Relationship between the Time-Dependence of a Transient-State Kinetic Isotope Effect and the Location of Complexes in a Reaction Sequence

Relationship between the Time-Dependence of a Transient-State Kinetic Isotope Effect and the Location of Complexes in a Reaction Sequence

We prove here a new transient-state kinetic rule which states that the ratios of the first derivatives of kinetic isotope effect time courses, extrapolated to zero time, provide integral values which specify the precise step number in the reaction sequence in single isotope substituted reactions. Th...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 13; pp. 4465 - 4472
Main Authors: Fisher, Harvey F, Palfey, Bruce A, Maniscalco, Steven J, Indyk, Lawrence
Format: Journal Article
Language:English
Published: United States American Chemical Society 06-04-2006
Subjects:
Isotopes
Kinetics
Mathematics
Models, Chemical
Time Factors
Online Access:Get full text
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Summary:We prove here a new transient-state kinetic rule which states that the ratios of the first derivatives of kinetic isotope effect time courses, extrapolated to zero time, provide integral values which specify the precise step number in the reaction sequence in single isotope substituted reactions. This rule defines such absolute numbers even where the steps involved are too fast to provide measurable concentrations of intermediates and when the full reaction sequence is unknown.
Bibliography:istex:2228BC7B9A1DD613B0FC4F3F39C3A80C55865E94
ark:/67375/TPS-S476GMG6-N
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:1089-5639
1520-5215
DOI:10.1021/jp057254x