Journal of Physical Chemistry A, Vol.119, No.28, 7734-7741, 2015
Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide
Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R](0) e [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 x 10(-21)) x (T/300 K)(15.92) x exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 x 10(-16)) x (T/300 K)(6.81) x exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 +/- 0.12) x 10(-12) x (T/300 K)(-3.17)+/-(0.14) (T = 221363 K, p = 0.50-0.80 Torr); k(T)(3) = 9.62 x 10(-11) x (T/300 K)(-5.99) x exp[-7100/(RT)] (T = 221473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as +/-20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k(298K)(CH3CO + NO) = (5.6 +/- 2.8) x 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed.