The Absolute Measurement of Rate Constants for Some Key Reactions Involving Free Radicals.
Annual rept. 1 Jul 72-31 May 73,
STANFORD RESEARCH INST MENLO PARK CALIF PHYSICAL SCIENCES DIV
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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.
- Physical Chemistry