Chapter 11

Solving equilibrium problems for

complex systems
Goal of this chapter
• To learn the multi equilibrium nature of chemical reactions
in aqueous solutions
• To learn how to develop independent equations for multi-
equilibrium system and solving the equations.
• To learn how to use approximation to solve equilibrium
calculations

1
 Multi-equilibrium nature of aqueous
solutions
• Aqueous solutions in analytical chemistry often contain
several species that interact with one another to
generate two or more equilibria that function simultaneously.
• Solutions of a multiple equilibrium problem requires the
development of independent equations as many as the
participants in the system to be studied.
• Three types of algebraic equations are used in solving
multiple-equilibrium problems:
- equilibrium constant expressions
- mass-balance equations
- a charge balance equation

2
 Mass balance equations
• Mass balance equations relate:
- the equilibrium concentration of various species in a solution
to one another
- and the relationship of analytical concentrations of the
various solutes with the equilibrium concentration of various
species in the solution.
• Building up mass balance equations needs knowledge/
information of the solution and chemical equilibria in the
solution.

3
 Mass balance equation examples
--Example: Write mass-balance expressions for a 0.0100 M
solution of HCl that is in equilibrium with an excess of solid
BaSO4.
• Equilibria in the solution:
BaSO4(s) Ba2+(aq) + SO42-(aq) (E11-1)
SO42-(aq) + H3O+(aq) HSO4-(aq) + H2O(l) (E11-2)
2H2O(l) H3O+(aq) + OH-(aq) (E11-3)
• Mass-balance equations:
- From (E11-1)&(E11-2), the equilibrium concentration of barium ion
and sulfate ions have follow relationship:
[Ba2+] = [SO42-] + [HSO4-]
- From (E11-3), (E11-2) and the fact that the analytical concentration of
HCl in the solution is 0.0100 M, we have:
[H3O+] = CHCl + [OH-] - [HSO4-] = 0.0100 + [OH-] - [HSO4-]

4
 Mass balance equation

Q Question
• Write mass balance expressions for a
system formed when a 0.0100 M NH3
solution is in equilibrium with a solid AgBr.

5
 Solution
The pertinent equilibria in the solution:
AgBr(s) Ag+ + Br-
Ag+ + NH3 Ag(NH3)+
Ag(NH3)+ + NH3 Ag(NH3)2+
NH3 + H2O NH4+ + OH-
2H2O H3O+ + OH-
• Find out the relationship between the components in the
solution:
1. Ag+ and Br- come from the dissolution of AgBr
2. Ag+ further react with NH3 to form Ag(NH3)+ and
Ag(NH3)2+
3. The analytical concentration of NH3 is 0.010 M, part of which
is consumed in the reactions to form complex with Ag+, and
dissociation.
6
4. NH3 dissociation is related to water dissociation.
 Solution
From AgBr dissolution and Ag+-NH3 complex formation:
[Br-] = [Ag+] +[Ag(NH3)+] + [Ag(NH3)2+]

From NH3 dissociation and Ag+-NH3 complex formation:

cNH3 = [NH3] + [NH4+] + [Ag(NH3)+] + 2[Ag(NH3)2+]

From NH3 and water dissociation equilibria:

[OH-] = [NH4+] + [H3O+]

7
 Charge balance equation
• In an electrolyte solution, the molar concentration of
positive charge always equals the molar concentration of
negative charge
• Example: Write a charge balance equation for the solution
described in the previous question.
• Equilibria in the solution:
AgBr(s) Ag+(aq) + Br-(aq)
Ag+(aq) + NH3(aq) Ag(NH3)+(aq)
Ag(NH3)+(aq) + NH3(aq) Ag(NH3)2+(aq)
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
2H2O(l) H3O+(aq) + OH-(aq)

• Charge balance equation:

[Ag+] + [Ag(NH)3+] + [Ag(NH3)2+] + [H3O+] + [NH4+] = [OH-] + [Br-]
8
 Systematic steps for solving problems
involving several equilibria
1. Write a set of balanced chemical equations for all pertinent
equilibria.
2. State the quantity being sought in terms of equilibrium
concentrations.
3. Write equilibrium-constant expressions for all equilibria
developed in step 1, and find the constant values in tables of
equilibrium constants.
4. Write mass-balance expressions for the system.
5. Write a charge balance expression for the system.
6. Count the number of UNKNOWN concentrations in the
equations, and compare that with the number of
INDEPENDENT equations.
--- If sufficient number of equations have been developed,9
proceed to step 7.
Systematic steps for solving problems
involving several equilibria
7a. Make suitable approximations to reduce the
number of unknown equilibrium concentrations
and thus, the number of equations needed to
provide an answer, and proceed to step 8; or
7b. Solve the simultaneous equations exactly for
the concentrations required by Step 2 by means
of computer program.
8. Solve manually the simplified algebraic equations
to give provisional concentrations for the species
in the solution.
9. Check the validity of the approximations.

10
 Use approximations to solve
equilibrium calculations
• Approximations can be used to simplify multi-equilibrium
problems and reduce the number of unknown equilibrium
concentration.
• Only mass-balance and charge balance equations can be
simplified.
• Approximations are made when:
1. The contribution of a species from an equilibrium (or
equilibria) is negligible when compared with another or
other sources.
2. The consumption of a species by a specific reaction (or
equilibrium) is negligible compared with other
consumption or contribution sources.
11
 Use approximations to solve
equilibrium calculations

• Make approximation assumptions need information and

knowledge of a specific solution system.
• The approximations could bring error to calculating
results. A process to check the validity of the
assumption should be performed after calculation (step
9).

12
Example of using approximations in
multi-equilibrium calculations
Q: Calculate the solubility of Fe(OH)3 in water.
Step 1: write equations for the pertinent equilibria
Fe(OH)3(s) Fe3+ + 3OH- (E11-4)
2H2O H3O+ + OH- (E11-5)

Step 2: Define the unknown (from E11-4)

Solubility of Fe(OH)3 = [Fe3+]
Step 3: Write all equilibrium-constant expression:
Ksp = [Fe3+][OH-]3 = 2.00 x 10-39 (11-1)
Kw = [H3O+][OH-] = 1.00 x 10-14 (11-2)

13
Example of using approximations in
multi-equilibrium calculations
Step 4&5: write mass balance and charge balance equations
(E11-4 & E11-5):
[OH-] = 3[Fe3+] + [H3O+] (11-3)
Step 6: Number of equations (= 3 (11-1, 11-2 & 11-3)) and
number of unknowns (= 3 ([H3O+], [OH-] & [Fe3+])
Step 7: Make approximation: [H3O+] << 3[Fe3+]
(Why ?, consider E11-4 and E11-5)
3[Fe3+] = [OH-] (11-4)

Fe(OH)3(s) Fe3+ + 3OH- (E11-4)

2H2O H3O+ + OH- (E11-5 14
 Example of using approximations in
multi-equilibrium calculations
Step 8: Solve the equations:
From equations (11-1)&(11-4):
[Fe3+](3[Fe3+])3 = 2.00 x 10-39
solubility = [Fe3+] = 9.27 x 10-11 M
Step 9: Check the validity of the approximation:
We assumed: [H3O+] << [Fe3+]
From calculation result: [OH-] = 3[Fe3+] = 3 x 9.27 x 10-11 = 2.78 x 10-10 M
Then, from Kw expression: [H3O+] = Kw/[OH-] = 1.00 x 10-14/2.78 x 10-10
= 3.60 x 10-5 M >> [Fe3+] = 9 x 10-11 M

Our assumption is invalid

15
 Example of using approximations in
multi-equilibrium calculations
Back to step 7: new assumption: 3[Fe3+] << [H3O+]
Step 8: Solving equations:
From equation (11-3: [OH-] = 3[Fe3+] + [H3O+] )
[H3O+] = [OH-],
From equation (11-2)
Kw = [H3O+][OH-] = [OH-]2 = 1.00 x 10-14
[OH-] = 1.00 x 10-7 M
From equation (11-1)
[Fe3+] = 2.00 x 10-39/(1.00 x 10-7)3 = 2.00 x 10-18 M
Step 9: Re-check assumption:
[Fe3+] = 2 x 10-18 M << [H3O+] = 1.00 x 10-7 M

The answer of the question:

Solubility = [Fe3+] = 2 x 10-18 M 16
 The effect of pH on solubility
Q: calculate the molar solubility of calcium oxalate in a
solution of pH = 4.00

Solution:
Step 1: write pertinent equilibria:
CaC2O4(s) Ca2+ + C2O42- (E11-6)
H2C2O4 + H2O H3O+ + HC2O4- (E11-7)
HC2O4- + H2O H3O+ + C2O42- (E11-8)
2H2O H3O+ + OH- (E11-9)
Step 2: Define unknown (from E11-6):
Solubility = [Ca2+]
(Q: why not: solubility = [C2O42-]
17
 The effect of pH on solubility

Step 3: Write all equilibrium constant expressions:

Ksp = [Ca2+][C2O42-] = 1.7 x 10-9 (11-5)
Ka1 = [H3O+][HC2O4-]/[H2C2O4] = 5.60 x 10-2 (11-6)
Ka2 = [H3O+][C2O42-]/[HC2O4-] = 5.42 x 10-5 (11-7)
Kw = [H3O+][OH-] = 1.00 x 10-14 (11-8)
Step 4: mass balance
[Ca2+] = [C2O42-] + [HC2O4-] + [H2C2O4] = solubility (11-9)

From question statement: solution pH = 4,

[H3O+] = 1.00 x 10-4 M, [OH-] = 1.00 x 10-10 M

18
 The effect of pH on solubility
Step 5: charge balance: Unclear
Step 6: Count the number of independent equations and
unknowns:
number of independent equations = 4
number of unknown = 4
([Ca2+], [C2O42-], [HC2O4-], [H2C2O4]

Step 7: Make approximation: Not necessary

19
 The effect of pH on solubility
Step 8: solve equations:
From Ka2 expression
[HC2O4-] = [H3O+][C2O42-]/Ka2 = 1.00 x 10-4 [C2O42-]/5.42 x 10-5
= 1.85 [C2O42-]
From Ka1 expression:
[H2C2O4] = [H3O+][HC2O4-]/Ka1 = 1.00 x 10-4 x 1.85[C2O42-]/5.60 x 10-2
= 3.30 x 10-3 [C2O42-]
From equation (11-9)
[Ca2+] = [C2O42-] + [HC2O4-] + [H2C2O4] = (1 + 1.85 + 3.30 x 10-3)[C2O42-]
= 2.85[C2O42-]
[C2O42-] = [Ca2+]/2.85
From Ksp expression:
Ksp = [Ca2+][C2O42-] = [Ca2+][Ca2+]/2.85 = 1.7 x 10-9

[Ca2+] = solubility = 7.0 x 10-5 M 20

 The effect of undissociated solutes
on the precipitation calculations
• Take AgCl as an example.
1. The first step of dissolution of this compound in water is:
AgCl(s) AgCl(aq)
Ks = [AgCl(aq)]/[AgCl(s)] = [AgCl(aq)] = 3.6 x 10-7 M
2. This will be followed by a dissociate reaction:
AgCl(aq) Ag+ + Cl-
Kd = [Ag+][Cl-]/[AgCl(aq)]
= [Ag+][Cl-]/Ks
• Therefore, [Ag+][Cl-] = KdKs = Ksp
• The Ksp value is what we will find in “Solubility Product
Constant” Table (Appendix 2) (1.82 x 10-10).
• In this case, the solubility of AgCl in water should equal to
[Ag+] + [AgCl(aq)]
21
 The effect of undissociated solutes
on the precipitation calculations
• For most strong electrolyte insoluable compounds, Ks is
relatively small, and the contribution of undissociated
species to the solubility of the compound in water is
negligble.
• For weak electrolyte compounds, Ks has relatively high
value, and the contribution from Ks has to be
considered in calculating the solubility of the compound
in water.

22
 Separation of metal ions using sulfide
precipitation through controlling solution pH
• Pertinent equilibria related to metal sulfide precipitation in an
aqueous solution
MS M2+ + S2- Ksp = [M2+][S2-]
H2S + H2O H3O+ + HS- Ka1 = [H3O+][HS-]/[H2S] = 9.6 x 10-8
HS- + H2O H3O+ + S2- Ka2 = [H3O+][S2-]/[HS-] = 1.3 x 10-14
• In a H2S gas saturated aqueous solution:
[H2S] = 0.10 M
Ka1Ka2 = [H3O+]2[S2-]/[H2S] = 1.2 x 10-21
[S2-] = 1.2 x 10-21 x 0.10/[H3O+]2 = 1.2 x 10-22/[H3O+]2
Ksp = [M2+][S2-]
Solubility = [M2+] = Ksp[H3O+]2/1.2 x 10-22 (11-10)

23
 Separation of metal ions using sulfide
precipitation through controlling solution pH
Q Example
• Most transition metal ions form sulfide precipitates from aqueous solutions.
The solubility of metal sulfides can be controlled through controlling
solution acidity. This method has been used in the old time to separate
transitional metal ions as sulfides to four groups. The metal ions in each
group are then identifies using spot test methods.
• Based on the Ksp value of the metal sulfides given below, divide the metal
ions (Cd2+, Fe2+, Hg2+, Mn2+, Ni2+, Pb2+) to four groups. If [M2+] < 10-6 M, we
suppose the MS is not dissolved in the solution. Calculate the pH value to
separate the metal ions into three group by using sulfide precipitation.
CdS, Ksp = 1.0 x 10-27
FeS, Ksp = 8 x 10-19
HgS, Ksp = 2 x 10-53
MnS, Ksp = 3 x 10-11
NiS, Ksp = 4 x 10-20
PbS, Ksp = 3 x 10-28
24
 Separation of metal ions using sulfide
precipitation through controlling solution pH

Solution:
• Based on [M2+] = 10-6 M and equation 11-10, the lowest
pH for a metal sulfide be considered not dissolving in a
solution can be calculated with follow equation:

1.22 × 10 −22
× 10 −6

[ H 3O + ] =
Ksp
1 1
pH = 13.95 + log Ksp = 13.95 − pKsp
2 2

25
 Separation of metal ions using sulfide
precipitation through controlling solution pH

Calculated lowest pH value for individual metal ions are

Metal ion pH Control pH <

Mn2+ 8.69 8.0
Fe2+ 4.90
Ni2+ 4.25 4.0
Cd2+ 0.45
Pb2+ 0.18 0 ([H3O+] = 1M
Hg2+ -12.39 What this means?

26
 The solubility of precipitates in the
presence of complexing agents
• The existence of complexing agents in a solution can
significantly change the solubility of some precipitates, if the
metal ions as a component of the precipitate can form a
stable complex with the complexing agent.
Example:
Al(OH)3(s) Al3+ + 3OH-
+
6F-

AlF63-

27
 The solubility of precipitates in the
presence of complexing agents
• Another example:
• When solid AgCl is in equilibrium with an aqueous
solution containing Cl- ions, the formation of Ag-Cl
complex can increase the solubility of the solid AgCl:
AgCl(s) AgCl(aq)
AgCl(aq) Ag+ + Cl-
AgCl(aq) + Cl- AgCl2-
AgCl2-(aq) + Cl- AgCl32-

•The solubility of solid AgCl in such a system is calculated as:

Solubility = [AgCl(aq)] + [Ag+] + [AgCl2-] + [AgCl32-]
28
 The significance of complex formation on
chemical equilibria in aqueous solution
• Complex formation of metal ions with anions and/or
neutral ligands are very popular in aqueous solutions.
• Complex formation of metal ions with amino acids and
other coordinating group in biomolecules plays critical
role in activating many enzymes.
• Complex formation is essential for hemoglobin to carry
oxygen in blood.
• Complex formation are useful in analytical chemistry to:
- analyze metal ions through complexation titration,
- form colored compounds which can be detected with
UV/Vis spectrometry,
- mask interference ions,
- dissolve samples.
29
 Equilibria in immunoassay for the
determination of drugs
• Principle of detection:
-Competition between fluorescence marked drug (D*)
molecules and drug (D) molecules in a sample to bind to
drug specific antibodies (Ab), which is prepared through
biotechnology.
-There is an equilibrium between the D* and D from the
sample binding to the specially prepared Ab.
-if D in the sample is high, there will be less D*
binding on the Ab.
-Through detect D* bound on the Ab, the concentration
of D is detected.

30
 The procedure for drug analysis
using immunoassay
Ab coated plastic vial

D*, D
Sample + D* solution

Laser bean
FL signal

D* D* D* D* D* D*
D D D
D D*, D D D D*
D* D*
D* D* D*
D D* D D D* D D D* D

Ab coated plastic vial

31
 Calibration
Working region
FL intensity

D concentration
32