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 sector of the self-discipline. choked with state-of-the-art examine suggested in a cohesive demeanour no longer came across in different places within the literature, every one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complex graduate type dedicated to the research of chemical physics.
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Additional resources for Advances in Chemical Physics, Volume 1
We assume kinetics either first order or pseudo first order in the substrate. In addition to the rate constants k,, k,, and k,, defined by Eqs. 40, we define the rate constant k , through the reaction ABA+C+. . -+ k4 X+Y+. 57) 48 JACOB BIGELEISEN AND MA4X WOLFSBERG The relative yields of x', X',Y,and k" from A'BA', ,4'BA, and A B A as /, the fraction of substrate converted, approaches 0 or 1 are given in Table 111. For simplicity we shall consider the case where 1 = i n = n. 59) etc. 64) R,, is still defined by Eq.
8 may be derived from Eq. 4, kuni =SR,pd(k,/k,), and the aforementioned assumptions. ~ (one-component systems). The functions f and 21 were defined in Section 11. Since in general v I z 2 v2,, one would expect the isotope effect a t lower pressures to be smaller than the high-pressure isotope effect. However, the temperature dependence of the isotope effect, which arises principally from the difference in differences of zeropoint energies, should remain independent of pressure. Only two experimental investigations have been carried out to study isotope effects in unimolecular reactions a t low pressures.
Only one case of the formulation Lvill be considered here. The three rotations of the molecule as a whole (as well as the three translations of the molecule, which make no contribution to the rate) will be considered to be adiabatic. -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.
Advances in Chemical Physics, Volume 1 by Ilya Prigogine, Stuart A. Rice