CHEMISTRY GLOSSARY

dissociation constant    →   konstanta disocijacije

Dissociation constant is a constant whose numerical value depends on the equilibrium between the undissociated and dissociated forms of a molecule. A higher value indicates greater dissociation.

The term dissociation is also applied to ionisation reactions of acids and bases in water. For example

which is often regarded as a straightforward dissociation into ions

The equilibrium constant of such a dissociation is called the acid dissociation constant or acidity constant, given by

The concentration of water [H₂O] can be taken as constant.

Similarly, for a base, the equilibrium

is also a dissociation; with the base dissociation constant or basicity constant, given by

K_a (K_b) is a measure of the strength of the acid (base).

universal gas constant    →   univerzalna plinska konstanta

Universal gas constant R has the value of 8.314 472(15) J K^-1 mol^-1. It corresponds to the volume work performed by one mole of gas heated by 1 K at standard pressure.

equilibrium constant    →   konstanta ravnoteže

The equilibrium constant (K) was originally introduced in 1863 by Norwegian chemists C.M. Guldberg and P. Waage using the law of mass action. For a reversible chemical reaction represented by the equation

chemical equilibrium occurs when the rate of the forward reaction equals the rate of the back reaction, so that the concentrations of products and reactants reach steady-state values.

The equilibrium constant is the ratio of chemical activities of the species A, B, C, and D at equilibrium.

To a certain approximation, the activities can be replaced by concentrations.

For gas reactions, partial pressures are used rather than concentrations

The units of K_p and K_c depend on the numbers of molecules appearing in the stoichiometric equation (a, b, c, and d).

The value equilibrium constant depends on the temperature. If the forward reaction is exothermic, the equilibrium constant decreases as the temperature rises. The equilibrium constant shows the position of equilibrium. A low value of K indicates that [C] and [D] are small compared to [A] and [B]; i.e. that the back reaction predominates.

The equilibrium constant is related to Δ_rG°, the standard Gibbs free energy change in the reaction, by

solubility product constant    →   konstanta produkta topljivosti

Solubility product constant (K_sp) (or the solubility product) is the product of the molar concentrations of the constituent ions, each raised to the power of its stoichiometric coefficient in the equilibrium equation. For instance, if a compound A_aB_b is in equilibrium with its solution

the solubility product is given by

Faraday’s laws of electrolysis    →   Faradayevi zakoni elektrolize

Faraday’s laws of electrolysis are two laws found by British chemist and physicist Michael Faraday (1791-1867) in his experiments on electrolysis:

1. The quantity of matter extracted on the electrode is proportional to the quantity of charge (Q = I·t) which has flown in electrolysis time.

where z = number of electrons changed in reaction and F = Faraday’s constant which equals 96 487 C mol^-1.

2. The masses of the elements liberated by the same quantity of electricity are directly proportional to their chemical equivalents.

96 487 C will discharge 1 mol Ag and 1/2 mol Cu. The relevant half reactions are:

Faraday cage    →   Faradayev kavez

Faraday cage is a container giving protection from electrical fields: an assembly of conducting material, for example, metal mesh or grid, placed around electrical equipment to protect it from external electrical fields. Faraday cages are named after the English scientist Michael Faraday (1791-1867).

lattice constants    →   konstante kristalne rešetke

Lattice constants are parameters specifying the dimensions of a unit cell in a crystal lattice, specifically the lengths of the cell edges and the angles between them.

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).

Nernst’s electrode potential equation    →   Nernstova jednadžba za elektrodni potencijal

For general reaction of some redox system

dependence of electrode potential of redox system upon activity of oxidised and reduced form in solution is described in Nernst’s equation for electrode potential:

where E = to electrode potential of redox system

E° = standard electrode potential of redox system

R = universal gas constant

T = thermodymical temperature

F = Faraday’s constant

z = number of electrons exchanged in redox reaction

a_O = activity of oxidised form

a_R = activity of reduced form

n = stechiometrical coefficient of oxidised form

m = stechiometrical coefficient of reduced form

Heyrovsky-Ilkovic equation    →   Heyrovsky-Ilkovičeva jednadžba

The Heyrovsky-Ilkovic equation describes the entire current-potential curve (polarographic wave) of a reversible redox system in polarography

where R is the gas constant, T is the absolute temperature, F is the Faraday constant, n denotes the number of electrons taking part in the electrode reaction. E_1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.

In order to obtain E_1/2 from the above equation, we plot a graph of ln[(i_d-i)/i] against E. The intercept on the x-axis gives then an accurate value of E_1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.