Determination of gas-phase ozonolysis rate coefficients of C(8-14) terminal alkenes at elevated temperatures using the relative rate method.

The rates of ozonolysis of a suite of terminal alkenes ranging from C8-14 are determined in the gas phase at an elevated temperature of 395.9 +/- 1.2 K and a pressure of similar to 650 Torr using the EXTreme RAnge chamber (EXTRA). Rates are found to be invariant with carbon number, whilst literature measurements conducted under ambient conditions exhibited an increase in rate coefficient after 10 carbon atoms. These earlier findings appear to contradict the intuitive notion that the inductive effect is a short-range process operating over a maximum distance of a few carbon atoms. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.