CHEMISTRY GLOSSARY

overpotential    →   prenapon

Overpotential (η) is a potential that must be applied in an electrolytic cell in addition to the theoretical potential required to liberate a given substance at an electrode. The value depends on the electrode material and on the current density.

positive pole    →   pozitivni pol

Positive pole is that half-cell in the electrochemical cell which has the most positive electrode potential.

cyclic voltammetry    →   ciklička voltametrija

Cyclic voltammetry (CV) is an electrochemical measuring technique used for the determination of the kinetics and mechanism of electrode reactions. The potential of the working electrode is controlled (typically with a potentiostat) and the current flowing through the electrode is measured. It is a linear-weep voltammetry with the scan continued in the reverse direction at the end of the first scan. This cycle can be repeated a number of times, and is used for corrosion studies.

electrical double layer    →   električni dvosloj

Electrical double layer is the structure of charge accumulation and charge separation that always occurs at the interface when an electrode is immersed into an electrolyte solution. The excess charge on the electrode surface is compensated by an accumulation of excess ions of the opposite charge in the solution. The amount of charge is a function of the electrode potential. This structure behaves essentially as a capacitor. There are several theoretical models that describe the structure of the double layer. The three most commonly used ones are the Helmholtz model, the Gouy-Chapman model, and the Gouy-Chapman-Stern model.

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.

fugacity    →   fugacitet

Fugacity (f) is a thermodynamic function used in place of partial pressure in reactions involving real gases and mixtures. For a component of a mixture, it is defined by

where μ is the chemical potential.

The fugacity of a gas is equal to the pressure if the gas is ideal. The fugacity of a liquid or solid is the fugacity of the vapour with which it is in equilibrium. The ratio of the fugacity to the fugacity in some standard state is the activity.

potentiometric titration    →   potenciometrijska titracija

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.

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