The kinetics and the mechanism of the thermal gas‐phase reaction between bis(trifluoromethyl)trioxide, CF₃O₃CF₃ and 1,1‐dichlorodifluoroethylene, CF₂CCI₂

Abstract

Abstract The thermal addition of CF 3 O 3 CF 3 (T) to CF 2 CCl 2 (E) has been investigated between 49.6 and 69.5°C. The initial pressure of CF 3 O 3 CF 3 was varied between 7 and 240 torr and that of CF 2 CCl 2 between 4 and 600 torr. Four products of formula CF 3 O (E) j OOCF 3 , where j = 1 → 4 are formed. The sum of the products Σ CF 3 O (E) j OOCF 3 is equal to the amount of trioxide decomposed. The reaction is homogeneous. Its rate is not affected by the total pressure and the presence of inert gas. It is a free radical telomerization with four basic steps: thermal decomposition of CF 3 O 3 CF 3 into CF 3 O . and CF 3 O 2 . , chain initiation by addition of CF 3 O . to olefin incorporated in, and telomeric radicals termination. The consumption of alkene is well represented by the equation: where ( d [ E ]/ d [ T ]) = is the mean chain length of telomerization. varies from 1.45 at 1.5 torr of E to 3.3 at 400 torr of E . Above this pressure E has no influence on . The estimated value of the constant for the addition of telomeric radicals to alkene is: