Kinetics of the reactions of CH3O and CD3O with NO

James A. McCaulley, Alfred Moyle, Jr., Michael F. Golde, Stuart M. Anderson, Frederick Kaufman

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Abstract

The kinetics of the reactions of CH3O and CD3O with NO have been studied using 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 pressure (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 yield of the CH3O + NO reaction was measured at 297 K (0.5 and 1.0 Torr) 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) × 10-12 exp[(250 ± 100)/T] cm3 s-1, kOIII = (1.8 ± 1.3) × 10-29 (T/300)-(3.2 ± 0.5) cm6 s-1 For the CD3O + NO reaction at 294 ± 2 K kDISP = (3.0 ± 0.4) × 10-12 cm3 s-1 and kOIII = (2.5 ± 0.4) × 10-29 cm6 s-1 While the uncertainty associated with the measured rate coefficients is ca. ±15%, the product channel-specific rate coefficients obtained from these expressions are less certain, ca. ±50%. 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) × 10-29 cm6 s-1 in He at 297 K.

Original languageEnglish (US)
Pages (from-to)4001-4009
Number of pages9
JournalJournal of the Chemical Society, Faraday Transactions
Volume86
Issue number24
DOIs
StatePublished - Dec 1 1990

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Kinetics
kinetics
coefficients
low pressure
Molecular beams
Mass spectrometry
Fluorescence
molecular beams
Lasers
mass spectroscopy
reactors
fluorescence
products
lasers
Temperature
temperature

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

McCaulley, James A. ; Moyle, Jr., Alfred ; Golde, Michael F. ; Anderson, Stuart M. ; Kaufman, Frederick. / Kinetics of the reactions of CH3O and CD3O with NO. In: Journal of the Chemical Society, Faraday Transactions. 1990 ; Vol. 86, No. 24. pp. 4001-4009.
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title = "Kinetics of the reactions of CH3O and CD3O with NO",
abstract = "The kinetics of the reactions of CH3O and CD3O with NO have been studied using 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 pressure (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 yield of the CH3O + NO reaction was measured at 297 K (0.5 and 1.0 Torr) 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) × 10-12 exp[(250 ± 100)/T] cm3 s-1, kOIII = (1.8 ± 1.3) × 10-29 (T/300)-(3.2 ± 0.5) cm6 s-1 For the CD3O + NO reaction at 294 ± 2 K kDISP = (3.0 ± 0.4) × 10-12 cm3 s-1 and kOIII = (2.5 ± 0.4) × 10-29 cm6 s-1 While the uncertainty associated with the measured rate coefficients is ca. ±15{\%}, the product channel-specific rate coefficients obtained from these expressions are less certain, ca. ±50{\%}. 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) × 10-29 cm6 s-1 in He at 297 K.",
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Kinetics of the reactions of CH3O and CD3O with NO. / McCaulley, James A.; Moyle, Jr., Alfred; Golde, Michael F.; Anderson, Stuart M.; Kaufman, Frederick.

In: Journal of the Chemical Society, Faraday Transactions, Vol. 86, No. 24, 01.12.1990, p. 4001-4009.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Kinetics of the reactions of CH3O and CD3O with NO

AU - McCaulley, James A.

AU - Moyle, Jr., Alfred

AU - Golde, Michael F.

AU - Anderson, Stuart M.

AU - Kaufman, Frederick

PY - 1990/12/1

Y1 - 1990/12/1

N2 - The kinetics of the reactions of CH3O and CD3O with NO have been studied using 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 pressure (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 yield of the CH3O + NO reaction was measured at 297 K (0.5 and 1.0 Torr) 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) × 10-12 exp[(250 ± 100)/T] cm3 s-1, kOIII = (1.8 ± 1.3) × 10-29 (T/300)-(3.2 ± 0.5) cm6 s-1 For the CD3O + NO reaction at 294 ± 2 K kDISP = (3.0 ± 0.4) × 10-12 cm3 s-1 and kOIII = (2.5 ± 0.4) × 10-29 cm6 s-1 While the uncertainty associated with the measured rate coefficients is ca. ±15%, the product channel-specific rate coefficients obtained from these expressions are less certain, ca. ±50%. 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) × 10-29 cm6 s-1 in He at 297 K.

AB - The kinetics of the reactions of CH3O and CD3O with NO have been studied using 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 pressure (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 yield of the CH3O + NO reaction was measured at 297 K (0.5 and 1.0 Torr) 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) × 10-12 exp[(250 ± 100)/T] cm3 s-1, kOIII = (1.8 ± 1.3) × 10-29 (T/300)-(3.2 ± 0.5) cm6 s-1 For the CD3O + NO reaction at 294 ± 2 K kDISP = (3.0 ± 0.4) × 10-12 cm3 s-1 and kOIII = (2.5 ± 0.4) × 10-29 cm6 s-1 While the uncertainty associated with the measured rate coefficients is ca. ±15%, the product channel-specific rate coefficients obtained from these expressions are less certain, ca. ±50%. 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) × 10-29 cm6 s-1 in He at 297 K.

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