A kinetic and product study of reaction of chlorine atom with CH3CH2OD

The reaction of atomic chlorine with CH3CH2OD 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 + CH3CH2OD reaction was determined using cyclohexane as a reference and found to be k(3) = (1.13 +/- 0.21) x 10(-11) 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 alpha and beta 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 + CH3CH2OH reaction was also determined using cyclohexane as the reference, and a value of k(2) = (1.05 +/- 0.07) x 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. (C) 2004 Wiley Periodicals, Inc.