Butler–Volmer equation

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The Butler–Volmer equation is one of the most fundamental relationships in

electrochemistry. 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:
Butler-Volmer dependence of the electrode current on overpotential η = E - Eeq. The
anodic and cathodic current are shown as ia and ik, respectively. The total current
i = ia + ik.

where:

• I: electrode current, A
• io: exchange current density, A/m2
• E: electrode potential, V
• Eeq: equilibrium potential, V
• A: electrode active surface area, m2
• T: absolute temperature, K
• n: number of electrons involved in the electrode reaction
• F: Faraday constant
• R: universal gas constant
• α: so-called symmetry factor, dimensionless

The equation is named after chemists John Alfred Valentine Butler and Max Volmer.

Limitations
The 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 Butler–Volmer equation in
electrochemistry is wide, and it is often considered to be "central in the
phenomenological electrode kinetics".[1]

In the region of the limiting current, when the electrode process is mass-transfer
controlled, the value of the current is:

where:

• D is the diffusion coefficient;

• δ is the diffusion layer thickness;
• C* is the concentration of the electroactive (limiting) species in the bulk of the
electrolyte.

The more general form of the Butler–Volmer equation, applicable to the mass transfer-
influenced conditions, can be written as[2]:
where:

• i is the current density, A/m2,

• Co and Cr refer to the concentration of the oxidized and the reduced form,
respectively,
• C(0,t) is the time-dependent concentration at the distance zero from the surface,
and
• η is the overpotential (η = E - Eeq).

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 equals to that in the bulk.

[edit] The limiting cases

There are two limiting cases of the Butler–Volmer equation:

• the low overpotential region (called "polarization resistance", i.e., when E ≈ Eeq),
where the Butler–Volmer equation simplifies to:

• the high overpotential region, where the Butler–Volmer equation simplifies to the
Tafel equation:

E − Eeq = a − blog(i) for a cathodic reaction, when E << Eeq, or

E − Eeq = a + blog(i) for an anodic reaction, when E >> Eeq

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.