Access

You are not currently logged in.

Access your personal account or get JSTOR access through your library or other institution:

login

Log in to your personal account or through your institution.

If You Use a Screen Reader

This content is available through Read Online (Free) program, which relies on page scans. Since scans are not currently available to screen readers, please contact JSTOR User Support for access. We'll provide a PDF copy for your screen reader.

The Mass Spectrometric Study of the Reaction of Methyl Radicals with Oxygen

M. Barber, J. Farren and J. W. Linnett
Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences
Vol. 274, No. 1358 (Jul. 30, 1963), pp. 306-318
Published by: Royal Society
Stable URL: http://www.jstor.org/stable/2414392
Page Count: 13
  • Read Online (Free)
  • Cite this Item
Since scans are not currently available to screen readers, please contact JSTOR User Support for access. We'll provide a PDF copy for your screen reader.
The Mass Spectrometric Study of the Reaction of Methyl Radicals with Oxygen
Preview not available

Abstract

The reaction between oxygen molecules and methyl radicals, produced by the photodissociation of methyl iodide, has been studied using a mass spectrometer which samples directly through a small hole from the gas emerging from the illuminated zone. The effect of adding hydrogen iodide has also been examined. It has been found that methanol and formaldehyde are formed in equimolar amounts together with a small quantity of methyl hydroperoxide. The yield of the latter is greatly increased by adding small percentages of hydrogen iodide. Larger additions produce some water and methane. To account for the results obtained here, together with those obtained by others, we suggest the following mechanism: \begin{align*}\mathrm{CH}_3I &\overset{hv}\rightarrow \mathrm{CH}_3 + I,\\ \mathrm{I + I} &\rightarrow \mathrm{I}_2,\\ \mathrm{CH}_3 + \mathrm{O}_2 + M &\rightarrow \mathrm{CH}_3\mathrm{O}_2 + M,\\ \mathrm{CH}_3 + \mathrm{O}_2 &\rightarrow \mathrm{HCHO + OH},\\ \mathrm{CH}_3\mathrm{O}_2 &\rightarrow \mathrm{HCHO + OH},\\ \mathrm{OH + CH}_3\mathrm{O}_2 &\rightarrow \mathrm{CH}_3\mathrm{OH + O}_2.\end{align*} A small proportion of the CH3O2 does succeed in abstracting hydrogen from the wall or somewhere and gives CH3O2H. In the presence of hydrogen iodide the products of hydrogen abstraction (CH3O2H, CH4 and H2O) by all three radicals (CH3O2, CH3 and OH) postulated in the above mechanism can be detected.

Page Thumbnails

  • Thumbnail: Page 
306
    306
  • Thumbnail: Page 
307
    307
  • Thumbnail: Page 
308
    308
  • Thumbnail: Page 
309
    309
  • Thumbnail: Page 
310
    310
  • Thumbnail: Page 
311
    311
  • Thumbnail: Page 
312
    312
  • Thumbnail: Page 
313
    313
  • Thumbnail: Page 
314
    314
  • Thumbnail: Page 
315
    315
  • Thumbnail: Page 
316
    316
  • Thumbnail: Page 
317
    317
  • Thumbnail: Page 
318
    318