Chem 329-001

Equilibrium Problem
Lecture 14
Use for Use for
Wednesday,
• Higher Concentrations • Interlocking Equilibria
• One Equilibrium • (concs too low to make assumptions)
March 22, 2023
Makes Assumptions No Assumptions Systematic
SCF/ICE Tables
Systematic
Treatment of
Equilibria
treatment of
equilibria
Lecture Outline

• Recap systematic treatment from Monday

• Explanation of “Systematic Treatment” (expand on Monday)
• Charge Balance expression (expand on Monday)
• Mass Balance expression(s)
“Systematic Treatment”- from Monday

Motivating Examples:

[HCl] = 1.0 × 10−8 M HCl. pH=?

(Hint: adding acid doesn’t bring the pH up to the basic pH of 8)

[CO2](aq) >> [O2](aq) Why…?

We can’t answer these questions looking at only one chemical reaction at a

time
“Systematic Treatment”- from Monday
Equilibrium Problem
Use for
• Higher Concentrations
• One Equilibrium
𝐶𝑂2 (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞)
𝐻2 𝐶𝑂3 (𝑎𝑞) ⇌ 𝐻 + + 𝐻𝐶𝑂3−
𝐻𝐶𝑂3− 𝐻2 𝐶𝑂3 (𝑎𝑞) ⇌ 𝐻+ + 𝐶𝑂32−
Because of these
Use for
𝐶𝑂2 (𝑔) 𝐶𝑂2 (𝑎𝑞)
• Interlocking Equilibria
• Concs too low to make
assumptions
+ −
𝐻𝐶𝑙(𝑎𝑞) → 𝐻(𝑎𝑞) + 𝐶𝑙(𝑎𝑞)

S 1E-8 0 0
Makes Assumptions No Assumptions
C -1E-8 +1E-8 +1E-8
Systematic F 0 1E-8 1E-8
SCF/ICE Tables Treatment of
Equilibria
pH ≠ 8.0

Because
[𝐻+ ]𝑓𝑟𝑜𝑚 𝐻𝐶𝑙 ≫ [𝐻 + ]𝑓𝑟𝑜𝑚 𝑤𝑎𝑡𝑒𝑟
Charge Balance- from Monday
“Systematic Treatment”

1) Write out the pertinent chemical reactions.

2) Write the charge balance equation.
3) Write the mass balance equation(s).
4) Write out the equilibrium constant expression.
5) Verify that you have at least as many equations as
unknowns.
6) Solve.
Charge Balance- Writing a CB
Identify all charged species in all
reactions

𝐶𝑎(𝑁𝑂3 )2(𝑠) → 𝐶𝑎2+ + 2𝑁𝑂3−

𝐻2 𝑂 + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝑂𝐻 −

2 𝐶𝑎2+ + 1[𝐻 + ] = 1 𝑁𝑂3− + 1[𝑂𝐻 − ]

Charge Balance- Writing a CB

𝟐 𝐶𝑎2+ + 𝟏[𝐻 + ] = 𝟏 𝑁𝑂3− + 𝟏[𝑂𝐻 − ]

These coefficients are because of the

charge. (They have nothing to do with
mole ratios.)
Charge Balance- Writing a CB

2 𝐶𝑎2+ + 1[𝐻 + ] = 1 𝑁𝑂3− + 1[𝑂𝐻 − ]

These coefficients are because of the

charge. (They have nothing to do with
mole ratios.)

All charged species are included. Only

charged species are included.
Charge Balance- Important aspects of CB

The charge balance is a property of the solution (not any individual reaction
or component)

Only 1 soln ⇒ only 1 CB equation

Mass Balance

My advice:
• Use the chemical reactions to identify all
the versions of a
molecule/ion/functional group
• Try to represent known absolute
concentrations if you can
• Try to represent relative concentrations
if you can
• Make as many of these equations as
you can
Mass Balance- Example with known concentration

Srinavasa dissolved 6.4538 g NaH2PO4 in 1.00 L of water.

6.4538 𝑔 𝑁𝑎𝐻2 𝑃𝑂4 1 𝑚𝑜𝑙𝑒 𝑁𝑎𝐻2 𝑃𝑂4

𝐹= × = 0.0538 𝑀
1.00 𝐿 119.98 𝑔𝑁𝑎𝐻2 𝑃𝑂4
− 2− 3−
= 𝐻3 𝑃𝑂4 + 𝐻2 𝑃𝑂4 + 𝐻𝑃𝑂4 + 𝑃𝑂4

Also
[Na+]=0.0538 M
Mass Balance- Example with indeterminate concs
Lavenia let solid mercury(I) azide dissolve to equilibrium in water.

1)Write out the pertinent rxns (even I can’t skip this step and figure this one out)
Based on this
reaction, we know 𝐻𝑔2 (𝑁3 )2 ⇌ 𝐻𝑔22+ + 2𝑁3− 𝑝𝐾𝑠𝑝 = 9.15
that the + −
concentration of azide 𝐻𝑁3 ⇌ 𝐻 + 𝑁3 𝑝𝐾𝑎 = 4.65
will be twice as high
as the concentration
of the mercury(I) 2[𝐻𝑔22+ ] = 𝑐𝑜𝑛𝑐 𝑎𝑙𝑙 𝑎𝑧𝑖𝑑𝑒𝑠
dimers
Mass Balance- Example with indeterminate concs
Lavenia let solid mercury(I) azide dissolve to equilibrium in water.

1)Write out the pertinent rxns (even I can’t skip this step and figure this one out)

𝐻𝑔2 (𝑁3 )2 ⇌ 𝐻𝑔22+ + 2𝑁3− 𝑝𝐾𝑠𝑝 = 9.15

+ −
𝐻𝑁3 ⇌ 𝐻 + 𝑁3 𝑝𝐾𝑎 = 4.65

Based on this 2[𝐻𝑔22+ ] = 𝑁3− + [𝐻𝑁3 ]

reaction, we know
that we have to
account for multiple
versions of azide
Mass Balance- Example with indeterminate concs
Lavenia let solid mercury(I) azide dissolve to equilibrium in water.

1)Write out the pertinent rxns (even I can’t skip this step and figure this one out)

2+ −
𝐻𝑔2 (𝑁3 )2 ⇌ 𝐻𝑔2 + 2𝑁3 𝑝𝐾𝑠𝑝 = 9.15
𝐻𝑁3 ⇌ 𝐻+ + 𝑁3− 𝑝𝐾𝑎 = 4.65

2+ −
MB: 2[𝐻𝑔2 ] = 𝑁3 + [𝐻𝑁3 ]
Mass Balance- Example with indeterminate concs
Lavenia let solid mercury(I) azide dissolve to equilibrium in water.

1)Write out the pertinent rxns (even I can’t skip this step and figure this one out)

2+ −
𝐻𝑔2 (𝑁3 )2 ⇌ 𝐻𝑔2 + 2𝑁3 𝑝𝐾𝑠𝑝 = 9.15
𝐻𝑁3 ⇌ 𝐻+ + 𝑁3− 𝑝𝐾𝑎 = 4.65
2[𝐻𝑔22+ ] = 𝑁3− + [𝐻𝑁3 ]

If we wanted to account for mercury atoms individually, we would need to double this term
again
Example question- work in groups
What is the concentration of AgCl2- when 0.1699 g AgNO3 is dissolved in 100. mL of 0.100
M HCl?
Set up the series of equations but do not solve this system.
Account for activity in this analysis

For silver and chloride ions

• 𝐾𝑠𝑝 = 1.8 × 10−10
• 𝐾1 = 2.0 × 106
• 𝐾2 = 1.3 × 104
• 𝐾3 = 1.4 × 10−4
(Assume precipitation of AgOH is negligible)

Hint: there should be 2 reactions that go to completion, 5 chemical reactions at

equilibrium, 7 equations, and 7 unknowns
Example question- work in groups

What is the pH of a solution of 1.0x10-8 M HBr?

What percentage of the concentration of hydronium ion

comes from the autoprotolysis of water?

Account for activities when solving this problem.