Slightly Soluble Salts

The dissolving equations for solid salts provide an interesting set of equilibrium
constant expressions. These dissolving equations will always have a solid as the only
reactant and the resulting aqueous ions as the products.
NaCl(s) ↔ Na+(aq) + Cl-(aq) K = [Na+ ][Cl-]
Zn(IO3 )2(s) ↔ Zn (aq) + 2IO3(aq)
2+ K = [Zn2+ ][IO3-]2
PbCl2(s) ↔ Pb (aq) + 2Cl (aq)
2+ - K =[Pb2+][Cl-]2
The equilibrium constants for slightly soluble salts are especially useful because of the
large amount of information that can be acquired from mathematical calculations are
available with these equations.
Cu(OH)2(s) ↔ Cu2+(aq) + 2OH (aq) K =2.2 x 10-20
Sample question: Tooth enamel consists of the compound hydroxyapatite. It has a
formula Ca5(PO4)3OH and has an equilibrium constant of 6.8 x 10-37. Write the
dissociation equation and comment on the value of the equilibrium constant.
Solution:

Ca5(PO4)3OH(aq) ↔ Ca5(PO4)3(aq) + OH(aq) K = 6.8 x 10-37

 Tooth enamel will not readily dissociated into the ions and stay as enamel on
your teeth (something you want to happen!)
Solubility Product Constant,Ksp

Fe(OH) 2(s) ↔ Fe2+(aq) + 2OH-(aq) K = [Fe2+][OH-]2

Sample question: Write the dissociation reaction and the solubility product constant
expression for each of the following solids.

(a) PbSO4(s) (b) Al(OH)3(s)

Solution:

(a) PbSO4(s) ↔ Pb2+(aq) + SO2-(4( (aq) Ksp =[ Pb2+][ SO2-] (b)

Al(OH)3(s) ↔ Al3+(aq) + 3OH- (aq) Ksp =[ Al3+][ OH-]3

Mathematics for Ksp

Conclusions from Ksp Size

PbI2(s) ↔ Pb2+(aq) + 2I-(aq) K = [Pb2+][ 2I-]2 = 7.90 x 10-9

We can see that there are twice as many iodide ions as there are lead ions in the
equilibrium system. Notice, too, that this number is very low indicating that little
dissociation is occurring.

For the dissociation of silver chromate, there are twice as many silver ions as there are
chromate ions. The value of Ksp is even lower meaning the amount of dissociation for
silver chromate is even smaller.

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Ag2CrO4(s) ↔ 2 Ag+ (aq) + CrO42- (aq) K = [Ag+]2 [CrO42-] = 1.10 x 10-12

Sample problem: Compare the amount of dissociation of the two sulfates listed below.

(a) Barium sulfate: BaSO4(s) ↔ Ba2+(aq) + SO4-2(aq) K = [Ba2+] [SO4-2] = 1.10 x 10-10

(b) Silver sulfate:: Ag2SO4(s) ↔ 2 Ag+(aq) + SO4-2(aq) K = [Ag+]2 [SO4-2] = 1.20x 10-5

Solution:

(a) For barium sulfate, there are equal amounts of the sulfate and barium ions
formed when barium sulfate dissolves. The Ksp is low meaning that the amount of
barium sulfate that does dissolve is low.

(b) There are twice as many silver ions as sulfate ions and the Ksp is much higher
meaning that more of the silver sulfate will dissolve in solution forming ions.

Calculating Ksp From Solubility

The Ksp of a slightly soluble salt can be calculated from its solubility. Solubilities are
usually given in grams/liter but occasionally are given in moles/liter.

 Given the solubility of copper (I) bromide to be 0.0287 grams/liter, the molarity
of the dissolved CuBr can be determined, and from the molarity of the dissolved
CuBr, the molarity of the individual ions in solution can be calculated.

𝟎. 𝟎𝟐𝟖𝟕𝐠/𝐥
𝐌𝐨𝐥𝐚𝐫𝐢𝐭𝐲 𝐂𝐮𝐁𝐫 𝐝𝐢𝐬𝐬𝐨𝐥𝐯𝐞𝐝 = 𝟎. 𝟎𝟎𝟎𝟐𝟎𝟎 𝐌 = 𝟐. 𝟎𝟎 𝐱 𝟏𝟎 − 𝟒 𝐌
𝟏𝟒𝟑. 𝟓𝐠/𝐦𝐨𝐥

CuBr(s) ↔ Cu+(aq) + Br- (aq)

In this case, the reacting ratio between the moles of solid dissolved and the moles of
ions in solution is 1:1, so when 2.00 x 10-4 mol/L of CuBr dissolve, the concentration
of the ions in solution will be [Cu+] = 2.00 x 10-4 mol/L and [Br-] = 2.00 x 10-4 mol/L.

𝐊𝐬𝐩 = [𝐂𝐮 + ][𝐁𝐫 − ] = (𝟐. 𝟎𝟎 𝐱 𝟏𝟎 − 𝟒 )(𝟐. 𝟎𝟎 𝐱 𝟏𝟎 − 𝟒 ) = 𝟒. 𝟎𝟎 𝐱 𝟏𝟎 −𝟖 .

Units for Ksp values are usually not expressed.

 Consider the salt calcium phosphate. The solubility of calcium phosphate is

5.10 x 10-5 g/L. First, we convert the solubility in grams/liter to moles/liter.
𝟓. 𝟏𝟎 𝐱 𝟏𝟎 − 𝟓𝐠/𝐋
𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚 𝑪𝒂𝟑(𝑷𝑶𝟒)𝟐 𝒅𝒊𝒔𝒔𝒐𝒍𝒗𝒆𝒅 = = 𝟏. 𝟔𝟕 𝐱 𝟏𝟎 − 𝟕𝐌
𝟑𝟏𝟎𝒈/𝒎𝒐𝒍

Using the dissolving equation, we determine the molarity of the ions in solution.

Ca3(PO4)2(s) ↔ 3Ca+2 (aq) + 2PO-34 (aq)

[Ca2+] = (3)(1.67 x 10-7M) = 5.01 x 10-7M and

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 [PO-34] = (2)(1.67 x10-7M) = 3.34 x 10-7M.

Ksp= [Ca2+] [PO-34] = (5.01 x 10-7M) (3.34 x 10-7M) = 1.4 x 10-32

Calculating Solubility From Ksp

Not only can the Ksp be calculated from the solubility but the solubility can be
calculated from the Ksp.

 Given the Ksp for AgBr as Ksp= 1.60 x 10-10 , we can use the dissolving
equation and some algebra to calculate the concentrations in mols/L of each
ion in solution.

AgBr(s) ↔ Ag+ (aq) + Br-(aq)

If we allow x to represent the mols/L of AgBr that dissolves, then, since the reacting
ratios in the equation are all ones, x will represent both [Ag +] and [Br-]. We can then
write the K expression for AgBr, set it equal to the given Ksp value, substitute the
assigned variables into the equation and solve.

Ksp =[ Ag+][ Br-] = 1.60 x 10-10 (x)(x)= 1.60 x 10-10 x = 1.26 x 10-5M

To find the solubility of AgBr in grams/liter, we simply need to multiply the moles/liter
by the molar mass and we will get the solubility in grams/liter.
Solubility of AgBr in g/L = (1.26 x 10-5mols/L)(188 g/mol) = 2.4 x 10-3g/L

 Let's try lead (II) fluoride. Here is the dissolving equation, the Ksp expression,
and the given Ksp value for PbF2.
PbF2(s) ↔ Pb2+ (aq) + 2F-(aq)

Ksp =[ Pb2+][ F-]= 4.0 x 10-8

Once again, we let x represent the solubility of PbF2 in moles/liter and therefore, the
concentration of lead ions in solution will be x and the concentration of fluoride ions
in solution will be 2x. Substitute these variables into the Ksp expression and solve for
x.

Ksp =[ Pb2+][ F-]= 4.0 x 10-8

(x)(2x)2 =4.0 x 10-8
4x = 4.0x10-8 x3 = 1.0 x 10-8
3

x = 2.2 x 10-3 mol/L

When we assigned the variables, x represented the molarity of the lead ions in
solution but x also represented the molarity of lead (II) fluoride that had dissolved, so
this is the solubility in moles/liter and to get grams/liter, we multiply by the molar
mass.
Solubility of PbF = (2.2 x 10-3mol/L)(245 g/mol) = 0.53 g

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Review Questions

1. What is the solubility product constant? Give an example. (Intermediate)

2. Why is solubility considered a special case for chemical equilibria? (Intermediate)

3. Nickel hydroxide is a slightly soluble salt. Its dissociation reaction is represented

below. Write down its solubility product constant expression, Ksp
Ni(OH)2(s) ↔ Ni 2+ (aq) + 2OH-(aq)

4. The Ksp for AgBr is 5.0 x10-13 . What is [Ag+] at equilibrium? (Intermediate)
5. The Ksp for PbF2 is 3.60 x10-8 . What is [F-] at equilibrium? (Intermediate)
6. Magnesium hydroxide is the key component in milk of magnesia, the suspension
used to cure indigestion. It has an equilibrium constant of 6.3 x 10-10. Write the
dissociation equation and comment on the value of the equilibrium constant.
7. Write the dissociation reactions for the following salts as well as the Ksp
expressions. (Intermediate)
(a) Calcium fluoride (b) chromium(II) carbonate (c) Arsenic(III) sulfide

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