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Chapter 18:
Solubility and
Simultaneous Equilibria
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Solubility of Salts
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Insoluble compound
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Jespersen/Brady/Hyslop
Solubility of Salts
Ch 5 Solubility Rules
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Now want to
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Quantitate solubilities
Explore conditions under which some compounds
precipitate and others dont
Applications in separation of ions
Especially toxic metal ions such as Hg2+, Tl3+, U3+, etc.
Jespersen/Brady/Hyslop
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Solubility Equilibria
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At Equilibrium
CaF2 (s) Ca2+ (aq) + 2 F (aq)
Now have saturated solution
Jespersen/Brady/Hyslop
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Solubility product
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Temperature dependence
Solubility of Salts
Consider AgCl in water
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Equilibrium law:
Ksp = [Ag+][Cl]
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Solubility equilibrium
Reflects solubility of compound
Product of ion concentrations
Jespersen/Brady/Hyslop
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Solubility product
Temperature dependence
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Table 18.1
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Ion Product
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Solubility Product
Ksp = [Ay+]x[Bx]y
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Ex.
BaSO4(s) Ba2+(aq) + SO42(aq)
Ksp = [Ba2+][SO42]
Ksp = [Ca2+][F]2
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Jespersen/Brady/Hyslop
Ksp = [Au3+][Cl]3
10
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Molar solubility
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11
I
C
E
(s)
Ag+ (aq) +
0.00
Cl (aq)
0. 00
1.34 x 105 M
1.34 x 105 M
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AgCl
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1.34 x 105 M
1.34 x 105 M
12
Your Turn!
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A. 2.6 x 10-21
B. 5.4 x 10-9
C. 2.4 x 10-23
D. 1.7 x 10-21
A2B3
2A3+ + 3B2-
13
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Cu+ (aq)
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( s)
I (aq)
0.00
0. 00
+x
x
+x
x
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15
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4. Concentration table
5a. Solve for x = solubility
Or
5b. Given solubilities, calculate Ksp
Jespersen/Brady/Hyslop
16
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Jespersen/Brady/Hyslop
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3 S2 (aq)
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Bi2S3 (s)
0.00
+3(1.0 105 )
3.0 1015
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Jespersen/Brady/Hyslop
18
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Ca2+ (aq)
Jespersen/Brady/Hyslop
2F (aq)
0.00
+2x
2x
19
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x =
20
Your Turn!
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A. 5.2 x 10-3
B. 3.3 x 10-3
C. 2.6 x 10-4
D. 3.7 x 10-4
Cu(IO3)2 (s)
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Cu2+ + 2IO3-
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Your Turn!
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3Ag+ + PO43-
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Ag3PO4 (s )
22
Your Turn!
A. 0.56 g
B. 0.72 g
C. 0.45 g
D. 0.39 g
PbCl2 (s )
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Pb2+ + 2Cl-
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s = 1.62 x 10-5 M
(1.62 x 10-5 mol/L) x (278.11 g/mol) x 0.1 L = 0.45 g
in 100 mL
Jespersen/Brady/Hyslop
23
Relative Solubilities
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CuI(s)
CaSO4(s)
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AgI(s)
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Relative Solubilities
x=
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K sp = solubility
most soluble
largest Ksp
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least soluble
smallest Ksp
Jespersen/Brady/Hyslop
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Relative Solubilities
2. Compare salts with different number of ions
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least soluble
Ksp
CuS
Ag2S
8.5 x 1045
1.6 x 1049
Bi2S3
1.1 x 1073
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Salt
Jespersen/Brady/Hyslop
#ions Calcd
Solubility (M)
2
9.2 x 1023
3
3.4 x 1017
5
1.0 x 1015
26
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Why?
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Filter
Add KI
PbI2 (yellow solid) precipitates out
Le Chateliers Priniciple
Add product I
Equilibrium moves to left and solid PbI 2 forms
Jespersen/Brady/Hyslop
27
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Jespersen/Brady/Hyslop
28
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2Ag+(aq) + CrO42(aq)
Ag2CrO4(s)
Ksp = [Ag+]2[CrO42] = 9.0 1012
Jespersen/Brady/Hyslop
29
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Ksp = 9.0 10
0.00
+x
x
0.10
= (0.10M) [x]
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12
0.10 M
+2x
9.0 10 12
x=
(0.010)
30
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0.00 M
+x
x
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12
9
.
0
10
3
x= 3
= 2.25 10 12
4
X = Solubility of Ag2CrO4 = 1.31 104 M
31
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Ag2CrO4(s)
I (No entries
C in this
E column)
0.00 M
+2x
2x
0.10 M
+x
0.10
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x=
9.0 10 12
=
0.4
2.25 10 11
32
+ CrO42(aq)
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Ag2CrO4(s)
I (No entries
C in this
E column)
0.00 M
+2x
2x
0.10 M
+x
0.10
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x=
9.0 10 12
=
0.4
2.25 10 11
10
M
Jespersen/Brady/Hyslop
Chemistry: The Molecular Nature of Matter, 6E
33
Your Turn!
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Jespersen/Brady/Hyslop
34
Your Turn!
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PbF2 (s)
Pb2+ + 2F-
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[Pb2+] = 0.10 M
[F-] = 2(3.1 x 10-6)M
K = [Pb2+][F-]2 = (0.1)(6.2 x 10-6)2
K = 3.8 x 10-12
Jespersen/Brady/Hyslop
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Jespersen/Brady/Hyslop
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Qsp = [Ay+]x[Bx]y
Solubility Product
Ksp = [Ay+]x[Bx]y
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Ion Product
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Precipitate
Qsp > Ksp supersaturated
will form (until
satisfy Ksp)
No precipitate
will form
Jespersen/Brady/Hyslop
38
Predicting Precipitation
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[Pb 2 +
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mmol of Pb 2 +
(100.0mL )(0.0500mmol / mL )
]=
=
mL of solution
300.0mL
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mmol of I
(200.0mL )(0.100mmol / mL )
[I ] =
=
mL of solution
300.0mL
Jespersen/Brady/Hyslop
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Jespersen/Brady/Hyslop
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PbI2(s)
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Before
rxn
After
Rxn
2I (aq)
5.00 5.00 =
0.00 mmol
Jespersen/Brady/Hyslop
20.00 2(5.00)
= 10 mmol
Chemistry: The Molecular Nature of Matter, 6E
42
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10.0mmol/300mL
= 3.33 x 102 M
3.33 x 102 M + 2x
3.33 x 102 M
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Equilibrium
+x
concns
Ksp = 1.4 108 = [Pb2+][I]2 = (x)(3.33 x 102)2
x=
1.4 10 8
(3.33 10 2 ) 2
= 1.3 10 5 M = [Pb 2 + ]
Jespersen/Brady/Hyslop
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Jespersen/Brady/Hyslop
44
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[Ba
2+
1mol BaCl2
150.0mL
[Ba2+] = 0.133 M
Jespersen/Brady/Hyslop
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2
1
mol
SO
50.0mL
2
4
[SO 4 ] = 0.0300M Na 2 (SO 4 )
[SO42] = 0.0100 M
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So BaSO
Jespersen/Brady/Hyslop
Chemistry: The Molecular Nature of Matter, 6E
4 will precipitate
46
pH and Solubility
Mg(OH)2(s) Mg2+(aq) + 2OH(aq)
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47
Your Turn!
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A. 2.1 x 10-3
B. 1.7 x 10-3
C. 4.9 x 10-5
D. 1.4 x 10-3
PbI2(s )
Pb2+ + 2I-
48
Your Turn!
10-10
10-7
10-9
10-7
Pb2+ + 2I-
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A. 3.9 x
B. 2.4 x
C. 6.1 x
D. 2.4 x
PbI2(s )
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[I-] = 0.20M
49
Your Turn!
10-8
10-3
10-4
10-4
Pb2+ + 2I-
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A. 4.9 x
B. 3.7 x
C. 1.1 x
D. 2.2 x
PbI2(s )
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[I-] = 0.20M
50
Your Turn!
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Part 2
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Ksp
Kb
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Ksp
Kb
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Jespersen/Brady/Hyslop
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Ksp
1/Ka2
HS (aq) + H+
1/Ka1
H2S (g)
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(aq)
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Learning Check
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X =1.5 M
Jespersen/Brady/Hyslop
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