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Solving Equilibrium

Problems for
Complex Systems

Solving Multiple-Equilibrium
Problems Using a Systematic Method
Mass-Balance Equations
Mass-balance equations relate the equilibrium concentrations of various
species in a solution to one another and to the analytical concentrations of
the various solutes.

This type of mass-balance expression is often referred to as the proton

balance equation because it accounts for all sources of protons.

Write mass-balance expressions for a 0.0100 M solution of HCl that is in
equilibrium with an excess of solid BaSO4.

Write mass-balance expressions for the system formed when a 0.010 M NH3
solution is saturated with the slightly soluble AgBr.

Charge-Balance Equation
no. moles/L positive charge = no. moles/L negative charge
This equation represents the charge-balance condition and is called the
charge-balance equation.
- Na+

- Mg2+

- PO43-

- 0.1 M NaCl

- 0.1 M MgCl2

For a neutral solution, can usually simplify the charge-balance equation by

neglecting [H3O+] and [OH-]
Homework: write the charge-balance equation for the previous two examples.
Steps for Solving Problems with Several Equilibria (check scheme
illustration in the book!)
Step 1. Write a set of balanced chemical equations for all pertinent equilibria.
Step 2. State the quantity being sought in terms of equilibrium concentrations.

Step 3. Write equilibrium-constant expressions for all equilibria developed in

Step 1, and find numerical values for the constants in tables of equilibrium
Step 4. Write mass-balance expressions for the system.
Step 5. If possible, write a charge-balance expression for the system.
Step 6. Count the number of unknown concentrations in the equations
developed in Steps 3, 4, and 5, and compare this number with the number of
independent equations. Step 6 is critical because it shows whether an exact
solution to the problem is possible. If the number of unknowns is identical to
the number of equations, the problem has been reduced to one of algebra
alone. In other words, answers can be obtained with sufficient perseverance.
On the other hand, if there are not enough equations even after
approximations are made, the problem should be abandoned. If a sufficient
number of equations have been developed, proceed to either Step 7.
Step 7. Make suitable approximations to reduce the number of unknown
equilibrium concentrations and thus the number of equations needed to
provide an answer, as defined in Step 2. Proceed to Steps 8 and 9.
Step 8. Solve manually the simplified algebraic equations to give provisional
concentrations for the species in the solution.
Step 9. Check the validity of the approximations.

Calculating Solubilities by the

Systematic Method
The Solubility of Metal Hydroxides
Calculate the molar solubility of Mg(OH)2 in water.
Step 1. Write Equations for the Pertinent Equilibria

Step 2. Define the Unknown

Step 3. Write All Equilibrium-Constant Expressions

Step 4. Write Mass-Balance Expressions

Step 5. Write the Charge-Balance Expression

Step 6. Count the Number of Independent Equations and Unknowns

Three independent equations.
Step 7. Make Approximations

Step 8. Solve the Equations

Step 9. Check the Assumptions

Calculate the molar solubility of Fe(OH)3 in water.


Step 7. Make Approximations

Check the Assumption

The Effect of pH on Solubility
Calculate the molar solubility of calcium oxalate in a solution that has
been buffered so that its pH is constant and equal to 4.00.
Step 1.


Step 2.
Step 3.

Step 4.

Since the problem states that the pH is 4.00


Step 5. Not possible as we do not know the nature of the buffer.

Step 6.

4 unknowns + 4 equations (check!)

Step 7. No need! We have enough equation!

Step 8. You should arrive in the mass balance to

Substitution in Ksp gives

The Effect of Undissociated Solutes on Precipitation Calculations

Read at home

The Solubility of Precipitates in the Presence of Complexing Agents

The solubility of a precipitate may increase dramatically in the presence of
reagents that form complexes with the anion or the cation of the

Practice problem
calculate the molar solubility of:
1. Calculate the molar solubility of Calcium oxalate in buffer
2. Calculate the molar solubility of Silver Bromide in Ammonia
3. Calculate the molar solubility of BaCO3 in water
4. Calculate the molar solubility of Calcium oxalate in water.
5. Calculate the molar solubility of lead carbonate in a solution
whose analytical concentrations are 0.05 M of benzoic acid and
0.08 M of sodium benzoate


Separation of Ions By Control of the

Concentration of the Precipitating
Calculation of the Feasibility of Separations
Can Fe3+ and Mg2+ be separated quantitatively as hydroxides from a solution
that is 0.10 M in each cation? If the separation is possible, what range of OHconcentrations is permissible?


(1) calculating the OH- concentration required to achieve quantitative

precipitation of Fe3+
(2) computing the OH- concentration at which Mg(OH)2 just begins to
- In this example, we consider a precipitation to be quantitative when all but 1
part in 1000 of the ion has been removed from the solution, that
is, when [Fe3+] < 1 x 10-4 M.

- Note that quantitative precipitation of Fe(OH)3 is achieved in a distinctly

acidic medium (pH = 2.5).
- Lets check for Mg2+

- Therefore, it is possible, in principle, to separate Fe3+ from Mg2+ by

maintaining the OH- concentration between these levels.