Single-pulse shock tube studies of hydrocarbon pyrolysis. Part 1.—Pyrolysis of cyclopropane

Abstract

The pyrolysis of cyclopropane + argon mixtures has been studied in a single-pulse shock tube over the temperature range 1060–1870 K. At a total pressure of 500 mmHg and temperatures below 1300 K, an apparent first-order rate constant of 10^11.9 exp (–230 kJ/RT) s^–1 was obtained. This is in agreement with extrapolations from low temperature data provided allowance is made for the deviation from limiting first-order behaviour with increasing temperature. Above 1300 K, radical chain decomposition of the cyclopropane and/or the propylene product was observed but the overall loss of cyclopropane, which is best fitted by the expression 10^4.75 exp(–48.5 kJ/RT) s^–1, was much lower than predicted by current unimolecular reaction rate theory. Various alternative mechanisms are examined but no acceptable explanation can yet be offered.