Chem 329-001

Lecture 12
Monday,
March 6, 2023
Activity &
Complexation
equilibria
Lecture Outline

• Recapitulation of previous lecture

• Why chemical activity matters
• Activity coefficients
• Example calculating using activity coefficients
• Metal-ligand complexation
Recap- Equilibrium when rates are equal

𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
Recap- Forward, reverse, Q, K, ΔG
Recap- Solubility equilibria
𝑀𝑛 𝑋𝑝 (𝑠) ⇌ 𝑛𝑀+𝑝 (𝑎𝑞) + 𝑝𝑋 −𝑛 (𝑎𝑞) 𝐾𝑠𝑝 = [𝑀+𝑝 ]𝑛 [𝑋 −𝑛 ]𝑝

Glucose(s) ⇌ Glucose(aq) 𝐾𝑠𝑝 = [glucose]

Recap- Calculating conc before equilibria
𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) 𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 − = 1.8 × 10−10

Example: What’s the concentration of

Ag+ with 1 µM AgNO3 and 1 µM NaCl

𝑄 = 1 × 10−6 1 × 10−6 = 1 × 10−12 < 𝐾

Then [Ag+]= 1 µM
Recap- Calculating concentration in reverse reaction
𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) 𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 − = 1.8 × 10−10

Example: What’s the concentration of Ag+ after a 50/50 mixture of 200.

µM AgNO3 and 200. µM NaCl are mixed and allowed to reach
equilibrium?
𝑄 = 100.× 10−6 100.× 10−6
= 1.00 × 10−8 > 𝐾

AgCl(s) Ag+ Cl-

I ---- 100. uM 100 uM
C --- -x -x
E --- 100.-x 100.-x
Activity- Why we care

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq) Fe3+ SCN −

K=
red yellow Fe(SCN)2+

Add KNO3 to
beaker on right
KNO3
Activity- Why we care

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq)

red yellow

Why did an inert salt cause

a chemical reaction

Fe3+ SCN −
K≠
Fe(SCN)2+
Activity- Why we care

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq)

red yellow

𝒜(Fe3+) 𝒜(SCN−)
K=
𝒜(Fe(SCN)2+)

3+
𝒜 (Fe3+ ) =𝛾 (Fe3+ ) [Fe ]
Activity Equilibrium
Activity Coefficient Concentration
(Effective Concentration)
Activity- Actual K expression
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
Dimensionless
𝒄 𝒅
𝓐𝑪 𝓐𝑫
𝑲𝒆𝒒 = 𝒂 𝒃
𝓐𝑨 𝓐𝑩
Activity
(also dimensionless)

𝒜𝑋 = 𝛾𝑋 𝑋
Activity
(Effective Concentration) Equilibrium
Concentration
Activity
Coefficient
Activity coefficient- Analogy to Ideal Gas Laws

𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]

𝑃𝑉 = 𝑛𝑅𝑇

van der Waals equation Ideal gas law is a useful

properly accounts for gas approximation that
particles’ size and doesn’t account for these
interactions things
Activity coefficient- Analogy to Ideal Gas Laws

𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]

𝑃𝑉 = 𝑛𝑅𝑇

Just as gas particles actually do interact with one another

Chemicals in solution actually interact with one another

(especially ions)
Activity coefficient- Analogy to Ideal Gas Laws

𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]
Chemicals in solution actually interact with one another
(especially ions)

γ is a measure of the deviation from ideality due to ion

interactions
Activity coefficient- Ion shielding

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq)

red yellow

KNO3
Activity coefficient- Ion shielding

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq)

red yellow
Activity coefficient- Shielding

Fe(SCN)2+(aq) ⇌ Fe3+(aq) + SCN–(aq)

K+ NO3-
K+ K+ NO3-
NO3 -
NO3-
K+ K+ K+ NO3 -
K+ K+ NO3 NO -
- NO3-
3 NO3-
K+ SCN- K+ Fe3+ NO3-
K+ K+ NO3- NO3 -

K+ K+ K+ NO3-
K+ NO3 NO3 - -
NO3 -
NO - NO3
-
K+ K+ 3

• The ionic atmosphere of opposite charge partially screens Fe3+ and SCN– ions from
each other.
• This decreases the attraction between Fe3+ and SCN–, and reduces the tendency to
complex.
Activity coefficient- Controlling factors

𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]

K+
K+
K+
• Ionic strength solution
K+
K+
K+
K+
K+
• Charge of ion
K+ SCN- K+
K+ K+ • Size of ion
K+ K+ K+
K+
K+ K+
Activity coefficient- Ionic Strength, μ

Charge on the ion

1
𝜇 = ෍ 𝑐𝑖 𝑧𝑖 2
2
𝑖
Concentration
1 2 2 2
𝜇 = 𝑐1 𝑧1 + 𝑐2 𝑧2 + 𝑐3 𝑧3 + ⋯
2
Activity coefficient- Davies Equation

Activity Charge on the

Coefficient Ion Ionic Strength (M)


−log  = 0.51z 2
− 0.3
1+ 

Valid at 25C and   0.10 M

This is does not take into account ion size…

Activity coefficient- Extended Debye-Hückel equation

Charge on
Activity the Ion Ionic Strength (M)
Coefficient

−0.51z 2

log  =
1 +  /305
You can find the hydrated ion
Hydrated Ion Size size in a table OR interpolate
(pm) the information:
𝑦 𝑥
Valid at 25C and   0.10 M =
∆𝑦 ∆𝑥
Calculated Activity Coefficients of Na+
1.00

Activity Coefficient,  0.95

Extended Debye-Huckel
Davies
0.90

0.85

0.80

0.75
0.00 0.02 0.04 0.06 0.08 0.10
Ionic Strength,  (M)
Activity Coefficients
• For neutral molecules,  = 1
• For gases at P  1,   1
• The Davies and Extended Debye-Huckel equation are valid for   0.10 M
Activity coefficient of H+ in solutions containing
HClO4 and varying amounts of NaClO4.
• At high ionic strength,
 increases with increasing .
• The “solvent” is no longer H2O, but a
mixture of H2O and the salt.
Activity coefficient- Effect on calculations
𝑃𝑏𝐼2 (𝑠) ⇌ 𝑃𝑏 2+ (𝑎𝑞) + 2𝐼 − (𝑎𝑞) 𝐾𝑠𝑝 = 𝛾𝑃𝑏2+ [𝑃𝑏 2+ ](𝛾𝐼− )2 [𝐼− ]2

What is the solubility of PbI2 in 1 mM KNO3?

PbI2(s) Pb2+ I-
I ---- 0 0
C --- X +2x
E --- x 2x
Activity coefficient- Effect on calculations
𝑃𝑏𝐼2 (𝑠) ⇌ 𝑃𝑏 2+ (𝑎𝑞) + 2𝐼 − (𝑎𝑞) 𝐾𝑠𝑝 = 𝛾𝑃𝑏2+ [𝑃𝑏 2+ ](𝛾𝐼− )2 [𝐼− ]2

What is the solubility of PbI2 in 1 mM KNO3?

New Procedure:
• Estimate ionic strength
• Calculate activity coeffs (Davies/Debye-Huckel equation)
• Calculate concentrations (ICE table and Ksp)
• Repeat until you have enough sig figs
Activity and Activity Coefficients

• Unless I tell you to “account for ionic strengths

effects” or “use activity”

• You do not need to calculate activity coefficients in

answering questions.
Lecture Outline

• Recapitulation of previous lecture

• Why chemical activity matters
• Activity coefficients
• Example calculating using activity coefficients
• Metal-ligand complexation
Metal complexation
Metal complexation- Reactions

Metals can have

multiple empty d
orbitals, so
they can bind to
many ligands
(or to the same
ligand multiple
times)
Metal complexation- Interlocking equilibria

Ions of solubility
and
complexation
… are same ions.
Therefore, these
are interlocking
equilibria
Metal complexation- Interlocking equilibria
Metal complexation- Interlocking equilibria

All of the
reactions are
happening.
…
All of the K
expressions are
true
Metal complexation- Regimes
• What chemistry
(complexation or
precipitate) or
• chemical reaction (which
complexation)
• dominates depends on
how much of each ion is in
solution and
• on the K or β expressions
Preview

We account for this complex reality using systematic

treatment of equilibria, which we will discuss after an intro
to acid/base chemistry
Questions