Pulse radiolysis study of the kinetics of electron reactions in liquid n-hexane at room temperature

Abstract

The behaviour of solvated electrons, ei-, produced by the pulse radiolysis of n-hexane at 20°C has been followed using optical absorption techniques. Rate constants for the reaction of eswith naphthalene, biphenyl, galvinoxyl, chloroform, carbon tetrachloride, perhoromethylcyclohexane, carbon dioxide, nitrous oxide and oxygen have been determined and are in the range 0 . 1 -1 . 8 ~ loL2 dm3 moI-' s-l.

A pulse radiolysis study of solvated electrons in dilute solutions of polar liquids in nonpolar solvents

“…(2,6). A 10 MeV linear accelerator introduced 5 or 10 ns pulses of radiation, electrons for n-hexane and cyclohexane, X rays from a tungsten target for i-octane.…”

“…The alkanes and alcohols were purified as described earlier (2). Dimethylformamide (DMF) was the quality 'for infrared spectroscopy' and was treated with moiecular sieve 4A before use.…”

“…Early observations (1) on mixtures of hydrocarbons and alcohols designed to produce liquids of intermediate polarity showed that as little as 47, v/v of methanol in cyclohexane gives an absorption spectrum similar to that of esin pure methanol and later work ( 2 ) showed that for es-in n-hexane containing 2% methanol and in pure methanol the two spectra were almost indistinguishable. Most studies on such polar-nonpolar mixtures have been confined to high concentrations of alcohols in alkanes (3)(4)(5) but it has been shown in a detailed spectral examination ( 2 ) that changes in the far infrared absorption of e > in 11-hexane occur in the presence of a few tenths of 17; of n-propanol or of water.…”

Picosecond measurements of geminate charge pair recombination in photoionized liquids

“…When the uv pulse is folowed by an intense infrared pulse at 1053 nm, an increased yield of free charge is observed which depends strongly on the relative timing of the two optical pulses. It has been suggested (14,15) that the infrared pulse acts by exciting the geminate electron which has an absorption cross-section of 3 x lo-'' cm' at 1053 nni (16). Since the ir photon has an energy of 1.2 eV while the Coulonib binding energy only amounts to 0.1-0.2 eV, ir excitation proniotes the charge pair well above its dissociation limit.…”

Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A Critical Review

“…For these electrons, the complexation manifests itself through a precipitous decrease in the electron mobility upon the addition of the solute: thermal emission of trapped electrons from the complexes to the CB is much less efficient than that of free "solvated electrons". No changes in the absorption band of the "solvated electron" in the NIR are observed upon the complexation of these electrons with the monomers and dimers of polar molecules [32].…”