CHEMISTRY GLOSSARY

referent electrode    →   referentna elektroda

Referent electrode is an electrode whose potential is known and completely independent of analyte concentration. Mostly used referent electrodes are calomel and silver/silver chloride electrode.

Table: Dependence of referent electrodes potentials on KCl concentration

silver/silver-chloride electrode    →   srebro/srebrov klorid elektroda

Silver/silver-chloride electrode is by far the most common reference type used today because it is simple, inexpensive, very stable and non-toxic. It is mainly used with saturated potassium chloride electrolyte, but can be used with lower concentrations such as 3.5 mol dm^-3 or 1 mol dm^-3 potassium chloride. Silver/silver-chloride electrode is a referent electrode based on the following halfreaction

standard hydrogen electrode    →   standardna vodikova elektroda

Standard hydrogen electrode is a system in which hydrogen ion and gaseous hydrogen are present in their standard states. The convention is to designate the cell so that the standard hydrogen electrode is written first.

The electrode is used as a reference (of zero) for the values of other standard electrode potentials.

CO2 ion selective electrode    →   CO2 ion selektivna elektroda

The carbon dioxide ion selective electrode uses a gas-permeable membrane to separate the sample solution from the electrode internal solution. Dissolved carbon dioxide in the sample solution diffuses through the membrane until an equilibrium is reached between the partial pressure of CO₂ in the sample solution and the CO₂ in the internal filling solution. In any given sample the partial pressure of carbon dioxide will be proportional to the concentration of carbon dioxide. The diffusion across the membrane affects the level of hydrogen ions in the internal filling solution:

The hydrogen level of the internal filling solution is measured by the pH electrode located behind the membrane. The internal filling solution contains a high concentration of sodium bicarbonate (e.g. 0.1 mol/L NaHCO₃) so that the bicarbonate level can be considered constant.

Ilkovic equation    →   Ilkovičeva jednadžba

Ilkovic equation is a relation used in polarography relating the diffusion current (i_d) and the concentration of the depolarizer (c), which is the substance reduced or oxidized at the dropping mercury electrode. The Ilkovic equation has the form

Where k is a constant which includes Faraday constant, π and the density of mercury, and has been evaluated at 708 for max current and 607 for average current, D is the diffusion coefficient of the depolarizer in the medium (cm²/s), n is the number of electrons exchanged in the electrode reaction, m is the mass flow rate of Hg through the capillary (mg/sec), and t is the drop lifetime in seconds, and c is depolarizer concentration in mol/cm³.

The equation is named after the scientist who derived it, the Slovak chemist, Dionýz Ilkovič 1907-1980).

polarography    →   polarografija

Polarography is a volumetric technique which is based on a diffusion controlled analyte travel to the surface of dropping mercury electrode (DME). The surface of the working electrode (dropping mercury electrode) is constantly renewed under dropping conditions and, thus, the conditions under which reaction takes place are readily reproducible. Depolarisation potential enables identification of ions present in the solution, and by measuring the diffusion current their concentration is calculated. Polarography was discovered in 1922 by the Czech chemist Jaroslav Heyrovský (1890-1967).

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:

electrodeposition    →   elektrodepozicija

Electrodeposition is a process of depositing solid materials on an electrode surface using electrolysis. It is a somewhat loosely used term that is applied to many technologies. There are a number of metal deposition technologies. However, not only metals but also different compounds can be electrodeposited. This is used most often for the formation of oxides (such as manganese dioxide and lead dioxide) by anodic oxidation of dissolved salts.

electrodialysis    →   elektrodijaliza

Electrodialysis is a procedure of dialysis accelerated with an electric field. Dialyser is divided into three sections. Solution flows through the middle section, between two semipermeable membranes alternately to positive ions and negative ions. An electrodes are placed in the neighbouring sections. Under the influence of electric field, positive ions will travel towards the cathode (the negative electrode), and negative ions towards the anode (the positive electrode), whereby travelling of ions through the membrane is accelerated. In this way, the feed water is separated into two streams: one of pure water and the other of more concentrated solution.

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