Abstract

Absolute rate constants have been measured for the gas-phase reactions of hydroxyl radicals with a series of chlorinated propanes: 1-chloropropane (k1), 2-chloropropane (k2), 1,2-dichloropropane (k3) and 1,2,3-trichloropropane (k4). Experiments were carried out using the pulsed laser photolysis–laser induced fluorescence technique over the temperature range 233–372 K. The kinetic data obtained were used to derive the following Arrhenius expressions (in units of cm3 molecule−1 s−1): k1 = (5.7 ± 1.0) × 10−12 exp[ − (526 ± 53)/T], k2 = (2.4 ± 0.6) × 10−12 exp[ − (365 ± 66)/T], k3 = (2.1 ± 0.5) × 10−12 exp[ − (453 ± 76)/T] and k4 = (1.5 ± 0.5) × 10−12 exp[ − (350 ± 100)/T]. The quoted errors for the pre-exponential factor, A, and E/R are given by ΔA = 2AσlnA and ΔE/R = 2σE/R, respectively. At room temperature, the rate constants obtained were as follows (in units of 10−13 cm3 molecule−1 s−1): k1 = (9.8 ± 1.0), k2 = (7.0 ± 0.7), k3 = (4.6 ± 0.6) and k4 = (4.6 ± 0.7). The results are compared with previous determinations and discussed in terms of structure–activity relationships.

Full Text
Published version (Free)

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call