Free Radicals by Mass Spectrometry. IV. The Rate of Combination of Methyl Radicals

1953 ◽  
Vol 21 (7) ◽  
pp. 1135-1144 ◽  
Author(s):  
K. U. Ingold ◽  
F. P. Lossing
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Methyl Radicals

FREE RADICALS BY MASS SPECTROMETRY: XI. THE MERCURY PHOTOSENSITIZED DECOMPOSITION OF C2–C4 OLEFINS

1956 ◽  
Vol 34 (6) ◽  
pp. 701-715 ◽  
Author(s):  
F. P. Lossing ◽  
D. G. H. Marsden ◽  
J. B. Farmer
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Hydrogen Atom ◽  
Mass Spectrometer ◽  
Cross Sections ◽  
Methyl Radicals ◽  
Allyl Radical

The mercury photosensitized (Hg3P1) decomposition of olefins has been examined using a reactor coupled directly to a mass spectrometer. The primary split of ethylene has been shown to be predominantly molecular, and that of propylene mainly into an allyl radical and a hydrogen atom. With 1-butene the split is predominantly at a C–C bond giving allyl and methyl radicals, although a rupture of a C–H bond occurs as well. With 2-butene and isobutene a C–H bond is broken. It is concluded that the allyl and methallyl radicals produced have large cross sections for reaction with excited mercury atoms.

FREE RADICALS BY MASS SPECTROMETRY: XIII. THE MERCURY PHOTOSENSITIZED DECOMPOSITION OF ALLENE AND BUTADIENE: THE C3H3 RADICAL

1957 ◽  
Vol 35 (8) ◽  
pp. 778-787 ◽  
Author(s):  
J. Collin ◽  
F. P. Lossing
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Hydrogen Atom ◽  
The Other ◽  
Methyl Radicals ◽  
Polymer Formation ◽  
Vinyl Radicals

The Hg(3P1) photosensitized decomposition of allene leads to the formation of a C3H3 radical. The reaction of this radical with added methyl radicals shows it to have the propargyl (ĊH2—C≡CH) structure rather than the alternative allenyl (CH2=C=ĊH) structure. The dissociation of 1,2-butadiene proceeds by two modes, one to give H2 + C4H4, and the other a split into CH3 and C3H3 radicals. The dissociation of 1,3-butadiene leads to the same final products, a shift of a hydrogen atom being required for the split into free radicals. No evidence was found for a dissociation of 1,3-butadiene into two vinyl radicals. Considerable polymer formation occurred with all three compounds.

Heats of formation of free radicals by mass spectrometry

1973 ◽  
Vol 95 (20) ◽  
pp. 6562-6566 ◽  
Author(s):  
D. K. Sen. Sharma ◽  
J. L. Franklin
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Heats Of Formation
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