By Ilya Prigogine, Stuart A. Rice

ISBN-10: 0470143479

ISBN-13: 9780470143476

ISBN-10: 0470697628

ISBN-13: 9780470697627

The Advances in Chemical Physics sequence offers the chemical physics and actual chemistry fields with a discussion board for severe, authoritative reviews of advances in each sector of the self-discipline. choked with state-of-the-art learn suggested in a cohesive demeanour no longer chanced on in other places within the literature, every one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complex graduate category dedicated to the research of chemical physics.

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Extra resources for Advances in Chemical Physics, Volume 1

Example text

While for the isosceles triangular model, the ratio is two. This factor of two is, however, canceled since the symmetric H,C1 complex has two different but equally probable methods of decomposition. In Eq. 4COB BIGELEISES AND JIAX IYOLFSBERG terms for a triangular activated state, while for a linear activated state three frequencies, one of which is a doubly degenerate bending frequency, contribute to these terms. II’heeler, Topley, and Eyrir@* carried out approximate calculations of the potential energy surface for the H,+C1 reaction on the assumption that the activated state is linear.

Estimated Maximum Ratios in Specific Rate Constants at 25' C. 2 Maximum values for inverse isotope effects may be similarly calculated by setting f of the reactants equal to unity, which is indeed the case if the isotopic reactants are atoms. ,* may be taken as unity which is the minimum value of this ratio. Maximal values are estimated by taking the values for normal strongly of bonded molecules. This maximum value of inverse effects may be obtained from the values in Table I by dividing by the square root of the ratio of masses of the heavier to the Iighter isotope.

47) 46 JACOB BIGELEISEN AND X 4 X WOLFSBERG TABLE 111. 4 ‘ k ( 1- s . 48) if the reaction is carried to a small fraction of completion. For complete conversion, Eq. 50) while Eq. 44 gwes kJk, We now consider systems where the starting abundances of both isotopes A and A‘ are appreciable. Under these conditions one must take into consideration all three species A’BA’,A‘BA, and ABd and the products X,Y ,X‘, and Y’ formed from each of them. The distribution of A and A’ between these species is not necessarily given by classical statistics.

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


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