Ionic polymerization of vinyl halides initiated by photoionization using photons with energies near the ionization threshold

Ion molecule reactions in vinyl fluoride by photoionization. Effects of vibrational excitation on major reaction pathways

“…As a result the kinetics depart from pseudo-first order, and the product distribution changes with the extent of reaction. These effects are clearly seen in the data of Herman and Harrison, 2 McAskill and Harrison, 3 and Sieck et al 6 The similarity in rate constants for relaxed ions determined by those workers with those of the present study is gratifying, as is the agreement in the deactivation rates calculated for our study and those calculated 5 for the data of McAskill and Harrison. 3 It is not completely clear why the earlier ICR studies 4 • 4 do report a change in product ratios with electron energy, indicating a changing vibrational population.…”

“…5 The "second order" distribution in the work of Harrison's laboratory 2 • 3 agrees with the 11. 7 eV value of Sieck et al 6 but indicates a higher degree of excitation than is seen in our work. Since direct ionization to states with ionization energies above 11.2 eV is not a favored process, the increase in the average excitation seen in these studies may be due to autoionization from superexcited neutral states in this energy region.…”

“…The C 3 products contained all possible isotopic combinations, including two (C 3 H 2 D; and C 3 D 3 F2) which could not arise from a single atom migration. However, no isotopic scrambling occurs in the vinyl fluoride product of Reaction (6). These findings indicate that the decomposition of intermediate I, while complex, is still more specific than a total scrambling model would indicate.…”

“…The ion cyclotron resonance (ICR) studies of O'Malley and Jennings 4 and Anicich and Bowers 5 show only second order kinetics, with a product distribution nearly identical to the third-order distribution of the single source studies. More recently Sieck et al 6 have studied Reactions (1)-(3) using photoionization by rare gas resonance lamps. Their data indicate that ions formed within 0.…”

Réactions ion–molécule de C2H3Cl+ avec le propane et le n-butane

“…Dans un mtlange de telle proportion l'ion moltculaire du chlorure de vinyle n'apparait pas, de mCme que les des produits provenant des kactions ion-molecule du chlorure de vinyle pur (8,(10)(11)(12)(13)(14). Les ions les plus importants mis en tvidence par les spectres de masse sont les suivants: C5H8+, C5H9+, C5HI0+ ( fig.…”