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Ion—molecule reactions in propylene and 1,3-butadiene have been studied using a mass spectrometer which utilizes photoionization as an ion source instead of electron impact. The light source used was a low-pressure hydrogen-discharge lamp with a LiF window (substantially Lyman alpha, 1216 Å). It has been shown that this method has two major advantages in the study of ion—molecule reactions compared with the electron-impact method; one is the lack of unimolecular fragmentation of the parent ion and the other the absence of hot filament, which enables one to get high pressure without suffering pyrolysis. Five reactions of C3H6+ with C3H6 and eight reactions of C4H6+ with C4H6 have been identified and the cross sections determined for these reactions. In propylene, the reaction leading to the formation of C3H7+ was found to be of the largest cross section and, although cross section was small, the reaction forming C3H3+ was found as a new reaction. It was shown that C3H6+ could not be the precursor of secondary C4H6+ in propylene, criticizing the Fuchs assignment. In 1,3-butadiene, three new reactions have been found; the reaction leading to the formation of C3H3+, the hydrogen-atom abstraction reaction just as in propylene, and the parent-minus-one reaction. The first one was of the largest cross section in all reactions in 1,3-butadiene. This reaction has been discussed in connection with the structure and the heat of formation of C3H3+.

Relative yields of parent and principal fragment ions from four paraffins and olefins by electron impact are measured for the first time. The characteristic features of the ion yields can be classified into four types related with the ionizing voltages. The decomposition processes for some fragment ions can be explained under some assumptions, and those for forbidden ions C2H5+ from isobutane and cis-2-butene under the assumption of hydrogen rerrangement.

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