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.
Ligand is an ion (F-, Cl-, Br-, I-, S2-, CN-, NCS-, OH-, NH2-) or molecule (NH3, H2O, NO, CO) that donates a pair of electrons to a metal atom or ion in forming a coordination complex. The main way of classifying ligands is by the number of points at which they are attached to, or bound to, the metal center. This is the denticity. Ligands with one potential donor atom are monodentate. Polydentate ligand is a ligand that is attached to a central metal ion by bonds from two or more donor atoms. Ligands with more than one potential donor atom are known as ambidentate, such as the thiocyanate ion, NCS-, which can bind to the metal center with either the nitrogen or sulphur atoms. Chelating ligands are those polydentate ligands which can form a ring including the metal atom.
Lithium was discovered by Johan August Arfvedson (Sweden) in 1817. The origin of the name comes from the Greek word lithos meaning stone, apparently because it was discovered from a mineral source whereas the other two elements, sodium and potassium, were discovered from plant sources. It is soft silvery-white metal. Lightest of metals. Reacts slowly with water and oxygen. Flammable. Can ignite in air. Reacts with water to give off a flammable gas. Lithium is obtained by passing electric charge through melted lithium chloride and from the silicate mineral called spodumene [LiAl(Si2O6)]. Used in batteries. Also for certain kinds of glass and ceramics. Some is used in lubricants.
Polarogram is a graph of current versus potential in a polarographic analysis. The position of a polarographic wave in a polarogram along the x axis (E1/2) provides an identity of the substance while the magnitude of the limiting diffusion current (id) provides the concentration of this substance.
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).
Potentiometric titration is a volumetric method in which the potential between two electrodes is measured (referent and indicator electrode) as a function of the added reagent volume. Types of potentiometric titrations for the determination of analytes in photoprocessing solutions include acid-base, redox, precipitation, and complexometric.
Potentiometric titrations are preferred to manual titrations, since they are more accurate and precise. They are also more easily adapted to automation, where automated titration systems can process larger volumes of samples with minimal analyst involvement.
A titration curve has a characteristic sigmoid curve. The part of the curve that has the maximum change marks the equivalence point of the titration. The first derivative, ΔE/ΔV, is the slope of the curve, and the endpoint occurs at the volume, V', where ΔE/ΔV has the maximum value.
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
Potential vs. SHE / V | |||||
calomel electrode | Ag/AgCl electrode | ||||
t / °C | 0.1 mol dm-3 | 3.5 mol dm-3 | sat. solution | 3.5 mol dm-3 | sat. solution |
15 | 0.3362 | 0.254 | 0.2511 | 0.212 | 0.209 |
20 | 0.3359 | 0.252 | 0.2479 | 0.208 | 0.204 |
25 | 0.3356 | 0.250 | 0.2444 | 0.205 | 0.199 |
30 | 0.3351 | 0.248 | 0.2411 | 0.201 | 0.194 |
35 | 0.3344 | 0.246 | 0.2376 | 0.197 | 0.189 |
Salt bridge is a permeable material soaked in a salt solution that allows ions to be transferred from one container to another. The salt solution remains unchanged during this transfer.
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.
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
Potential vs. SHE / V | ||
---|---|---|
t / °C | 3.5 mol dm-3 | sat. solution |
15 | 0.212 | 0.209 |
20 | 0.208 | 0.204 |
25 | 0.205 | 0.199 |
30 | 0.201 | 0.194 |
35 | 0.197 | 0.189 |
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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