Mechanisms and rates of the reactions of CH3O and CH2OH radicals with H atoms

Hoyermann, K.; Loftfield, Norman; Sievert, Rolf M.; Wagner, H. Gg.

doi:10.1016/s0082-0784(81)80086-0

Cited by 48 publications

(32 citation statements)

References 30 publications

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“…The pair of hydroxymethyl (65,70) reactions are in direct competition with each other. The decomposition reaction (65) produces H-atoms that go on to reaction (1).…”

Section: Shock Tubesmentioning

confidence: 99%

“…Offsetting this trend, to some degree, is the considerably higher oxygen concentration in the flame compared to shock-tube and reactor conditions investigated earlier in this article. Even in a stoichiometric flame, the reaction of hydroxymethyl with oxygen (70) consumes 16 times more CH 2 OH than the thermal decomposition reaction (65). Despite the elevated O 2 levels, the methoxy radical still predominantly undergoes decomposition, rather than reaction with oxygen.…”

Section: Reaction Path Analysismentioning

confidence: 99%

“…This reaction has been identified as a significant source of methyl radicals in methanol pyrolysis (2). The only studies of the reaction products are those of Hoyermann CH OH ϩ H : 2 and co-workers [65,66], who used a discharge fast flow-reactor and mass-spectrometric techniques at low-pressure and ambient temperature. At these conditions, the contribution of the disproportionation reaction (66) was approximately 75%, while the later study confirmed the remainder proceeded through reaction (65).…”

Section: Sensitivity Analysismentioning

confidence: 99%

“…The rate constant of reaction (65) has been calculated in other studies by specifying the reverse reaction rate constant and the thermochemistry of the involved species. These values require reevaluation in light of the revised heat of formation of hydroxymethyl [38].…”

Section: Sensitivity Analysismentioning

confidence: 99%

“…at Dom-14 k ϭ 2.2 ϫ 10 2000 K. 65 browsky et al [23] used a temperature independent rate constant of for reaction (Ϫ65), while 13 1.5 ϫ 10 Grotheer et al [13] have adopted a fit that yields a value of at These values again cor- 13 1.9 ϫ 10 2000 K. respond to very high rate constants for reaction (65), from…”

Section: 0817 Givingmentioning

confidence: 99%

See 4 more Smart Citations

A comprehensive mechanism for methanol oxidation

Held

Dryer

1998

Int. J. Chem. Kinet.

177

172

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A comprehensive detailed chemical kinetic mechanism for methanol oxidation has been developed and validated against multiple experimental data sets. The data are from static-reactor, flow-reactor, shock-tube, and laminar-flame experiments, and cover conditions of temperature from pressure from and equivalence ratio from 0.05-633-2050 K, 0.26-20 atm, 2.6. Methanol oxidation is found to be highly sensitive to the kinetics of the hydroperoxyl radical through a chain-branching reaction sequence involving hydrogen peroxide at low temperatures, and a chain-terminating path at high temperatures. The sensitivity persists at unusually high temperatures due to the fast reaction of comparedThe branching ratio ofwas found to be a more important parameter under the higher temperature conditions, H O 2 due to the rate-controlling nature of the branching reaction of the H-atom formed through CH 3 O thermal decomposition.

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“…The pair of hydroxymethyl (65,70) reactions are in direct competition with each other. The decomposition reaction (65) produces H-atoms that go on to reaction (1).…”

Section: Shock Tubesmentioning

confidence: 99%

Section: Reaction Path Analysismentioning

confidence: 99%

Section: Sensitivity Analysismentioning

confidence: 99%

Section: Sensitivity Analysismentioning

confidence: 99%

Section: 0817 Givingmentioning

confidence: 99%

See 3 more Smart Citations

A comprehensive mechanism for methanol oxidation

Held

Dryer

1998

Int. J. Chem. Kinet.

177

172

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Rate Constants and CH₃O Product Yield of the Reaction OH + CH₃OH → Products

Hägele

Lorenz

Rhäsa

et al. 1983

Ber Bunsenges Phys Chem

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Absolute rate constants and CH,O product yield for the reaction of OH radicals with methanol have been determined using a combined laser photolysis/resonance fluorescence (laser induced fluorescence) technique. The rate coefficient for total OH (k, = k, + k2) is found to be k, = (1.2 i 0.3). lo-" exp[-(810 * 50) K/T] cm3/molecule. s over the temperature range 295-420 K. -The branching ratio of CH,O formation, 9 = k, /k, + k,, where (1) OH + CH,OH -+ CH,O + H,O and (2) OH + CH,OH -+ CH20H + H,O, is found to be 0. 1 1 f 0.03 and 0.22 f 0.07 at 298 and 393 K, respectively. From the temperature dependence of 9 it is predicted that channel (1) is dominant in the combustion temperature region.

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A Study of the Reaction of CH₂(ã¹A₁) with H₂O in the Gas Phase

Hack

Wagner

Wilms

1988

Ber Bunsenges Phys Chem

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The reaction: was investigated in a quasistatic flash photolysis system at room temperature in the pressure range 0.5 ≦ p/mbar < 1.5 with He as the main carrier gas. The concentrations of CH2(ã1A1) produced in laser photolysis of CH2CO at λL = 308 nm, and the absolute concentration of the reaction product OH were monitored by laser induced fluorescence. In addition the population of the rotational states of the initial product OH (X, n̈ = 0, K) was measured. The time delay between photolysis and probe pulse delivered the time resolution. — The overall 1CH2 depletion rate determined from Stern‐Volmer plots is k1 (298 K) = (1.3 ± 0.2) · 1014 cm3/mol s. The channel: is determined to be the dominant reaction path in the range 0.5 ≦ k1a/k1 ≦ 1.0. The physical deactivation is found to be less than 50% of k1, in agreement with previous measurements. The bearing of these results on the reaction CH3 + OH and on the thermal CH3OH dissociation is briefly discussed.

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Mechanisms and rates of the reactions of CH3O and CH2OH radicals with H atoms

Cited by 48 publications

References 30 publications

A comprehensive mechanism for methanol oxidation

A comprehensive mechanism for methanol oxidation

Rate Constants and CH₃O Product Yield of the Reaction OH + CH₃OH → Products

A Study of the Reaction of CH₂(ã¹A₁) with H₂O in the Gas Phase

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Mechanisms and rates of the reactions of CH3O and CH2OH radicals with H atoms

Cited by 48 publications

References 30 publications

A comprehensive mechanism for methanol oxidation

A comprehensive mechanism for methanol oxidation

Rate Constants and CH3O Product Yield of the Reaction OH + CH3OH → Products

A Study of the Reaction of CH2(ã1A1) with H2O in the Gas Phase

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Product

Resources

About

Rate Constants and CH₃O Product Yield of the Reaction OH + CH₃OH → Products

A Study of the Reaction of CH₂(ã¹A₁) with H₂O in the Gas Phase