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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:
D‡H - bD‡S = constant
where the parameter b is independent of temperature. This equation (or
some equivalent form) is said to represent an ¡®isokinetic relationship¡¯. The
temperature T = b (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
D‡H with D‡S are often spurious and the calculated value of b is meaningless,
because errors in D‡H lead to compensating errors in D‡S. Satisfactory
methods of establishing such relationships have been devised.
See also compensation effect, isoequilibrium relationship, isoselective
relationship.
1994, 66, 1129
IUPAC Compendium of Chemical Terminology 2nd Edition (1997)
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