Ion selective electrode (ISE) is an electrode or electrode assembly with a potential that is dependent on the concentration of an ionic species in the test solution and is used for electroanalysis. Ion-selective electrodes are often membrane type electrodes.
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.
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 |
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:
Dropping mercury electrode (DME) is a working electrode arrangement for polarography in which mercury continuously drops from a reservoir through a capillary tube (internal diameter 0.03 - 0.05 mm) into the solution. The optimum interval between drops for most analyses is between 2 and 5 s. The unique advantage to the use of the DME is that the constant renewal of the electrode surface, exposed to the test solution, eliminates the effects of electrode poisoning.
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).
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 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.
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.
Generalic, Eni. "Ion selektivne elektrode." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
Glossary
Periodic Table