A kinetic and product study of reaction of chlorine atom with CH 3 CH 2 OD

The reaction of atomic chlorine with CH 3 CH 2 OD has been examined using a discharge fast flow system coupled to a mass spectrometer combined with the relative rate method (RR/DF/MS). At 298 ± 2 K, the rate constant for the Cl + CH 3 CH 2 OD reaction was determined using cyclohexane as a reference and found to be k 3 = (1.13 ± 0.21) × 10 −10 cm 3 molecule −1 s −1 . Mass spectral studies of the reaction products resulted in yields greater than 97% for the combined hydrogen abstraction at the α and β sites (3a + 3b) and less than 3% at the hydroxyl site (3c). As a calibration of the apparatus and the RR/DF/MS technique, the rate constant of the Cl + CH 3 CH 2 OH reaction was also determined using cyclohexane as the reference, and a value of k 2 = (1.05 ± 0.07) × 10 −10 cm 3 molecule −1 s −1 was obtained at 298 ± 2 K, which was in excellent agreement with the value given in current literature. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 584–590, 2004