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Do not confuse
solubility (s)
with solubility
product Ksp.
2 Temperature Factor -
i) Solids/Liquids- Solubility increases with Temperature (mostly)
Increase K.E. increases motion and collision between solute / solvent.
ii) gas - Solubility decreases with Temperature
Increase K.E. result in gas escaping to atmosphere.
3 Pressure Factor -
i) Solids/Liquids - Very little effect
Solids and Liquids are already lose together, extra pressure will not
increase solubility.
ii) Gas- Solubility increases with Pressure.
Increase pressure squeezes gas solute into solvent.
NaOCH2CH3 (s) + H2O (l) D Na+ (aq) + OH- (aq) + CH3CH2OH (aq) Ksp = [Na+] [OH-] [CH3CH2OH]
Solubility rule provides information on the specie that will form a precipitate.
In general, a molar solubility of 0.01M or greater for a substance is
considered soluble.
http://www.ausetute.com.au/solrules.html
13 Solubility and Solubility Product March 14
Precipitation Experiment
Consider the reaction:
3 Ca2+ + 2PO43- (aq) D Ca3(PO4)2 (s)
To solve,
It is always convenient to write the equation as a dissolution of solid
Ca3(PO4)2 (s) D 3 Ca2+ + 2PO43- (aq)
Direction Direction
Ksp
Reaction Reaction
Q (i) Q Q (h)
Unsaturated. Sat. Supersaturated.
Q is small, system Point Q is large, system will
consist mostly of ion. adjust to reduce high
No ppt. forms ion concentration.
(s) g (aq) Solid forms
(s) f (aq)
Precipitate forms.
Ag+ I- Ag+ I-
Ag+ I-
AgI(s) AgI(s)
Add I-
via NaI AgI(s)
AgI(s) D Ag+(aq) + I-(aq)
add common ion i.e.,
NaI to solution
Direction of Reaction
Reduce solubility
i.e., less AgI will dissolve in soln which
means more ppt. forms in solution
18 Solubility and Solubility Product March 14
...according to LeChatelier
AgI(s) Ag+ I-
AgI(s) D Ag+ + I-
Q analogy:
Increase I-
Ag+ I- Ksp < Q
AgI(s) Ag+ I-
Ksp Q
1.0510 -6 = s = s (0.05M + s)
= s (0.05M)
2.0 10 -11 = s
Check assumption
indeed 9.9210-5 << 0.025
Zn(IO3)2 (s) D Zn2+ (aq) + 2IO3-2(aq) Sr(IO3)2 (s) D Sr +2(aq) + 2IO3- (aq)
i Lots 0 0 i Lots 0 0
-m +m +2m + 2n -n +n +2n + 2m
e Lots +m +2m + 2n e Lots +n +2n + 2m
- -
K sp = [Zn2+ ] [IO3 ]2 K sp = [Sr+2 ] [IO3 ]2
K sp
- K sp -
[IO4 ]2 =
[IO3 ] = 2
[Sr+2 ]
[Zn2+ ]
3.3 10-7
n= 3 = 7.948 10-4 , m = 11.818 n =9.393 10-3
657.2
March 14
Calculation: Same type problem different data
At 25C, the solubility product of AgI and PbI2 is 8.310-17 M and
7.910-9M, respectively. What are the values of [I-], [Ag+], and [Pb2+] in a
solution at equilibrium with both substances ? (Answer behind)
29
8.3 10-17 = [s] [2t] but t = 1.25 103
March 14
8.3 10-17 = [s] [2(1.25 103 )] = 2.50 103 s
s = 3.32 10-13 M= [Ag+ ] , [I- ] = s + 2t = 3.32 10-13 +2.5010-3 = 2.5010-3M [Ag+ ]=3.32 1014 M, [Pb+2] =1.25 103 M, [I- ] =2.5 103 M
[Ag+ ] = 3.32 10-13 M
[Pb+2] = 1.25 103 M
[I- ] = 2.5010-3M
Common Ion Effect
B&L 17.44 (7th Ed.): The Ksp for cerium iodate, Ce(IO3)3, is 3.2 10-10
a) Calculate the molar solubility of Ce(IO3)3 in pure water.
b) What concentration of NaIO3 in solution would be necessary to reduce the Ce3+ concentration
in a saturated solution of Ce(IO3)3 by a factor of 10 below that calculation in part (a).
- 3 [Ce3+ ]
a) Ksp = [Ce+3 ] [IO3 ] b) reduce Ce 3+
by factor of 10:
10
-10 3 4 3.2 10 =1.86 10 [IO 3]Total
-10 -4 3
3.2 10 = s 27s = 27s
1.185 10 -11 = s4 1.7204 10-6 = [IO 3]Total
** The IO3- in solution must be the same as Ce+3 for this condition
32 Solubility and Solubility Product March 14
Qualitative Analysis
Ions are precipitated selectively by adding a precipitation ion until the Ksp of one
compound is exceeded without exceeding the Ksp of the others. An extension of this
approach is to control the equilibrium of the slightly soluble compound by
simultaneously controlling an equilibrium system that contains the precipitating ion.
Qualitative analysis of ion mixtures involves adding precipitating ions to separate the
unknown ions into ion groups. The groups are then analyzed further through
precipitation and complex ion formation.
8.51 10-17 Note x = 1.5 10-3 therefore need second iteration for 1.510-3 +x .
2x > = 4.256 10 , x > 2.1310
-13 -13
M
2.0 10-4 [Pb2+ ] = 1.510-3 + 1.27810-3 = 2.77810-3
Second iteration, 9.8 10-9 = [1.5 10-3 + 1.27810-3] [2x]2
[I- ] = 2x+y = 2x, y << x, 2x = 1.8810-3 M
[I- ] = 4.25610-13 M
[I- ] = 2x = 1.8810-3 M for PbI 2 (s) to precipitate
Solubility of metal salts affected presence of Lewis Base: e.g., NH3, CN-, OH-
39
Solubility and Solubility Product March 14
Formation Constants Table
Complex Kf Complex Kf Complex Kf
[Ag(CN)2] 5.6e18 [Cr(OH)4] 8e29 [HgI4]2 6.8e29
Zn2+
(aq)
+ NH 3 (aq) ! Zn(NH 3 )2+
4 (aq)
i 1.110 -3
0.150 0
-x -1.110-3 +1.110-3
[e] 1.110-3 -x 0.150 1.110-3 1.110-3
1.110-3
1.110 -x =
-3
= 8.7410-10 , [Zn2+ ] eq = 8.7410-10M
2.8 109 [0.1456] 4
K = 8.3104