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 zone of the self-discipline. packed with state-of-the-art examine suggested in a cohesive demeanour now not discovered in other places within the literature, each 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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Advances in Chemical Physics, Volume 1

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 quarter of the self-discipline. full of state of the art learn suggested in a cohesive demeanour no longer discovered somewhere else within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complex graduate classification dedicated to the learn of chemical physics.

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V. EXPERIMENTAL METHODS The theoretical calculations of the maximum isotopic effects on rate constants summarized in Table I lead one to expect differences in isotopic reaction rates ranging from a few per cent for most elements to orders of magnitude for the isotopes of hydrogen. Two methods can be used to measure the rates of 36 JACOB BIGELEISEN AND MAX WOLFSBERG chemical reactions: (1) measurement of absolute rates and (2) competitive methods. In a small number of favorable cases an accuracy of one-tenth of a per cent can be attained in the measurement of the rate constant by absolute methods.

The distribution of A and A’ between these species is not necessarily given by classical statistics. 52) where N , is the atom fraction of A . If the concentrations are expressed in mole fractions 47 ISOTOPE EFFECTS I N CHEMICAL KINETICS A ’ B A , and A B A According to Eqs. 57. 53) Solution of Eqs. 56) Apart from the molecular species H , or systems at very low temperatures, the values of 6 for all chemical species is of the order of lo-, or less6 Thus the correction for nonclassical equilibrium distribution to any species is at most one per cent.

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. 52) where N , is the atom fraction of A . If the concentrations are expressed in mole fractions 47 ISOTOPE EFFECTS I N CHEMICAL KINETICS A ’ B A , and A B A According to Eqs. 57. 53) Solution of Eqs. 56) Apart from the molecular species H , or systems at very low temperatures, the values of 6 for all chemical species is of the order of lo-, or less6 Thus the correction for nonclassical equilibrium distribution to any species is at most one per cent.

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