THERMODYNAMICS OF ELECTRON TRAPPING AND OF SOME REVERSIBLE ATTACHMENT-DETACHMENT REACTIONS IN LIQUID HYDROCARBONS

Thermodynamic parameters for electron trapping from the quasi-free sta te have been calculated from equilibrium trapping and detrapping rates in n-hexane, cyclohexane, n-pentane, propane, 3-methypentane, and iso octane, in consistence with the variation of effective mobility with t emperature. From these, the derived free energy and entropy of solutio n show systematic variation with V-0, the energy of the lowest conduct ing state in the liquid. For several reversible attachment-detachment processes, the thermodynamic parameters of the reaction have been eval uated by referring to the quasi-free state of the electron in which th e 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-hexan e and cyclohexane the attachment reaction is nearly or partially diffu sion-controlled. In isooctane, neopentane, and tetramethylsilane the r eaction is inefficient (eta less than or equal to 0.1). Electron trapp ing is speculated within the context of Anderson localization.