A Study of the Methyl-Oxygen and the Methyl-Nitric Oxide Reactions by Flash Photolysis<sup>1</sup>

Sleppy, W. C.; Calvert, Jack G.

doi:10.1021/ja01513a002

Cited by 51 publications

(29 citation statements)

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“…and the extrapolation of the ratio of second-order rate constants kz/k, to infinite pressure, yielding the limiting value k,/k, = 0.16 [12]. An independent study of the competition for methyl radicals between reaction (3) and the third-order process : Sleppy and Calvert's technique [13] differs from our own in three respects. First, their photolytic radiation comprised all wavelengths transmitted by quartz, whereas we filtered out all wavelengths shorter that c 300 nm with Pyrex glass.…”

Section: B the Combination Of The Methyl Radical With Nitric Oxide Amentioning

confidence: 95%

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

Basco

James

Suart

1970

Int J of Chemical Kinetics

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Combination reactions of the methyl radical have been studied by following the decay of the absorbance of the methyl radical during the course of the reaction by means of kinetic spectroscopy. The limiting values of the second-order rate constants at high pressure were determined for two reactions at room temperature:k, = (2.6 f 0.3) x 1O1O 1 mole-1 sec-1 CH, + N O ( + M ) .+ CH,NO ( + M ) :The extinction coefficient of the methyl radical was found to have a maximum value of (1.02 f 0.06) x lo4 1 mole-l cm-l at 216.4 nm. Integration of the extinction coefficient over the absorption band of the methyl radical gave an oscillator strength of 1.0 x

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Section: B the Combination Of The Methyl Radical With Nitric Oxide Amentioning

confidence: 95%

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

Basco

James

Suart

1970

Int J of Chemical Kinetics

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“…Nitric oxide reacts readily with alkyl radicals remov ing them from the system and breaking the chain reactions in which they are involved (25,27,81) as shown in reaction 30.…”

Section: (24)mentioning

confidence: 99%

Vapor Phase Nitration of Butane in a Molten Salt Reactor

Fear¹,

Burnet²

1966

Ind. Eng. Chem. Proc. Des. Dev.

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“…In the study here reported an accurate rate could be determined after only a few tenths of one per cent conversion of the reactants. The concentrations of the products were determined a t the characteristic absorption regions: peroxyacetic acid, 8 Fig. 1, and recorded during run 2 of Table I).…”

Section: Procedures and Resultsmentioning

confidence: 99%

“…Reaction [4] would not have the three-body restrictioil which has been observed for the reaction of methyl radicals with 0 2 (6,7,8), and it would be considerably faster. \Ve consider the mechanism here proposed to be a reasorlable postulate which is consistei~t with the facts a t hand and is worthy of further testing.…”

Section: Revised Lldechanisnz Of Acetaldehyde Photooxidationmentioning

confidence: 91%

The Mechanism of the Photooxidation of Acetaldehyde at Room Temperature

Calvert¹,

Hanst²

1959

Can. J. Chem.

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The initial rates of product formation in the photooxidation of acetaldehyde a t room temperature have been determined through the use of infrared spectrometry. The rates of forrnation of the products peroxyacetic acid, carbon monoxide, carbon dioxide, methanol, formic acid, and acetic acid were determined in experiments with various pressures of acetaldehyde, oxygen, and added gases. The amounts of methylhydroperoxide and acetylperoxide formed in all of the experiments arere below the detection limit of the analytical methods. The results require that some modification and corrections be made to the mechanism suggested by McDowell and Sharples. INTRODUCTIONRecently 14cDowell and Sharples (1) published a series of kinetic studies of the photooxidation of acetaldehyde and propionaldehyde. The reactions were followed by the titration of the peroxyacid formed. Reported here is a study of the photooxidation of acetaldehyde in which a more detailed product analysis has been made through infrared absorption spectroscopy. The results show that the simple mechanism which McDowell and Sharples have inferred from their rate studies is very incomplete, and in some respects, it is incorrect. Soine suggested modifications and corrections to their mechanism are presented. E X P E R I M E N T A L Apparatus and MaterialsOur experiments were basically similar to those of McDowell and Sharples (1). We used comparable amounts of acetaldehyde in oxygen, and we photolyzed a t rooin temperature with light in the range 3000-3300 A. In order to accelerate the rates and facilitate the identification of the products of the chain-initiating and chain-tern~iilatii~g reactions, we used intensities about 1000 times those enlployed by ;\iIcDowell and Sharples.The acetaldehyde (Eastman-Kodak, white-label, fractionated a t reduced pressure), oxygen (Linde tank gas), and other added gases were mixed in a 10-cm Pyrex-body infrared absorption cell which was mounted in the sample beam of a Perkin-Elmer Model 21 double beam infrared spectrometer. The side of the cell was exposed to the radiation from a Pyrex-jacketed, water-cooled, high pressure mercury arc (AH-6) which was fastened about 10 inches from the cell. The absorption characteristics of the water jacket and the cell body limited the effective radiation t o the range 3000-3300 A. The inaxirnuin intensity of the light absorbed by the aldehyde was near 3100 A.T h e other reactant gases and standards for analysis were obtained as follows: tetramethylethylene was the research grade Phillips product; peroxyacetic acid and acetylperoxide were obtained from Becco and purified by distillation a t reduced pressure; ozone was prepared as needed by a simple ozonizer apparatus; the oxides of carbon were reagent gases of the Air Reduction Co.; inethailol was the Mallinckrodt Ailalytical 'Ma?zuscript received M a y g6, 1969.

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A Study of the Methyl-Oxygen and the Methyl-Nitric Oxide Reactions by Flash Photolysis¹

Abstract: R e la tiv e Energy of th e F la sh (4000-3000 A.) as a F unction of Timej F la sh Energy, 4800 J o u le s. .. . 50 16. A b so rp tio n S p e c tra of Azomethane Before and A fte r th e F l a s h .

Cited by 51 publications

References 1 publication

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

Vapor Phase Nitration of Butane in a Molten Salt Reactor

The Mechanism of the Photooxidation of Acetaldehyde at Room Temperature

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A Study of the Methyl-Oxygen and the Methyl-Nitric Oxide Reactions by Flash Photolysis1

Abstract: R e la tiv e Energy of th e F la sh (4000-3000 A.) as a F unction of Timej F la sh Energy, 4800 J o u le s. .. . 50 16. A b so rp tio n S p e c tra of Azomethane Before and A fte r th e F l a s h .

Cited by 51 publications

References 1 publication

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

A Quantitative study of alkyl radical reactions by kinetic spectroscopy. Part I. Mutual combination of methyl radicals and combination of methyl radicals with nitric oxide

Vapor Phase Nitration of Butane in a Molten Salt Reactor

The Mechanism of the Photooxidation of Acetaldehyde at Room Temperature

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A Study of the Methyl-Oxygen and the Methyl-Nitric Oxide Reactions by Flash Photolysis¹