CHEMISTRY GLOSSARY

activity    →   aktivitet

Activity (a) is a thermodynamic function used in place of concentration in equilibrium constants for reactions involving nonideal gases and solutions. For the species i activity is defined as

where a_i is the activity of the species i, c_i is its molar concentration, and f_i is a dimensionless quantity called the activity coefficient.

activity coefficient    →   koeficijent aktiviteta

Activity coefficient (γ or f) is a fractional number which, when multiplied by the molar concentration of a substance in solution, yields the chemical activity. This term gives an idea of how much interaction exists between molecules at higher concentration.

In solutions of very low ionic strength, when m is less than 0.01, the Debye-Hückel limiting law can be used to calculate approximate activity coefficients

where γ_i = activity coefficient of the species i, z_i = charge on the species i and μ = ionic strength of the solution.

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).

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.

TISAB    →   TISAB

TISAB (Total Ionic Strength Adjustment Buffer) is a buffer solution which maintains a constant activity of an analyte in solution.

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

glass electrode    →   staklena elektroda

Glass electrode is a hydrogen-ion responsive electrode usually consisting of a bulb, or other suitable form, of special glass attached to a stem of high resistance glass complete with internal reference electrode and internal filling solution system. Glass electrode is also available for the measurement of sodium ions.

The glass electrode, which consists of a thin wall glass bulb, has an extremely high electrical resistance. The membrane of a typical glass electrode (with a thickness of 0.03 mm to 0.1 mm) has an electrical resistance of 30 MΩ to 600 MΩ. The surface of a glass membrane must be hydrated before it will function as a pH electrode. When a glass surface is immersed in an aqueous solution then a thin solvated layer (gel layer) is formed on the glass surface in which the glass structure is softer. This applies to both the outside and inside of the glass membrane.

The simplest explanation for the working of the thin glass electrode is that the glass acts as a weak acid (Glass-H).

The hydrogen ion activity of the internal solution is held constant. When a solution of different pH from the inside comes in contact with the outside of the glass membrane, the glass is either deprotonated or protonated relative to the inside of the glass. The difference in pH between solutions inside and outside the thin glass membrane creates electromotive force in proportion to this difference in pH.

indicator electrode    →   indikatorska elektroda

Indicator electrode is working in one of the electrodes in some classical two-electrode cells, e.g., in a potentiometric electroanalytical setup where the potential of the measuring electrode (against a reference electrode) is a measure of the concentration (more accurately activity) of a species in the solution.

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

pH    →   pH

pH is a convenient measure of the acid-base character of a solution, usually defined by

where c(H⁺) is the concentration of hydrogen ions in moles per litre. The more precise definition is in terms of activity rather than concentration.

A solution of pH 0 to 7 is acid, pH of 7 is neutral, pH over 7 to 14 is alkaline.