1. The Absolute Measurement of Rate Constants for Some Key Reactions Involving Free Radicals.
- Author
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STANFORD RESEARCH INST MENLO PARK CALIF PHYSICAL SCIENCES DIV, Alfassi,Z. B., Beadle,P. C., Benson,S. W., Choo,K. Y., Golden,D. M., STANFORD RESEARCH INST MENLO PARK CALIF PHYSICAL SCIENCES DIV, Alfassi,Z. B., Beadle,P. C., Benson,S. W., Choo,K. Y., and Golden,D. M.
- Abstract
Absolute values of the rate constant for isopropyl radical combination have been determined over the temperature range 683-808K. It was found that isopropyl radicals react heterogeneously in a first-order manner with fused silica, probably to produce propylene. The four species (n-butane, 2,3-dimethylbutane, 2,2',3,3',-tetramethylbutane, and isobutane) were decomposed under (VLPP) very low-pressure conditions at temperatures in the vicinity of 1100K. Three model transition states were constructed that fit the low-pressure data thus obtained. Study of the pyrolysis, tBu-NO to tBu+ NO by VLPP yielded the Arrhenius parameters. A new free-volume model for the transition state for dissociation is shown to fit the data.
- Published
- 1973