Abstract
AbstractThe decomposition kinetics of n‐pentyl radicals in the high temperature regime where steady state distributions are not achieved and reversible isomerization to decomposing 2‐pentyl radicals is of importance has been analyzed through the solution of the time‐dependent master equation. The reactions are characterized by low activation thresholds and lead to large rate constants that vary with time. Particular attention is paid to branching ratios for direct decomposition of the n‐pentyl radical and the decomposition that follows reversible isomerization to the 2‐pentyl species. The behavior of the system under a variety of conditions is described and the use of branching ratios as a possible means of characterizing the reactions in a manner that is compatible with present methods for employing kinetic data for simulating complex chemical phenomenon is considered. At higher temperatures, rate constants and branching ratios collapse to limiting values. The combination of limiting and the onset of steady state behavior complicates the situation at lower temperatures. The overall behavior of such systems is highly dependent on the magnitude of the barrier to isomerization. The extent of departures from the high pressure‐branching ratios are defined.
Published Version
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