Decomposition of Methanol Induced by Methoxy Radicals

Takezaki, Yoshimasa; Takeuchi, Chisato

doi:10.1063/1.1740452

Cited by 28 publications

(11 citation statements)

References 9 publications

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“…This is a more likely case, since NO2 greatly suppresses the M e 0 concentration and thereby prevents its attack on CH20. The rate of NOz attack on CHtO is very slow a t these temperatures [ 171. and about 1.1 times that obtained by Takezaki and Takeuchi [8].…”

Section: This Equation Was Written Assuming Stoichiometry Equation (Bmentioning

confidence: 52%

“…Takezaki and Takeuchi [8] (TT) pyrolyzed DMP in the presence of excess methanol, which acted as a radical trap, and found that log kl(sec-') = 15.61 - (1)…”

Section: Dimethyl Peroxide Decompositionmentioning

confidence: 99%

“…Reaction (8) has been inferred to be wall catalyzed and to have rate constant k8 = 0.01 sec-I at room temperature [15]; at 400°K it may well be somewhat faster.…”

Section: Dimethyl Peroxide With Added No2mentioning

confidence: 99%

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The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

Barker

Benson

Golden

1977

Int J of Chemical Kinetics

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The decomposition of dimethyl peroxide (DMP) was studied in the presence and absence of added NO, to determine rate constants k l and k z in the temperature range of 391-432OK:The results reconcile the studies by Takezaki and Takeuchi, Hanst and Calvert, and Batt and McCulloch, giving log kl(sec-1) = (15.7 f 0.5) -(37.1 f 0.9)/2.3 RT and k , = 5 X 104MM-'sec-1. The disproportionation/recombination ratio k7t,/k7, = 0.30 f 0.05 was also determined: Me0 + NO, (+ &I) % MeONOz (+ M ) M e 0 + NO, 3 CH,O + HONO When 0 2 was added to DMP mixtures containing NO,, relative rate constants klZ/k?a CH,O + 0 2 3 CHIO + HOZ were obtained over the temperature range of 396-442'K: A review of literature data produced kTa = 109.s*~.~M-1~sec-1, giving log k12(M-1.sec-1) = (8.5 f 1.5) -(4.0 =k 2.8)/2.3 RT, where most of the uncertainty is due to the limited temperature range of the experiments. *Present address:

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Section: This Equation Was Written Assuming Stoichiometry Equation (Bmentioning

confidence: 52%

“…Takezaki and Takeuchi [8] (TT) pyrolyzed DMP in the presence of excess methanol, which acted as a radical trap, and found that log kl(sec-') = 15.61 - (1)…”

Section: Dimethyl Peroxide Decompositionmentioning

confidence: 99%

See 1 more Smart Citation

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

Barker

Benson

Golden

1977

Int J of Chemical Kinetics

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“…It is also well apparent that in order to achieve a rate equation for a particular reaction, a steady-state concentration of intermediate(s) due to some equilibrium steps in the reaction path must be generated [48,49]. Since a steady-state concentration of the X 2 3+ complex can be considered only at a certain ratio of Mn 2+ to amino acid, the autocatalytic equation can not be applied until such ratio is created.…”

Section: Reaction Mechanism For the Catalyzed Processmentioning

confidence: 99%

Conclusive evidence for delayed autocatalytic behavior of Mn(II) ions at a critical concentration

Bahrami

Zahedi

2008

JICS

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The kinetics of the permanganic oxidation process of glycine, L-alanine and L-leucine in strong acid media were investigated using a spectrophotometric technique. Conclusive evidence has proven that the autocatalytic activity of Mn(II) in these reactions in strong acidic media is analogous to that of weak acid media, but in the former, Mn(II) ions should acquire a critical concentration for them to show autocatalytic characteristics. This critical concentration depends on the nature of the amino acid used. Considering the delayed autocatalytic behavior of Mn(II) ions, we herein present the rate equations and mechanisms satisfying observations for both catalytic and noncatalytic routes. The correspondence of the pseudo-order rate constants of the catalytic and noncatalytic pathways to Eyring law verify both the critical concentration as well as the delayed autocatalytic behavior concepts. In general, the onset of delayed behavior can be attributed to the concentration ratio of Mn(II) to amino acid which can be of a certain value for any particular amino acid.

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“…I-Iowever, the results of a number of inore recent studies have indicated that the methanol reaction should be re-exainined. Thus Tal<ezalti and Talteuchi (4) showed that methculol is readily decomposecl by CI-1:;O radicals froill the pyrolysis of dimethyl peroxide. From detailecl stuclies 011 the photolyses of CI-I~COOCI-I~ and CH:1COOCD3, Wijne~i (5) has coiicli~ded that CI-130 radicals are very efficient in abstraction reactions.…”

Section: Istizoductiokmentioning

confidence: 99%

PRIMARY METHOXY RADICAL FORMATION IN THE REACTION OF METHANOL VAPOR WITH Hg 6(³P₁) ATOMS

Knight¹,

Gunning²

1961

Can. J. Chem.

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X study has been ~n a d e of the decomposition of methanol vapor by I-Ig O(VJ1) atollis, ut~der static conditions, a t 25' C. A system constr~icted entirely of quartz was c~i~ployed to eliminate the darli rcactiori between methanol vapor and pyrex glass to for111 trimethyl borate. Etiiphasis it1 this investigation was placed ou the determin;itioli of the nature of the primary processes operative, and to this end, the reaction was studied ill some detail in the presence of nitric oxide.For pure methanol, the major primary proclucts were fou~id to be hydrogen and ethylene glycol. The primary quantum yield for hydrogen was 0.46. Millor products of primary origiri were formaldehyde (0.01), ethane (0.005), and dimethyl ether (O.OOB), with the numbers in parentheses showing the primary quantum yielcls.In the presence of nitric oside, thc major products became methyl nitrite, riitro~is oxide, a~i d water. The q u a n t u~n yield of methyl nitrite rose steadily with increasing NO concentrations. For a 1 :I C H 3 0 H : NO inisture, the primary quantunl yield for methyl nitrite was found to be 0.56. The behavior of the reaction in the presence of NO establishes fairly unec~uivocally that the ~iiajor primary process invol\~es 0-1-1 b o~l d scission to form methoxy radicals ancl H atoms. These primary radicals t1ie11 form hydrosy~netliyl radicals by abstraction reactions with the substrate. The ethylene glycol product arises by reconibi~iation of the secondary hydroxymethyl radicals. These conclusions were f~rrther substantiatecl by mass spectrometric alialysis of the products of the decomposition of CDsOFI. It w;ls shown that CD:rOIl is ;l significant product of the reaction. ISTIZODUCTIOKThe reaction of methanol vapor with I-Ig Ci(3PI) atoms has been studied previously (1, 2), aiid in detail by Phibbs and Dar\vent (3) from 25-500'. From the fact that 1-12 (+ = 0.43) and I-IOCI-I2CI-1201-I were the inajor products a t 25', the). concluded (3) quite reasonably that the major primary process was:The observed products could also be explained by the two-step sequence:For both [I] ancl [S] the [-I atoms for~ned are nssunied to attack the methyl group of the substrate:I'hibbs and Darwe~it rejectecl [2] as a n important PI-inlary process since they found that CI-IBOD substrate produced little IID. I-Iowever, the results of a number of inore recent studies have indicated that the methanol reaction should be re-exainined. Thus Tal

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Decomposition of Methanol Induced by Methoxy Radicals

Cited by 28 publications

References 9 publications

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

Conclusive evidence for delayed autocatalytic behavior of Mn(II) ions at a critical concentration

PRIMARY METHOXY RADICAL FORMATION IN THE REACTION OF METHANOL VAPOR WITH Hg 6(³P₁) ATOMS

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Decomposition of Methanol Induced by Methoxy Radicals

Cited by 28 publications

References 9 publications

The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2

The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2

Conclusive evidence for delayed autocatalytic behavior of Mn(II) ions at a critical concentration

PRIMARY METHOXY RADICAL FORMATION IN THE REACTION OF METHANOL VAPOR WITH Hg 6(3P1) ATOMS

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The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

PRIMARY METHOXY RADICAL FORMATION IN THE REACTION OF METHANOL VAPOR WITH Hg 6(³P₁) ATOMS