Solubility and Simultaneous Equilibria: Chemistry: The Molecular Nature of Matter, 6E

Chapter 18:
Solubility and
Simultaneous Equilibria
Chemistry: The Molecular Nature
of Matter, 6E

Jespersen/Brady/Hyslop

Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Solubility of Salts
Precipitation reactions (CH 5)
Exchange reactions in which one product is water
insoluble compound
CaCl
2
(l) + Na
2
CO
3
(aq) CaCO
3
(s) + 2 NaCl (aq)
Insoluble compound
Compound having water solubility of less than 0.01
mole of dissolved material per liter of solution
S > 0.01 M
2
Solubility of Salts
Ch 5 Solubility Rules
Guidelines for what is insoluble
Doesnt mean compound wont dissolve at all
Just not very much
Now want to
Quantitate solubilities
Explore conditions under which some compounds
precipitate and others dont
Applications in separation of ions
Especially toxic metal ions such as Hg
2+
, Tl
3+
, U
3+
, etc.
3
Why Study Solubility?
Tooth decay
Acids from foods dissolve enamel, [Ca
5
(PO
4
)
3
OH] =
hydroxyapatite
Reduced by fluoride which replaces OH
to form
fluorapatite = [Ca
5
(PO
4
)
3
F] and CaF
Lower solubility means it doesnt dissolve as readily
in acid
Upper and Lower GI
X-ray of upper and lower gastrointestinal tract
Clarified by barium sulfatevery insoluble
BaSO
4
toxic, but safe, as it doesnt dissolve
4
Solubility Equilibria
Solids in equilibrium with ions in solution
When ionic salt dissolves in water
Assume dissociates into separate hydrated ions
Initially, no ions in solution
CaF
2
(s) Ca
2+
(aq) + 2 F
(aq)
As dissolution occurs, ions build up and collide
Ca
2+
(aq) + 2 F
(aq) CaF
2
(s)
At Equilibrium
CaF
2
(s) Ca
2+
(aq) + 2 F
(aq)
Now have saturated solution
5
Solubility and Solubility Product
Solubility
Amount of salt that dissolves in given amount of
solvent to give saturated solution
Concentration
Infinite number of values
Solubility product
Product of molar concentrations of ions in saturated
solution raised to appropriate powers
Equilibrium constant
Only one value for given solid at given temperature
Temperature dependence
Solubilities and thus K
sp
change with T
6
Solubility of Salts
Consider AgCl in water
Only a very small amount dissolves
Equilibrium exists when solution is saturated
AgCl(s) Ag
+
(aq) + Cl
(aq)
Equilibrium law:
K
sp
= [Ag
+
][Cl
]
K
sp
= solubility product constant
Solubility equilibrium
Reflects solubility of compound
Product of ion concentrations
7
Solubility and Solubility Product
Solubility
Amount of salt that dissolves in given amount of
solvent to give saturated solution
Solubility product
Product of molar concentrations of ions in
saturated solution raised to appropriate powers
Temperature dependence
Solubilites and thus K
sp
change with temperature
Table 18.1
Solubility product constants at 25 C
More in Table C.6 (Appendix p. A45)
8
Ion Product vs. Solubility Product
For: A
x
B
y
(s) x A
y+
(aq) + y B
x
(aq)
Ion Product Q
sp
= [A
y+
]
x
[B
x
]
y

Like solubility product, except initial concentrations
are used
Any dilution of salt that results in an unsaturated
solution
Varies with concentration
Solubility Product K
sp
= [A
y+
]
x
[B
x
]
y

Ion product value for saturated solution becomes
constant
Uses equilibrium concentration
9
Writing K
sp
Equilibrium Laws
For: A
x
B
y
(s) xA
y+
(aq) + y B
x
(aq)
K
sp
= [A
y+
]
x
[B
x
]
y

Ex.
BaSO
4
(s) Ba
2+
(aq) + SO
4
2
(aq) K
sp
= [Ba
2+
][SO
4
2
]
CaF
2
(s) Ca
2+
(aq) + 2F
(aq) K
sp
= [Ca
2+
][F
]
2

Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq) K
sp
= [Ag
+
]
2
[CrO
4
2
]
AuCl
3
(s) Au
3+
(aq) + 3Cl
(aq) K
sp
= [Au
3+
][Cl
]
3

10
Calculation using K
sp
and Molar
Solubilities
Molar solubility
Moles of salt dissolved in one liter of saturated
solution
Assume what little dissolved, dissociates 100%
Assumes there is some solid
Quantity is not important
Solid is not included in mass action expression
A. Given Solubilites, Calculate K
sp
B. Given K
sp
, Calculate Solubility
11
A. Given Solubilites , Calculate K
sp

Ex 1. At 25 C, the solubility of AgCl is 1.34 x
10
5
M. Calculate the solubility product for AgCl.
AgCl (s) Ag
+
(aq) + Cl

(aq)
K
sp
= [Ag
+
][Cl
]

K
sp
= (1.34 x 10
5
)(1.34 x 10
5
)
K
sp
=1.80 x 10
10
AgCl (s) Ag
+
(aq) + Cl

(aq)
I 0.00 0. 00

C
E
1.34 x 10
5
M

1.34 x 10
5
M

1.34 x 10
5
M

1.34 x 10
5
M

12
Your Turn!
The solubility of a salt, A
2
B
3
, is found to be
3.010
5
M. What is the value of

K
sp
?
A. 2.6 x 10
-21

B. 5.4 x 10
-9

C. 2.4 x 10
-23

D. 1.7 x 10
-21

A
2
B
3
2A
3+
+ 3B
2-

[A] = 2(3.0 x 10
-5
) [B] = 3(3.0 x 10
-5
)
K = [A]
2
[B]
3
= (6.0 x 10
-5
)
2
(9.0 x 10
-5
)
3

K = 2.6 x 10
-21

13
B. Given K
sp
, Calculate Solubility
Ex. 2 What is the molar solubility of CuI in
water? What are the equilibrium
concentrations of Cu
+
and I
?
Step 1. Write balanced equation for
dissociation of salt
CuI (s) Cu
+
(aq) + I
(aq)
Step 2. Write equilibrium law
K
sp
= [Cu
+
][I
]
Step 3. K
sp
for salt
K
sp
= 8.0 10
8

14
Ex. 2 Molar Solubilities from K
sp

Step 4. Concentration Table

Step 5. Plug into and solve K
sp
expression
K
sp
= 8.0 10
8
= (x)(x)
x
2
= 8.0 10
8

x = 2.8 10
4
M = calculated molar solubility
of CuI = [Cu
+
] = [I
]
Conc (M) CuI (s) Cu
+
(aq) + I

(aq)
Initial 0.00 0. 00

Change
Equilm
+x +x

x

x

x

15
Molar Solubility and K
sp
Problems
Strategy for solving:
1. Write balanced equation for dissociation of salt
2. Write equilibrium law
3. K
sp
for salt (from table)
4. Concentration table
5a. Solve for x = solubility
Or
5b. Given solubilities, calculate K
sp
16
sp

Ex. 3 Calculate K
sp
for Bi
2
S
3
given solubility is
1.0 x 10
15
M at 25 C.
Step 1. Write balanced equation for
dissociation of salt
Bi
2
S
3
(s) 2 Bi
3+
(aq) + 3 S
2
(aq)
Step 2. Write equilibrium law
K
sp
= [Bi
3+
]
2
[S
2
]
3

Step 3. Use Concentration Table to
determine concentrations of each ion

17
sp

Bi
2
S
3
(s) 2 Bi
2+
(aq) 3 S
2
(aq)
I (No entries 0.00 0.00

C in this
E column)
+3(1.0 10
5
)

+2(1.0 10
15
)
3.0 10
15
2.0 10
15
K
sp
= (2.0 x 10
15
)
2
(3.0 x 10
15
)
3
K
sp
= (4.0 x 10
30
)(27 x 10
45
)

K
sp
= 1.1 x 10
73
Step 4. Solve for K
sp

18
B. Given K
sp
, Calculate Solubilities
Ex. 4 Calculate the solubility of CaF
2
in water
at 25 C, if K
sp
= 4.0 x 10
11
.
CaF
2
(s) Ca
2+
(aq) + 2F

(aq)
Step 1: Write Equilibrium Law
K
sp
= [Ca
2+
][F
]
2
Step 2: Concentration Table

Conc (M) CaF
2
(s) Ca
2+
(aq) 2F

(aq)
Initial (No entries 0.00 0.00

Change in this
Equilm column)
+2x +x

2x

x

19
Ex. 4 Molar Solubilities from K
sp

Step 3. Plug into and solve K
sp
expression
K
sp
= [Ca
2+
][F
]
2
= (x) (2x)
2

4.0 10
11
= 4x
3

4
10 0 . 4
x
11
3

3
11
10 0 . 1

x
X = 2.15 10
4
M = molar solubility of CaF
2
[Ca
2+
] = X = 2.15 10
4
M
[F
] = 2x = 2(2.15 10
4
M) = 4.3 10
4
M

20
Your Turn!
Given K
sp
= 1.4 x 10
7
for Cu(IO
3
)
2
, calculate
the solubility of this salt.

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(IO
3
)
2
(s) Cu
2+
+ 2IO
3
-

K
sp
= 1.4 x 10
-7
= s (2s)
2

s = 3.3 x 10
21
Your Turn!
What is the molar solubility of Ag
3
PO
4
in water? What
is the molar concentration of each ion in solution?
K
sp
= 8.9 10
17

A. 5.4 x 10
-9
[Ag
+
] = 5.4 x 10
-9
[PO
4
3-
] = 5.4 x 10
-9

B. 4.3 x 10
-5
[Ag
+
] = 1.3 x 10
-4
[PO
4
3-
] = 4.3 x 10
-5

C. 5.4 x 10
-9
[Ag
+
] = 1.6 x 10
-8
[PO
4
3-
] = 5.4 x 10
-9

D. 9.7 x 10
-7
[Ag
+
] = 2.7 x 10
-4
[PO
4
3-
] = 9.7 x 10
-7

Ag
3
PO
4
(s ) 3Ag
+
+ PO
4
3-

K
sp
= 8.9 x 10
-17
= [Ag][PO] = (3s)
3
(s)
s = 4.3 x 10
[Ag
+
] = 3s = 1.3 x 10
-4
M
[PO
4
3-
] = s = 4.3 x 10
-5
M

22
Your Turn!
What is the solubility of PbCl
2
in grams per 100.0 mL
at 25
o
? K
sp
= 1.7 x 10
-5
.
A. 0.56 g
B. 0.72 g
C. 0.45 g
D. 0.39 g
PbCl
2
(s ) Pb
2+
+ 2Cl
-

K
sp
= 1.7 x 10
-5
= [Pb
2+
][Cl
-
]
2
= s (2s)
2

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

23
Relative Solubilities
K
sp
gives information about solubility of salts
Must be careful when comparing relative
solubilities
Two possible cases when comparing:
1. Must compare salts that contain the same number
of ions
AgI(s) K
sp
= 1.5 x 10
16
CuI(s) K
sp
= 5.0 x 10
12

CaSO
4
(s) K
sp
= 6.1 x 10
5

Each salt dissolves to produce 2 ions
Salt cation + anion
K
sp
= [cation][anion]
24
1. Must compare salts that contain the same number
of ions
If solubility = x
Then [cation] = [anion] = x
K
sp
= x
2

So can compare solubilities by comparing K
sp
s
CaSO
4
> CuI > AgI
most soluble least soluble
largest K
sp
smallest K
sp

solubility K x
sp

25
2. Compare salts with different number of ions
Each produces different number of ions
Each uses different K
sp
expression
No way to predict relative solubility based on K
sp

Bi
2
S
3
> Ag
2
S > CuS
Most soluble least soluble
26
Salt K
sp
#ions Calcd
Solubility (M)
CuS 8.5 x 10
45
2 9.2 x 10
23
Ag
2
S 1.6 x 10
49
3 3.4 x 10
17
Bi
2
S
3
1.1 x 10
73
5 1.0 x 10
15
Common Ion Effect
Up until now all calculations in pure water
What happens if I add another salt to a solution
containing one of the ions in our insoluble salt?
Consider PbI
2
(s) Pb
2+
(aq) + 2I
(aq)
Saturated solution of PbI
2
in water
Filter
Add KI
PbI
2
(yellow solid) precipitates out
Why?
Le Chateliers Priniciple
Add product I

Equilibrium moves to left and solid PbI
2
forms

27
Common Ion Effect
Common ion
Ion in solution that is supplied by more than one
solute
Common Ion Effect
Lowering of solubility of ionic compound by
addition of common ion
28
Ex. 5 Common Ion Effect
A. What is the molar solubility of Ag
2
CrO
4
in
0.10M AgNO
3
solution? K
sp
= 9.0 10
12
.
B. What is the molar solubility of
Ag
2
CrO
4
in pure water?
C. What is the molar solubility of
Ag
2
CrO
4
in 0.100 M Na
2
CrO
4
?

Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq)
K
sp
= [Ag
+
]
2
[CrO
4
2
] = 9.0 10
12

29
A. Molar solubility of Ag
2
CrO
4
in 0.10M AgNO
3

solution? K
sp
= 9.0 10
12

K
sp
= 9.0 10
12
= (0.10M)
2
[x]

x = Solubility of Ag
2
CrO
4
= 9.0 10
10
M
[Ag
+
] = 0.10 M
[CrO
4
2
] = 9.0 10
10
M

) 010 . 0 (
10 0 . 9
x
12
Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq)
I (No entries 0.10 M 0.00

C in this
E column)
+x

+2x
x

0.10

30
B. Solubility of Ag
2
CrO
4
in pure water
Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq)
I (No entries 0.00 M 0.00 M

C in this
E column)
+x

+2x
x

2x

K
sp
= [Ag
+
]
2
[CrO
4
2
] = (2x)
2
(x) = 9.0 10
12
= 4x
3
3
12
3
12
10 25 . 2
4
10 0 . 9
x

X = Solubility of Ag
2
CrO
4
= 1.31 10
4
M
[CrO
4
2
] = x = 1.31 10
4
M
[Ag
+
] = 2x = 2.62 10
4
M
31
C. Solubility of Ag
2
CrO
4
in 0.100 M Na
2
CrO
4
?

Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq)

C in this
E column)
+x

+2x
2x

0.10

K
sp
= (2x)
2
(0.10) = 9.0 10
12
= 4x
2
(0.10)

11
12
10 25 . 2
4 . 0
10 0 . 9
x

2
CrO
4
= 4.7 10
6
M
[CrO
4
2
] = x = 4.7 10
6
M
[Ag
+
] = 2x = 9.5 10
6
M
32
33
C. Solubility of Ag
2
CrO
4
in 0.100 M Na
2
CrO
4
?

Ag
2
CrO
4
(s) 2Ag
+
(aq) + CrO
4
2
(aq)

C in this
E column) 2x

0.10

K
sp
= (2x)
2
(0.10) = 9.0 10
12
= 4x
2
(0.10)

11
12
10 25 . 2
4 . 0
10 0 . 9
x

2
CrO
4
= 4.7 10
6
M
[CrO
4
2
] = x = 4.7 10
6
M
[Ag
+
] = 2x = 9.5 10
6
M
+x

+2x
Your Turn!
What effect would adding copper(II) nitrate
have on the solubility of CuS?
A. The solubility would increase
B. The solubility would decrease
C. The solubility would not change
34
Your Turn!
The molar solubility of PbF
2
in 0.10 M Pb(NO
3
) solution
is 3.1 10
6
M. What is K
sp
for PbF
2
?
A. 1.2 x 10
-6

B. 3.1 x 10
-7

C. 9.6 x 10
-13

D. 3.8 x 10
-12

PbF
2
(s) Pb
2+
+ 2F
-

[Pb
2+
] = 0.10 M [F
-
] = 2(3.1 x 10
-6
)M
K = [Pb
2+
][F
-
]
2
= (0.1)(6.2 x 10
-6
)
2

K = 3.8 x 10
-12

35
Predicting if Precipitate will Form
In making a solution containing various ions,
will the salt precipitate at the given
concentrations?
For precipitate of salt to form, solution must be
supersaturated.
Same as asking if given mixture of reactants
and products is an equilibrium mixture
Can judge by calculating ion product, Q
Comparing with solubility product, K
sp

36
In making a solution containing various ions,
will the salt precipitate at the given
concentrations?
For precipitate of salt to form, solution must be
supersaturated.
Same as asking if given mixture of reactants
and products is an equilibrium mixture
Can judge by calculating ion product, Q
Comparing with solubility product, K
sp

37
38
For: A
x
B
y
(s) x A
y+
(aq) + y B
x
(aq)
Ion Product Q
sp
= [A
y+
]
x
[B
x
]
y

Solubility Product K
sp
= [A
y+
]
x
[B
x
]
y

Precipitate
will form (until
satisfy K
sp
)
Q
sp
> K
sp
supersaturated
No precipitate
will form
Q
sp
= K
sp

Q
sp
< K
sp
saturated
unsaturated
Predicting Precipitation
Ex. 6 Does a precipitate of PbI
2
(K
sp
=1.4 x 10
8
)
form if 100.0 mL of 0.0500 M Pb(NO
3
)
2
are mixed
with 200.0mL of 0. 100 M NaI?
PbI
2
(s) Pb
2+
(aq) + 2I
(aq)
K
sp
= [Pb
2+
][I
]
2
= 1.4 10
8

Strategy for solving
1. Calculate concentrations in solution to be prepared
2. Calculate Q
sp
= [Pb
2+
][I
]
2

3. Compare Q
sp
to K
sp

39
Ex. 6 Predicting Precipitation
Step 1. Calculate concentrations
Here diluting 100 mL to 300mL
V
total
= 100.0 mL + 200.0 mL = 300.0 mL

[Pb
2+
]
o
= 1.67 10
2
M

[I
] = 6.67 10
2
M
mL
mL mmol mL
0 . 300
) / 100 . 0 )( 0 . 200 (
solution of mL
I of mmol
] I [

mL
mL mmol mL
0 . 300
) / 0500 . 0 )( 0 . 100 (
solution of mL
Pb of mmol
] Pb [
2
2

40
Step 2. Calculate Q
sp

Q
sp
= [Pb
2+
][I
]
2
= (1.6710
2
M)(6.6710
2
M)
2
Q
sp
=7.43 10
5

Step 3. Compare Q
sp
and K
sp

Q
sp
= 7.43 10
5

K
sp
= 1.4 x 10
8

Q
sp
> K
sp
so precipitation will occur
How much precipitate will form and what will ion
concentrations be at the end?
K
sp
small
So most ions precipitate out as PbI
2
Reaction essentially goes to completion
41
If reaction goes essentially to completion, what
will final equilibrium concentrations be?
1. Do stoichiometric calculations for precipitate
formation
2. Then do equilibrium calculations to determine ion
concentrations in solution.
Step 1. Stoichiometric Calculation

Pb
2+
(aq) + 2I

(aq) PbI
2
(s)
Before
rxn
(100mL)(0.0500M)
= 5.00 mmol
(200mL)(0.100M)
= 20.00 mmol
No effect on K
sp
After
Rxn
5.00 5.00 =
0.00 mmol
20.00 2(5.00)
= 10 mmol

42
Step 2. System at equilibrium
Some small amount of PbI
2
redissolves to form
equilibrium [Pb
2+
]
Basically a common ion problem
PbI
2
(s) Pb
2+
(aq) + 2I
(aq)
Initial concns 0.00 10.0mmol/300mL
= 3.33 x 10
2
M

Equilibrium
concns
3.33 x 10
2
M + 2x
3.33 x 10
2
M

+x
K
sp
= 1.4 10
8
= [Pb
2+
][I
]
2
= (x)(3.33 x 10
2
)
2
] Pb [ 10 3 . 1
) 10 33 . 3 (
10 4 . 1
x
2 5
2 2
8

M
43
3.33 x 10
2
M >> 2x, so approximation valid

Final equilibrium concentrations of Pb
2+
and
I
in 100.0 mL of 0.0500 M Pb(NO

3
)
2
mixed
with 200.0mL of 0. 100 M NaI
[I
] = 3.33 x 10
2
M
[Pb
2+
] = 1.3 x 10
5
M
44
Suppose you mix 100.0 mL of 0.200 M BaCl
2

with 50.0 mL of 0.0300 M Na
2
SO
4
. Will
BaSO
4
(K
sp
= 1.1 10
10
) precipitate?
BaSO
4
(s) Ba
2+
(aq) + SO
4
2
(aq)
K
sp
= [Ba
2+
][SO
4
2
]
Step 1. Calculate concentrations

[Ba
2+
] = 0.133 M

mL
mL
mol
mol
M
0 . 150
0 . 100
BaCl 1
Ba 1
BaCl 200 . 0 ] Ba [
2
2
2
2

45

[SO
4
2
] = 0.0100 M
Step 2. Calculate Q
sp

Q
sp
= [Ba
2+
][SO
4
2
] = (0.133)(0.0100)
Q
sp
= 1.33 10
3

Step 3. Compare Q
sp
and K
sp

K
sp
= 1.1 10
10

1.33 10
3
>> 1.1 10
10

Q
sp
>> K
sp

So BaSO
4
will precipitate

mL
mL
mol
mol
M
0 . 150
0 . 50
) (SO Na 1
SO 1
) (SO Na 0300 . 0 ] SO [
4 2
2
4
4 2
2
4

46
pH and Solubility
Mg(OH)
2
(s) Mg
2+
(aq) + 2OH
(aq)
OH
shift equilibrium to left

Add H
+
shift equilibrium to right
Le Chateliers Principle
Ag
3
PO
4
(s) 3Ag
+
(aq) + PO
4
3
(aq)
Add H
+
solubility
H
+
(aq) + PO
4
3
(aq) HPO
4
2
(aq)
AgCl(s) Ag
+
(aq) + Cl
(aq)
Add H
+
- has no effect on solubility Why?
Cl
is very, very weak base, so neutral anion

So adding H
+
doesnt effect Cl
concentration
47
Your Turn!
What is the molar solubility of PbI
2
in pure
water? K
sp
= 9.8 x 10
-9

A. 2.1 x 10
-3

B. 1.7 x 10
-3

C. 4.9 x 10
-5

D. 1.4 x 10
-3

PbI
2
(s ) Pb
2+
+ 2I
-

K = 9.1 x 10 = [Pb
2+
][I
-
] = s (2s)
2

s = 1.4 x 10
-3
M

48
Your Turn!
2
in 0.20M
NaI solution? K
sp
= 7.9 10
9

A. 3.9 x 10
-10

B. 2.4 x 10
-7

C. 6.1 x 10
-9

D. 2.4 x 10
-7

PbI
2
(s ) Pb
2+
+ 2I
-
[I
-
] = 0.20M
K = 7.9 x 10
-9
= [Pb
2+
][I
-
]
2
= [Pb
2+
](0.20)
2

[Pb
2+
] = 2.4 x 10
-7
M
Molar solubility = [Pb
2+
] = 2.4 x 10
-7
M
49
Your Turn!
2
in 0.20M
Pb(NO
3
) solution? K
sp
= 7.9 10
9

A. 4.9 x 10
-8

B. 3.7 x 10
-3

C. 1.1 x 10
-4

D. 2.2 x 10
-4

PbI
2
(s ) Pb
2+
+ 2I
-
[I
-
] = 0.20M
K = 7.9 x 10
-9
= [Pb
2+
][I
-
]
2
= (0.20) [I
-
]
2

[I
-
] = 2.2 x 10
-4
M
Molar solubility = 1/2 [I
-
] = 1.1 x 10
-4
M
50
Your Turn!
From the previous two Your Turn problems,
what can you conclude about the relative
effect of added Pb
2+
vs. added I
?
A. Adding Pb
2+
increases the solubility of PbI
2

more than I
-
.
B. Adding I
-
decreases the solubility of PbI
2

more than Pb
2+
.
C. Adding Pb
2+
decreases the solubility of
PbI
2
more than I
-
.
D. They both have the same effect on the
solubility of PbI
2
.

51
Solubility and Simultaneous
Equilibria
Part 2
Metal Oxides Undergo Reaction
with Water
53
Usually ignore reaction of ionic solid with water
If the anion of a salt is very basic, a subsequent
reaction of the anion with water occurs
Such is the case of many metal oxides
K
b
for O
2
= 1 10
22

So Ag
2
O actually dissociates to form Ag
+
and OH

K
sp
value listed takes this subsequent reaction into account
Ag
2
O(s) 2Ag
+
(aq) + O
2
(aq) K
sp

O
2
(aq) + H
2
O 2OH
(aq) K
b
Ag
2
O(s) + H
2
O 2Ag
+
(aq) + 2OH
(aq) K
net

Metal Sulfides Also Undergo Reaction
With Water
54
Sulfide ion (S
2
) is also very basic
Doesnt exist in aqueous solution
Metal sulfides also undergo a subsequent
reaction with water
Ag
2
S(s) 2Ag
+
(aq) + S
2
(aq) K
sp

S
2
(aq) + H
2
O OH

(aq) + HS
(aq) K
b
Ag
2
S(s) + H
2
O 2Ag
+
(aq) + OH
(aq) + HS

(aq) K
net

Actual K
sp
=[Ag
+
]
2
[OH
][HS
]

H
+
reacts with O
2
to produce H
2
O
Releases metal ion from solid
Recall that oxide ion is too powerful a base to exist in
aqueous solution
Ex. Fe
2
O
3
(s) + 6H
+
(aq) 2Fe
3+
(aq) + 3H
2
O
How do water-insoluble metal oxides form?
Usually in basic solution
Elimination of water is often involved
Metal ion must be capable of reacting with OH
to extract
oxide ion and leave water or H
+

Ex: 2Ag
+
(aq) + 2OH
(aq) Ag
2
O(s) + H
2
O
2Fe
3+
(aq) + 3OH
(aq) Fe
2
O
3
(s) + 3H
+
(aq)

Most Water-Insoluble Metal Oxides
Dissolve in Acid
55
Sulfur is below oxygen in Group VIA
As a result, metal sulfides are similar to
metal oxides
S
2
(like O
2
) is too strong of a base to exist in
water
Sulfides dissolve by reacting with water
Ex. Na
2
S(s) + H
2
O 2Na
+
(aq) + HS
(aq) + OH
(aq)
Formation of Insoluble Metal Sulfides
56
Basic Salts Are More Soluble In
Acids
57
Subsequent reactions assist the solubility of solids
If anion of salt is basic, it will react in acidic
solution to dissolve more fully
Net reaction of such dissolutions is called K
spa

ZnS(s) Zn
2+
(aq) + S
2
(aq) K
sp

S
2
(aq) + H
+
(aq) HS
(aq) 1/K
a2
HS
(aq) + H
+
(aq) H
2
S

(g) 1/K
a1

ZnS(s) + 2H
+
(aq) Zn
2+
(aq) + H
2
S(aq) K
spa
K
spa
(acidic) and K
sp
(basic) are listed in Table 18.2
Learning Check
58
What is the molar solubility of BaCO
3
in 3.0 M
HCl?
K
sp
BaCO
3
= 5.0 x 10
9

H
2
CO
3
: K
a1
= 4.3 x 10
7
K
a2
= 4.7 x 10
11

BaCO
3
(s) + 2H
+
(aq) Ba
2+
(aq) + H
2
CO
3
(aq)
X =1.5 M

Reaction of Metal ions with HS

Metal sulfides can form
Some metal ions are so reactive that they react
with H
2
S directly
These active ions include Cu
2+
, Pb
2+
, and Ni
2+
A typical reaction is:
Cu
2+
(aq) + H
2
S(aq) CuS(s) + 2H
+
(aq)
Large value of K indicates that
Equilibrium lies far to right
Only forward reaction important
Sulfides require closer investigation

59

Solubility and Simultaneous Equilibria: Chemistry: The Molecular Nature of Matter, 6E

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Chapter 18:

in 100.0 mL of 0.0500 M Pb(NO

shift equilibrium to left

is very, very weak base, so neutral anion

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