The Butler-Volmer equation describes how the electrical current on an electrode depends on the electrode potential and describes both the cathodic and anodic reactions that occur on the electrode. It relates the electrode current density to the exchange current density and involves factors such as the electrode potential, equilibrium potential, temperature, number of electrons transferred in the reaction, and charge transfer coefficients. At high overpotentials, the Butler-Volmer equation simplifies to the Tafel equation with constants relating to the specific reaction and temperature.
The Butler-Volmer equation describes how the electrical current on an electrode depends on the electrode potential and describes both the cathodic and anodic reactions that occur on the electrode. It relates the electrode current density to the exchange current density and involves factors such as the electrode potential, equilibrium potential, temperature, number of electrons transferred in the reaction, and charge transfer coefficients. At high overpotentials, the Butler-Volmer equation simplifies to the Tafel equation with constants relating to the specific reaction and temperature.
The Butler-Volmer equation describes how the electrical current on an electrode depends on the electrode potential and describes both the cathodic and anodic reactions that occur on the electrode. It relates the electrode current density to the exchange current density and involves factors such as the electrode potential, equilibrium potential, temperature, number of electrons transferred in the reaction, and charge transfer coefficients. At high overpotentials, the Butler-Volmer equation simplifies to the Tafel equation with constants relating to the specific reaction and temperature.
The Butler-Volmer equation describes how the electrical current on an electrode depends on the electrode potential and describes both the cathodic and anodic reactions that occur on the electrode. It relates the electrode current density to the exchange current density and involves factors such as the electrode potential, equilibrium potential, temperature, number of electrons transferred in the reaction, and charge transfer coefficients. At high overpotentials, the Butler-Volmer equation simplifies to the Tafel equation with constants relating to the specific reaction and temperature.
The ButlerVolmer equation (also known as Erdey- j : electrode current density, A/m2 (dened as i = Grz-Volmer equation) is one of the most fundamen- I/A) tal relationships in electrochemical kinetics. It describes how the electrical current on an electrode depends on the jo : exchange current density, A/m2 electrode potential, considering that both a cathodic and E : electrode potential, V an anodic reaction occur on the same electrode: Eeq : equilibrium potential, V { [ ] [ ]} T : absolute temperature, K a zF c zF j = j0 exp (E Eeq ) exp (E Eeq ) RT RT z : number of electrons involved in the electrode or in a more compact form: reaction F : Faraday constant { [ ] [ ]} a zF c zF R : universal gas constant j = j0 exp exp RT RT c : so-called cathodic charge transfer coecient, where: dimensionless a : so-called anodic charge transfer coecient, di- mensionless : activation overpotential (dened as = (E Eeq ) ).
The right hand gure shows plots valid for =1- .
The equation is named after chemists John Alfred Valen- tine Butler[1] and Max Volmer.
1 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 Butler Volmer 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 cur- rent density is:
The upper graph shows the current density as function of the zF D
overpotential . The anodic and cathodic current densities ilimiting = C
are shown as ja and jc, respectively for =a=c=0.5 and j0 =1mAcm2 (close to values for platinum and palladium). The where: lower graph shows the logarithmic plot for dierent values of D is the diusion coecient;
1 2 4 REFERENCES
is the diusion 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 simplies 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.
2 The limiting cases
There are two limiting cases of the ButlerVolmer equa- tion:
the low overpotential region (called polarization re-
sistance, i.e., when E E ), where the Butler Volmer equation simplies to:
zF i = i0 (E Eeq ) RT the high overpotential region, where the Butler Volmer equation simplies to the Tafel equation:
E Eeq = ab log(i) for a cathodic reaction,
when E << E , or E Eeq = a + b log(i) for an anodic reaction, when E >> E
where a and b are constants (for a given reaction and tem-
perature) and are called the Tafel equation constants. The theoretical values of a and b are dierent for the cathodic and anodic processes.
3 See also Advanced Simulation Library Nernst equation Goldman equation
4 References [1] Mayneord, W. V. (1979). "John Alfred Valentine But- ler. 14 February 1899-16 July 1977. Biographical Memoirs of Fellows of the Royal Society. 25: 144126. doi:10.1098/rsbm.1979.0004. [2] J. O'M. Bockris, A.K.N.Reddy, and M. Gamboa-Aldeco, Modern Electrochemistry 2A. Fundamentals of Elec- trodics., Second Edition, Kluwer Academic/Plenum Publishers, p.1083, 2000. 3
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5.2 Images File:Current_density_versus_potential_according_to_butler_volmer_equation.svg Source: https://upload.wikimedia.org/ wikipedia/commons/3/3a/Current_density_versus_potential_according_to_butler_volmer_equation.svg License: CC BY-SA 4.0 Contributors: Own work Original artist: Toshiyouri
