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