508

Lecture #15 of 26
 509

Time-Dependence in
Electrochemistry
Chapters 4 and 5
 510

Q: What’s in this set of lectures?

A: B&F Chapters 4 & 5 main concepts:

● Section 4.4.2: Fick’s Second Law of Diffusion

● Section 5.1: Overview of step experiments

● Section 5.2: Potential step under diffusion controlled

● Sections 5.3 & 5.9:Ultramicroelectrodes

● Sections 5.7 – 5.8: Chronoamperometry/Chronocoulometry

 511

Looking forward… Section 4.4.2 and Chapter 5

● Fick’s Second Law of Diffusion
● Linear Diffusion = time-dependent current (Cottrell Equation)
● Anson Plots for surface adsorbed species
● Radial Diffusion = time-independent current (at steady-state)
● Ultramicroelectrodes (UMEs)
● Scanning Electrochemical Microscopy (SECM)
● Single molecule electrochemistry
Bard and scanning electrochemical microscopy (SECM)… 512

http://electrochem.cwru.edu/ed/encycl/art-m04-microscopy.htm
 513

http://electrochem.cwru.edu/ed/encycl/art-m04-microscopy.htm
 514

http://electrochem.cwru.edu/ed/encycl/art-m04-microscopy.htm
 515

Fan & Bard, Science, 1995, 267, 871

 the magic of “thin layer electrochemistry”... 516

𝐶𝑂∗ − 𝐶𝑂 𝑥 = 0
𝐽𝑖 𝑥 = −𝐷𝑖
C(x)/C* 𝜕𝑂
… Recalling Section 1.4.2 (Semi-Empirical)
1

surface
tip

0
distance
1
surface
tip

0
distance
 517
A feasibility assessment… 1 molecule is trapped within a 1
µm x 1 µm x 10 nm volume between an SECM tip and a
surface. What’s the value of the limiting current?
?

surface
tip
0 distance
δ0
Δ𝐶
𝑖 = −𝑛𝐹𝐴𝐷 m
𝛿

1 mol 1
𝐶1 molecule = 1 molecule
6.022 x 1023 molecules 10 x 10−7 cm 1 x 10−4 cm 2

𝐶1 molecule = 1.66 x 10−10 mol/cm3

 518
A feasibility assessment… 1 molecule is trapped within a 1
µm x 1 µm x 10 nm volume between an SECM tip and a
surface. What’s the value of the limiting current?
?

surface
tip
0 distance
δ0
Δ𝐶
𝑖 = −𝑛𝐹𝐴𝐷 m
𝛿

2 1.66 x 10−10 mol/cm3

𝑖 = 1 eq/mol 96485 C/eq 1 x 10−4 cm 1 x 10−5 cm2 /s
10 x 10−7 cm
= 1.6 x 10−12 A = 1.6 pA

… so we’re talking about pA's. We can measure that!

 519

Fan & Bard, Science, 1995, 267, 871

Reviewed in Bard & Fan, Acc. Chem. Res., 1996, 29, 572
 520

Q: What was in this set of lectures?

A: B&F Chapters 4 & 5 main concepts:

● Section 4.4.2: Fick’s Second Law of Diffusion

● Section 5.1: Overview of step experiments

● Section 5.2: Potential step under diffusion controlled

● Sections 5.3 & 5.9:Ultramicroelectrodes

● Sections 5.7 – 5.8: Chronoamperometry/Chronocoulometry

 521

A detailed review of Section 4.4.2 and Chapter 5

● Fick’s Second Law of Diffusion
● Linear Diffusion = time-dependent current (Cottrell Equation)
● Anson Plots for surface adsorbed species
● Radial Diffusion = time-independent current (at steady-state)
● Ultramicroelectrodes (UMEs)
● Scanning Electrochemical Microscopy (SECM)
● Single molecule electrochemistry
 522

Liquid-Junction Potentials
Chapter 2
 523

Q: What’s in this set of lectures?

A: B&F Chapter 2 main concepts:

● “Section 2.1”: Salt; Activity; Underpotential deposition

● Section 2.3: Transference numbers; Liquid-junction

potentials

● Sections 2.2 & 2.4: Donnan potential; Membrane potentials;

pH meter; Ion-selective electrodes
Refresher… the equilibrium potential and the Nernst Equation 524

O + ne– ⇌ R

0
𝑅𝑇 𝑎𝑅 activity of R
𝐸=𝐸 − ln
𝑛𝐹 𝑎𝑂 activity of O

the standard potential

(look it up in the back of your book or in the CRC table)

… the activity is the product of the activity coefficient and the concentration…

𝑅𝑇 γ𝑅 𝐶𝑅
𝐸= 𝐸0 − ln
𝑛𝐹 γ𝑂 𝐶𝑂
𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
Refresher… the equilibrium potential and the Nernst Equation 525

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
E0'

0′
𝑅𝑇 𝐶𝑅
𝐸=𝐸 − ln
𝑛𝐹 𝐶𝑂

the formal potential… this depends on the identity and

concentration of all ionizable species present in solution
However, equilibrium “constants”… are not constants… 526

BaSO4

CH3COOH

H2O

Fig. 10-1, p. 268 in Skoog & West

… let’s focus on the solubility of BaSO4… 527

BaSO4(s) ⇌ SO42-(aq) + Ba2+(aq)

A (activity) = 1.0 for any pure solid compound

in its standard state at room temperature
… let’s focus on the solubility of BaSO4… 528

BaSO4(s) ⇌ SO42-(aq) + Ba2+(aq)

the activity coefficient

for SO42-
the concentration
of SO42-
… let’s focus on the solubility of BaSO4… 529

BaSO4(s) ⇌ SO42-(aq) + Ba2+(aq)

the thermodynamic equilibrium constant

the concentration equilibrium constant

… the greater the charge on an ion, the greater the depression of its 530
activity coefficient by an inert salt…

(~10 mM) ~100 mM

𝐼

Ionic strength, I = 0.5(zA2[A] + zB2[B] + zC2[C] + …)

… so, for NaCl, what is I? [NaCl]! Fig. 10-3, p. 272 in Skoog & West
… the greater the charge on an ion, the greater the depression of its 531
activity coefficient by an inert salt… but at high concentration, this trend flips!

Bockris & Reddy, Fig. 2.18

… let’s focus on the solubility of BaSO4… 532

BaSO4(s) ⇌ SO42-(aq) + Ba2+(aq)

… but what are these values? That is, how do we calculate them…
… and why do they depend on the concentration of salt?
… in all three of these cases, K' > K, at not too large of an ionic strength 533

less ionic more ionic

BaSO4(s) ⇌ SO42-(aq) + Ba2+(aq)

2H2O ⇌ H3O+ + OH–

CH3COOH + H2O ⇌ H3O+ + CH3COO–

general observation: K' always shifts (from K) to favor

the most ionic state of the equilibrium
Refresher… the equilibrium potential and the Nernst Equation 534

0′
𝑅𝑇 𝐶𝑅
𝐸=𝐸 − ln
𝑛𝐹 𝐶𝑂
Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

Refresher… the equilibrium potential and the Nernst Equation 535

0′
𝑅𝑇 𝐶𝑅
𝐸=𝐸 − ln
𝑛𝐹 𝐶𝑂
Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
Refresher… the equilibrium potential and the Nernst Equation 536

0′
𝑅𝑇 𝐶𝑅
𝐸=𝐸 − ln
𝑛𝐹 𝐶𝑂
Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
… now, γFe3+ < γFe2+, agreed?…
 537
Debye–Hückel equation 0.51𝑧𝑥2 𝐼
(in water at 25 °C) − log γ𝑥 =
1 + 3.3α𝑥 𝐼
α = effective diameter of hydrated ion (nm)

Table 10-2, p. 274 in Skoog & West

 538
Debye–Hückel equation 0.51𝑧𝑥2 𝐼
(in water at 25 °C) − log γ𝑥 =
1 + 3.3α𝑥 𝐼
α = effective diameter of hydrated ion (nm)
… the derivation is long… but the main idea is that you balance
thermal motion (Boltzmann) with electrostatics (Poisson/Gauss)…
Physicist & P-Chemist Physicist & P-Chemist

Peter Joseph William Debye Erich Armand Arthur Joseph Hückel

(1884–1966) (1896–1980)
from Wiki
 539
Debye–Hückel equation 0.51𝑧𝑥2 𝐼
(in water at 25 °C) − log γ𝑥 =
1 + 3.3α𝑥 𝐼
α = effective diameter of hydrated ion (nm)
… the “limiting law” is when I → 0 (< 10 mM)…
… and then the Debye–Hückel
equation simplifies to just the
numerator:

− log γ𝑥 = 0.51𝑧𝑥2 𝐼

Bockris & Reddy, Fig. 3.23

Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+540
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
… now, γFe3+ < γFe2+, agreed?… So…

γ𝑅 γ𝑅
> 1.0 and ln >0
γ𝑂 γ𝑂

… and we conclude that in the presence of added salt… you tell me!
Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+541
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
no added salt…

γ𝑂 ≈ γ𝑅 ≈ 1.0
γ𝑅
ln ≈0
γ𝑂
Question: How, qualitatively, is the equilibrium potential for Fe2+/Fe3+542
affected by the addition of a supporting electrolyte, KF, at a
concentration of 0.1 M?

Fe3+ + 1e– ⇌ Fe2+

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
no added salt… with added salt…

γ𝑂 ≈ γ𝑅 ≈ 1.0
γ𝑅
ln ≈0
γ𝑂 γ𝑅 γ𝑅
> 1.0 and ln >0
γ𝑂 γ𝑂
ANSWER: E0' shifts to more negative potentials
Question: What if the redox species were positive/neutral charged, 543
like Tl+/0, and we increased the concentration of supporting electrolyte
to ~0.1 M?
Tl+ + 1e– ⇌ Tl0
𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
cathodic reaction
Im-Tl+, to bring Tl+
to the electrode with added salt…
increasing
supporting
Id-Tl+, to bring Tl+
electrolyte to the electrode

𝜸𝑹 𝜸𝑹
> 𝟏. 𝟎 and 𝒍𝒏 >𝟎
𝜸𝑶 𝜸𝑶

ANSWER: E0' shifts to more negative potentials

Question: What if the redox species were negatively charged, like 544
[FeIII(CN)6]3–/[FeII(CN)6]4–, and we increased the concentration of
supporting electrolyte to ~0.1 M? (FROM e-LAB!)

[FeIII]3– + 1e– ⇌ [FeII]4–

𝑅𝑇 γ𝑅 𝑅𝑇 𝐶𝑅
0
𝐸=𝐸 − ln − ln
𝑛𝐹 γ𝑂 𝑛𝐹 𝐶𝑂
with added salt…
Fe(CN)63-/Fe(CN)64-

No added salt
(note ipc and iR)

𝜸𝑹 𝜸𝑹
< 𝟏. 𝟎 and 𝒍𝒏 <𝟎
𝜸𝑶 𝜸𝑶

ANSWER: E0' shifts to more positive potentials

… practical “activity”… even of solids! Underpotential deposition (UPD) 545

Eeq … aCo(s) < 1… because the activity

of a solid is proportional to its
surface coverage!

Co0 ⇌ Co2+ + 2e– B&F, pg. 420

… but what are these

small cathodic current "bumps"
Co2+ + 2e– ⇌ Co0 that occur at Eapp > Eeq?
… practical “activity”… even of solids! Underpotential deposition (UPD) 546

Eeq … aCo(s) < 1… because the activity

of a solid is proportional to its
surface coverage!

Co0 ⇌ Co2+ + 2e– B&F, pg. 420

Coδ+

gold

cobalt Co2+ + 2e– ⇌ Co0 UPD of cobalt

gold

OPD of cobalt
Mendoza-Huizar, Robles, & Palomar-Pardavé, J. Electroanal. Chem., 2003, 545, 39