Вы находитесь на странице: 1из 14

Biopotential electrodes

A complex interface

Basics of Instrumentation, Measurement and Analysis 2011, 2012


the interface problem

metal electrolyte

M+ To sense a signal
I a current I must flow !
e-

? A - But no electron e- is
passing the interface!

2
metal cation
leaving into the electrolyte

No current

One atom M out of the metal


is oxidized to form
one cation M+ and giving off
one free electron e-
to the metal.

4
metal cation
joining the metal

No current

One cation M+
out of the electrolyte
becomes one neutral atom M
taking off one free electron
from the metal.

6
half-cell voltage
No current, 1M salt concentration, T = 25C

metal: Li Al Fe Pb H Ag/AgCl Cu Ag Pt Au
Vh / Volt -3,0 negativ 0 0,223 positiv 1,68

8
Nernst equation
For arbitrary concentration and temperature

E = RT/(zF)ln(c/K)

E electrode potential
R = 8.314 J /(mol*K) molar gas constant
T absolute temperature
z valence
F = 96485 C/mol Faradays constant
c concentration of metal ion in solution
K metal solution pressure,
or tendency to dissolve

9
electrode double layer
No current

13
current influence
with current flowing
the half-cell voltage changes
this voltage change is called
overpotential or polarization:
Vp = Vr + Vc + Va
activation, depends on direction of reaction
concentration (change in double layer)
ohmic (voltage drop)

16
polarizable electrode

perfectly polarizable electrode:


- only displacement current,
electrode behave like a capacitor
example: noble metals like platinum Pt

18
nonpolarizable electrode

perfectly nonpolarizable electrode:


- current passes freely across
interface,
- no overpotential
examples:
- silver/silver chloride (Ag/AgCl),
- mercury/mercurous chloride
(Hg/Hg2Cl2) (calomel)

20
chemical reactions
silver / silver chloride

22
electrical behaviour

equivalent circuit

26
equivalent circuit
electrode-electrolyte

27
more precise approximation of
double layer Randles circuit
electrode-electrolyte

Rct active charge transfer resistance


W Warburg element reflecting diffusion
with impedance ZW = AW/(j)0.5
AW Warburg coefficient

28

Вам также может понравиться