Accession Number:

AD0432304

Title:

SECONDARY ISOTOPE EFFECTS IN THE CHEMICALLY ACTIVATED SEC-BUTYL-D SUB O AND -D SUB * SYSTEMS AND SEC-BUTYL-D SUB 1 AND -D SUB 9 SYSTEMS,

Descriptive Note:

Corporate Author:

WASHINGTON UNIV SEATTLE

Report Date:

1964-03-10

Pagination or Media Count:

36.0

Abstract:

The decomposition of chemically activated secbutyl- radicals, produced by H- and D- atom addition to cis-butene-2 has been studied at 195 and 300 K over a range of pressures. These measurements, as well as internal comparison experiments with cis-butene-2, reveal a large normal secondary intermolecular kinetic isotope ratio which varies with the pressure and temperature, and whose minimum value is a factor of 4 and whose maximum value averages around 7. The absolute magnitude of the ratio, and its temperature, pressure, and energy dependence are in satisfactory agreement with the theory of these chemical activation systems some aspects of this dependence are discussed. Evidence against a significant mechanistic isotope effect on the energetics is presented. Calculated isotope effects for all of the possible sec-butyl radical systems, to be formed by H- and D-atom addition to butene-d subzero and -d sub 8. Author

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Distribution Statement:

APPROVED FOR PUBLIC RELEASE