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Electrochemical Kinetics
Electrochemical kinetics is the field of electrochemistry that studies the rate of electrochemical processes. This includes the study of how process conditions, such as concentration and electric potential, influence the rate of oxidation and reduction (redox) reactions that occur at the surface of an electrode, as well as an investigation into electrochemical reaction mechanisms. Two accompanying processes are involved in the electrochemical reaction and influence the overall reaction rate: * electron transfer at the interface between the electrode and the electrolyte * transport of the redox species from the interior of the solution to the surface of the electrode; the transport can occur by diffusion, convection and migration. Contributors to this field include Alexander Frumkin, John Alfred Valentine Butler, Max Volmer, and Julius Tafel. Butler-Volmer equation An elementary charge transfer step can be described by the Butler–Volmer model proposed by John Alfred Valenti ...
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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 outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase (typically an external electrical circuit, but not necessarily, as in electroless plating) between electrodes separated by an ionically conducting and electronically insulating electrolyte (or ionic species in a solution). When a chemical reaction is driven by an electrical potential difference, as in electrolysis, or if a potential difference results from a chemical reaction as in an electric battery or fuel cell, it is called an ''electrochemical'' reaction. Unlike in other chemical reactions, in electrochemical reactions electrons are not transferred directly between atoms, ions, or molecules, but via the af ...
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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 directorship of the Physical Chemistry and Electrochemistry Institute of the Technische Hochschule Berlin, in Berlin-Charlottenburg. After World War II, he went to the Soviet Union, where he headed a design bureau for the production of heavy water. Upon his return to East Germany ten years later, he became a professor at the Humboldt University of Berlin and was president of the East German Academy of Sciences. Education From 1905 to 1908, Volmer studied chemistry at the Philipps University of Marburg. After that, he went to the University of Leipzig, where he was awarded a doctorate in 1910, based on his work on photochemical reactions in high vacuums. He became an assistant lecturer at Leipzig in 1912, and after completion of his Habilit ...
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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 respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced. Measurement and interpretation In aqueous solutions, redox potential is a measure of the tendency of the solution to either gain or lose electrons when it is subjected to change by introduction of a new species. A solution with a higher (more positive) reduction potential than the new species will have a tendency to gain electrons from the new species (i.e. to be reduced by oxidizing the new species) and a solution with ...
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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 related to a cell's ''voltage efficiency''. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density (typically small) is achieved. Thermodynamics The four possible polarities of overpotentials are listed below. * An electrolytic cell's anode ...
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Thermodynamic 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 work and heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as manifestations of the kinetic energy of free motion of microscopic particles such as atoms, molecules, and electrons. From the thermodynamic viewpoint, for historical reasons, because of how it is defined and measured, this microscopic kinetic definition is regarded as an "empirical" temperature. It was adopted because in practice it can generally be measured more precisely than can Kelvin's thermodynamic temperature. A thermodynamic temperature reading of zero is of particular importance for the third law of thermodynamics. By convention, it is reported on the ''Kelvin scale'' ...
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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 amount of substance, i.e. the pressure–volume product, rather than energy per temperature increment per ''particle''. The constant is also a combination of the constants from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. It is a physical constant that is featured in many fundamental equations in the physical sciences, such as the ideal gas law, the Arrhenius equation, and the Nernst equation. The gas constant is the constant of proportionality that relates the energy scale in physics to the temperature scale and the scale used for amount of substance. Thus, the value of the gas constant ultimately derives from historical decisions and accidents in the setting of units of energy, temperature and amount of substa ...
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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 SI base units, which took effect on 20 May 2019, the Faraday constant has the exactly defined value given by the product of the elementary charge ''e'' and Avogadro constant ''N''A: : : :. Derivation The Faraday constant can be thought of as the conversion factor between the mole (used in chemistry) and the coulomb (used in physics and in practical electrical measurements), and is therefore of particular use in electrochemistry. Because 1 mole contains exactly entities, and 1 coulomb contains exactly elementary charges, the Faraday constant is given by the quotient of these two quantities: :. One common use of the Faraday constant is in electrolysis calculations. One can divide the amount of charge (the current integrated over time) ...
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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 expressions. The symmetry factor and the charge transfer coefficient are dimensionless. According to an IUPAC definition, for a reaction with a single rate-determining step, the charge transfer coefficient for a cathodic reaction (the cathodic transfer coefficient, ''αc'') is defined as: :\frac = - \frac \left( \frac \right)_ The anodic transfer coefficient (''αa'') is defined by analogy: :\frac = \frac \left( \frac \right)_ where: *\nu: stoichiometric number, i.e., the number of activated complexes formed and destroyed in the overall reaction (with ''n'' electrons) * R: universal gas constant * T: absolute temperature * n: number of electrons involved in the electrode reaction * F: Faraday constant * E: electrode potential * I ...
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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 overpotential. The exchange current density is the current in the absence of net electrolysis and at zero overpotential. The exchange current can be thought of as a background current to which the net current observed at various overpotentials is normalized. For a redox reaction written as a reduction at the equilibrium potential, electron transfer processes continue at electrode/solution interface in both directions. The cathodic current is balanced by the anodic current. This ongoing current in both directions is called the exchange current density. When the potential is set more negative than the formal potential, the cathodic current is greater than the anodic current. Written as a reduction, cathodic current is positive. The net c ...
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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 area at a given point in space, its direction being that of the motion of the positive charges at this point. In SI base units, the electric current density is measured in amperes per square metre. Definition Assume that ''A'' (SI unit: m2) is a small surface centred at a given point ''M'' and orthogonal to the motion of the charges at ''M''. If ''I'' (SI unit: A) is the electric current flowing through ''A'', then electric current density ''j'' at ''M'' is given by the limit: :j = \lim_ \frac = \left.\frac \_, with surface ''A'' remaining centered at ''M'' and orthogonal to the motion of the charges during the limit process. The current density vector j is the vector whose magnitude is the electric current density, and whose dire ...
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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 is known for the discovery of an electrosynthetic rearrangement reaction of various alkylated ethyl acetoacetates to form hydrocarbons, now called the Tafel rearrangement, and the Tafel equation, which relates the rate of an electrochemical reaction to the overpotential. He is also credited for the discovery of the catalytic mechanism of hydrogen evolution (the Tafel mechanism). Tafel retired aged 48 due to ill health, but continued to write book reviews until his death. Life Tafel suffered from insomnia and eventually had a complete nervous breakdown. He committed suicide in Munich Munich ( ; german: München ; bar, Minga ) is the capital and most populous city of the German state of Bavaria. With a population of 1,558, ...
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