Solubility Product

The solubility of a mineral is governed by the solubility product,

the equilibrium constant for a reaction such as:

CaSO4(anhydrite) ↔ Ca2+ + SO42-

The solubility product is given by:

aCa 2 + aSO 2 −
K SP = 4

aCaSO4

If anhydrite is a pure solid, then aCaSO4 = 1.

and in dilute solutions: aCa2+ ≈ (Ca2+) and aSO42- ≈ (SO42-).
 aCa 2 + aSO 2 −
K SP = 4

aCaSO4
KSP ≈ [Ca2+][SO42-] = 10-4.5

What is the solubility of anhydrite in pure water?

If anhydrite dissolution is the only source of both Ca2+ and
SO42-, then:
[Ca2+] = [SO42-] = x
x2 = 10-4.5
x = 10-2.25 = 5.62x10-3 mol/L
MWanhydrite = 136.14 g/mol
Solubility = (5.62x10-3 mol/L)(136.14 g/mol) = 0.765 g/L
 Saturation index
In a natural solution, it is not likely that [Ca2+] = [SO42-], for
example, because there will be more than one source of each
of these ions. In this case we use saturation indices to
determine if the water is saturated with respect to anhydrite.

KSP = 10-4.5 ≈ [Ca2+]eq[SO42-]eq

IAP = [Ca2+]act[SO42-]act

Saturation
Ω=
[
Ca ] [SO ]
2+
act
2−
4 act
=
IAP
index K SP K SP
Suppose a groundwater is analyzed to contain 5x10-2 mol/L Ca2+ and
7x10-3 mol/L SO42-. Is this water saturated with respect to anhydrite (CaSO4(s))?

CaSO4 ↔ Ca2+ + SO42-

KSP = 10-4.5
IAP = (5x10-2)(7x10-3) = 3.5x10-4 = 10-3.45
Ω = 10-3.45/10-4.5 = 101.05 = 11.22

Ω > 1, i.e., IAP > KSP, so the solution is supersaturated

and anhydrite should precipitate
If Ω = 1, i.e., IAP = KSP, the solution would be saturated
(equilibrium conditions)
If Ω < 1, i.e., IAP < KSP, the solution would be undersaturated;
the mineral should dissolve
 How much salt should precipitate?
Returning to the previous example, i.e., the groundwater with
5x10-2 mol/L Ca2+ and 7x10-3 mol/L SO42-, how much
anhydrite should precipitate at equilibrium?

If x mol/L of anhydrite precipitate, then at equilibrium:

[Ca2+] = 5x10-2 - x; [SO42-] = 7x10-3 - x
and [Ca2+][SO42-] = 10-4.5
(5x10-2 - x)(7x10-3 - x) = 10-4.5
x2 - (5.7x10-2)x + (3.18x10-4) = 0
After solving for the quadratic equation:
x1 = 5.07x10-2 mol/L; x2 = 6.26x10-3 mol/L
We choose x2 (=6.26x10-3)because the first root
(x1=5.07x10-2) causes [SO4] to be negative.

So, 6.26x10-3 mol/L of anhydrite precipitates, or:

(6.26x10-3 mol/L)(136.1 g/mol) = 0.852 g/L

and
[Ca2+] = (5x10-2) - (6.26x10-3) = 4.37x10-2 mol/L

[SO42-] = (7x10-3) - (6.26x10-3) = 7.4x10-4 mol/L

 [Ca2+]/[SO42-] increases with precipitation of anhydrite
Before precipitation:
5x10-2/7x10-3 = 7.1
After precipitation: 6.26x10-3 mol/L of
anhydrite precipitates
4.37x10-2/7.4x10-4 = 59
Precipitation not only reduces
the concentrations of ions
and actually changes the
chemical composition if the
remaining solution…
Because the initial
[Ca2+]/[SO42-] > 1, the remaining
Solution is enriched in Ca2+;
if [Ca2+]/[SO42-]i < 1, the This process occurs when salts
solution would be enriched precipitate when water undergoes
in SO42- evaporative concentration
such as in a desert lake
 The common-ion effect

Natural waters are very complex and we may have saturation

with respect to several phases simultaneously.

Example: What are the concentrations of all species in a

solution in equilibrium with both barite and gypsum?

1) Law of mass action expressions:

CaSO4·2H2O ↔ Ca2+ + SO42- + 2H2O,
KSP = [Ca2+][SO42-] = 10-4.6

BaSO4 ↔ Ba2+ + SO42-,

KSP = [Ba2+][SO42-] = 10-10.0
 [Ca2+][SO42-] = 10-4.6
[Ba2+][SO42-] = 10-10.0
Eliminate [SO42-] by substituting 10-4.6/[Ca+]:
[Ba2+]•10-4.6/[Ca2+] = 10-10.0

2) Species: Ca2+, Ba2+, SO42-, H+, OH-

H2O ↔ H+ + OH-
Kw = [H+][OH-] = 10-14

3) Mass-balance: [Ba2+] + [Ca2+] = [SO42-]

4) Charge-balance:
2[Ba2+] + 2[Ca2+] + [H+] = 2[SO42-] + [OH-]
 −4.6 −10.0
[Ca ]2+
= 10 [
Ba ]2+
= 10
[SO
2−
4 ], [SO ]
2−
4

10−4.6  10−10.0 
 2−  + 
[
SO4   ] SO4  [
2−
2 −  = SO4
] [ ]


10-4.6 + 10-10.0 = [SO42-]2

[SO42-] = (10-4.6 + 10-10.0)1/2 = 10-2.3 mol/L
[Ca2+] = 10-4.6/10-2.3 = 10-2.3 mol/L
[Ba2+] = 10-10.0/10-2.3 = 10-7.7 mol/L
The least soluble salt (barite, KSP=10-10), contributes a negligible
amount of sulfate to the solution. The more soluble salt
(gypsum, KSP=10-4.6) supresses the solubility of the less
soluble salt (the common-ion effect). Barite can replace
gypsum because barite is less soluble than gypsum.
The solubility of gypsum is hardly affected by the
presence of barite:

Solubility of barite alone:

[Ba2+][SO42-] = 10-10.0
[Ba2+]2 = 10-10.0
[Ba2+] = 10-5.0 mol/L
Solubility of gypsum alone:
[Ca2+][SO42-] = 10-4.6
[Ca2+]2 = 10-2.3
[Ca2+] = 10-2.3 mol/L
 Replacement reactions
We can also calculate [Ba2+]/[Ca2+] in equilibrium
with both barite and gypsum.
−4.6 −10.0
[Ca ]
2+
= 10 [
Ba ] 2+
= 10
[SO
2−
4 ] [SO ]
2−
4

[Ba2+] 10-10
= = 10-5.4, or [Ca2+] = 250,000[Ba2+]
[Ca2+] 10-4.6
What would happen if a solution with [Ba2+]/[Ca2+] = 10-3
([Ca2+] = 1,000[Ba2+]) came into contact with a gypsum-
bearing rock?
Barite will precipitate (taking Ba2+ out of the solution) and
gypsum will dissolve until [Ba2+]/[Ca2+] = 10-5.4.
 Hydrolysis
The interaction between water and one or both ions of a salt
that results in the formation of the parental acid or base, or both.
We classify salts by the strength of the acid and base from
which they form:
1. Strong acid + strong base do not hydrolyze
2. Strong acid + weak base cations + OH- = acidic soln
3. Weak acid + strong base anions + H+ = basic soln
4. Weak acid + weak base release both cation & anions
Most common rock-forming minerals of the crust are salts
of weak acids and strong bases, e.g., carbonates and silicates
of alkali metals (Group 1) and alkaline earths (Group 2)
form these salts…this is why groundwater in carbonate aquifers
is commonly basic
 Hydrolysis

2−
K 2CO 3 → 2K + CO
+
3
2− -
CO + H 2O ↔ HCO + OH
3 3
−
K H1
-
HCO + H 2O ↔ H 2CO 3 + OH
3
−
K H2
K H1 = ?
K H2 = ?
 Dissociation
-
H 2CO 3 ↔ HCO + H 3
+
K A1
HCO-3 ↔ CO 23− + H + K A2

What is the pH of a solution prepared by dissolving 0.1 mol

of K2CO3 in 1 L of water?