Unimolecular Rate Expression for Cyclohexene Decomposition and Its Use in Chemical Thermometry under Shock Tube...

The methods used in deriving the rate expressions from comparative rate single-pulse shock tube studies, recent direct shock tube studies, and high-pressure flow experiments bearing on the data for the reverse Diels-Alder decomposition of cyclohexene to form ethylene and 1,3-butadiene are reviewed. This current interest is due to the increasing need for accurate kinetics and physical data (particularly the temperature) for realistic simulations in practical areas such as combustion. The rate constants derived from the direct shock tube studies and high-pressure flow experiments are somewhat larger than those used in comparative rate single-pulse shock tube experiments. For the latter, it is shown that they have been derived from a variety of independent experiments that include rate constants for unimolecular decomposition and isomerization processes that are considered to be well understood. The possibility of non-Arrhenius behavior in the unimolecular rate constants as a consequence of the large range covered in rate constants (as much as 12 orders of magnitude) for the comparative rate experiments has been examined and ruled out as a source of the discrepancy. Our analysis shows that there is the need to consider the possibility of radical-induced decompositions for verifying the correctness of the reaction mechanisms in studying unimolecular reactions. In the case of cyclohexene decomposition, recent experiments demonstrating the presence of residual amounts of H atoms in shock tube experiments suggest that addition to the double bond can also lead to the formation of ethylene and 1,3-butadiene and hence to rate constants larger than the true values. This possibility is even more likely to occur in high-pressure flow experiments. As a result, the internal standard method must be used with care and a radical inhibitor should always be present in sufficiently large quantities to suppress possible chain reactions. The present analysis results have important implications for the determination of temperatures in shock tubes.