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 severe, authoritative reviews of advances in each region of the self-discipline. full of state of the art examine mentioned in a cohesive demeanour now not came upon in other places within the literature, every one quantity of the Advances in Chemical Physics sequence serves because the ideal complement to any complicated graduate category dedicated to the examine of chemical physics.


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One can now calculate vl* for both the linear and triangular complexes by using the data for HT and H, at one temperature. 5 8 JACOB BIGELEISEN AND MAX WOLFSBERG The results are summarized in Tables V and VI. 03). The choice of vl* thus leads to very good agreement with experiment over the given temperature range. For the linear model the agreement between theory and experiment over the temperature range is not as good. TABLE V. Frequency Assignment for Triangular H,C1 Complex. 16' I< 200 cm-1 approximated 720i cm-l calculated by WTE for a linear model IObT Fig.

21 permit us to make some general predictions about isotope effects. 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.

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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