Chem 329-001

Lecture 11
Wednesday,
March 1, 2023
Equilibria within
Analytical Chemistry
Lecture Outline

• Review of equilibria from General Chemistry

• Equilibria in analytical chemistry
• Solubility
Gen Chem review- Equilibrium ≡ rxn rates are equal
Review of Gen Chem- source of K expression
Review of Gen Chem- K expression is dimensionless

𝒄
𝑪 𝑫𝒅
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫 𝑲𝒆𝒒 =
𝑨 𝒂 𝑩𝒃

1. Concentration of solutes expressed as mol/L

2. Concentration of gases expressed in bars
3. Concentration of pure solids, pure liquids, and solvents omitted
because they are unity
Review of Gen Chem- Change rxn, change K
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
𝒄 𝒅
𝑪 𝑫
𝑲𝒆𝒒 = 𝒂 𝒃
𝑨 𝑩
Ex: Flipped Others
𝒄𝑪 + 𝒅𝑫 ⇋ 𝒂𝑨 + 𝒃𝑩 Multiplying the reaction by a constant puts the K
𝒂 to that power
𝟏 𝑨 𝑩𝒃
𝑲𝒆𝒒 = = 𝒄 The Keq of 2 reactions added together is the
𝑲𝒆𝒒 𝑪 𝑫𝒅 product of those reactions

Take the inverse of K

Review of Gen Chem- K and Reaction quotient (Q)
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
𝒄 𝒅
𝑪 𝑫
𝑸= 𝒂 𝒃
𝑨 𝑩
Current, actual concentrations

If Q < K Not at equilibrium

Reactants are converted to products until equilibrium is reached.

If Q = K At equilibrium
If Q > K Not at equilibrium
Products are converted to reactants until equilibrium is reached.
Review of Gen Chem- ΔG and spontaneous rxn

DG: The difference in Gibb’s free

energy between products and
reactants under standard state
conditions (1 M, 1 bar, pure
liquid, pure solid).
ΔG < 0
Q<K DG: Slope at any point on the
ΔG = 0 ΔG > 0 line that connects reactants and
Q=K Q>K products.
At equilibrium
−∆𝑮𝟎ൗ
𝑲= 𝒆 𝑹𝑻
Review of Gen Chem- Le Chatelier’s Principle

𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫

𝒄
𝑪 𝑫𝒅
𝑲𝒆𝒒 = 𝒂
𝑨 𝑩𝒃
Review of Gen Chem- ICE tables

If this ICE table blows your mind

then you need to review your gen
chem materials
Equilibria in Analytical chemistry- Why

𝑎𝐴(𝑠) + 𝑏𝐵(𝑎𝑞) + 𝑐𝐶(𝑔) ⇌ 𝑑𝐷(𝑙) + e𝐸(𝑔) + 𝑓𝐹(𝑎𝑞)

𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝐾𝑒𝑞 =
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Equilibrium expressions are the algebra by which
KC KP we represent many chemistries

E.g. Solution phase and gas phase (or both)

E.g. Ksp- solubility

Ksp Ka ≈ Kb Kisomerism Kf- ion complexation
Ka/Kb- acid/base chemistry
Kiso- organic isomerism (though that’s really more organic
Kf Kredox chemistry)
Kredox- loss/gain of electrons
Equilibria in Analytical chemistry- Conventions
Equilibria in Analytical chemistry- Conventions

Equilibrium reactions can be shown in many ways

Frequently, only one reaction and K expression will match the

K values you have from tables

E.g. You must use

− 𝐶𝐻3 𝐶𝑂2 − [𝐻 + ]
𝐶𝐻3 𝐶𝑂2 𝐻 ⇌ 𝐶𝐻3 𝐶𝑂2 + 𝐻+ 𝐾𝑎 = [𝐶𝐻3 𝐶𝑂2 𝐻]

Or you have to calculate K somehow

Equilibria in Analytical chemistry- Activity not conc

+
• p𝐻 ≠ −log 𝐻

• That’s not what the

probe actually
measures
Equilibria in Analytical chemistry- [X], [Y], … = ?

The generic question in

equilibria is going to be: Ksp Ka ≈ Kb
Kf Kredox
What is the concentration of
analyte X?
• Each of the types of
equilibrium can produce a
different “X” and
• a different set of conditions
Solubility equilibria- Definition

𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞)

𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

Examples
PbI2, n=1, p=2
Ag2SO4, n=2, p=1
Fe(NO3)3, n=1, p=3
Hg2Cl2 *n=1, p=1
Solubility equilibria- Regimes

𝑃𝑏𝐼2 (𝑠) ⇌ 𝑃𝑏 2+ (𝑎𝑞) + 2𝐼 − (𝑎𝑞)

𝐾𝑠𝑝 = [𝑃𝑏 2+ ][𝐼− ]2

Is adding NaI to induce

precipitation the forward or
reverse reaction?

Why does that matter?

Solubility equilibria- Regimes
𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞) 𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

Q<K Q=K Q>K

Solubility equilibria- low concentration
𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞) 𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

Q<K
Favors forward reaction
If more material is added it will dissolve

𝑎𝑚𝑜𝑢𝑛𝑡 𝑎𝑑𝑑𝑒𝑑
Calculate concentration as
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
Solubility equilibria- low concentration
𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞) 𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

K=Q
Favors neither reaction direction
If more material is added it will settle
(and join dynamic equilibrium)

Calculate concentration using an ICE

table
Solubility equilibria- low concentration
𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞) 𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

Q>K
Favors reverse reaction
Material will precipitate out. Additional
material will induce crystalization

Calculate concentration using an ICE table

(with “product” as starting material)
Questions