The Solvated Electron in Alcohols and Other Polar Liquids

The mobility of eh was determined by measuring the equivalent conductance following pulse irradiation (Schmidt and Buck, 1966 Schmidt and Anbar, 1969). After correcting for the contribution of H30 and OH ions, they found the equivalent conductance of eh = 190 10 mho cm2. From this, these authors obtained the mobility p(eh) = 1.98 x 10 3 cm2/v.s. and the diffusion coefficient D(eh) = 4.9 x 10-5 cm2/s using the Nernst-Einstein relation, with about 5% uncertainty. The equivalent conductance of eh is the same as that for the OH - ion within experimental uncertainty. It is greater than that of the halide ion and smaller than that of eam 

3 THE SOLVATED ELECTRON IN ALCOHOLS AND OTHER POLAR LIQUIDS 

The absorption spectrum of radiation-produced eam is identical to that in dilute metal-ammonia solutions. It has a broad, structureless absorption in the red and IR, with a peak at about 1.88 pm and a half-width of 0.2 eV on the high-energy side. The absorption is intense with max = 4.8 x 104 M 1cm 1, giving an 

Farhataziz et al. (1974a, b) studied the effect of pressure on eam and found that as the pressure is increased from 9 bar to 6.7 Kbar at 23° (1) the primary yield of e decreases from 3.2 to 2.0 (2) hv increases from 0.67 to 0.91 eV (3) the half-width of the absorption spectrum on the high-energy side increases by 35% and (4) the extinction coefficient decreases by 19%, which is similar to eh. The pressure effects are consistent with the large volume of ean (98 ml/M), whereas the reduction in the observed primary yield at 0.1 ps is attributable to the reaction eam + NH4+. Some of the properties of eam have been discussed by several authors in Solvated Electron (Hart, 1965). 

Hentz and Kenney-Wallace (1972, 1974) made a detailed study of esin 25 neat alcohols and three alkane solutions in 1-hexadecanol at 30° using a 5-ns electron pulse. Most data were new, but in some cases they confirmed earlier observations (Dorfman, 1965 Baxendale and Wardman, 1971). The authors found the spectrum fully developed at the end of the pulse, with no spectral change thereafter. The spectra are all broad, asymmetric, and structureless, 

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The Solvated Electron in Alcohols and Other Polar Liquids... 

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