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.
The Heyrovsky-Ilkovic equation describes the entire current-potential curve (polarographic wave) of a reversible redox system in polarography
where R is the gas constant, T is the absolute temperature, F is the Faraday constant, n denotes the number of electrons taking part in the electrode reaction. E1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.
In order to obtain E1/2 from the above equation, we plot a graph of ln[(id-i)/i] against E. The intercept on the x-axis gives then an accurate value of E1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.
Activation energy (Ea) is the energy that must be added to a system in order for a process to occur, even though the process may already be thermodynamically possible. In chemical kinetics, the activation energy is the height of the potential barrier separating the products and reactants. It determines the temperature dependence on the reaction rate.
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
Calomel electrode is a type of half cell in which the electrode is mercury coated with calomel (Hg2Cl2) and the electrolyte is a solution of potassium chloride and saturated calomel. In the calomel half cell the overall reaction is
Table: Dependence of potential of calomel electrode upon temperature and concentration of KCl according to standard hydrogen electrode
Potential vs. SHE / V | |||
---|---|---|---|
t / °C | 0.1 mol dm-3 | 3.5 mol dm-3 | sat. solution |
15 | 0.3362 | 0.254 | 0.2511 |
20 | 0.3359 | 0.252 | 0.2479 |
25 | 0.3356 | 0.250 | 0.2444 |
30 | 0.3351 | 0.248 | 0.2411 |
35 | 0.3344 | 0.246 | 0.2376 |
Electromotive force (e.m.f. or EMF) is the difference in electric potential that exists between two dissimilar electrodes immersed in the same electrolyte or otherwise connected by ionic conductors.
Generalic, Eni. "Poluvalni potencijal." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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