Temperature (290–400 K) and pressure (5–900 Torr) dependence of the kinetics of the reactions of chlorine atoms with propene and 1-butene

Rate constants for reactions of chlorine atoms with propene (k1) and 1-butene (k2) were measured relative to that of chlorine atoms with n-butane (k3) at 295–400 K in 5–900 Torr of N2 using gas chromatographic analysis. Experiments were also performed using an FTIR smog chamber to measure k1 relative to cyclohexane (k4) at 290–302 K in 700 Torr of N2. In contrast to previous studies which reported large negative activation energies, no discernable influence of temperature on the kinetics of these reactions was observed for experiments conducted near ambient temperature and pressure (∣Ea(1)∣ ⩽ 300 cal mole−1, ∣Ea(2)∣ ⩽ 150 cal mole−1).