Conversion of CH{sub 4} to CH{sub 3}OH. Reactions of CoO{sup +} with CH{sub 4} and D{sub 2}, Co{sup +} with CH{sub 3}OD and D{sub 2}O, and CO{sup +}(CH{sub 3}OD) with Xe

Journal Article · Wed Aug 24 04:00:00 EDT 1994 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja00096a044· OSTI ID:102764

Chen, Y M; Clemmer, D E; Armentrout, P B ^[1]

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1. Univ. of Utah, Salt Lake City, UT (United States)

The mechanisms and energetics involved in the conversion of CH{sub 4} to CH{sub 3}OH by CoO{sup +} are examined by using guided ion beam mass spectrometry. The forward and reverse reactions, CO{sup +} + CH{sub 4} CO{sup +} + Ch{sub 3}OH, the collisional activation of Co{sup +}(CH{sub 3}OH), and the related reactions, CoO{sup +} + D{sub 2} Co{sup +} + D{sub 2}O, are studied. It is found that the oxidations of methane and D{sub 2} by CoO{sup +}, both exothermic reactions, do not occur until overcoming activation barriers of 0.56 x 0.08 and 0.75 x 0.04 eV, respectively. The behavior of the forward and reverse reactions in both systems is consistent with reactions that proceed via the insertion intermediates R-Co{sup +}-OH, where R = CH{sub 3} or H. The barrier is probably attributable to a four-centered transition state associated with addition of RH across the CoO{sup +} bond. In the Co{sup +} + CH{sub 3}OH system (where CH{sub 3}OD labeled reactant is used), reactions explained by initial C-H and O-H activation are also observed. The reaction mechanisms and potential energy surfaces for these systems are derived and discussed. Phase space theory calculations are used to help verify these details for the CoO{sup +} + D{sub 2} system. Thermochemistry for several species including CoOH{sup +}, CoD{sup +}, CoH, CoCH{sub 3}{sup +}, Co{sup +}(CH{sub 3}OD), CoOCH{sub 3}{sup +}, and possibly OCoCH{sub 3}{sup +} is derived from measurements of reaction thresholds. 59 refs., 8 figs., 4 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 102764
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 116; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
40 CHEMISTRY
66 PHYSICS
CATALYSIS
CHEMICAL ACTIVATION
COBALT COMPLEXES
COBALT IONS
COMPILED DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
HEAVY WATER
MASS SPECTROSCOPY
METHANE
METHANOL
OXIDATION
SYNTHESIS
THERMODYNAMICS
XENON