On the kinetics of thermal electron attachment to perfluoroethers

In this Letter we report the results of the measurements of the rate coefficients for thermal attachment to several perfluoroethers namely perfluorodiglyme (C6F14O3), perfluorotriglyme (C8F18O4), perfluoropolyether (CF3–(OCF(CF3)CF2)n–(OCF2)m–OCF3) and perfluorocrownether ((C2F4O)5). Rate coefficients were obtained under thermal conditions in the temperature range 298–378 K. The increase of the rates with temperature follows the Arrhenius law and the activation energies have been obtained from the slope of the ln(k) vs. 1/T. The respective values of the rate coefficients (at 298 K) and activation energies are as follows: 7.7 ± 1.2 × 10−11 cm3 s−1 (0.18 ± 0.005 eV), 6.7 ± 2.1 × 10−11 cm3 s−1 (0.25 ± 0.004 eV), 2.1 ± 0.2 × 10−10 cm3 s−1 (0.16 ± 0.010 eV), 3.1 × 10−11 cm3 s−1 (0.27 ± 0.003 eV) for C6F14O3, C8F18O4, CF3–(OCF(CF3)CF2)n–(OCF2)m–OCF3 and (C2F4O)5.