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.
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.
Graphite is an allotrope of carbon. The atoms are arranged in layers as a series of flat, hexagonal rings. Graphite is a good conductor of heat and electricity. The layers cleave easily, making graphite useful as a solid lubricant. A process to make pure synthetic graphite was invented by the American chemist Edward Goodrich Acheson (1856–1931). The process consists of heating a mixture of clay (aluminum silicate) and powdered coke (carbon) in an iron bowl. The reaction involves the production of silicon carbide, which loses silicon at 4150 °C to leave graphite.
Haber process is an industrial process for producing ammonia by reaction of nitrogen with hydrogen:
The reaction is reversible and exothermic, so that a high yield of ammonia is favoured by low temperature. However, the rate of reaction would be too slow for equilibrium to be reached at normal temperatures, so an optimum temperature of about 450 °C is used, with a catalyst of iron containing potassium aluminium oxide promoters. The higher the pressure the greater the yield, although there are technical difficulties in using very high pressures. A pressure of about 250 atmospheres is commonly employed. The removal of ammonia from the batch as soon as it is formed ensures that an equilibrium favouring product formation is maintained. The nitrogen is obtained from air. Formerly, the hydrogen was from water gas and the water-gas shift reaction (the Bosch process) but now the raw material (called synthesis gas) is obtained by steam reforming natural gas.
The process is of immense importance for the fixation of nitrogen for fertilisers and explosives. It was developed in 1908 by German chemist Fritz Haber (1868-1934) and was developed for industrial use by Carl Bosch (1874-1940), hence the alternative name Haber-Bosch process.
For a given reaction the half-life, t1/2, of a reactant is the time required for its concentration to reach a value that is the arithmetic mean of its initial and final (equilibrium) value.
Half-life is constant for first-order reactions.
Half-life is not constant for second-order reactions but rather it varies with initial concentration and k.
Hesse’s law says that reaction heat of some chemical change does not depend on the way in which the reaction is conducted, but only on starting and ending system state. Hesse’s law is also known as the law of constant heat summation. Hesse’s law is also known as the law of constant heat summation. The law was first put forward in 1840 by the Swiss-born Russian chemist Germain Henri Hess (1802-1850).
Hesse’s law can be used to obtain thermodynamic data that cannot be measured directly. For example, it is very difficult to control the oxidation of graphite to give pure CO. However, enthalpy for the oxidation of graphite to CO2 can easily be measured. So can the enthalpy of oxidation of CO to CO2. The application of Hess’s law enables us to estimate the enthalpy of formation of CO.
C(s) + O2(g) →← CO2(g) | ΔrH1 = -393 kJ mol-1 |
CO(g) + 1/2O2(g) →← CO2(g) | ΔrH2 = -283 kJ mol-1 |
C(s) + 1/2O2(g) →← CO(g) | ΔrH3 = -110 kJ mol-1 |
The equation shows the standard enthalpy of formation of CO to be -110 kJ/mol.
Reversible cell is an electrical cell the chemical action in which can be reversed by passing through it a current opposite in direction to that generated by the cell.
Generalic, Eni. "Millonova reakcija." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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