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 quarter of the self-discipline. jam-packed with state-of-the-art examine stated in a cohesive demeanour now not chanced on in other places 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 examine of chemical physics.

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4 ‘ k ( 1- s . 48) if the reaction is carried to a small fraction of completion. For complete conversion, Eq. 50) while Eq. 44 gwes kJk, We now consider systems where the starting abundances of both isotopes A and A‘ are appreciable. 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 .

Fractional error in k'lk, determined by isotopic analysis of unreacted substrate, as a function of the amount of reaction. approaches the precision of the isotopic analysis when the fraction reacted is greater than 90 per cent. At higher amounts of conversion the precision drops as a result of errors in the determination of the fraction of the substrate unreacted. 1 per cent, k'/k is 3, and the error in f , the fractional amount of reaction, is determined by the absolute error in measuring the amount of unreacted substrate.

I n the chemical competitive method, the isotopic compounds ,-1 or A ’ compete with a cheniically different species, B , for reaction with c‘. The method is, therefore, not applicable to unimolecuiar reactions and requires samples of A and A’ of appreciable isotopic enrichment. Furthermore, the species B must react with C at a rate of similar order of magnitude as A or A’ do. 6) in the experiment where A and B are intercompared. Similarly, dX‘ K’(n‘,--n’) dY - k,(b,--y) ISOTOPE EFFECTS I N CHEMICAL KINETICS 37 in the experiment where A’ and B are intercompared.

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