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Equilibrium & Solubility:

The Solubility Product Constant, Ksp

1 Prof. Zvi C. Koren 20.07.2010


Precipitation Reactions
Gross rxn.: Pb(NO3)2(aq) + 2KI(aq) PbI2(s) + 2KNO3(aq)
(recall double-replacement rxns)

Net-Ionic rxn.:
Pb2+ + 2NO3- + 2K+ + 2I- PbI2(s) + 2K+ + 2NO3-
Pb2+ + 2I- PbI2(s)

2 Prof. Zvi C. Koren 20.07.2010


Solubility of a Salt
Solubility of a Salt = S, units of moles/L

PbI2(s)
Pb2+ + 2I

Equilibrium
between:
Pb2+ 2I dissolved
saturated
solution of and
PbI2 PbI2 (s) undissolved
(precipitate)

3 Prof. Zvi C. Koren 20.07.2010


Solubility Product Constant, Ksp
For example,
Al2S3(s) 2Al3+ + 3S2-
2x 3x

K sp = [Al3+]2 [S2-]3 = (2x)2 (3x)3 = 108x5


solubility product constant

Let x = solubility of salt: x moles salt dissolved / L

two types of problems: Solubility Ksp

Note:
Dont confuse solubility with solubility product constant

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5 Prof. Zvi C. Koren 20.07.2010
Case 1: Ksp Solubility
Problem:
Calculate the solubility of magnesium fluoride in g/L.
Ksp = 6.4x109 @250C.

Solution:
1. Write the equilibrium dissolution rxn: MgF2(s) Mg2+ + 2F
x 2x
2. Write the Ksp expression: Ksp = [Mg2+][F]2

3. Do the stoichometric ICE-box right on the equilibrium rxn.


Let x = solubility of the salt in moles/L.
4. Calculate using Ksp expression: Ksp = (x)(2x)2
6.4x109 = 4x3
Solubility of MgF2 = x = 1.17x103 mole of MgF2 dissolves/L @250C.
in g/L: (1.17x103 mole of MgF2 /L)(62.3018 g/mole) = 0.073 g MgF2 /L
6 Prof. Zvi C. Koren 20.07.2010
Case 2: Solubility Ksp
Experimental
Determination of Atomic Absorption (AA)
Ion Concentrations Spectrometer
Problem:
Calculate the solubility product constant, Ksp, of magnesium fluoride.
Solubility = 1.17x103 mole/L @250C = [Mg2+]

Solution:
1. Write the equilibrium dissolution rxn: MgF2(s) Mg2+ + 2F
x 2x
2. Write the Ksp expression: Ksp = [Mg2+][F]2

3. Do the stoichometric ICE-box right on the equilibrium rxn.


Let x = solubility of the salt in moles/L = 1.17x103 mole/L
4. Calculate using Ksp expression:
Ksp = (x)(2x)2 = (1.17x103)(2.34x103)2 = 6.41x109
7 Prof. Zvi C. Koren 20.07.2010
Ksp in your Kishkes

8 Prof. Zvi C. Koren 20.07.2010


The Meaning of the Ion-Product in Ksp
Consider MX(s) M+ + X

Ksp = [M+][X]

This equation pertains to:


just before precipitation, or
after precipitation

Maximum Concentrations BEFORE Precipitation:


[M+] and [X] are the maximum concentrations that can live with each
other (peaceful coexistence) without attacking each other and
creating a ppt.
Maximum Concentrations AFTER Precipitation:
[M+] and [X] are the maximum concentrations that can live with each
other after a precipitate of MX(s) is formed, no matter how much ppt is
present: Saturated solution.
9 Prof. Zvi C. Koren 20.07.2010
Reaction Quotient, Q (Again):
Can a Precipitation Reaction Occur?
Recall:
Al2S3(s) 2Al3+ + 3S2- ppt = precipitate

K sp = [Al3+]eq
2 [S2-]3
eq
Q < Ksp Q > Ksp Q = Ksp

no ppt ppt no ppt;


Q = [Al3+]2 [S2-]3
Unsaturated Saturated equil.:
solution solution max concs.

(continued)
10 Prof. Zvi C. Koren 20.07.2010
Can a Precipitation Reaction Occur?
Question:
50.0 mL of 0.34 M Pb(NO3)2 solution is mixed with 25.0 mL of
0.10 M NaCl. Will a precipitate be formed?
Answer:
Overall rxn.: Pb(NO3)2 (aq) + 2 NaCl(aq)
? PbCl2(s) + 2 NaNO3(aq)
Net ionic rxn.: Pb2+ + 2Cl ? PbCl2(s)
Ksp = [Pb2+] [Cl]2 = 1.7x105 Qsp = [Pb2+][Cl]2
eq eq
Calculate concentrations after mixing, but before rxn.:
[Pb2+] = (50.0/75.0)(3.4x10-1 M) = 2.27x101 M
[Cl] = (25.0/75.0)(1.0x10-1 M) = 3.33x102 M
Q = (2.27x10-1)(3.33x10-2)2 = 2.5x104 > Ksp = 1.7x105 ppt!
What are the concentrations of all ions and how many moles of
precipitate are obtained? (see next slide)
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(continued)
What are the concentrations of all ions and how many moles of
precipitate are obtained?
I 0.227 0.0333
Net ionic rxn.: Pb2+ + 2Cl- PbCl2(s), K >> 1
K >> 1: C -0.0167 -0.0333 +0.0167
E,I 0.210 - 0.0167
C +x +2x -x
E 0.210+x 2x 0.0167-x
1.7x10-5 = Ksp = [Pb2+][Cl-]2
= (0.210+x)(2x)2 (0.210)(4x2), x = 4.5x10-3 M
Concentrations of ions:
[Cl-] = 2x = 9.0x10-3 M
Check: Ksp = [Pb2+][Cl-]2 1.7x10-5
[Pb ] = 0.210+x 0.21 M
2+

Moles of ppt formed:


PbCl2(s): 0.0167-0.0045 (0.0122 mole/L)x(0.075 L) = 9.15x10-4 mole
12 Prof. Zvi C. Koren 20.07.2010
The Common Ion Effect (Again)
What happens to the solubility of a salt when there is a common ion?
sparingly soluble salt: MX(s) M+ + X
+
soluble salt: MA(aq) M+ + A- or LX(aq) L+ + X
according to Le Chateliers Principle, the solubility of the sparingly
soluble salt will decrease in the presence of a common ion.

13 Prof. Zvi C. Koren 20.07.2010


The Common Ion Effect - Calculations
Question:
The solubility of AgCl is 0.0019 g/L.
If some AgCl is placed in 500.0 mL of a 0.50 M solution of NaCl, how
many grams of AgCl dissolve?
Answer:
Note the presence of 2 salts, one sparingly soluble and one soluble.
0.50 M
1. Write the total dissolution rxn: NaCl(aq) Na+ + Cl
0.50 M
2. Write the equilibrium dissolution rxn: AgCl(s) Ag+ + Cl
x x+0.50
3. Write the Ksp expression for the sparingly soluble salt:
Ksp = [Ag+][Cl] = (x)(x+0.50) (x)(0.50)
4. Do the stoichometries (and ICE-box for sp. sol. salt) right on the rxns.
Let x = solubility of the salt in moles/L
14 (continued) Prof. Zvi C. Koren 20.07.2010
(continued)
From before: Ksp = [Ag+][Cl] = (x)(x+0.50) (x)(0.50)

Need to calculate Ksp from solubility:


Given: The solubility of AgCl is 0.0019 g/L.
x = Solubility = 0.0019 g/L (1 mole/143.321 g) 1.33x10-5 M
[Ag+] = x = 1.33x10-5 M, [Cl-] = x = 1.33x10-5 M.
Ksp = 1.77x10-10

1.77x10-10 = Ksp = [Ag+][Cl] = (x)(x+0.50) (x)(0.50)


x = 3.54x10-10 mole/L 5.07x10-8 g AgCl dissolve /L (0.500 L)
2.5x10-8 g AgCl dissolve!

15 Prof. Zvi C. Koren 20.07.2010


Selective Separation of Ions & Solubility

Ag+ AgCl(s) AgCl(s)


Cl
PbCl2(s) Pb2+ + CrO42 PbCrO4(s)
Pb2+

Cu2+ Cu2+
16 Prof. Zvi C. Koren 20.07.2010
Selective Separation of Ions & Solubility - Calculations
Separation of Two Ions by Difference in Solubility: Cl and CrO42

Which salt is more insoluble, AgCl or Ag2CrO4?


Ksp: 1.8x1010 9.0x1012

Check Solubilities!!! Let x = solubility of a salt in moles/L:

AgCl(s) Ag+ + Cl ,
x x
Ksp = [Ag+][Cl-] = x2 x = 1.3x105 mol/L

Ag2CrO4(s) 2Ag+ + CrO42 ,


2x x
Ksp = [Ag+]2 [CrO42] = (2x)2(x) x = 1.3x104 mol/L
Surprise, surprise!
17 (continued) Prof. Zvi C. Koren 20.07.2010
Selective Separation of Ions & Solubility (continued)
Separation of Two Ions by Difference in Solubility: Cl and CrO42
Question:
A solution contains 0.010 M NaCl and 0.0010 M K2CrO4.
Solid AgNO3 is added slowly to the solution.
a) Which precipitates first?
b) What is [Cl-] when the second precipitate begins to form?
Answer:
First calculate [Ag+] required to just begin the precipitation of each salt:
To just begin precipitation of AgCl when [Cl] = 0.010 M:
Ksp = [Ag+][Cl-] [Ag+] = 1.8x10-8 M.
To just begin precipitation of Ag2CrO4 when [CrO42] = 0.0010 M:
Ksp = [Ag+]2 [CrO42] [Ag+] = 9.5x10-5 M.
AgCl precipitates first!
When does Ag2CrO4 begin to precipitate?
When [Ag+] = 9.5x10-5 M Ksp = [Ag+][Cl-] [Cl-] = 1.9x10-6 M
% Cl- remaining in solution = 100x(1.9x10-6 M)/(0.010 M)= 0.019%
18 Prof. Zvi C. Koren 20.07.2010
Simultaneous Equilibria

Two or more equilibria rxns occurring at the same time

PbCl2(s) is only sparingly soluble in water (Ksp = 1.7x105).


What is its solubility in certain other ionic solutions, e.g., CrO42 ?
PbCl2(s) + CrO42
? PbCrO4(s) + 2Cl, K = ?
K = K1K2 = 9.4x108
Simultaneous Equilibria:
PbCl2(s) Pb2+ + 2Cl, K1 = Ksp(PbCl2)

Pb2+ + CrO42 PbCrO4(s), K2 = 1/Ksp(PbCrO4)


PbCl2 is soluble in a solution of CrO42, but it becomes another ppt.
When a salt solution is added to a salt precipitate Check Krxn!!!
19 Prof. Zvi C. Koren 20.07.2010
Solubility and pH
Some sparingly soluble salts are more soluble in water than normally
expected. Why???
Answer: Because the resultant anion can undergo hydrolysis as a base.
For example:
PbS(s) Pb2+ + S2, Ksp(PbS) = 3.2x1028
AND
S2 + H2O HS + OH, K = Kb(S2) = Kw/Ka(HS) = 1x105
K2(H2S)*
PbS(s) + H2 O Pb2+ + HS + OH,
K = 3x1023 >> Ksp
PbS is more soluble in water than expected
*(Note: For H2S: Ka1 = 1x107, Ka2 = 1x1019)
20 (continued) Prof. Zvi C. Koren 20.07.2010
Solubility and pH Salt in an Acidic Solution
How can we determine the ability of a salt to be dissolved by an acid?
(A powerful display of the wonders of chemical principles!!!)
Example: CaCO3(s) + H+ ? What is the value of K for this rxn?
The Trick: Build this rxn from other known salt solubility and acid-
base hydrolysis rxns.:
CaCO3(s) Ca2+ + CO32-, K = Ksp = 3.8x10-9
CO32- + H2O HCO3- + OH-, K = Kb(CO32-) = Kw/Ka(HCO3-) = 2.1x10-4
H+ + OH- H2O, K = 1/ Kw = 1.0x1014
CaCO3(s) + H+ Ca2+ + HCO3-, K = 80.0 > 1 (but read on)
But Also:
HCO3- + H+ H2CO3, K = 1/Ka1 = 1/4.2x10-7 = 2.4x106
But Also:
H2CO3(aq) CO2(g) + H2O, K 105
CaCO3(s) + 2H+ Ca2+ + CO2(g) + H2O, K 1013
(Note: CO2(g) bubbles out of system, so equil. moves even more to right!)
In general: Must examine all possible subsequent rxns.
21 Prof. Zvi C. Koren 20.07.2010
Solubility and pH Metal Hydroxides
Question:
The Ksp of Mg(OH)2 is 1.5x10-11.
If solid Mg(NO3)2 is added to a
solution with a pH of 9.00,
at what [Mg2+] does precipitation
begin?
Answer:
Mg(OH)2(s) Mg2+ + 2OH-,
Ksp = [Mg2+][OH-]2
pH = 9.00 [OH-] = 1.0x10-5 M.
[Mg2+] = 0.15 M.
What happens to the solubility of
this hydroxide as the pH is changed,
up or down?
22 Prof. Zvi C. Koren 20.07.2010
Solubility and Complex Ion Formation
ligands
Complex Metal surrounded by two or more groups
(neutral or cation) (anion or molecule )
Complex-Ion Formation and Formation Constant:
Ag+ + 2NH3(aq) Ag(NH3)2+, Kf = K1K2 = 1.6x107
Rxn in two steps:
Ag+ + NH3(aq) Ag(NH3)+, K1
Ag(NH3)+ + NH3(aq) Ag(NH3)2+, K2
Dissolving a Precipitate by Complex-Ion Formation:
We know that the solubility of AgCl(s) in water is only slight, Ksp =
1.8x10-10. Can another solvent, e.g., NH3(aq), better disssolve the solid?
AgCl(s) + 2NH3(aq) Ag(NH3)2+ + Cl-. K = ?
If K > Ksp, then bingo! Build this rxn from others. Thats the trick!
AgCl(s) Ag+ + Cl-, Ksp K = KspKf
Ag+ + 2NH3(aq) Ag(NH3)2+, Kf = 2.9x10-3. Yesh!
23 Prof. Zvi C. Koren 20.07.2010
Solubility and Complex Ion Formation - Calculations
Problem:
How many moles of ammonia must be added to dissolve 0.050 mol
of solid AgCl present in 1.0 L of water?
Answer:
I 0.050 mol/L y
AgCl(s) + 2NH3(aq) Ag(NH3)2+ + Cl-, K = 2.9x10-3.
C -0.050 -0.10 +0.050 +0.050
E - y-0.10 0.050 0.050
2.9x10-3 = K = [Ag(NH3)2+][Cl-] / [NH3]2
y-0.10 = [NH3] = 0.93 M
y = 1.03 mol/L
And
n = (1.03 mol/L) x (1 L) = 1.03 mol NH3 must be added initially.

24 Prof. Zvi C. Koren 20.07.2010