Reactions with CO, CO2, COF2, and COS

CO and CO2. At 77 K OF2 mixes with CO or CO2 homogeneously in a 1 1 molar ratio [1 ]. The reaction of OF2 with CO yields COF2 as the main product. The reaction path and the formation of other products (CO2, O2, F2, FCOOF, and [FC0]202) depend on the experimental conditions. The kinetic results of the thermal reaction in a static system (323 to 353 K) [2] and in shock waves (76 to 1400 K) [3] as well as of the photochemical reaction (283 to 308 K, 1 = 365 nm) [4] are presented in Kohlenstoff D3, 1976, p. 13. The increase in yield of OF radicals in the photolysis of OF2-CO2 mixtures in a nitrogen matrix compared with its yield without added CO2 is reported [5]. 

At 25°C OF2 reacts with COF2 in the presence of alkali fluorides MF (M = K, Rb, Cs) as catalysts yielding CF3OOOCF3. The proposed mechanism [6] 

The thermal reaction between 323 and 363 K and the photochemical reaction with light of 366 nm at 273 K give the primary products SOF2 and CO plus SOF4, SO2F2, and COF2 [8,9] for details, see Kohlenstoff D5, 1977, p. 134. 

A mixture of OF2 on silica gel (60/80 mesh) and liquid OF2 at 254 Torr in 3-or4-mm internal diameter tubes exploded spontaneously when the temperature exceeded 77 K. With a 5-mm tube there was no explosion [1,2], see [3] for an explanation. Mixtures of liquid OF2 with pyrogenic silica (Cab-O-Sil) in 10- to 12-mm tubes are shock sensitive but are chemically stable at -78°C. Explosions of silica gel and liqu id OF2 mixtures might be due to traces of water [4, 5]. 

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