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

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 severe, authoritative reviews of advances in each sector of the self-discipline. full of state-of-the-art learn mentioned in a cohesive demeanour no longer came across somewhere else within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complicated graduate category dedicated to the research of chemical physics.


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The latter is mainly a matter of convenience, since it can usually be obtained ex- 44 JACOB BIGELEISEN A N D MAX M’OLFSBERG perimentally either by extrapolation or by successive approximation in the cumulative product method. If R,, is known in the successive fraction method, the intercept gives (k/k’- 1). This is the equivalent of an additional experiment in the cumulative product met hod. For the case where ( f 2 - f l ) is appreciable one obtains the result given by Schmitt, llyerson, and Daniels,Ss which is valid only for small differences between Rr(3-4) and Rr(1--9, in addition to assumptions implicit in Eqs.

Few details of the work by Gray and Pritchard are available. 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.

S’+I’+ . . or I -4’, it follows --d;l/dt = k ( A ) ( B ) b ( C ) C.. ) r. 14) Simultaneous solution of this set of differential equations with the boundary condition -4’= -4‘, when -4 = ‘4, yields (V. 4 has reacted, and R,, is the initial ratio (A/A’)n. 16) Eq. 15 can be written The method then consists of the determination of the isotopic ratios R,, of the original substrate and R,, after astoichiometrically measured fraction, f, has reacted. 1, if the primed isotope is the light one and the reaction shows a normal isotope effect.

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