760

Lecture #21 of 26
 761

The Double Layer

Chapter 13
 762

Q: What’s in this set of lectures?

A: B&F Chapter 13 main concepts:

● Section 1.2.3: Double layer structure

● Sections 13.1 & 13.2: Gibbs adsorption isotherm,

Electrocapillar(it)y, Surface excess,
Lippmann’s equation, Point of Zero Charge

● Section 13.3: Models: Helmholtz, Gouy–Chapman

(Poisson–Boltzmann), Gouy–Chapman–Stern

● Section 13.5: Specific adsorption

 763
RECALL:

splice a Helmholtz capacitor to a

GC capacitor, right here… and
then thank Stern!

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.3.6

RECALL: the mathematical details are in B&F, pp. 551 – 552, but 764
qualitatively, what GCS does is it uses the smaller capacitance of either
CH or CD(GC)…

CH << CD(GC)
C d ≈ CH

CD(GC) << CH
Cd ≈ CD(GC)
And lastly, what effect does specific adsorption have on the pzc? 765
The answer is hinted at in the data that we saw earlier…

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.2.2

 … but to really reveal specific 766
pzc
adsorption, one must look
carefully at the concentration
(activity) dependence of the pzc.
If there is one, then specific
adsorption is occurring…

The sign of the shift in pzc is the

sign of the ion that is adsorbing…

… for this we define the Esin–

Markov coefficient for a given σM
(= 0), as the following slope:

Bockris and Reddy, Plenum Press, 1973, Figure 7.57

… why a negative shift with anion adsorption? 767

this is meant to indicate excess

charges, not all charges…
(–)
+ –

+
–
+
pzc –
+ –
EWE
+
–
+

(+)
… why a negative shift with anion adsorption? 768

this is meant to indicate excess

charges, not all charges…
(–)
+ –
+ –
+
+
–
+ +
pzc –
+ – –
+ –
+
–
+ –
+
EWE –

(+)
… why a negative shift with anion adsorption? 769

(–)
EWE
– +
– +
– +
– +
– + -
pzc
– + +
–
– +
+
–
– + +
–
(+)
… at the pzc, qM = 0 and there is no excess positive or negative charge 770
in the solution…

(–)

pzc

(+)
… now, an adsorbing anion is added and thus fixed negative charge is 771
added to the solution side of the interface… this new qS is matched by
an equal and opposite qM on the electrode side…
(–)

image + –
charges
+ –
Result: We are no longer
at the pzc (on the metal)
old pzc at this potential
+ –
(before
adsorption)
+ –

+ –

(+)
… a new pzc exists, which is the potential required to neutralize charges 772
in the metal, but due to charges on both sides of the interface… notice
the location of the +/– capacitive charging in the diffuse layer, in this case
(–)
+
–

– +
new pzc
old pzc
– +

– + +

(+)
 … but to really reveal specific 773
pzc
adsorption, one must look
carefully at the concentration
(activity) dependence of the pzc. image
If there is one, then specific charges
adsorption is occurring…

The sign of the shift in pzc is the

sign of the ion that is adsorbing…

… for this we define the Esin–

Markov coefficient for a given σM
(= 0), as the following slope: specific
adsorption

Bockris and Reddy, Plenum Press, 1973, Figure 7.57

… a new pzc exists, which is the potential required to neutralize charge, 774
due to charges on both sides of the interface… specific adsorption!

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.3.8

… what about uncharged adsorbates, like organic molecules? 775

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.9.1

… what about uncharged adsorbates, like organic molecules? 776

… Gunk that is redox-

active… and whose
what is the origin capacitance is called
of these sharp chemical, or quantum,
Cd peaks? capacitance

~25 µF
… Gunk is blocking ~80%
of surface!
~5 µF,
why

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.9.2

In conclusion, with the Guoy–Chapman–Stern Model we have a semi- 777
quantitative understanding of this interface with some predictive power…
…. but don’t forget my questions
from the start of this series of
lectures on the double layer…

… What is the potential

difference between the two
sides? E
app

What is the potential difference

between one side and near the R R
middle?
~Eapp/2
NEW QUESTION: Can anyone
explain how a corrosion reaction
can be potential dependent
when the electron never M+
transfers across the OHP
metal|solution interface?
IHP
An ion transfers across the double layer… mind = blown, again!
 778

Q: What was in this set of lectures?

A: B&F Chapter 13 main concepts:

● Section 1.2.3: Double layer structure

● Sections 13.1 & 13.2: Gibbs adsorption isotherm,

Electrocapillar(it)y, Surface excess,
Lippmann’s equation, Point of Zero Charge

● Section 13.3: Models: Helmholtz, Gouy–Chapman

(Poisson–Boltzmann), Gouy–Chapman–Stern

● Section 13.5: Specific adsorption

In conclusion, with the Guoy–Chapman–Stern Model we have a semi- 779
quantitative understanding of this interface with some predictive power…
Now what about starting
with this behavior…

… plus adding in Faradaic

charge-transfer reaction
kinetics?!?!?!

… Oh yeah!!! …

… Now we're talking!

… still don’t forget about

the location of the
reactants and products
within/outside of the
double layer during OHP
Faradaic charge transfer IHP
 780

Interfacial Charge-Transfer
Kinetics
Chapter 3
 781

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

RECALL… since the continuity of mass equation is “better than” the conservation 782
of mass law, and it is highly relevant to electrochemistry and in fact all science
and engineering fields, we better know it…

… it is introduced to most undergraduate students studying chemical engineering,

materials science, and physics, but only partially to chemists (first half) and
mechanical engineers (second half)…

… anyway, here it is for species A along dimension x… Enjoy!

𝜕𝑐A 𝜕𝑁A
= ෍ 𝑅A,𝑖 −
𝜕𝑡 𝑖 𝜕𝑥

rate of change of the mass action (R)ate laws rate of change of the
(c)oncentration of species A that effect species A, flux (N) of species A with
with respect to (t)ime e.g. RA = k2[A][B] respect to position (x)
… differences in chemical potential, 𝜇𝑖 , drive (R)eactions… differences in electrochemical potential, 𝜇ҧ 𝑖 , drive
https://en.wikipedia.org/wiki/Continuity_equation volumetric fluxes (dN/dx)
From transition state theory (TST) (activated complex theory (ACT)), 783
the standard Gibb’s free energy of activation, ΔG‡ is defined as
follows… and electron-transfer reactions exhibit unique behavior…
(or transition state)
… Marcus Theory… the idea… 784

• Has anyone ever told you that the overall thermodynamics of a

reaction are not related to the kinetics of the reaction? … Well,
this is not true for (at least) electron-transfer reactions!
• What we know
• KINETICS: Kinetics of a reaction are dependent on the activation
energy, and temperature, by the empirical Arrhenius equation… and
are related to the free energy of the transition state by the Eyring
equation and transition-state theory (activated-complex theory):
𝐸 ‡
− 𝑎 κ𝑘𝐵 𝑇 −∆𝐺
𝑘𝐸𝑇 = 𝐴𝑒 𝑅𝑇 𝑘𝐸𝑇 = 𝑒 𝑅𝑇
ℎ

• THERMODYNAMICS: A reaction is favorable if the ΔG is negative,

and thus ΔE (Ecell) is positive

• What is new?
The kinetics of an electron-transfer reaction (kET) are dependent
on the driving force for the overall reaction (i.e. ΔG0 (ΔE0, E0cell))
… Marcus Theory (Nobel Prize in Chemistry in 1992)

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-bio.html
… Marcus Theory… the idea… 785

Rudy asked: For an electron-transfer event, how does one satisfy the
Franck–Condon principle and the conservation of energy?
• Franck–Condon principle: Nuclei are fixed during electron-transfer between
orbitals (IUPAC Gold Book); Born–Oppenheimer approximation is relevant

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-lecture.pdf
… Marcus Theory… the idea… 786

• Minor assumptions to go from internal (potential) energy to free energy

(ΔG = ΔH – TΔS) The nuclear reorganization energy, λ, is the
• Three regions of electron transfer: free energy required to reorganize the solvent
(outer) and bonds (inner) when the electron
(I) Normal, (II) Barrierless, (III) Inverted moves from the reactant to the product
potential-energy surface, while at the nuclear
arrangement of the reactant (and ΔG0 = 0)

–ΔG0 = λ
–ΔG0 < λ –ΔG0 > λ

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-lecture.pdf
… Marcus Theory… Experimental Confirmation! 787

• Minor assumptions to go from internal (potential) energy to free energy

(ΔG = ΔH – TΔS) The nuclear reorganization energy, λ, is the
• Three regions of electron transfer: free energy required to reorganize the solvent
(outer) and bonds (inner) when the electron
(I) Normal, (II) Barrierless, (III) Inverted moves from the reactant to the product
potential-energy surface, while at the nuclear
arrangement of the reactant (and ΔG0 = 0)

–ΔG0 = λ
–ΔG0 < λ –ΔG0 > λ

Closs & Miller, Science, 1988, 240, 440

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-lecture.pdf
… Marcus Theory… Experimental Confirmation! 788

• Minor assumptions to go from internal (potential) energy to free energy

(ΔG = ΔH – TΔS)
• Three regions of electron transfer:
(I) Normal, (II) Barrierless, (III) Inverted
Foreshadowing…

Ebias-1

Ebias-2

Ebias-3

Closs & Miller, Science, 1988, 240, 440

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-lecture.pdf