CHEM 251

Analy.cal Chemistry for Biologists

Chapter 11
Solving Equilibrium Problems for
Complex Systems
 Solving Multiple-Equilibrium
Problems
• Write independent equations as there are chemical
species in the system being studied.
• Solubility of BaSO4 in acidic medium;

BaSO4(s) ↔ Ba2+ + SO42- (1)

SO42- + H3O+ ↔ HSO4- +H2O (2)
2H2O ↔ H3O+ + OH- (3)
• If hydronium ions are added; second eq will shift to
right, which will decrease the sulfate conc and make the
first reaction to the right as well. So, the solubility of
BaSO4 would increase.
 Solving Multiple-Equilibrium
Problems
If acetate ions are added to the barium sulfate solu>on;

BaSO4(s) ↔ Ba2+ + SO42-

Ba2+ + OAc- ↔ BaOAc+
The solubility of barium sulfate would increase since
acetate form a soluble complex with barium ions.
 Solving Multiple-Equilibrium
Problems
• Solubility of BaSO4 in acidic medium;
BaSO4(s) ↔ Ba2+ + SO42- (1)
SO42- + H3O+ ↔ HSO4- +H2O (2)
2H2O ↔ H3O+ + OH- (3)
• Equilibrium-constant expression
• Mass-balance equation
• Charge-balance equation
 Mass-Balance Equa9ons
Mass-balance equations: The expression that relate
the equilibrium concentrations of various species in a
solution to one another and to the analytical
concentrations of the various solutes.

These equations are a direct result of the

conservation of mass and moles.
 Mass-Balance Equations
A weak acid HA dissolved in water for example:
HA+ H2O Û H3O+ + A- (1)
2H2O Û H3O+ + OH- (2)

mass equation 1: cHA = [HA] + [A-]

cHA is analytical concentration, [HA] and [A-] are
equilibrium concentration.

mass equation 2: [H3O+] = [A-] + [OH-]

since [H3O+] = [H3O+]from HA + [H3O+]from H2O ,
where [H3O+]from HA = [A-] , [H3O+]from H2O = [OH-]
 Mass-Balance Equations
[H3O+] = [A-] + [OH-]
• This type of mass-balance expression is oOen
referred to as the proton balance equa:on .
 Charge-Balance Equation
Charge-Balance Equation: An expression relating the
concentrations of anions and cations based on
charge neutrality in any solution.
Charge balance equation:

n1[C1+n1] + n2[C2+n2] + ..... = m1[A1-m1] + m2[A2-m2] + .....

no. moles/L posi>ve charges = no. moles/L nega>ve charge

 Charge-Balance Equation
Example: A solution contains H+, OH–, K+, H2PO4–,
HPO42–，, and PO43–，what is the charge balance
equation?

Solution:
[H+] + [K+] = [H2PO4–] + 2[HPO42–] + 3[PO43–] + [OH–]
Solubility of Metal Hydroxides
The Effect of pH on Solubility
The Effect of Undissociated Solutes
on Precipita.on Calcula.ons
Separation of Ions By Control of the
Concentration of the Precipitating Agent
• Several precipitating agents permit separation of ions
based on solubility differences. Such separations
require close control of the active reagent
concentration at a suitable and predetermined level.
• Most often, such control is achieved by controlling the
pH of the solution with suitable buffers.
• This technique is applicable to anionic reagents in
which the anion is the conjugate base of a weak acid.
• Examples include sulfide ion (the conjugate base of
hydrogen sulfide), hydroxide ion (the conjugate base of
water), and the anions of several organic weak acids.