Journal of Physical Chemistry, Vol.100, No.14, 5964-5969, 1996
Thermodynamics of Electron Trapping and of Some Reversible Attachment-Detachment Reactions in Liquid Hydrocarbons
Thermodynamic parameters for electron trapping from the quasi-free state have been calculated from equilibrium trapping and detrapping rates in n-hexane, cyclohexane, n-pentane, propane, 3-methypentane, and isooctane, in consistence with the variation of effective mobility with temperature. From these, the derived free energy and entropy of solution show systematic variation with V-0, the energy of the lowest conducting state in the liquid. For several reversible attachment-detachment processes, the thermodynamic parameters of the reaction have been evaluated by referring to the quasi-free state of the electron in which the solute reaction is believed to take place. The calculated encounter reaction efficiency (eta) Of the attachment process in the quasi-free state generally decreases with the effective mobility. Only in n-hexane and cyclohexane the attachment reaction is nearly or partially diffusion-controlled. In isooctane, neopentane, and tetramethylsilane the reaction is inefficient (eta less than or equal to 0.1). Electron trapping is speculated within the context of Anderson localization.