Half-wave potential (E1/2) is a potential at which polarographic wave current is equal to one half of diffusion current (id). In a given supporting electrolyte, the half-wave potential is unique for each element and its different valence states and chemical forms. Observation of a current peak at a specific half-wave potential therefore identifies the chemical species producing the current.
For general reaction of some redox system
dependence of electrode potential of redox system upon activity of oxidised and reduced form in solution is described in Nernst’s equation for electrode potential:
where E = to electrode potential of redox system
E° = standard electrode potential of redox system
R = universal gas constant
T = thermodymical temperature
F = Faraday’s constant
z = number of electrons exchanged in redox reaction
aO = activity of oxidised form
aR = activity of reduced form
n = stechiometrical coefficient of oxidised form
m = stechiometrical coefficient of reduced form
Redox potential is the potential of a reversible oxidation-reduction electrode measured with respect to a reference electrode, corrected to the hydrogen electrode, in a given electrolyte.
Standard electrode potential (E°) (standard reduction potentials) are defined by measuring the potential relative to a standard hydrogen electrode using 1 mol solution at 25 °C. The convention is to designate the cell so that the oxidised form is written first. For example,
The e.m.f. of this cell is -0.76 V and the standard electrode potential of the Zn2+|Zn half cell is -0.76 V.
The Lennard-Jones potential (or 12-6 potential) is a mathematically simple model that describes the interaction between two non-bonded and uncharged atoms (known as the van der Waals interaction). It was first proposed in 1924 by British physicist Sir John Edward Lennard-Jones (1894-1954). The Lennard-Jones Potential is given by the following equation
V(r) = 4e[(sigma/r)12-(sigma/r)6)]where V is the intermolecular potential between the two atoms or molecules, ε is the well depth and a measure of how strongly the two particles attract each other, σ is the distance at which the intermolecular potential between the two particles is zero, r is the distance of separation between centres of both particles.
Potential energy (Ep) is the energy stored in a body or system as a consequence of its position, shape, or state (this includes gravitation energy, electrical energy, nuclear energy, and chemical energy). Gravitational potential energy is the energy associated with the state of separation between bodies that attracts each other via gravitational force. Elastic potential energy is the energy associated with the state of compression or extension of an elastic object. Thermal energy is associated with the random motions of atoms and molecules in a body.
Amperometry is determining the concentration of a material in a sample by measuring electric current passing through a cell containing the solution.
Butler-Volmer equation is an activation controlled reaction, the one for which the rate of reaction is controlled solely by the rate of the electrochemical charge transfer process, which is in turn an activation-controlled process. This gives rise to kinetics that are described by the Butler-Volmer equation:
where io is exchange current density, η is overpotential (η = E - Eo), n is number of electrons, αA is anodic transfer coefficient, and αC is cathodic transfer coefficient
Cyclic voltammetry (CV) is an electrochemical measuring technique used for the determination of the kinetics and mechanism of electrode reactions. The potential of the working electrode is controlled (typically with a potentiostat) and the current flowing through the electrode is measured. It is a linear-weep voltammetry with the scan continued in the reverse direction at the end of the first scan. This cycle can be repeated a number of times, and is used for corrosion studies.
Negative pole is that half-cell in electrochemical cell that has the most negative electrode potential.
Generalic, Eni. "Elektrokemijski potencijal." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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