CHEMISTRY GLOSSARY

electrochemical cell    →   elektrokemijski članak

Electrochemical cell is a device that converts chemical energy into electrical energy or vice versa when a chemical reaction is occurring in the cell. It consist of two electronically conducting phases (e.g., solid or liquid metals, semiconductors, etc) connected by an ionically conducting phase (e.g. aqueous or non-aqueous solution, molten salt, ionically conducting solid). As an electric current passes, it must change from electronic current to ionic current and back to electronic current. These changes of conduction mode are always accompanied by oxidation/reduction reactions.

An essential feature of the electrochemical cell is that the simultaneously occurring oxidation-reduction reactions are spatially separated. E.g., in a spontaneous chemical reaction during the oxidation of hydrogen by oxygen to water, electrons are passed directly from the hydrogen to the oxygen.

In contrast, in the spontaneous electrochemical reaction in a galvanic cell the hydrogen is oxidised at the anode by transferring electrons to the anode and the oxygen is reduced at the cathode by accepting electrons from the cathode. The ions produced in the electrode reactions, in this case positive hydrogen ions and the negative hydroxyl (OH^-) ions, will recombine in the solution to form the final product of the reaction: water. During this process the electrons are conducted from the anode to the cathode through an outside electric circuit where the electric current can drive a motor, light a light bulb, etc. The reaction can also be reversed: water can be decomposed into hydrogen and oxygen by the application of electrical power in an electrolytic cell.

inhibitor    →   inhibitor

Inhibitor is a chemical that stops (or at least decreases the rate of) a chemical reaction.

irreversible galvanic cell    →   nepovrativi galvanski članak

Irreversible galvanic cell is a chemical source of direct current, in which reactions that take place on the electrodes are irreversible.

electrolytic cell    →   elektrolitska ćelija

Electrolytic cell is an electrochemical cell that converts electrical energy into chemical energy. The chemical reactions do not occur spontaneously at the electrodes when they are connected through an external circuit. The reaction must be forced by applying an external electric current. It is used to store electrical energy in chemical form (rechargeable battery). It is also used to decompose or produce (synthesise) new chemicals by the application of electrical power. This process is called electrolysis, e.g., water can be decomposed into hydrogen gas and oxygen gas. The free energy change of the overall cell reaction is positive.

limiting reactant    →   mjerodavni reaktant

Limiting reactant is a reactant in a chemical reaction that limits the amount of product that can be formed. The reaction will stop when the entire limiting reagent is consumed. These other reactants are present in excess.

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

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:

mineral acid    →   mineralna kiselina

Mineral acid is an acid made from minerals by chemical reaction, e.g. hydrochloric acid is produced from sodium chloride and sulphuric acid is made from sulphur.

fuel cell    →   gorivi članak

Fuel cell is a device that converts chemical energy into electrical energy. It is different from a battery in that the energy conversion continues as long as fuel and oxidising agent are fed to the fuel cell; that is, in principle indefinitely. (A battery is manufactured with a limited amount of chemicals, and it is exhausted when all the chemicals have reacted.) It is a galvanic cell where spontaneous chemical reactions occur at the electrodes. The fuel is oxidised at the anode, and the oxidising agent (almost always oxygen or air) is reduced at the cathode. Presently, the most commonly used fuel is hydrogen. More conventional fuels (e.g., petrol or natural gas) must be converted (reformed) into hydrogen before they can be utilised in a fuel cell.

Some fuel cells employ an aqueous solution as electrolyte, that can be either acidic or basic (alkaline), or an ion-exchange membrane soaked in aqueous solution can act as the electrolyte. These fuel cells operate at relatively low temperatures (from room temperature to not much above the boiling point of water). Some fuel cells employ molten salts (especially carbonates) as electrolytes and have to operate at temperatures of several hundred degrees centigrade (Celsius). Others employ ionically conductive solids as electrolyte and must operate close to 1 000 °C.

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.