By Ilya Prigogine, Stuart A. Rice
The Advances in Chemical Physics sequence presents the chemical physics and actual chemistry fields with a discussion board for serious, authoritative reviews of advances in each zone of the self-discipline. full of state of the art examine pronounced in a cohesive demeanour no longer came upon somewhere else within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the ideal complement to any complicated graduate type dedicated to the examine of chemical physics.
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Extra resources for Advances in Chemical Physics, Volume 1
Since t has been defined so that the subscripts 1 and 2 refer to the light and heavy isotopes, respectively, vIL* 2 vzL*. Moreover G ( u ) and 421 are positive. G(u)increases with increasing u to the maximum value of $. Similarly (s2'sl)f is always greater than unity. Since in general the binding is greater in the reacting molecule than in the transition complex, we would expect k , > k,, apart from the classical statistical factor. In the case where the isotopic reactants are atoms, G ( u ) d ( 2 1 ) is zero and k,/k, may well become less than unity.
The isotope effect does not appear to change much n i t h pressure. Strangly enough these authors find that the reaction exhibits an inverse isotope effect = 8. with k,(C,H,)/K,(C,D,) U’eston’s experiment was carried out with tritium a t the tracer level and, therefore, in the labeled molecule only 1 hydrogen atom out of 6 equivalent ones is replaced. The reaction studied thus has both an intermolecular and an intramolecular isotope effect. Up to the approximation of no secondaryisotope effects, the high-pressure rate of isomerization of a protium atom in the labeled molecule will not differ significantly from that of the unlabeled molecule.
The reaction studied thus has both an intermolecular and an intramolecular isotope effect. Up to the approximation of no secondaryisotope effects, the high-pressure rate of isomerization of a protium atom in the labeled molecule will not differ significantly from that of the unlabeled molecule. 9at 775’K. The absoluteerrorof themeasurementisnaturally magnified by the statistical correction for the intramolecular dilution. Because of this intramolecular dilution, a reliable temperature coefficient of the ratio of rate constants cannot be obtained by a least square treatment of the experimental data.