825

Lecture #23 of 26
 826

Interfacial Charge-Transfer
Kinetics
Chapter 3
 827

Q: What’s in this set of lectures?

A: B&F Chapter 3 main concepts:

● Sections 3.1 & 3.6: Homogeneous Electron-Transfer (ET)

(Arrhenius, Eyring, Transition-State
Theory (Activated Complex Theory),
Marcus Theory)

● Sections 3.2, 3.3, 3.4 & 3.6: Heterogeneous ET (Butler–

Volmer Equation, Tafel Equation,
Volcano Plot, Gerischer Theory,
Quantum Mechanical Tunneling)

● Section 3.5: Multistep ET Mechanisms

… and where α (or β) introduces asymmetry into this J–E curve 828

the Butler–Volmer Equation

-
-
-
-

+
Note: These quadrants are
+ flipped… but at least they
+ are (–, –) and (+, +) now
+
note that for a one-electron-transfer reaction and α (or β) < 1/2, 829
oxidation is preferentially accelerated at any η value

-
-
-
-

+
+ Note: These quadrants are
+ flipped… but at least they
are (–, –) and (+, +) now
+
note that for a one-electron-transfer reaction and α (or β) > 1/2, 830
reduction is preferentially accelerated at any η value

-
-
-
-

+
+ Note: These quadrants are
+ flipped… but at least they
are (–, –) and (+, +) now
+
… now, more specifically, α (actually β) is related to the symmetry of 831
the barrier in the vicinity of the crossing point…

tan = opposite/adjacent

derive this by
applying “TOA” to
the two triangles on
the right…

tan θ = αFE/x
tan ϕ = (1 – α)FE/x

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 3.3.3

 832
… if the barrier is symmetrical…

this means that the cathodic and

anodic barriers are affected equally
by the change in potential.

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 3.3.4

 833
… if the R side is steeper than the O side…

this means that a change in the

electrode potential affects the anodic
barrier more than the cathodic
barrier.

Note that in the limit of a

vertical potential-energy
“curve” for R at the crossing
point, α = 0 and 100% of the
potential change accelerates
oxidation.

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 3.3.4

 834
… if the R side is more shallow than the O side…

this means that a change in the

electrode potential affects the
cathodic barrier more than the anodic
barrier.

Note that in the limit of a

vertical potential-energy
“curve” for O at the crossing
point, α = 1 and 100% of the
potential change accelerates
reduction.

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 3.3.4

… two limiting cases for the Butler–Volmer Equation are important… 835

… first, if η is small, then exp(x) can be approximated by a Taylor/

Maclaurin series expansion as 1 + x…

𝑖 = −𝑖0 1 + −α𝑓𝜂 − 1 + 1 − α 𝑓𝜂 = +𝑖0 𝑓𝜂

What’s small for one term?

B–V: exp(0) = 1 T/M: 1 + 0 = 1 (error = 0%)
B–V: exp(1) = 2.7 T/M: 1 + 1 = 2 (error = -26%)
so small means η < 30 mV (αfη = (0.5)(1 / 26 mV)(30 mV) = 0.58)
B–V: exp(0.58) = 1.78 T/M: 1 + 0.58 = 1.5 (error = -11%)
… two limiting cases for the Butler–Volmer Equation are important… 836

… first, if η is small, then exp(x) can be approximated by a Taylor/

Maclaurin series expansion as 1 + x…

𝑖 = −𝑖0 1 + −α𝑓𝜂 − 1 + 1 − α 𝑓𝜂 = +𝑖0 𝑓𝜂

Note: no α!
… and ohmic
… two limiting cases for the Butler–Volmer Equation are important… 837

… if, instead, η is large, then either ic or ia can be neglected…

… and we obtain the famous Tafel Equation which has two versions:

for η << 0: (current negative, or reducing/cathodic)

𝑖 = −𝑖0 exp −α𝑓𝜂 ... ln 𝑖 = ln 𝑖0 − α𝑓η

for η >> 0: (current positive, or oxidizing/anodic)

𝑖 = +𝑖0 exp − 1 − α 𝑓𝜂 … ln 𝑖 = ln 𝑖0 + 1 − α 𝑓η
… “η is large” means > 60 mV or so… 838
… both β and i0 can be obtained from a J–E curve in one direction…

Slope-1 = Tafel Slope

(“mV per decade”)
Note: The x axis is flipped… sorry
… “η is large” means > 60 mV or so… 839
Quick Quiz: Which catalyst is best?
(A) jo = 10-4 A cm-2 and 120 mV decade-1
(B) jo = 10-7 A cm-2 and 60 mV decade-1

It depends on the desired j…

For 1 mA cm-2, (A) is best… but…

… for 1 A cm-2, (B) is best…

… where catalyst (A) requires η = 480 mV,
while catalyst (B) requires η = 420 mV!
Note: The x axis is flipped… sorry
… Take-home point: Always report over-
potentials at a specific current density
What does real data look like, so that I can indicate the overpotential? 840

… wait, where is E0(O2,H+/H2O)?

… 1.23 V vs. SHE… but how
can we tell where that occurs
given this SCE scale and no
mention of the pH value?
… Oh… this is in base?
Gotcha! Now I see why
plotting on an RHE
scale is nice for
H+-dependent
reactions
… wait, the Tafel Slope (in units of mV/decade) changes? 841

Yup! … this is a consequence of a

change in the mechanism of the
reaction, resulting from a change in
the chemical state of the catalyst,
for example…
… but even in this case,
overpotentials can and should be
reported for a given current density
Recall, and for clarity, that we have already encountered an 842

overpotential… and seen a case where it is important…

O + ne– ⇋ Rn– (insoluble)

CR* = 0
CO* = the bulk concentration of O
e.g. Ag+ + e– ⇋ Ag0
Repeating a derivation akin to one we did in Chapter 1…

𝑹𝑻
𝟎′ ∗ 𝑹𝑻 𝒊𝒍 − 𝒊
𝑬=𝑬 + ln 𝐶O + ln
𝒏𝑭 𝒏𝑭 𝒊𝒍
Eeq
𝑹𝑻 𝒊𝒍 − 𝒊
𝑬 − 𝑬𝐞𝐪 = 𝜼𝐜𝐨𝐧𝐜 = ln
𝒏𝑭 𝒊𝒍
Recall, and for clarity, that we have already encountered an 843

overpotential… and seen a case where it is important…

O + ne– ⇋ Rn– (insoluble)

CR* = 0
CO* = the bulk concentration of O
… Interpretation: An extra potential, beyond Eeq, is required to drive mass
transfer of species to the electrode surface…
Repeating a derivation akin to one we did in Chapter 1…

𝑹𝑻
𝟎′ ∗ 𝑹𝑻 𝒊𝒍 − 𝒊
𝑬=𝑬 + ln 𝐶O + ln
𝒏𝑭 𝒏𝑭 𝒊𝒍
Eeq
𝑹𝑻 𝒊𝒍 − 𝒊
𝑬 − 𝑬𝐞𝐪 = 𝜼𝐜𝐨𝐧𝐜 = ln
𝒏𝑭 𝒊𝒍
Recall, and for clarity, that we have already encountered an 844

overpotential… and seen a case where it is important…

𝑹𝑻 𝒊𝒍 − 𝒊
𝜼𝐜𝐨𝐧𝐜 = ln
𝒏𝑭 𝒊𝒍
… Interpretation: An extra potential, beyond Eeq, is required to drive mass
transfer of species to the electrode surface…
What’s happening here (not electrocatalysis)? 845

O + ne– ⇋ Rn– (insoluble)

 846

An overpotential that is derived from rate-limiting mass transfer

alone is called a concentration overpotential, ηconc…

… it is also called a concentration polarization.

Kinetic overpotential is often just called overpotential, but can

also be called activation overpotential…

… okay, that summarizes this topic nicely… there is lots more to

learn that your book lays out in great detail related to complex
reactions and mechanisms, but this suffices for our course
 847

Q: What was in this set of lectures?

A: B&F Chapter 3 main concepts:

● Sections 3.1 & 3.6: Homogeneous Electron-Transfer (ET)

(Arrhenius, Eyring, Transition-State
Theory (Activated Complex Theory),
Marcus Theory)

● Sections 3.2, 3.3, 3.4 & 3.6: Heterogeneous ET (Butler–

Volmer Equation, Tafel Equation,
Volcano Plot, Gerischer Theory,
Quantum Mechanical Tunneling)

● Section 3.5: Multistep ET Mechanisms

Let’s summarize the steady-state behavior from the entire course… 848

… by examining I–E data when stirred away from electrode (non-hysteretic)…

… and for each applied potential, E, let’s think about what resistance (not
impedance, as no AC contribution) is limiting the observed behavior…

RCT RDL RMT Ru

Incorrect circuit representation of an electrochemical cell
(but good enough at this stage for illustration purposes)
Let’s summarize the steady-state behavior from the entire course… 849

… by examining I–E data when stirred away from electrode (non-hysteretic)…

… and for each applied potential, E, let’s think about what resistance (not
impedance, as no AC contribution) is limiting the observed behavior…
−1
𝜕𝐼
… so, we want to know what dictates 𝑅 = at each E…
𝜕𝐸
Fe3+/2+ and H+
electrocatalysis

H+/H2
electrocatalysis
RECALL… Let’s compare total capacitance (C) and differential 850
capacitance (Cd) as follows:

Ez = pzc
Let’s summarize the steady-state behavior from the entire course… 851

… by examining I–E data when stirred away from electrode (non-hysteretic)…

… and for each applied potential, E, let’s think about what resistance (not
impedance, as no AC contribution) is limiting the observed behavior…
−1
𝜕𝐼
… so, we want to know what dictates 𝑅 = at each E…
𝜕𝐸
… but this will be difficult because we have several convoluting factors…

RCT ZMT

Ru
when this is fully charged,
it has infinite resistance…
CDL … equals an open circuit
Correct circuit representation of an electrochemical cell
… what are the limiting behaviors of each major resistance and can we begin to
piece out which resistance is responsible for observed steady-state I–E
behavior at various E, while recalling that Eapp(I) = ECT(I) + EMT(I) + Eu(I) + …? …
… what are the limiting behaviors of each major resistance and can we 852
piece out which is responsible for observed steady-state I–E behavior? …

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #1 853

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #1 854

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #2 855

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #2 856

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #3 857

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #3 858

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #4 859

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #4 860

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #5 861

electro-
catalysis

mass
transfer

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #5… You get the idea! … 862
… what do ELJ, EDonnan, and/or activity coeffs. do to these plots? Shift them
left/right!

electro-
catalysis
I (A)

mass
transfer

E (V)

(solution)
ohmic drop
Let’s try some examples… EXAMPLE #5… You get the idea! … 863
… what do ELJ, EDonnan, and/or activity coeffs. do to these plots? Shift them
left/right!

electro-
catalysis
E (V)

mass
transfer

I (A)
(solution)
… while
ohmica little
drop difficult to look at initially…
… ultimately, this may be clearer, because for each I, add the series E values…
… in fact many fuel cell J–E data are plotted this way (J is fine when same areas)
But how do we learn even more about our complex systems? 864

Steady-state reactions and processes can be amazingly complex (e.g. see

everything we have covered thus far in the course)… ideally, we need to
piece out each mechanistic component from interrelated processes… we do
this by performing studies over various time regimes… thus, we need to
change the temporal response of our measurements!

• R(R)DE: stirring removes mass-transport limits, which is nice… rotating the

electrode does the same thing… so precisely change the rotation rate… we
can also surround the disk/button by a second ring electrode to observe
products of redox reactions
• EIS: sweep/scan potentials over very small range… as CVs… but then change
the region (DC)… and also change the sweep/scan rate (AC)… model using
ZFit/ZSim
• CV: change the scan rate… mechanisms by Saveant’s “Foot of the Wave”
analysis (e.g. ECE, etc.)… model using BASi DigiSim, EC Lab, etc.
• UME: sweep/scan forward and backward very quickly
Costentin, Drouet, Robert & Savéant, J. Am. Chem. Soc., 2012, 134, 11235
Costentin, Nocera & Brodsky, PNAS, 2017, 114, 11303
 865

Q: What’s in this final set of lectures?

A: B&F Chapters 9, 10, and 6 main concepts:

● Sections 9.1 – 9.4: Rotating (Ring-)Disk

Electrochemistry

● Sections 10.1 – 10.4: Electrochemical Impedance

Spectroscopy

● Sections 6.1 – 6.6, 11.7, 14.3: Linear Sweep Voltammetry (LSV),

Cyclic Voltammetry (CV), Thin-
Layer Electrochemistry, Molecular
Electrocatalysis

… to learn even more about your experimental systems…

… go beyond steady-state conditions and modulate things!