A RELATIVE RATE STUDY OF THE REACTION OF CL ATOMS WITH A SERIES OF ALKYL NITRATES AND NITRO ALKANES IN AIR AT 295+/-2-K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with nitro methane, nitro ethane, nitro propane, nitro butane, nitro pentane, ethyl nitrate, isopropyl nitrate, n‐propyl nitrate, 2‐pentyl nitrate, and 2‐heptyl nitrate. Decay rates of these organic species were measured relative to one or more of the following reference compounds; n‐butane, ethane, chloroethane, and methane. Using rate constants of 2.25 × 10−10 5.7 × 10−11, 8.04 × 10−12, and 1.0 × 10−13 cm3 molecule−1 s−1 for the reaction of Cl atoms with n‐butane, ethane, chloroethane, and methane, respectively, the following rate constants were derived, in units of cm3 molecule−1 s−1: nitro methane, <7 × 10−15; nitro ethane, (2.05 ± 0.14) × 10−13; nitro propane, (1.13 ± 0.05) × 10−11; nitro butane, (5.13 ± 0.68) × 10−11; nitro pentane, (1.40 ± 0.14) × 10−10; ethyl nitrate, (3.70 ± 0.24) × 10−12; n‐propyl nitrate, (2.15 ± 0.13) × 10−11; i‐propyl nitrate, (3.94 ± 0.48) × 10−12; 2‐pentyl nitrate, (1.00 ± 0.06) × 10−10; and 2‐heptyl nitrate, (2.84 ± 0.50) × 10−10. Quoted errors represent 2σ and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295 ± 2 K and atmospheric pressure (≃740 torr) of synthetic air. The results are discussed with respect to the previous literature data and to the modeling of these compounds in the atmosphere. Copyright © 1990 John Wiley & Sons, Inc.