Journal of the Chemical Society - Faraday Transactions p. 4001 - 4009 (1990)
Update date:2022-08-24
Topics:
McCaulley, James A.
Moyle, Alfred M.
Golde, Michael F.
Anderson, Stuart M.
Kaufman, Frederick
The kinetics of the reactions of CH3O and CD3O with NO have been studiedusing a discharge flow reactor.CH3O and CD3O were detected using laser-excited fluorescence (LEF) near 300 nm.Total rate coefficients for the reaction of CH3O with NO were measured as a function of temperature (220-473 K) and presure (0.75-5.0 Torr) of He or Ar.Total rate coefficients for the CD3O + NO reaction were measured at ca. 294 K over the pressure range 0.75-5.0 Torr He.Using molecular-beam mass spectrometry, the CH3ONO zield of the CH3O + NO reaction was measured at 297 K (0.5 and 1.0 percentTorr) and 223 K (1.0 Torr), showing that disproportionation to H2CO + HNO is the major channel at low pressures.These results were combined to obtain the following expressions for the disproportionation and low-pressure recombination rate coefficients.For the CH3O + NO reaction, kDISP=(1.3 +/- 0,4) x 10-12 exp <(250 +/- 100)/Τ> cm3s-1, kolll=(1.8 +/- 1.3) x 10-29 (Τ/300)-(3.2+/-0.5) cm6 s-1.For the CD3O + NO reaction at 294 +/- 2 K, kDISP =(3.0 +/- 0.4) x 10-12 cm3 s-1, and kolll = (2.5 +/- 0.4) x 10-29 cm6 s-1.While the uncertainty associated with the measured rate coefficients is ca. +/- l5percent, the product channel-specific rate coefficients obtained from these expressions are less certain, ca. +/- 50percent.Using MBMS, the CH3NO2 yield of the CH3 + NO2 reaction was measured at 297 K )0.5 and 1.0 Torr) and 223 K (1.0 Torr).Combined with the previously reported rate coefficient, these results indicate a low-pressure, third-order recombination rate coefficient of (6 +/- 2) x 10 -29cm 6 s-1 in He at 297 K.
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