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

The thermal addition of CF₃O₃CF₃(T) to CF₂CCl₂(E) has been investigated between 49.6 and 69.5°C. The initial pressure of CF₃O₃CF₃ was varied between 7 and 240 torr and that of CF₂CCl₂ between 4 and 600 torr. Four products of formula CF₃O(E)_j OOCF₃, where j = 1 → 4 are formed. The sum of the products Σ CF₃O(E)_jOOCF₃ 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 CF₃O₃CF₃ into CF₃O^. and CF₃O₂^., chain initiation by addition of CF₃O^. to olefin incorporated in, and telomeric radicals termination. The consumption of alkene is well represented by the equation: where (dE]/dT]) = 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: