The infrared absorption of the products from electrically dissociated H 2 0 or D 2 0 vapor and other hydrogen-oxygen systems trapped at liquid nitrogen temperature was measured between 4000 and 300 cm-'. Four new absorption bands were found in the deuterated systems at 857, 820,760, and about 440 cm-'. By isotopic substitution of 180 the frequencies are shifted to 806, 775, 717, and -420 cm-' as expected for 0-0 vibrations. In the hydrogen systems this region is obscured by the strong libration bands of H 2 0 and H 2 0 2 molecules. Temperature and composition effects show that more than one new species is involved. Accordingly the new spectra are assigned to the often postulated polyoxides, H 2 0 3 and H 2 0 4 , stabilized in the water-peroxide matrix. The more abundant, and also more stable, H 2 0 3 has a half-life of some 5 h at -65 "C.The observed frequencies are consistent with zigzag chain structures linked by single covalent bonds as in hydrogen polysulfides. Relative concentrations of the polyoxides are estimated at 5 to 10 mole% depending on the composition of the starting material. Possible mechanisms of formation and decomposition are discussed.

The formation of C6H7+ species in ion/molecule reactions in gaseous vinyl chloride was studied in a high pressure photoionization mass spectrometer and in a Fourier transform ion cyclotron resonance (FT-ICR) spectrometer. Collision-induced dissociation (CID) mass spectra of C4H5Clt, C4H6Clt, and C6H7' species suggest a "butadiene-like" structure for the two former ions, and a non-benzenium structure for the last species. The C6H7+ ions are formed in a two-step mechanism involving C4H5' as intermediate ions. These processes are in competition with condensation reactions leading to the formation of C6H7-&1+ species.Key words: ion-molecule reactions, gaseous vinyl chloride, collision-induced dissociation.

The slow oxidation of solid ammonia by gaseous ozone a t low temperature proceeds through an unstable intermediate, ammonium ozonide, after the equationThe red solid appears on warming around -130 "C, reaches maximum concentration a t about -115", and is all decomposed by -90". The infrared spectra show, besides the characteristic bands of the NH4+ and NOS-ions, two strong bands a t 800 and 1 140 cm-1, and two faint ones a t 1 260 and 2 053 cm-' which must belong to the vn, v2, v l and v l + v? modes of the 03-ion. These frequencies are appreciably higher than the corresponding ones of the ozone molecule, which indicates a stronger bonding in the ozonide ion contrary to most predictions.By analogy with ozone the bond lengths in the ion are estimated to be 1.22 A and the interbond angle, about 100".

We have reinvestigated in detail the infrared spectra between 4000 and 600 cm−1 of the solid products formed by reacting liquid ozone at −190 °C with a stream of hydrogen gas dissociated in an electrodeless discharge. Extreme care was exercised to get "clean" spectra, free from any contaminants. All the spectra thus obtained showed very clearly the characteristic absorption bands of H2O2 at 2840 and 1430 cm−1, and the much weaker one at 880 cm−1; with deuterium atoms the former bands were shifted to 2100 and 1080 cm−1 respectively. Thus previous contentions that hydrogen peroxide is not one of the primary products of that reaction are disproved. The other infrared bands of H2O2 were not conspicuous, due either to their diffuse nature in the vitreous spectra or to extensive overlapping by the strong absorption of H2O, the other major component. Warming the material up to −110 °C caused some devitrification, but no significant change in the spectra. No new bands which could be assigned unambiguously to the hypothetical molecule H2O4 were observed.

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