期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 119, 期 39, 页码 9978-9985出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b06975
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资金
- Deutsche Forschungsgemeinschaft [BE2505/4-3]
The reaction of sulfur hexafluoride with gas-phase hydrated electrons (H2O)(n)(-), n approximate to 60-130, is investigated at temperatures T = 140-300 K by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. SF6 reacts with a temperature-independent rate of 3.0 +/- 1.0 x 10(-10) cm(3) s(-1) via exclusive formation of the hydrated F- anion and the SF5 center dot radical, which evaporates from the cluster. Nanocalorimetry yields a reaction enthalpy of Delta H-R,H-298K = 234 +/- 24 kJ mol(-1). Combined with literature thermochemical data from bulk aqueous solution, these result hi an F5S-F bond dissociation enthalpy of Delta H-298K = 455 +/- 24 kJ mol(-1), in excellent agreement with all high-level quantum chemical calculations in the literature. A combination with gas-phase literature thermochemistry also yields an experimental value for the electron affinity of SF5 center dot, EA(SF5 center dot) = 4.27 +/- 0.25 eV.
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