CHEMISTRY GLOSSARY

Nernst’s electrode potential equation    →   Nernstova jednadžba za elektrodni potencijal

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

a_O = activity of oxidised form

a_R = activity of reduced form

n = stechiometrical coefficient of oxidised form

m = stechiometrical coefficient of reduced form

conditional electrode potential    →   uvjetni elektrodni potencijal

Conditional or formal electrode potential (E°’) is equal to electrode potential (E) when overall concentrations of oxidised and reduced form in all its forms in a solution are equal to one. Conditional electrode potential includes all effects made by reactions that do not take part in the electron exchange, but lead to change of ion power, changes of pH, hydrolysis, complexing, precipitating, etc.

At 298 K (25 °C) and by converting natural (Napierian) logarithms into decimal (common, or Briggian) logarithms, Nernst’s equation for electrode potential can be written as follows:

standard electrode potential    →   standardni elektrodni potencijal

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.

electrode potential    →   elektrodni potencijal

Electrode potential is defined as the potential of a cell consisting of the electrode in question acting as a cathode and the standard hydrogen electrode acting as an anode. Reduction always takes place at the cathode, and oxidation at the anode. According to the IUPAC convention, the term electrode potential is reserved exclusively to describe half-reactions written as reductions. The sign of the half-cell in question determines the sign of an electrode potential when it is coupled to a standard hydrogen electrode.

Electrode potential is defined by measuring the potential relative to a standard hydrogen half cell

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

By convention, at p(H₂) = 101325 Pa and a(H⁺) = 1.00, the potential of the standard hydrogen electrode is 0.000 V at all temperatures. As a consequence of this definition, any potential developed in a galvanic cell consisting of a standard hydrogen electrode and some other electrode is attributed entirely to the other electrode

Heyrovsky-Ilkovic equation    →   Heyrovsky-Ilkovičeva jednadžba

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. E_1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.

In order to obtain E_1/2 from the above equation, we plot a graph of ln[(i_d-i)/i] against E. The intercept on the x-axis gives then an accurate value of E_1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.

Butler-Volmer equation    →   Butler-Volmerova jednadžba

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 i_o is exchange current density, η is overpotential (η = E - E_o), n is number of electrons, α_A is anodic transfer coefficient, and α_C is cathodic transfer coefficient

cell potential    →   potencijal članka

Cell potential (E) is difference between anode and cathode potential. If the cell potential is positive, then the reaction is spontaneous.

redox potential    →   redoks potencijal

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.

Schrodinger equation    →   Schrodingerova jednadžba

Schrödinger equation is the basic equation of wave mechanics which, for systems not dependent on time, takes the form:

where Ψ is the wavefunction, V is the potential energy expressed as a function of the spatial coordinates, E its total energy, ² is the Laplacian operator, h is Planck’s constant, and m is the mass.

Arrhenius equation    →   Arheniusova jednadžba

In 1889, Svante Arrhenius explained the variation of rate constants with temperature for several elementary reactions using the relationship

where the rate constant k is the total frequency of collisions between reaction molecules A times the fraction of collisions exp(-E_a/RT) that have an energy that exceeds a threshold activation energy E_a at a temperature of T (in kelvin). R is the universal gas constant.