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Lecture 21

The document discusses the structure and properties of electrified interfaces. It covers the electrical double layer model, Gibbs adsorption isotherm, electrocapillary equation, and electrosorption phenomena. The electrical double layer model has evolved over time from early concepts to the currently accepted model. The Gibbs adsorption isotherm relates surface excess of species to chemical potential and surface tension. The electrocapillary equation links surface excess to surface potential. Electrodes can be represented by electrical circuits including a double layer capacitance and faradaic impedance.

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359 views29 pages

Lecture 21

The document discusses the structure and properties of electrified interfaces. It covers the electrical double layer model, Gibbs adsorption isotherm, electrocapillary equation, and electrosorption phenomena. The electrical double layer model has evolved over time from early concepts to the currently accepted model. The Gibbs adsorption isotherm relates surface excess of species to chemical potential and surface tension. The electrocapillary equation links surface excess to surface potential. Electrodes can be represented by electrical circuits including a double layer capacitance and faradaic impedance.

Uploaded by

rajamathe
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
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2 Structure of electrified interface

1. The electrical double layer


2. The Gibbs adsorption isotherm
3. Electrocapillary equation
4. Electrosorption phenomena
5. Electrical model of the interface

2.1 The electrical double layer

Historical milestones
-The concept electrical double layer Quincke 1862
-Concept of two parallel layers of opposite charges Helmholtz 1879 and
Stern 1924
-Concept of diffuse layer Gouy 1910; Chapman 1913
- Modern model Grahame 1947

Presently accepted model of the electrical double layer

2.2 Gibbs adsorption isotherm


Definitions

G total Gibbs function of the system


GGG - Gibbsfunctions of phases
Gibbs function of the surface phase

G = G { GG }

Gibbs Model of the interface

The amount of species j in the surface phase:


njnj { nj + nj

Concentration

Surface excess

Distance

Hypothetical surface

Gibbs surface excess j


j = njs/A
A surface area

Gibbs adsorption isotherm


Change in G brought about by changes in T,p, A and nj
dG=-SdT + Vdp + dA + jdnj
G

surface energy work needed to create a unit area by cleavage


T , p ,n

n
j

- chemical potential

T , p , ni j

dG =-SdT + Vdp + + jdnj


dG =-SdT + Vdp + + jdnj
and
dG = dG {dGdGSdT + dA + + jdnj

Derivation of the Gibbs adsorption isotherm


dG = -SdT + dA + + jdnj
Integrate this expression at costant T and p
G = A + jnj
Differentiate G
dG = Ad + dA + njdj + jdnj
The first and the last equations are valid if:
Ad + njdj = 0

or

d= - jdj

Gibbs model of the interface - Summary

2.3 The electrocapillary equation


Cu Ag AgCl KCl, H2O,L Hg Cu

M = F(g +- e)

Lippmann equation

Differential capacity of the interface

d M
d 2
C
2
dE
dE

Capacity of the diffuse layer

Thickness of the diffuse layer

2.4 Electrosorption phenomena

2.5 Electrical properties of the


interface

In the most simple case ideally polarizable electrode the


electrochemical cell can be represented by a simple RC circuit

Implication electrochemical cell has a time constant that


imposes restriction on investigations of fast electrode process
Time needed for the potential across the interface to reach
The applied value :
Ec - potential across the interface
E - potential applied from an external generator

Time constant of the cell

RuCd

E
Ec
R u Cd

1 exp t

Ru Cd

Typical values Ru=50 C=2F gives =100s

Current flowing in the absence of a redox reaction nonfaradaic current


In the presence of a redox reaction faradaic impedance is connected in parallel
to the double layer capacitance. The scheme of the cell is:

The overall current flowing through the cell is :


i = if + inf
Only the faradaic current if contains analytical or kinetic information

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