CHEMISTRY GLOSSARY

Onsager relations    →   Onsagerove relacije

Onsager relations are an important set of equations in the thermodynamics of irreversible processes. They express the symmetry between the transport coefficients describing reciprocal processes in systems with a linear dependence of flux (J_i) on driving forces (X_j).

In Onsager’s theory the coupling coefficients are equal, L_ij = L_ji. This is known as reciprocal relations. The theory was developed by the Norwegian chemist Lars Onsager (1903-1976) in 1931.

Ostwald’s dilution law    →   Ostwaldov zakon razrjeđenja

Ostwald’s dilution law is a relation for the concentration dependence of the molar conductivity Λ of an electrolyte solution, viz.

where c is the solute concentration, K_c is the equilibrium constant for dissociation of the solute, and L₀ is the conductivity at cΛ = 0. The law was first put forward by the German chemist Wilhelm Ostwald (1853-1932).

photoelectric effect    →   fotoelektrični efekt

Photoelectric effect is the complete absorption of a photon by a solid with the emission of an electron. The energy of a photon (hν) is

polarogram    →   polarogram

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 (E_1/2) provides an identity of the substance while the magnitude of the limiting diffusion current (i_d) provides the concentration of this substance.

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).

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.

practical salinity    →   praktični salinitet

Practical salinity S_P is defined on the Practical Salinity Scale of 1978 (PSS-78) in terms of the conductivity ratio K₁₅ which is the electrical conductivity of the sample at temperature t₆₈ = 15 °C and pressure equal to one standard atmosphere, divided by the conductivity of a standard potassium chloride (KCl) solution at the same temperature and pressure. The mass fraction of KCl in the standard solution is 0.0324356 (32.4356 g of KCl in 1 kg of solution). When K₁₅ = 1, the Practical Salinity P S is by definition 35. The conductivity of that reference solution is C(35,1568,0) = 42.914 mS/cm = 4.2914 S/m (Siemens per meter). Note that Practical Salinity is a unit-less quantity. Though sometimes convenient, it is technically incorrect to quote Practical Salinity in "psu". When K₁₅ is not unity, S_P and K₁₅ are related by the PSS-78 equation

At a temperature of t₆₈ = 15 °C, R_t is simply K₁₅ and Practical Salinity S_P can be determined from the above equation. For temperatures other than t₆₈ = 15 °C, Practical Salinity S_P is given by the following function of R_t (k = 0.0162)

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

salt bridge    →   solni most

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.

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