Cryogenic mass spectrometry of reactive fluorine-containing species: II. Applications to synthesis via pyrolysis, photolysis and microwave discharge

Abstract Chemical synthesis in a novel cryogenic inlet and reactor system using pyrolysis, photolysis, and microwave discharge was demonstrated. Thermally unstable nitrosodifluoramine was synthesized by pyrolysis of N 2 F 4 in the presence of excess NO. The photolysis of difluorodiazirine, CF 2 N 2 , was found to result in products C 2 F 4 , CF 2 NNCF 2 , and one or more of the following compounds: CF 2 NCF 2 NCF 2 , CF 2 CF 2 N NCF 2 , CF 2 CF 2 N NCF 2 C F 2 . Microwave discharge of a 1:1 mixture of NF 3 and Cl 2 resulted in the synthesis of CIF and N 2 . The appearance potentials of NF 2 + from NF 2 , N 2 F 4 , and NF 2 NO were found to be 11.79±0.12 eV, 12.63±0.1 eV, and 12.12±0.12 eV, respectively. This information was used to calculate the NN bond energy in F 2 NNO. The value obtained is in agreement with the thermochemical value reported in the literature.