Solubility Equilibria: Chemistry 40S M. Patenaude GPHS Science Dept

Solubility Equilibria
Chemistry 40S
M. Patenaude
GPHS Science Dept
Chem 30S Review…Solubility Rules
 Salts are generally more soluble in HOT water
(Gases are more soluble in COLD water)
 Alkali Metal salts are very soluble in water.
NaCl, KOH, Li3PO4, Na2SO4 etc...
 Ammonium salts are very soluble in water.
NH4Br, (NH4)2CO3 etc…
 Salts containing the nitrate ion, NO3-, are very soluble
in water.
 Most salts of Cl-, Br- and I- are very soluble in water -
exceptions are salts containing Ag+ and Pb2+.
soluble salts: FeCl2, AlBr3, MgI2 etc...
“insoluble” salts: AgCl, PbBr2 etc...
Dissolving a salt...
 A salt is an ionic compound -
usually a metal cation bonded
to a non-metal anion.
 The dissolving of a salt is an
example of equilibrium.
 The cations and anions are
attracted to each other in the
salt.
 They are also attracted to the
water molecules.
 The water molecules will start to
pull out some of the ions from
the salt crystal.
 At first, the only process
occurring is the dissolving of the
salt - the dissociation of the salt
into its ions.
 However, soon the ions floating in

the water begin to collide with the
salt crystal and are “pulled back
in” to the salt. (precipitation)
 Eventually the rate of dissociation

is equal to the rate of
precipitation.
 The solution is now “saturated”.

It has reached equilibrium.
Solubility Equilibrium:
Dissociation = Precipitation
In a saturated solution,
Na+ and Cl - ions
there is no change in
surrounded by amount of solid
water molecules
precipitate at the
bottom of the beaker.
Concentration of the
solution is constant.
The rate at which the

NaCl Crystal
salt is dissolving into
solution equals the rate
Dissolving NaCl in water of precipitation.
Dissolving silver sulfate, Ag2SO4, in water
 When silver sulfate dissolves it dissociates into ions.
When the solution is saturated, the following
equilibrium exists:
Ag2SO4 (s)  2 Ag+ (aq) + SO42- (aq)

 Since this is an equilibrium, we can write an
equilibrium expression for the reaction:
Ksp = [Ag+]2[SO42-]
Notice that the Ag2SO4 is left out of the expression! Why?
Since K is always calculated by just multiplying concentrations, it is
called a “solubility product” constant - Ksp.
Writing solubility product expressions...
 For each salt below, write a balanced equation
showing its dissociation in water.
 Then write the Ksp expression for the salt.
Iron (III) hydroxide, Fe(OH)3

Nickel sulfide, NiS
Silver chromate, Ag2CrO4
Zinc carbonate, ZnCO3
Calcium fluoride, CaF2 Try Problems 1 - 8
Some Ksp Values
Note:
These are experimentally determined, and may
be slightly different on a different Ksp table.
Calculating Ksp of Silver Chromate
 A saturated solution of silver chromate, Ag 2CrO4, has
[Ag+] = 1.3 x 10-4 M. What is the Ksp for Ag2CrO4?
Ag2CrO4 (s)  2 Ag+ (aq) + CrO42- (aq)

---- ----
1.3 x 10-4 M
Ksp = [Ag+]2[CrO42-]
Ksp = (1.3 x 10-4 )2 (6.5 x 10-5) = 1.1 x 10-12

Calculating the Ksp of silver sulfate
 The solubility of silver sulfate is 0.014 mol/L. This
means that 0.0144 mol of Ag2SO4 will dissolve to make
1.0 L of saturated solution. Calculate the value of the
equilibrium constant, Ksp for this salt.
Ag2SO4 (s)  2 Ag+ (aq) + SO42- (aq)

--- ---
+ 2s +s
2s s
Ksp = [Ag+]2[SO42-] = (2s)2(s) = (4s2)(s) = 4s3
We know: s = 0.0144 mol/L
Ksp = 4(0.0144)3 = 1.2 x 10-5

Calculating solubility, given Ksp
 The Ksp of NiCO3 is 1.4 x 10-7 at 25°C. Calculate its
molar solubility.
NiCO3 (s)  Ni2+ (aq) + CO32- (aq)

--- ---
+s +s
s s
Ksp = [Ni2+][CO32-]
1.4 x 10-7 = s2
7
s= 1.4 x 10 = 3.7 x 10-4 M
Other ways to express solubility...
 We just saw that the solubility of nickel (II) carbonate
is 3.7 x 10-4 mol/L. What mass of NiCO3 is needed to
prepare 500 mL of saturated solution?
3.7 x 10  4 mol NiCO3 0.500 L 118.72 g

x x  0.022 g
1L 1mol NiCO3
0.022 g of NiCO3 will dissolve to make 500 mL solution.
Try Problems 9 - 26
Calculate the solubility of MgF2 in water. What
mass will dissolve in 2.0 L of water?
MgF2 (s)  Mg2+ (aq) + 2 F- (aq)
---- ----
+s + 2s
s 2s
Ksp = [Mg2+][F-]2 = (s)(2s)2 = 4s3
Ksp = 7.4 x 10-11 = 4s3
s = 2.6 x 10-4 mol/L
2.6 x 10 4 mol MgF2 2.0 L 62.31g

x x  0.032 g MgF2
1L 1mol MgF2
Solubility and pH
 Calculate the pH of a saturated solution of silver
hydroxide, AgOH. Refer to the table in your booklet
for the Ksp of AgOH.
AgOH (s)  Ag+ (aq) + OH- (aq)

---- ----
+s +s
s s
Ksp = 2.0 x 10-8 = [Ag+][OH-] = s2

s = 1.4 x 10-4 M = [OH-]
pOH = - log (1.4 x 10-4) = 3.85
pH = 14.00 - pOH = 10.15
The Common Ion Effect on Solubility
The solubility of MgF2 in pure water is 2.6 x 10-4 mol/L.
What happens to the solubility if we dissolve the MgF2 in
a solution of NaF, instead of pure water?
Calculate the solubility of MgF2 in a
solution of 0.080 M NaF.
MgF2 (s)  Mg2+ (aq) + 2 F- (aq)
---- 0.080 M
+s + 2s
s 0.080 + 2s
Ksp = 7.4 x 10-11 = [Mg2+][F-]2 = (s)(0.080 + 2s)2
Since Ksp is so small…assume that 2s << 0.080
7.4 x 10-11 = (s)(0.080)2
s = 1.2 x 10-8 mol/L

Explaining the Common Ion Effect
The presence of a common ion in a solution will
lower the solubility of a salt.
 LeChatelier’s Principle:
The addition of the common ion will shift the
solubility equilibrium backwards. This means
that there is more solid salt in the solution
and therefore the solubility is lower!
Ksp and Solubility
 Generally, it is fair to say that salts with very small
solubility product constants (Ksp) are only sparingly
soluble in water.
 When comparing the solubilities of two salts, however,

you can sometimes simply compare the relative sizes
of their Ksp values.
 This works if the salts have the same number of ions!
 For example… CuI has Ksp = 5.0 x 10-12 and CaSO4

has Ksp = 6.1 x 10-5. Since the Ksp for calcium sulfate
is larger than that for the copper (I) iodide, we can say
that calcium sulfate is more soluble.
But be careful...
Solubility
Salt Ksp
(mol/L)
CuS 8.5 x 10-45 9.2 x 10-23
Ag2S 1.6 x 10-49 3.4 x 10-17
-73 -15
Bi2S3 1.1 x 10 1.0 x 10
Do you see the “problem” here??

Mixing Solutions - Will a Precipitate Form?
If 15 mL of 0.024-M lead nitrate is mixed with 30 mL
of 0.030-M potassium chromate - will a precipitate form?
Pb(NO3)2 (aq) + K2CrO4 (aq)  PbCrO4 (s) + 2 KNO3 (aq)
Pb(NO3)2 (aq) + K2CrO4 (aq)  PbCrO4 (s) + 2 KNO3 (aq)
Step 1: Is a sparingly soluble salt formed?

We can see that a double replacement reaction can
occur and produce PbCrO4. Since this salt has a
very small Ksp, it may precipitate from the mixture.
The solubility equilibrium is:
PbCrO4 (s)  Pb2+ (aq) + CrO42- (aq)
Ksp = 2 x 10-16 = [Pb2+][CrO42-]
If a precipitate forms, it means the solubility

equilibrium has shifted BACKWARDS.
This will happen only if Qsp > Ksp in our mixture.

Step 2: Find the concentrations of the ions that form the
sparingly soluble salt.
Since we are mixing two solutions in this example,
the concentrations of the Pb2+ and CrO42- will be
diluted. We have to do a dilution calculation!
Dilution: C1V1 = C2V2

C1V1 (0.024 M)(15 mL) 2
[Pb2+] = V   0.0080 M Pb
2 (45 mL)
C1V1 (0.030 M)(20 mL) 2-

  0.020 M CrO 4
[CrO42-] = V2 (45 mL)
Step 3: Calculate Qsp for the mixture.
Qsp = [Pb2+][CrO42-] = (0.0080 M)(0.020 M)
Qsp = 1.6 x 10-4
Step 4: Compare Qsp to Ksp.
Since Qsp >> Ksp, a precipitate will form when

the two solutions are mixed!
Note: If Qsp = Ksp, the mixture is saturated

If Qsp < Ksp, the solution is unsaturated
Either way, no ppte will form!

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Solubility Equilibria

 However, soon the ions floating in

 Eventually the rate of dissociation

 The solution is now “saturated”.

The rate at which the

Ag2SO4 (s)  2 Ag+ (aq) + SO42- (aq)

Iron (III) hydroxide, Fe(OH)3

Ag2CrO4 (s)  2 Ag+ (aq) + CrO42- (aq)

Ksp = (1.3 x 10-4 )2 (6.5 x 10-5) = 1.1 x 10-12

Ag2SO4 (s)  2 Ag+ (aq) + SO42- (aq)

Ksp = [Ag+]2[SO42-] = (2s)2(s) = (4s2)(s) = 4s3

We know: s = 0.0144 mol/L

Ksp = 4(0.0144)3 = 1.2 x 10-5

NiCO3 (s)  Ni2+ (aq) + CO32- (aq)

3.7 x 10  4 mol NiCO3 0.500 L 118.72 g

0.022 g of NiCO3 will dissolve to make 500 mL solution.

Ksp = [Mg2+][F-]2 = (s)(2s)2 = 4s3

Ksp = 7.4 x 10-11 = 4s3

s = 2.6 x 10-4 mol/L

2.6 x 10 4 mol MgF2 2.0 L 62.31g

AgOH (s)  Ag+ (aq) + OH- (aq)

Ksp = 2.0 x 10-8 = [Ag+][OH-] = s2

Ksp = 7.4 x 10-11 = [Mg2+][F-]2 = (s)(0.080 + 2s)2

Since Ksp is so small…assume that 2s << 0.080

7.4 x 10-11 = (s)(0.080)2

s = 1.2 x 10-8 mol/L

 When comparing the solubilities of two salts, however,

 This works if the salts have the same number of ions!

 For example… CuI has Ksp = 5.0 x 10-12 and CaSO4

CuS 8.5 x 10-45 9.2 x 10-23

Ag2S 1.6 x 10-49 3.4 x 10-17

Do you see the “problem” here??

Step 1: Is a sparingly soluble salt formed?

Ksp = 2 x 10-16 = [Pb2+][CrO42-]

If a precipitate forms, it means the solubility

This will happen only if Qsp > Ksp in our mixture.

Dilution: C1V1 = C2V2

C1V1 (0.030 M)(20 mL) 2-

Qsp = [Pb2+][CrO42-] = (0.0080 M)(0.020 M)

Qsp = 1.6 x 10-4

Step 4: Compare Qsp to Ksp.

Since Qsp >> Ksp, a precipitate will form when

Note: If Qsp = Ksp, the mixture is saturated

Either way, no ppte will form!

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