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Chem 329 - Spring 2023 - Dorris - Lecture 12 - Activity and Complexation - For Students
Chem 329 - Spring 2023 - Dorris - Lecture 12 - Activity and Complexation - For Students
Lecture 12
Monday,
March 6, 2023
Activity &
Complexation
equilibria
Lecture Outline
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
Then [Ag+]= 1 µM
Recap- Calculating concentration in reverse reaction
𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) 𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 − = 1.8 × 10−10
Add KNO3 to
beaker on right
KNO3
Activity- Why we care
Fe3+ SCN −
K≠
Fe(SCN)2+
Activity- Why we care
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
𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]
𝑃𝑉 = 𝑛𝑅𝑇
𝒜𝑋 = 𝛾𝑋 𝑋 ≈ [𝑋]
Chemicals in solution actually interact with one another
(especially ions)
KNO3
Activity coefficient- Ion shielding
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
−log = 0.51z 2
− 0.3
1+
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 25C and 0.10 M =
∆𝑦 ∆𝑥
Calculated Activity Coefficients of Na+
1.00
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
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
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
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