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Butler-Volmer Equation in Electrochemistry

The document summarizes the Butler-Volmer equation, which describes how the electrical current on an electrode depends on the electrode potential. It considers both the cathodic and anodic reactions that can occur on the same electrode. The equation relates the electrode current to factors like the electrode potential, temperature, and charge transfer coefficients. It is widely useful in electrochemistry as it can describe both reaction-controlled and diffusion-controlled regions. There are simplified forms for the low and high overpotential limiting cases as well.

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Bramuda Maulana
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998 views3 pages

Butler-Volmer Equation in Electrochemistry

The document summarizes the Butler-Volmer equation, which describes how the electrical current on an electrode depends on the electrode potential. It considers both the cathodic and anodic reactions that can occur on the same electrode. The equation relates the electrode current to factors like the electrode potential, temperature, and charge transfer coefficients. It is widely useful in electrochemistry as it can describe both reaction-controlled and diffusion-controlled regions. There are simplified forms for the low and high overpotential limiting cases as well.

Uploaded by

Bramuda Maulana
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 DOCX, PDF, TXT or read online on Scribd
  • Butler-Volmer Equation Overview
  • Detailed Explanation and Variables
  • Limiting Cases of the Equation

Adry Arisgraha

1306392600
Teknik Metalurgi Material

ButlerVolmer equation
The ButlerVolmer equation is one of the most fundamental
relationships in electrochemical kinetics. It describes how the
electrical current on an electrode depends on the electrode
potential, considering that both a cathodic and an anodic reaction
occur on the same electrode:

or in a more compact form:

or in a more compact form:



Butler-Volmer dependence of the electrode current on overpotential = E -
E
eq
. The anodic and cathodic current are shown as i
a
and i
k
, respectively. The
total current i = i
a
+ i
k
.
where:
: electrode current, A
: electrode active surface area, m
2

: electrode current density, A/m
2
(defined as i = I/A)
: exchange current density, A/m
2

: electrode potential, V
: equilibrium potential, V
: absolute temperature, K
: number of electrons involved in the electrode reaction
: Faraday constant
: universal gas constant
: so-called cathodic charge transfer coefficient, dimensionless
: so-called anodic charge transfer coefficient, dimensionless
: activation overpotential (defined as ).

Mass-transfer control
The previous form of ButlerVolmer equation is valid when the
electrode reaction is controlled by electrical charge transfer at the
electrode (and not by the mass transfer to or from the electrode
surface from or to the bulk electrolyte). Nevertheless, the utility of
the ButlerVolmer equation in electrochemistry is wide, and it is
often considered to be "central in the phenomenological electrode
kinetics".[2]
In the region of the limiting current, when the electrode process is
mass-transfer controlled, the value of the current density is:

where:
D is the diffusion coefficient;
is the diffusion layer thickness;
C
*
is the concentration of the electroactive (limiting) species in
the bulk of the electrolyte.
C(0,t) is the time-dependent concentration at the distance zero
from the surface.
The above form simplifies to the conventional one (shown at the
top of the article) when the concentration of the electroactive
species at the surface is equal to that in the bulk.

The limiting cases
There are two limiting cases of the ButlerVolmer equation:
the low overpotential region (called "polarization resistance", i.e.,
when E E
eq
), where the ButlerVolmer equation simplifies
to:
;
the high overpotential region, where the ButlerVolmer equation
simplifies to the Tafel equation:
for a cathodic reaction, when E <<
E
eq
, or
for an anodic reaction, when E >>
E
eq

where a and b are constants (for a given reaction and
temperature) and are called the Tafel equation constants. The
theoretical values of a and b are different for the cathodic and
anodic processes.


Mayneord, W. V. (1979). "John Alfred Valentine Butler. 14 February
1899-16 July 1977". Biographical Memoirs of Fellows of the Royal
Society 25: 144126. doi:10.1098/rsbm.1979.0004. edit
Jump up ^ J. O'M. Bockris, [Link], and M. Gamboa-Aldeco,
"Modern Electrochemistry 2A. Fundamentals of Electrodics.", Second
Edition, Kluwer Academic/Plenum Publishers, p.1083, 2000.
[Link]

(http://en.wikipedia.org/wiki/File:Butler_volmer_equation_graph_nl.png)Adry Arisgraha 1306392600 Teknik Metalurgi Material
total current i = ia + ik. where: • : electrode current, A • : electrode active surface area, m2 • : electrode current
The above form simplifies to the conventional one (shown at the top of the article) when the concentration of the electroact

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