The thermal decomposition of FSOOSFB, P, in the presence of CO has been investigated between 130.1" and 161.9"C at total pressures between 50 and 600 torr. The reaction is homogeneous, and the only final products formed are C02 and S2F10. The rate of reaction is proportional to the pressure of P. The partial pressures of CO and 0 2 and the total pressure have no influence on the course of reaction:The results are explained by the following mechanism:(1) P = 2 OSFs rate-determining step (la) OSF5 + CO = C02 + SF5 fast reaction (Ib) 2 SFS = S2F10
The kinetics of the thermal decomposition of CF303CF3 has been investigated in the pressure range of 15599 torr at temperatures between 59.8 and 90.3OC and also in the presence of CO between 42 and 7°C. The reaction is homogeneous. In the absence of CO the only reaction products are CF302CF3 and 0 2 . The rate of reaction is strictly proportional to the trioxide pressure, and is not affected by the total pressure, the presence of inert gases, and oxygen.The following mechanism explains the experimental results:(1)In the presence of CO there appear COz, (CF30C0)2, and CF302C(O)OCF3 as products.With increasing temperature the amount of peroxicarbonate decreases, while the amounts of oxalate and COz increase. The rate of decomposition of the trioxide above a limiting pressure of about 10 torr CO is strictly first order and independent of CO pressure, total pressure, and the pressure of the products.International Journal of Chemical Kinetics, Vol. 13, 639-649 (1981)
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