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758

Lecture #18 of 20+

758

759

The Double Layer

Chapter 13

759

760

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

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… data for aqueous NaF from B&F is qualitatively similar… 761

RECALL:
Flat? … Eh; not really.

Why were both of these

measured using fluoride
salts?

In order to minimize
specific adsorption!

Grahame, Chem. Rev., 1947, 41, 441

761

762
RECALL:
For the purposes of this class, we want to understand the
microscopic origin of the most prominent features of these
Cd vs. E data:

a) A minimum in Cd exists at the pzc.

b) Cd is quasi-constant at potentials well positive and well

negative of the pzc.

c) This quasi-constant Cd is larger when E is (+) of pzc than

when it is (–) of pzc.

d) Cd increases with salt concentration at all potentials, and

the "dip" near the pzc disappears.

762

763
RECALL:

Three traditional models for double layer structure:

1) Helmholtz
2) Gouy–Chapman (GC)
3) Gouy–Chapman–Stern (GCS)

… let’s take a look at each of these…

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Models of Electrical Double Layer: 764

RECALL:
1) The Helmholtz Model: this is the
simplest possible model. It postulates
that ions (anions and cations) occupy
a plane located a distance, d, from
the electrode surface, and that the
effective "dielectric constant"
operating in the double layer is
potential independent:

… for a parallel plate capacitor, C is

independent of E because the
permittivity of the capacitor, εε0, and
its spacing, d, are both independent
d
of applied potential… http://www.cartage.org.lb/

764

… the Helmholtz model says that the electrical double layer acts like, 765
and looks like (rare in EChem), a parallel plate capacitor…
RECALL:

… Cd is therefore independent of E because the permittivity of the capacitor,

εε0, and its spacing, d, are both independent of applied potential…

… Question: What value for Cd do we calculate by plugging in to this model

the known "dielectric constant" (permittivity = IUPAC) of water?

765

… recall, here’s what the double layer really looks like… 766

RECALL:

766

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… and here’s what the double layer looks like in the Helmholtz 767
approximation… RECALL:

now, what’s εr?

4Å = 0.4 x 10-9 m

767

… first, what’s εr for water? Well, that depends… can it rotate? (BRIEFLY) 768

for water at
RECALL:
20 oC… Scenario is where electric
field oscillates slow enough
78.4 that molecules do reorient

Scenario is where electric

field oscillates too quickly
for molecules to reorient

5.9
{

Electrochemical impedance spectroscopy range

768

… and here’s what the double layer looks like in the Helmholtz 769
approximation… RECALL:

Answer: εr ≈ 78
(static relative permittivity)

4Å = 0.4 x 10-9 m

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… and here’s what the double layer looks like in the Helmholtz 770
approximation… RECALL:

Is this what is observed? Nope!… OK, now what?

4Å = 0.4 x 10-9 m

770

… now, what if the water dielectric is saturated, and thus fixed? 771
… so that water cannot rotate…
RECALL:
εr ≈ 6

… much more reasonable!

4Å = 0.4 x 10-9 m

771

772
… if we can measure γ, we can determine σM…
… and if we can determine σM, we can determine C…
RECALL:
… and all of this only works for liquid electrodes whose surface areas change
over time… Crazy!
𝑑γ
σM = −
𝑑𝐸 𝜇𝑖

electrocapillary
curve

… Aside: One can determine Epzc of a solid electrode using its capacitance

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… if the Helmholtz model is correct, we’d get this exactly: (BRIEFLY) 773
RECALL:
𝑑γ
σM = −
𝑑𝐸 𝜇𝑖

electrocapillary
curve

773

… here are electrocapillary data for various electrolytes… (BRIEFLY) 774

… hey, you can already see that the Helmholtz Model fails a little…
… mostly on the left…
RECALL:

774

(BRIEFLY) 775

RECALL:

Notwithstanding, notice particularly the following:

a) the γ vs. E parabola is independent of salt…
… at potentials negative of the pzc…
b) … but strongly dependent on salt positive of pzc…
c) … and pzc itself depends on the electrolyte…
… we’ll get to this shortly…

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… if C is dependent on potential, then the γ vs. E parabola will be 776

asymmetric…

… for example…

776

… and a flat Cd is in no way observed… we need a more sophisticated 777

model…

H.H. Girault, Analytical and Physical Electrochemistry, EPFL Press, 2004, Figure 5.13

777

… and specifically, one where the model of the double layer captures 778
these elements

these Cd's are

not constant

… and there is a minimum in

the Cd at the pzc…

H.H. Girault, Analytical and Physical Electrochemistry, EPFL Press, 2004, Figure 5.13

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779

Three traditional models for double layer structure:

1) Helmholtz
2) Gouy–Chapman (GC)
3) Gouy–Chapman–Stern (GCS)

… let’s take a look at each of these…

779

780
Models of Electrical Double Layer:

2) The Gouy–Chapman Model: this model adopts all the same assumptions
used in Debye–Hückel Theory, which are the following:

a) ions are considered to be point charges; their polarizability is neglected

b) interactions between ions, and between ions and the electrode are
purely electrostatic (i.e. no specific (chemical) adsorption); thus, the IHP
and OHP will not exist in this model since these planes explicitly require
finite ion size = polarizability)

c) the metal is considered a planar surface with a surface charge density, σM

d) ions are distributed according to Maxwell–Boltzmann statistics…

780

781
RECALL: 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

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782
… d) ions are distributed according to Maxwell–Boltzmann statistics…

where e is the elementary charge, and ϕ is the electric potential relative

to the bulk solution
ni0

ni

782

the charge density, i.e. charge per unit volume, ρ(x), is defined as: 783

… so substituting from the last slide…

… and now the Poisson Equation gives us another expression for ρ(x):

… substituting, we get the Poisson–Boltzmann Equation (no Maxwell)…

783

… if we apply the Poisson–Boltzmann Equation to a 1:1 electrolyte, we 784

obtain the following (see B&F, pp. 547–548):

… and if we further assume that ϕ0 is small, we get…

𝜙 = 𝜙 0 exp −𝜅𝑥
… where

… here, κ has units of 1/distance… we commonly refer to κ-1 as λD,

the "Debye (screening) length" characterizing the solution

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… Does a more sophisticated model of the double layer better capture 785
features observed experimentally?
… the electric potential variation near the electrode under
the Gouy–Chapman Model (compare with the Helmholtz Model…)
… the thickness of the capacitor
changes as a function of
𝜙 = 𝜙 0 exp −𝜅𝑥 electric potential… such that a
larger |E – Epzc| has a thinner
space–charge region… and
therefore a larger capacitance

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.3.3

785

… how does the Gouy–Chapman Model do in terms of predicting the 786

correct value of Cd?

Bard & Faulkner, 2nd Ed., Wiley, 2001, Figure 13.3.5

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787

About Gouy–Chapman Theory we can say the following:

a) it predicts a “dip” in Cd, that becomes more capacitive with
increased ionic strength = Good!
b) but it predicts a Cd that is WAY too high as the potential becomes
far from the pzc = Bad!...
c) and the Cd is symmetrical about the pzc (why?); this is not what is
observed experimentally…

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788
Getting close?

… Notably, near
the pzc?

788

… example: How thick is the diffuse layer from an electrode in, say, 789
aqueous 0.1 M NaClO4 solution?
Answer: The diffuse layer thickness is approximated by λD. Let’s calculate it.

ions
ions / m3

789

… example: How thick is the diffuse layer from an electrode in, say, 790
aqueous 0.1 M NaClO4 solution?
Answer: The diffuse layer thickness is approximated by λD. Let’s calculate it.

≈ 1 nm… about the same thickness as the compact layer…

Wow!

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… example: How thick is the diffuse layer from an electrode in, say, 791
aqueous 0.1 M NaClO4 solution?

791

… and related, this means that the electrostatic repulsion between charged 792
colloid particles, for example, is very short range at high electrolyte
concentrations… suspensions of these particles frequently precipitate

Paul Hiemenz, Raj Rajagopalan. Principles of Colloid and Surface Chemistry, Third Edition.
Dekker, New York: 1997, p. 514

792

793

Three traditional models for double layer structure:

1) Helmholtz
2) Gouy–Chapman (GC)
3) Gouy–Chapman–Stern (GCS)

… let’s take a look at each of these…

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794
Models of Electrical Double Layer:

3) The Gouy–Chapman–Stern Model: basically, the idea is to use both the

Helmholtz Model and the Gouy–Chapman Model in series:
Parallel plate capacitance of Potential-dependent non-parallel-plate
the compact layer from capacitance of the (D)iffuse layer from
the (H)elmholtz model (E) the GC model
(E)

Potential-dependent non-
parallel-plate capacitance
of the (d)ouble layer from
the GCS model

794

795
Models of Electrical Double Layer:

3) The Gouy–Chapman–Stern Model: basically, the idea is to use both the

Helmholtz Model and the Gouy–Chapman Model in series:
Parallel plate capacitance of Potential-dependent non-parallel-plate
the compact layer from capacitance of the (D)iffuse layer from
the (H)elmholtz model (E) the GC model
(E)

But, wait a minute! This is modeling just one interface with two sides, but there
are two capacitors (and thus in total seemingly four sides)… what gives?

If it barks like a dog, and it smells

like a dog, then maybe we should
model it as being a dog…
… What are the units?
This means that the electric potential drop across the Helmholtz Layer
(inside of the OHP) will be linear, and a quasi-exponential potential drop
will extend from this point and into the bulk solution…

795

… our three models for the potential distribution near a charged electrode 796
immersed in an electrolyte solution…

Helmholtz (H) Gouy–Chapman (GC) Gouy–Chapman–Stern

(GCS)
http://electrochem.cwru.edu/

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… History… 797
Physician & Physicist

Physicist

Hermann Ludwig Ferdinand von Helmholtz

(1821–1894)

Physicist P-Chemist
Otto Stern
(1888–1926)
Nobel Prize (Physics, 1943)

Louis Georges Gouy David Leonard Chapman

(1854–1926) (1869–1958) from Wiki

797

798

splice a Helmholtz capacitor to a

GC capacitor, right here… and
then thank Stern!

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

798

… the mathematical details are in B&F, pp. 551 – 552, but qualitatively, 799
what GCS does is it uses the smaller capacitance of either CH or CD(GC)…

CH << CD(GC)
Cd ≈ CH

CD(GC) << CH
Cd ≈ CD(GC)

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And lastly, what effect does specific adsorption have on the pzc? 800
The answer is hinted at in the data that we saw earlier…

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

800

… but to really reveal specific 801

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

801

… why a negative shift with anion adsorption? 802

this is meant to indicate excess

charges, not all charges…
(–)
+ –

+
–
+
pzc –
+ –
EWE
+
–
+

(+)

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… why a negative shift with anion adsorption? 803

this is meant to indicate excess

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

(+)

803

… why a negative shift with anion adsorption? 804

(–)
EWE
– +
– +
– +
– +
– + -
pzc
– + +
–
– +
– +
– + +
–
(+)

804

… at the pzc, qM = 0 and there is no excess positive or negative charge 805

in the solution…

(–)

pzc

(+)

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… now, an adsorbing anion is added and thus fixed negative charge is 806
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)
+ –

+ –

(+)

806

… a new pzc exists, which is the potential required to neutralize charges 807
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
– +

– + +

(+)

807

… but to really reveal specific 808

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

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… a new pzc exists, which is the potential required to neutralize charge, 809
due to charges on both sides of the interface… specific adsorption!
(SKIPPED)

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

809

… what about uncharged adsorbates, like organic molecules? (SKIPPED) 810

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

810

… what about uncharged adsorbates, like organic molecules? 811

… 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

811

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In conclusion, with the Guoy–Chapman–Stern Model we have a semi- 812

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!

812

813

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

813

In conclusion, with the Guoy–Chapman–Stern Model we have a semi- 814

quantitative understanding of this interface with some predictive power…
(BRIEFLY)
Now what about starting
with this approximate
behavior (an active area of
research)…

… 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 OHP
double layer during
IHP
Faradaic charge transfer

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