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enthalpy of activation, Math - title
The standard enthalpy of activation Math - text 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 Math - ei, where Math - text denotes the standard concentration (usually Math - text).
Math - e
The quantity Math - text is the standard entropy of activation, and care must be taken with standard states. In this equation Math - text is the Boltzmann constant, Math - text the absolute temperature, Math - text the Planck constant, and Math - text 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 Math - text on the symbol are often omitted. The symbol is frequently (but incorrectly) written Math - text, where the standard symbol is omitted and the Math - text is placed after the Math - text.
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
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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.
Last update: 2008-10-07; version: 2.0.2.
DOI of this term: doi:10.1351/goldbook.E02142.
Original PDF version (may be out of date): http://www.iupac.org/goldbook/E02142.pdf.
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