Observations on solvated electrons in aliphatic hydrocarbons at room temperature by pulse radiolysis

Abstract

The spectra of solvated electrons (e;) in n-hexane, cyclohexane, methylcyclohexane and isopeatane at room temperature have been obtained. Electron-cation recombination reactions are second order and have rate constants 1-20 x 1014 M-1 s-1 at 20°C. The rate constants for the reaction of e; with pyrene and carbon tetrachloride in n-hexane are 1.0 x 10l2 M-' s-' and the latter reaction has an activation energy of 5+ 1 kcal mol-'. The relationship of these observations to mobilities of electrons in hydrocarbons measured by conductivity is discussed.

Conductivity of solvated electrons in hexane investigated with terahertz time-domain spectroscopy

“…46 -50 Early radiolysis and ͑time-resolved͒ photoionization experiments were largely concerned with the pathways and efficiency of the generation process of the excess electrons, [51][52][53][54] the mechanism of charge transport, [55][56][57][58] and the electron-ion recombination process. [59][60][61][62][63][64][65][66][67] Later experiments examined the variation of the electron mobility with temperature, 53,68 pressure, 57,68 -72 and molecular geometry, 48,56 the connection between electron mobility and free-ion yield, 51,53,54 and recombination rates of electrons with electron scavengers. 59,[73][74][75] From these studies, possible pathways and typical time scales for photogenerated electrons have emerged.…”

“…[59][60][61][62][63][64][65][66][67] Later experiments examined the variation of the electron mobility with temperature, 53,68 pressure, 57,68 -72 and molecular geometry, 48,56 the connection between electron mobility and free-ion yield, 51,53,54 and recombination rates of electrons with electron scavengers. 59,[73][74][75] From these studies, possible pathways and typical time scales for photogenerated electrons have emerged. They are illustrated in Fig.…”

Electron trapping in alcohol clusters in γ-irradiated alcohol-2,2,4-trimethylpentane- 2,2-dimethylbutane glasses at 77 K

“…Free ion yields in TMP and DMB are higher than those in 2MP and MCH (27,34,35). Thus it appears that quasifree electron scavenging by alcohol clusters (4) is not the mechanism of eiC formation in alcohol-hydrocarbon systems.…”

Estimated Distribution Functions of Electronic Redox Levels and the Rate of Chemical Reactions of Excess Electrons in Dielectric Liquids

“…The rate constants of chemical reactions of electrons in diclcctric liquids have been measured by various authors and compared with the mobilities of the electrons in those solvents [4,5,11,14,29]. Beck and Thomas [29] have discussed their results on the basis of the transition state which is formed when the orbital of the electron overlaps with that of the solute.…”