Adding sodium sulfate to a solution is a good method to
remove Ba
2+
ions from solution!
If your drinking water were suspected to have lead ions in
it, suggest a method to prove or disprove this suspicion.
The Reaction Quotient in
Precipitation Reactions
Compare Qsp with Ksp
If Qsp < Ksp
Forward process is favored
No precipitation occurs; if solid is present, more solid can
dissolve
If Qsp = Ksp
Solution is just saturated
Solid and solution are in equilibrium; neither forward nor reverse
process is favored
If Qsp > Ksp
Reverse process is favored
Precipitation occurs to form more solid
Predicting Precipitate Formation
If 100 mL of 0.00075 M sodium sulfate is mixed with
50 mL of 0.015 M barium chloride, will a precipitate
form? (Ksp of barium sulfate is 1.1 x 10-10)

Solution:
Find the amount (moles) of solute at the instant of
mixing
Find the molarity of each solute at the instant of mixing
Find the concentration of each ion in the solution
Solve for Qsp and compare with Ksp
Initiation of Precipitation
What [Ba
2+
] is necessary to start the precipitation of
BaSO
4
in a solution that is 0.0015 M in Na
2
SO
4
?
Assume that Ba
2+
comes from addition of a solid
soluble ionic compound such as BaCl
2
. For BaSO
4
,
Ksp = 1.1 x 10
-10
Fractional Precipitation
A method to remove selected ions from solution
while leaving others with similar properties in solution
Example: silver halides
AgCl Ksp = 1.8 x 10
-10
AgBr Ksp = 3.3 x 10
-13
AgI Ksp = 1.5 x 10
-16

These Ksp values show that AgI is less soluble than
AgBr, and that AgBr is less soluble than AgCl.
Concentration Required to Initiate
Precipitation
Solid silver nitrate is slowly added to a solution that
is 0.0010 M each in NaCl, NaBr, and NaI. Calculate
the [Ag
+
] required to initiate the precipitation of each
of the silver halides.

Plan: Use Ksps of each halide and calculate for
[Ag
+
]

Answers:
To precipitate AgI, [Ag
+
] > 1.5 x 10
-13
M
To precipitate AgBr, [Ag
+
] > 3.3 x 10
-10
M
To precipitate AgCl, [Ag
+
] > 1.8 x 10
-7
M
Fractional Precipitation
Calculate the percentage of I
-
precipitated before
AgBr precipitates
Use [Ag
+
] when AgBr just begins to precipitate
Substitute into Ksp of AgI to determine unprecipitated I
-
Determine percentage I
-
unprecipitated using I
-
original
Calculate the percentages of I- and Br- precipitated
before Cl- precipitates
Use [Ag+] when AgCl just begins to precipitate
Substitute into Ksps of AgBr and AgI
(Same as above)
Simultaneous Equilibria:
Solubility Product Constants and
Complex Ion Equilibria
Complex Ion Equilibria
A metal ion coordinated to several neutral
molecules or anions forms compounds called
complex ions.
Familiar examples of complex ions include:
+
+ +
2 3 2 2 3
4 3 2 3
) Pt(NH Cl ) Co(NH
) Cu(NH ) Ag(NH
| || |
| |
+
+
+ +
=
+

2
4 3
4
3
2
d
3
2 2
4 3
) Cu(NH
NH Cu
K
NH 4 Cu ) Cu(NH
Complex Ion Equilibria
The dissociation of complex ions can be
represented similarly to equilibria.
| || |
| |
+
+
+ +
=
+

2 3
2
3
d
3 2 3
) Ag(NH
NH Ag
K
NH 2 Ag ) Ag(NH
Complex Ion Equilibria
Complex ion equilibrium constants are called
dissociation constants.
Example: Calculate the concentration of silver ions
in a solution that is 0.010 M in [Ag(NH
3
)
2
]
+
.
K
d
= 6.3 x 10
-8
Complex Ion Equilibria
| || |
| |
( )( )
( )
8
2
d
8
2 3
2
3
d
10 3 . 6
010 . 0
2
K
10 3 . 6
) Ag(NH
NH Ag
K

+
+
=

=
= =
x
x x
| |
+

= =
=
=
Ag 10 4 . 5
10 6 . 1
10 3 . 6 4
4
10 3
10 3
M x
x
x
Complex Ion Equilibria and
Precipitate Dissolution
Copper(II) hydroxide, which is light blue colored,
dissolves in aqueous ammonia to form dark blue,
[Cu(NH
3
)
4
]
2+
.
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
Cu(OH) 4 NH Cu(NH ) 2 OH
Cu(OH) Cu 2 OH
Cu 4NH Cu(NH )
2 s 3 aq 3 4 aq
2
2 s aq
2
aq
aq
2
3 3 4 aq
2
+

+

+
+

+
+
+ +
Complex Ion Equilibria
How many moles of ammonia must be added to
2.00 L of water so that it will just dissolve 0.010
mole of silver chloride, AgCl?
What is the stoichiometric amount of NH
3
needed to
form Ag(NH
3
)
2
+
?
STOICHIOMETRIC amount
What is the equilibrium NH
3
concentration needed to
maintain the silver-ammonia complex?
EQUILIBRIUM amount