Solubility and Equilibria

Three parts to the chapter:

Learning about precipitation reactions
Learning about the solubility constant
expression Ksp and how to use it
Learning about the solubilities of various
classes of ionic solids and how to use that
knowledge to analyze for the presence of
unknown ions in solution
 Solubility equilibria

MmXx (s)  m Mn+ (aq) + x Xy- (aq)

 Many ionic compounds are only slightly

soluble in water and equations are
written to represent the equilibrium
between the compound and the ions
present in a saturated aqueous solution.
 The rates of these processes must be
equal.
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 Solubility equilibria
For a dissolution process, we give the equilibrium
constant expression the name solubility
product (constant) Ksp. For

MmXx (s)  m Mn+ (aq) + x Xy- (aq)

Ksp = [Mn+]m [Xy-]x

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The Solubility Equilibrium Equation And Ksp

CaF2 (s) Ca2+ (aq) + 2 F- (aq)

Ksp = [Ca2+][F-]2 Ksp = 5.3x10-9

As2S3 (s) 2 As3+ (aq) + 3 S2- (aq)

Ksp = [As3+]2[S2-]3
 Learning Check

Write the reactions and mass action expressions for the dissolution
of the following substances in water:

Ag2CO3
Ag2CO3(s) 2Ag+(aq) + CO32-(aq)

Ksp = [Ag+]2[CO32–]

(NH4)2SO4
(NH4)2SO4(s) 2NH4+(aq) + SO42-(aq)

Ksp = [NH4+]2[SO42–]

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Some Values For Solubility Product Constants
(Ksp) At 25 oC
 Problem
If a saturated solution of BaSO4 is prepared by dissolving solid
BaSO4 in water, and [Ba2+] = 1.05 x 10-5 molL-1, what is the Ksp
for BaSO4?

 2
BaSO 4 (s)  Ba 2 (aq)  SO 4 (aq)

 
K sp  Ba 2 SO 4
2


K sp  x 2 if x  Ba 2  SO 4   2
  1.05 x 10 -5
M

K sp  1.05 x 10 -5  2

K sp  1.1 x 10 -10

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 Molar solubility
If we know the Ksp value for a solid, we can calculate
the molar solubility, which is the number of moles
of the solid that can dissolve in a given amount
of solvent.

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 Problem
The solubility of PbSO4 in water is 0.038 g/L.
Calculate the solubility product constant of PbSO4
at 20 C? The molar mass of PbSO4 is 303 gmol-1.

Answer: Ksp = 1.6 x 10-8

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 Problem
Calculate the solubility of A2X3 in pure water,
assuming that neither kind of ion reacts with water.
For A2X3, Ksp = 1.1 x 10-23.

Answer: 1.0 x 10-5 mol/L

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 Problem
Which has the greater molar solubility:
AgCl with Ksp = 1.8 x 10-10
or
Ag2CrO4 with Ksp = 1.1 x 10-12?
Answer: The molar solubility of AgCl is 1.3 x 10-5 M
while the molar solubility of Ag2CrO4 is 6.5 x 10-5 M.
Silver chromate has a higher molar solubility.

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 The common-ion effect
MmXx (s)  m Mn+ (aq) + x Xy- (aq)

If we have dissolved a solid in pure water and we add to

this solution another solution containing one of the
common ions, then Le Chatalier’s Principle tells us what
will happen:
The presence of the common-ion in the
added solution will force the dissolution
reaction to the left, meaning more solid
will form!
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 The common-ion effect

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15
Molar
Learning Check: Common Ion Effect

What is the molar solubility of Ca3(PO4)2 in 0.1 M Na3PO4?

Ksp= 2.0 × 10−29

1. Na3PO4 is strong electrolyte - ionized at the start

Na3PO4 → 3Na+(aq) + PO43-(aq)
0.1 M → 0.3 M 0.1 M
2. Ca3(PO4)2 3Ca2+(aq) + 2PO43-(aq)
I 0 0.1 M
C -x +3x +2x
E 3x 0.1 + 2x ≈ 0.1

(3x)3(0.1)2 = Ksp x = 4.2 × 10-10 M

 Problem
Calculate the molar solubility of
MgF2 (Ksp = 7.4 x 10-11) in pure
water and in 0.10 molL-1 MgCl2 at
25 °C.
Answer: The molar solubility is 2.6 x 10-4 M in
pure water and 1.4 x 10-5 M in 0.10 M
magnesium chloride.

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 Criteria for precipitation and its completeness

Can we predict if a solid will form if we mix two solutions of

different ions?
Consider the mixing of two different solutions, one with Ca2+ ions
and one with F- ions. A formation of solid is the dissolution
reaction in reverse, so we can express the reaction using the
dissolution equation

CaF2 (s)  Ca2+ (aq) + 2 F- (aq) Ksp = [Ca2+ ][F-]2

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 Criteria for precipitation and its completeness
When we mix the solutions
(BE CAREFUL – mixing ALWAYS changes the
concentrations of both our ions!)
the system is most likely not at equilibrium.
Like in other equilibrum problems, we can use a
reaction quotient Qsp (often called the ion
product) to tell us in which direction the system must
go to reach equilibrium
Qsp = 2+ -
[Ca ][F ]2

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 Criteria for precipitation and its completeness

If Qsp > Ksp, the solution is supersaturated, so

the system is not at equilibrium. The
concentration of the ions is greater than it
would be at equilibrium, and so the reaction
wants to shift from ions towards the solid.
We expect precipitation to occur!
If Qsp = Ksp, the solution is saturated, and the
system is at equilibrium.
No precipitation occurs!
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 Criteria for precipitation and its completeness

If Qsp < Ksp, the solution is unsaturated, so

the system is not at equilibrium. The
concentration of the ions is less than it
would be at equilibrium, and so the reaction
wants to shift from solid towards the ions.

No precipitation can occur!

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 Problem
Will a precipitate form when 0.150 L of 0.10
molL-1 Pb(NO3)2 and 0.100 L of 0.20 molL-1
NaCl are mixed?

Ksp of PbCl2 is 1.2 x 10-5

Answer: Qsp = 3.8 x 10-4 > Ksp so precipitation

should occur.

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 Complete precipitation
Generally we treat precipitation as complete if 99.9% of the
original ion concentration has been lost to the
precipitate.
For example, if our initial [Pb2+] is 0.10 M, then
precipitation by adding I- is complete when our solution
contains a [Pb2+] less than 1 x 10-4 M.

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 Problem
A typical Ca2+ concentration in seawater is 0.010 M. Will the
precipitation of Ca(OH)2 be complete from a seawater sample in
which [OH-] is maintained at 0.040 M?

Ksp of Ca(OH)2 is 5.5 x 10-6

Answer: Since the final [Ca2+] is 3.4 x 10-3 M,

which is 34 % of 0.010 M, the precipitation is not
complete.
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 Fractional precipitation
If we have a solution with
both CrO42- ions and Br- ions
and add a large amount of Ag+ ions at
once,
then both Ag2CrO4 and AgBr
will precipitate
in our container at the same time.

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 Fractional precipitation
If we slowly add the Ag+ solution instead the solid with the
significantly lower molar solubility (AgBr in this case –
do the calculations to check this for yourself)

will precipitate first

and consume the added Ag+
preferentially.

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 Fractional precipitation
In other words,
the concentration of Ag+
CAN NOT become large enough
to precipitate Ag2CrO4
until the AgBr
precipitation is complete.

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 Fractional precipitation

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 Learning Check
What concentration of I- is needed to precipitate one ion but not the
other in a mixture of 0.1 M Pb2+ and 0.1 M Ag+?
AgI(s) ↔ Ag+(aq) + I-(aq) PbI2(s) ↔ Pb2+(aq) + 2I-(aq)
Ksp = [Ag+][I-] = 8.3 × 10-17 Ksp = [Pb2+][I-]2 = 7.9 × 10-9
[I-] = 8.3 × 10-16 M [I-] = 2.8 ×10-4 M

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 Problem
AgNO3 is slowly added to a solution with [Cl-] = 0.115 M and
[Br-] = 0.264 M. What percent of the Br- remains
unprecipitated at the point at which AgCl (s) begins to
precipitate?
Ksp values
AgCl = 1.8 x 10-10 AgBr = 5.0 x 10-13

Answer: 0.12 % of Br- remains.

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 Solubility and pH
If a solid dissolves to give a basic anion in solution,
addition of strong acid will increase the
solubility of the solid.
CaCO3 (s)  Ca2+ (aq) + CO32- (aq) Ksp = 2.8 x 10-9

Carbonate, CO32-, is a basic anion that will react

with a proton to give HCO3-
CO32- (aq) + H3O+ (aq)  HCO3- (aq) + H2O (l)
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 Solubility and pH
CO32- (aq) + H3O+ (aq)  HCO3- (aq) + H2O (l)

This reaction will shift to the right (products) as the

pH becomes more acidic which means CO32- (aq)
decreases.

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 Learning Check

At what pH will one ion precipitate but not the other in a

mixture of 0.1 M Mn2+, 0.1 M Fe3+?

Fe(OH)3(s) ↔ Fe3+(aq) + 3OH-(aq) Mn(OH)2(s) ↔ Mn2+(aq) + 2OH-(aq)

Ksp = [Fe3+][OH-]3 = 1.6 × 10-39 Ksp = [Mn2+][OH-]2 = 1.6 × 10-13

Fe: pH = 1.40 Mn: pH = 8.10

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34
Molar
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