Advances in Chemical Physics, Volume 1 by Ilya Prigogine, Stuart A. Rice

By Ilya Prigogine, Stuart A. Rice

The Advances in Chemical Physics sequence offers the chemical physics and actual chemistry fields with a discussion board for serious, authoritative reviews of advances in each quarter of the self-discipline. choked with state of the art examine said in a cohesive demeanour no longer came across in other places within the literature, every one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complicated graduate classification dedicated to the learn of chemical physics.


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4SD MAX WOLFSBERG of secondary isotope effects. Secondary isotope effects occur when the isotopic atoms are not directly involved in the bond breaking and bond forming of a reaction. Examples of secondary isotope effects will be given in a subsequent section. From the definition of secondary isotope effect, vlL*/r2L* = 1 should be valid to a high degree of approximation. Then one only calculates f/#* in order to compute secondary isotope effects. The major contributions to /,if* arise froiii large shifts in large frequencies.

All the internal degrees of freedom will be taken as active and as vibrations (except for the actual motion along the decomposition path in the activated complex). 5) * where k , is the high pressure rate constant, w is a dimensionless integration variable, and * For all the assumptions leading to this final equation, the reader is referred to Marcus' original paper. Some of the assumptions could conceix-ably have an isotope effect. The assumptions necessary t o arrive at the zero-pressure isotope effect ratio, Eqs.

This procedure, furthermore, eliminates the difficult corrections which would have to be applied for isotopic discrimination in the mass spectrometer. If the substrate or products contain the isotopes A and A in groups or substituents other than the reaction center, there may be complications from isotopic homogeneity. This has been pointed out previously. 1 per cent discrimination. The isotopic inhomogeneity problem may arise in either intermolecular or intramolecular reactions even when working with isotope concentrations down to the tracer level.

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