The standard
enthalpy of
activation is the
enthalpy change that appears in the thermodynamic form of the rate equation obtained from
conventional
transition state theory. This equation is only correct for a first order reaction, for which the
rate constant has the dimension reciprocal time. For a second order reaction, for which the
rate constant has the dimension (reciprocal time) × (reciprocal concentration), the left hand side
should be read as
, where
denotes the
standard concentration (usually
).
The quantity
is the standard
entropy of activation, and care must be taken with standard states. In this equation
is the
Boltzmann constant,
the absolute temperature,
the
Planck constant, and
the
gas constant. The
enthalpy of
activation is approximately equal to the
activation energy; the conversion of one into the other depends on the
molecularity. The
enthalpy of
activation is always the standard quantity, although the word standard and the superscript
on the symbol are often omitted. The symbol is frequently (but incorrectly) written
, where the standard symbol is omitted and the
is placed after the
.
Source:
PAC, 1996, 68, 149
(A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC
Recommendations 1996))
on page 164
PAC, 1994, 66, 1077
(Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994))
on page 1113
PAC, 1993, 65, 2291
(Nomenclature of kinetic methods of analysis (IUPAC Recommendations 1993))
on page 2294
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.
https://doi.org/10.1351/goldbook.