CHEMISTRY GLOSSARY

conditional electrode potential    →   uvjetni elektrodni potencijal

Conditional or formal electrode potential (E°’) is equal to electrode potential (E) when overall concentrations of oxidised and reduced form in all its forms in a solution are equal to one. Conditional electrode potential includes all effects made by reactions that do not take part in the electron exchange, but lead to change of ion power, changes of pH, hydrolysis, complexing, precipitating, etc.

At 298 K (25 °C) and by converting natural (Napierian) logarithms into decimal (common, or Briggian) logarithms, Nernst’s equation for electrode potential can be written as follows:

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).

Gibbs free energy    →   Gibbsova slobodna energija

Gibbs free energy (G) is an important function in chemical thermodynamics, defined by

where H is the enthalpy, S the entropy, and T the thermodynamic temperature. Gibbs free energy is the energy liberated or absorbed in a reversible process at constant pressure and constant temperature. Sometimes called Gibbs energy and, in older literature, simply free energy.

Changes in Gibbs free energy, ΔG, are useful in indicating the conditions under which a chemical reaction will occur. If ΔG is negative the reaction will proceed spontaneously to equilibrium. In equilibrium position ΔG = 0.

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

mass    →   masa

Mass (m) is the quantity of matter contained in a particle or body regardless of its location in the universe. Mass is constant, whereas weight is affected by the distance of a body from the centre of the Earth (or of other planet). The SI unit is kilogram.

According to the Einstein equation

all forms of energy possess a mass equivalent.

mass-energy equivalence    →   ekvivalencija mase i energije

In the special theory of relativity Einstein demonstrated that neither mass nor energy were conserved separately, but that they could be traded one for the other and only the total "mass-energy" was conserved. The relationship between the mass and the energy is contained in what is probably the most famous equation in science,

Where m is the mass of the object and c is the velocity of light. Cockcroft and Walton (1932) are routinely credited with the first experimental verification of mass-energy equivalence.

Newton’s gravitational law    →   Newtonov zakon gravitacije

Every object in the universe attracts every other object with a force (gravitational force F_G) directed along the line through centres of the two objects that is proportional to the product of their masses and inversely proportional to the square of the distance between them.

m₁ and m₂ are masses of the two objects and r is the distance between them. G is universal constant of gravitation, which equals 6.67•10^-26 N m² kg^-2. Strictly speaking, this law applies only to objects that can be considered pointlike object. Otherwise, the force has to be found by integrating the forces between various mass elements.

It is more properly to express Newton’s gravitational law by vector equation:

in which r₁ and r₂ are position vectors of masses m₁ and m₂.

Gravitational forces act on distance. Newton’s gravitational law is derived from Kepler’s law for planetary motion, using a physical assumption considering Sun as the centre and the source of gravitational force.

Additionally, every object moves in the direction of the force acting on it, with acceleration that is inversely proportional to the mass of object. For bodies on the surface of Earth, the distance r in gravitational law formula is practically equal to the Earth radius, R_E. If the mass of the body on Earth surface is m and the mass of earth is M_E, the gravitational force acting on that body can be expressed as:

where g is gravitational acceleration which is, although dependent on geographical latitude, usually considered as constant equal to 9.81 m s^-2.

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