A quantity derived from the pressure dependence of the
rate constant of a reaction (mainly used for reactions in solution),
defined by the equation:
providing that the rate constants of all reactions (except first-order reactions) are expressed in pressure-independent concentration units, such as
at a fixed temperature and pressure. The volume of
activation is interpreted, according to
transition state theory, as the difference between the partial molar volumes of the
transition state (
) and the sums of the partial volumes of the reactants at the same temperature and pressure, i.e.
where
is the order in the reactant R and
its
partial molar volume.
Source:
PAC, 1994, 66, 1077
(Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994))
on page 1175
See also:
PAC, 1996, 68, 149
(A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996))
on page 191
Green Book, p. 56
Cite as:
IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A.Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
doi:10.1351/goldbook.
