CHEMISTRY GLOSSARY

electrode of the first kind    →   elektroda prvog reda

Electrode of the first kind is a simple metal electrode immersed in a solution containing its own ion (e.g., silver immersed in a silver nitrate solution). The equilibrium potential of this electrode is a function of the concentration (more correctly of activity) of the cation of the electrode metal in the solution (see Nernst’s electrode potential equation).

electrode of the second kind    →   elektroda drugog reda

Electrodes of the second kind are metal electrodes assembly with the equilibrium potential being a function of the concentration of an anion in the solution. Typical examples are the silver/silver-chloride electrode and the calomel electrode. The potential of the metal is controlled by the concentration of its cation in the solution, but this, in turn, is controlled by the anion concentration in the solution through the solubility product of the slightly soluble metal salt. Contrast with electrode of the first kind and electrode of the third kind.

electrode of the third kind    →   elektroda trećeg reda

Electrode of the third kind is a metal electrode assembly with the equilibrium potential being a function of the concentration of a cation, other than the cation of the electrode metal, in the solution. The assembly consists of a metal in contact with two slightly soluble salts (one containing the cation of the solid metal, the other the cation to be determined, with both salts having a common anion) immersed in a solution containing a salt of the second metal (e.g., zinc metal--zinc oxalate--calcium oxalate--calcium salt solution). The potential of the metal is controlled by the concentration of its cation in the solution, but this is controlled by the anion concentration in the solution through the solubility product of the slightly soluble metal salt, which, in turn is controlled by the concentration of the cation of the second slightly soluble salt. These electrodes are very sluggish and unstable due to a series of equilibria to be established to produce a stable potential.

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.

activation energy    →   energija aktivacije

Activation energy (E_a) 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    →   amperometrija

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    →   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

calomel electrode    →   kalomel elektroda

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

electromotive force    →   elektromotorna sila

Electromotive force (e.m.f. or E_MF) is the difference in electric potential that exists between two dissimilar electrodes immersed in the same electrolyte or otherwise connected by ionic conductors.

electron volt    →   elektronvolt

Electron volt (eV) is a non-SI unit of energy used in atomic and nuclear physics, equal to approximately 1.602 177×10^-19 J. The electron volt is defined as the kinetic energy acquired by an electron upon acceleration through a potential difference of 1 V.