Enthalpy (H) is a thermodynamic property of a system defined by
where U is the internal energy of the system, p its pressure, and V its volume. J.W. Gibbs put the concept of an ensemble forward in 1902. In a chemical reaction carried out in the atmosphere the pressure remains constant and the enthalpy of reaction (ΔH), is equal to
For an exothermic reaction ΔH is taken to be negative.
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 Kp and Kc 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 ΔrG°, the standard Gibbs free energy change in the reaction, by
Racemisation is a conversion, by heat or by chemical reaction, of an optically active compound into an optically inactive form which half of the optically active substance becomes its miror image (enantiomer).
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:
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 (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.
Generalic, Eni. "Kemijska reakcija." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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