Oxygen difluoride photolysis

Nitric oxide and OF2 inflame on contact emission and absorption spectra of the flame have been studied (24). Oxygen difluoride oxidizes SO2 to SO, but under the influence of uv kradiation it forms sulfuryl fluoride [2699-79-8] SO2F2, and pyrosulfuryl fluoride [37240-33-8] S20 F2 (25). Photolysis of SO —OF2 mixtures yields the peroxy compound FSO2OOF [13997-94-9] (25,26). 

Oxygen Difluoride as a Source of the OF Radical. The existence of the OF radical [12061 -70-0] was first reported in 1934 (27). This work was later refuted (28). The OF radical was produced by photolysis of OF2 in a nitrogen or argon matrix at 4 K. The existence of the OF species was deduced from a study of the kinetics of decomposition of OF2 and the kinetics of the photochemical reaction (25,26) ... 

Perfluoroepoxides have also been prepared by anodic oxidation of fluoroalkenes (39), the low temperature oxidation of fluoroalkenes with potassium permanganate (40), by addition of difluorocarbene to perfluoroacetyl fluoride (41) or hexafluoroacetone (42), epoxidation of fluoroalkenes with oxygen difluoride (43) or peracids (44), the photolysis of substituted l,3-dioxolan-4-ones (45), and the thermal rearrangement of perfluorodioxoles (46). 

This study has established that oxygen difluoride dissociates photo-lytically into a paramagnetic species in which there is a hyperfine interaction between the unpaired electron and one fluorine nucleus. The photolytic rate of formation of the radical species increased with temperature. The decay of the signal intensity in the absence of light after photolysis did not depend on temperature. The kinetics have been interpreted in terms of a photolytic formation scheme. The radical has been characterized by means of the EPR spectrum, but not identified. However, the characteristics of the spectrum show that the radical was Oa-F, rather than F ... 

Oxygen.— The rates of hydrolysis of oxygen difluoride in basic aqueous solution show a one-third-order dependence on hydroxide-ion concentration. At pH = 10, the activation energy for this hydrolysis is 8.5kcalmol. The rate law for photolysis of hydrogen peroxide, in the presence of hydroxyl-amine or of methylamine, is... 

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