Abstract:
Some information concerning the mechanism of the radiolysis of perfluorinated carboxylic acids
is presented from an examination of the e.s.r. spectra of radicals trapped in polycrystallinc samples
of the acids between 77 and 300 K. Three types of radicals have been identified iny-irradiatcd samples
of RCF2COOH (R = F, CF3, CF3CF2, C6H13, CF2COOH, CF2CF2COOH). These arc (1)
parent radical anions RCF2COOH", (2) primary fluoralkyl radicals RCF2, and (3) secondary radicals
RCFCOOH. The radical anions lose F~ on thermal annealing to yield additional RdFCOOH
radicals, but when samples containing RCF2COOH~ are u.v.-irradiatcd at 77 K these species disappear
without the appearance of any identifiable radical product, as do the corresponding species in non
fluorinated carboxylic acids. The RCF2 radicals are believed to originate from the cationic species
formed in the initial ionization following proton transfer and elimination of CO2.
