The kinetics and the mechanism of the thermal decomposition of bis(trifluoromethyl) trioxide. The influence of carbonmonoxide on its decomposition

Abstract

Abstract The kinetics of the thermal decomposition of CF 3 O 3 CF 3 has been investigated in the pressure range of 15–599 torr at temperatures between 59.8 and 90.3°C 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 CF 3 O 2 CF 3 and O 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: equation image In the presence of CO there appear CO 2 , (CF 3 OCO) 2 , and CF 3 O 2 C(O)OCF 3 as products. With increasing temperature the amount of peroxicarbonate decreases, while the amounts of oxalate and CO 2 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. equation image The addition of larger amounts of O 2 to the CO containing system chaqnges the course of the reaction.