A. Mozumder, THERMODYNAMICS OF ELECTRON TRAPPING AND OF SOME REVERSIBLE ATTACHMENT-DETACHMENT REACTIONS IN LIQUID HYDROCARBONS, Journal of physical chemistry, 100(14), 1996, pp. 5964-5969
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.