Publication costs assisted by the Naval Research Laboratory Reactions of atomic or molecular bromine with atomic or molecular oxygen in argon matrices produce several bromine-oxygen compounds which are identifiable by infrared spectroscopy. The molecules BrO, OBrO, BrBrO, BrOBr, and a molecule thought to be (BrO)2 were identified through oxygen-18 isotopic enrichment experiments and by similarities between their infrared spectra and those of the lighter halogen oxides. The BrO fundamental frequency observed at 729.9 cm"1 is lower than the value previously extrapolated from gas phase emission data. Helium-neon laser photolysis experiments were used to differentiate between bromine atom and bromine molecule reaction products.curve was downward concave. A similar curve was obtained from the activation entropy ( 5*) vs. the concentration. One residue of PEG is strongly hydrated with one and weakly with additional water molecules, because unfrozen water is not monomeric. The AH* and AS* values in frozen 30,10, and 1 % solutions are the same and largest in all cases. This was explained by the concept that the probe was occluded in hydrated PEG as the result of freezing and a large energy was necessary for breaking the hydrogen bond of hydration water to rotate the probe.

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Oxygen difluoride has been shown to react with carbonyl fluoride over a cesium fluoride catalyst to give good yields of the unusual compound bis(trifluoromethy1) trioxide, a stable material having a melting point of -138 O and a normal boiling point of -16". Its formulation as a symmetrical trioxide is supported by its infrared spectrum, nuclear magnetic resonance, and other data. A possible mechanism for its formation is given.n the great majority of its chemical reactions, oxygen

have shown the existence of an inner-sphere perchloratochromium(III) in concentrated perchloric acid.

Simultaneous matrix deposition of F2 and NO molecules at high dilution in argon and nitrogen onto an 8°K CsI window produces three new infrared absorptions in addition to those of normal, FN-bonded nitrosyl fluoride, FNO. The infrared features at 1886.6, 734.9, and 492.2 cm−1 (Ar matrix) and their 15N and 18O isotopic counterparts were assigned to the previously unobserved FO-bonded isomer NOF, which appears to be a bent molecule having a molecular geometry similar to that of nitrosyl fluoride. Controlled fluorine atom diffusion at 20°K, in the absence of photolytic radiation, results in increased yields of the NOF molecule, while matrix photolysis experiments at 8°K have established that this species undergoes intramolecular photorearrangement to the more stable FNO form when exposed to radiation comprised of wavelengths below 280 nm.