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isokinetic relationship

When a series of structurally related substrates undergo the same general reaction or when the reaction conditions for a single substrate are changed in a systematic way, the enthalpies and entropies of activation sometimes satisfy the relation:
Δ ‡ H − β Δ ‡ S = constant
where the parameter β is independent of temperature. This equation (or some equivalent form) is said to represent an 'isokinetic relationship'. The temperature T = β (at which all members of a series obeying the isokinetic relationship react at the same rate) is termed the 'isokinetic temperature'. Supposed isokinetic relationships as established by direct correlation of Δ ‡ H with Δ ‡ S are often spurious and the calculated value of β is meaningless, because errors in Δ ‡ H lead to compensating errors in Δ ‡ S. Satisfactory methods of establishing such relationships have been devised.
PAC, 1994, 66, 1077 (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1129
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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: (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
Last update: 2014-02-24; version: 2.3.3.
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