Electrochemical Kinetics
   HOME

TheInfoList



OR:

Electrochemical kinetics is the field of
electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outco ...
that studies the rate of electrochemical processes. This includes the study of how process conditions, such as
concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', ''molar concentration'', ''number concentration'', an ...
and
electric potential The electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as the amount of work energy needed to move a unit of electric charge from a reference point to the specific point in ...
, influence the rate of oxidation and reduction (
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
) reactions that occur at the surface of an
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
, as well as an investigation into electrochemical
reaction mechanism In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of ...
s. Two accompanying processes are involved in the electrochemical reaction and influence the overall reaction rate: *
electron transfer Electron transfer (ET) occurs when an electron relocates from an atom or molecule to another such chemical entity. ET is a mechanistic description of certain kinds of redox reactions involving transfer of electrons. Electrochemical processes ar ...
at the interface between the
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
and the
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
* transport of the redox species from the interior of the solution to the surface of the electrode; the transport can occur by
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
,
convection Convection is single or multiphase fluid flow that occurs spontaneously due to the combined effects of material property heterogeneity and body forces on a fluid, most commonly density and gravity (see buoyancy). When the cause of the convec ...
and
migration Migration, migratory, or migrate may refer to: Human migration * Human migration, physical movement by humans from one region to another ** International migration, when peoples cross state boundaries and stay in the host state for some minimum le ...
. Contributors to this field include
Alexander Frumkin Alexander Naumovich Frumkin (Алекса́ндр Нау́мович Фру́мкин) (October 24, 1895 – May 27, 1976) was a Russian/Soviet Union, Soviet electrochemistry, electrochemist, member of the Russian Academy of Sciences since 1 ...
, John Alfred Valentine Butler,
Max Volmer Max Volmer (; 3 May 1885 – 3 June 1965) was a German physical chemist, who made important contributions in electrochemistry, in particular on electrode kinetics. He co-developed the Butler–Volmer equation. Volmer held the chair and director ...
, and
Julius Tafel Julius Tafel (2 June 1862 – 2 September 1918) was a Swiss chemist and electrochemist. Work He worked first with Hermann Emil Fischer on the field of organic chemistry, but changed to electrochemistry after his work with Wilhelm Ostwald. He ...
.


Butler-Volmer equation

An elementary charge transfer step can be described by the Butler–Volmer model proposed by John Alfred Valentine Butler and
Max Volmer Max Volmer (; 3 May 1885 – 3 June 1965) was a German physical chemist, who made important contributions in electrochemistry, in particular on electrode kinetics. He co-developed the Butler–Volmer equation. Volmer held the chair and director ...
. The reaction rate is given by the Butler-Volmer equation: : j = j_0 \left\, \; \eta = \mathrm-\mathrm In this equation j is the net
current density In electromagnetism, current density is the amount of charge per unit time that flows through a unit area of a chosen cross section. The current density vector is defined as a vector whose magnitude is the electric current per cross-sectional ar ...
, j_0 is the
exchange current density In electrochemistry, exchange current density is a parameter used in the Tafel equation, Butler–Volmer equation and other electrochemical kinetics expressions. The Tafel equation describes the dependence of current for an electrolytic process to ...
, \alpha is the
charge transfer coefficient Charge transfer coefficient, and symmetry factor (symbols ''α'' and ''β'', respectively) are two related parameters used in description of the kinetics of electrochemical reactions. They appear in the Butler–Volmer equation and related expres ...
, z is the number of electrons transferred in the reaction, F is the
Faraday constant In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefinition of S ...
, R is the
molar gas constant The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per ...
, T is the
absolute temperature Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic wor ...
, \eta is the electrode
overpotential In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly rela ...
, E_ is the thermodynamic equilibrium
reduction potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
and E is the observed value of this potential. The equation yields a negative
current density In electromagnetism, current density is the amount of charge per unit time that flows through a unit area of a chosen cross section. The current density vector is defined as a vector whose magnitude is the electric current per cross-sectional ar ...
for a reduction reaction (negative
overpotential In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly rela ...
) and a positive current density for an oxidation reaction (positive overpotential). The sign of the current density has no physical meaning and is defined by an international convention.


See also

*
Tafel equation The Tafel equation is an equation in electrochemical kinetics relating the rate of an electrochemical reaction to the overpotential. The Tafel equation was first deduced experimentally and was later shown to have a theoretical justification. The ...


Bibliography

*


External links

* Electrochemistry {{Electrochem-stub