Reactions of methyl radicals with acetaldehyde and acetaldehyde‐d1. I. relative rates of atom abstraction reactions at 785°K

I. Bárdi, T. Bérces, I. Szilágyi

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Abstract

The role of ethenoxy radicals in the pyrolysis of CH3CDO was studied by mass spectrometric analysis of the isotopic composition of the methane, ethane, and recovered aldehyde. Experimental evidence was obtained for the formation of ethenoxy radicals and for their reaction with acetaldehyde. Mixtures of CH3CHO and CH3CDO were pyrolyzed in order to minimize H‐D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions (Formula Presented.) and (Formula Presented.) furnished the rate constant ratios (k2a + k2b)/k1a = 2.7 and k1b/k1a = 0.62 at 785°K. It is concluded that at the usual temperatures of CH3CHO pyrolysis the rate of alkyl hydrogen capture is comparable to that of formyl hydrogen abstraction. The results and conclusions are discussed and compared with previous work.

Original languageEnglish
Pages (from-to)285-294
Number of pages10
JournalInternational Journal of Chemical Kinetics
Volume8
Issue number2
DOIs
Publication statusPublished - 1976

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Acetaldehyde
acetaldehyde
Aldehydes
Hydrogen
Pyrolysis
aldehydes
Atoms
Ethane
pyrolysis
Methane
atoms
Rate constants
hydrogen
ethane
Kinetics
Temperature
methane
Chemical analysis
kinetics
methyl radical

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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title = "Reactions of methyl radicals with acetaldehyde and acetaldehyde‐d1. I. relative rates of atom abstraction reactions at 785°K",
abstract = "The role of ethenoxy radicals in the pyrolysis of CH3CDO was studied by mass spectrometric analysis of the isotopic composition of the methane, ethane, and recovered aldehyde. Experimental evidence was obtained for the formation of ethenoxy radicals and for their reaction with acetaldehyde. Mixtures of CH3CHO and CH3CDO were pyrolyzed in order to minimize H‐D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions (Formula Presented.) and (Formula Presented.) furnished the rate constant ratios (k2a + k2b)/k1a = 2.7 and k1b/k1a = 0.62 at 785°K. It is concluded that at the usual temperatures of CH3CHO pyrolysis the rate of alkyl hydrogen capture is comparable to that of formyl hydrogen abstraction. The results and conclusions are discussed and compared with previous work.",
author = "I. B{\'a}rdi and T. B{\'e}rces and I. Szil{\'a}gyi",
year = "1976",
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journal = "International Journal of Chemical Kinetics",
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publisher = "John Wiley and Sons Inc.",
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TY - JOUR

T1 - Reactions of methyl radicals with acetaldehyde and acetaldehyde‐d1. I. relative rates of atom abstraction reactions at 785°K

AU - Bárdi, I.

AU - Bérces, T.

AU - Szilágyi, I.

PY - 1976

Y1 - 1976

N2 - The role of ethenoxy radicals in the pyrolysis of CH3CDO was studied by mass spectrometric analysis of the isotopic composition of the methane, ethane, and recovered aldehyde. Experimental evidence was obtained for the formation of ethenoxy radicals and for their reaction with acetaldehyde. Mixtures of CH3CHO and CH3CDO were pyrolyzed in order to minimize H‐D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions (Formula Presented.) and (Formula Presented.) furnished the rate constant ratios (k2a + k2b)/k1a = 2.7 and k1b/k1a = 0.62 at 785°K. It is concluded that at the usual temperatures of CH3CHO pyrolysis the rate of alkyl hydrogen capture is comparable to that of formyl hydrogen abstraction. The results and conclusions are discussed and compared with previous work.

AB - The role of ethenoxy radicals in the pyrolysis of CH3CDO was studied by mass spectrometric analysis of the isotopic composition of the methane, ethane, and recovered aldehyde. Experimental evidence was obtained for the formation of ethenoxy radicals and for their reaction with acetaldehyde. Mixtures of CH3CHO and CH3CDO were pyrolyzed in order to minimize H‐D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions (Formula Presented.) and (Formula Presented.) furnished the rate constant ratios (k2a + k2b)/k1a = 2.7 and k1b/k1a = 0.62 at 785°K. It is concluded that at the usual temperatures of CH3CHO pyrolysis the rate of alkyl hydrogen capture is comparable to that of formyl hydrogen abstraction. The results and conclusions are discussed and compared with previous work.

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