Pulse Radiolysis Studies. VII. The Absorption Spectra and Radiation Chemical Yields of the Solvated Electron in the Aliphatic Alcohols

1965 ◽  
Vol 42 (2) ◽  
pp. 708-712 ◽  
Author(s):  
Myran C. Sauer ◽  
Shigeyoshi Arai ◽  
Leon M. Dorfman
Keyword(s):  
Absorption Spectra ◽  
Pulse Radiolysis ◽  
Aliphatic Alcohols ◽  
Solvated Electron ◽  
Radiation Chemical

Pulse Radiolysis Studies. IV. The Solvated Electron in the Aliphatic Alcohols

1964 ◽  
Vol 41 (4) ◽  
pp. 979-985 ◽  
Author(s):  
Irwin A. Taub ◽  
Douglas A. Harter ◽  
Myran C. Sauer ◽  
Leon M. Dorfman
Keyword(s):  
Pulse Radiolysis ◽  
Aliphatic Alcohols ◽  
Solvated Electron

Étude par radiolyse pulsée des propriétés spectrales et cinétiques de l'électron solvaté dans l'hexane-1,2,6-triol liquide

1995 ◽  
Vol 73 (1) ◽  
pp. 117-122 ◽  
Author(s):  
J.-P. Jay-Gerin ◽  
J. Chevrel ◽  
C. Ferradini ◽  
E. Ray ◽  
M.H. Klapper ◽  
...  
Keyword(s):  
Absorption Spectrum ◽  
Optical Absorption ◽  
Linear Accelerator ◽  
Pulse Radiolysis ◽  
Order Reaction ◽  
Kinetic Properties ◽  
Solvated Electron ◽  
Solvent Viscosity ◽  
First Order ◽  
Short Times

The optical absorption spectrum of the solvated electron (es−) in liquid hexane-1,2,6-triol has been measured by nanosecond pulse radiolysis at different temperatures (10–40 °C) to investigate the influence of high solvent viscosity values on the spectral and kinetic properties of es−. The wavelength at the absorption maximum, λmax, is equal to 560 nm, and its variation with temperature, if it exists in the considered zone, is less than the experimental error. At 20 °C and 150 ns, the value of the product [Formula: see text] of the yield of es− and the molar extinction coefficient at λmax is 2.55 × 104 molecule/(M cm 100 eV). In the context of this work, we have compared results obtained with both a linear accelerator and a Febetron, a comparison that has allowed us to evaluate the influence of variations of the dose per pulse and to extend measurements to short times. In the case of experiments performed with the linear accelerator, es− is found to decay at all wavelengths by a first-order reaction (or by a pseudo-first-order reaction) with an activation energy of ~45 kJ mol−1. By contrast, kinetic curves obtained with the Febetron seem to show a competition in which a second-order law is followed at short times. The fact that the shape of the spectra seems to vary as a function of the dose per pulse indicates the possible intervention of another species whose formation is favored by the use of high radiation doses. In other respects, the kinetics of electron solvation does not seem to be controlled by the viscosity of the solvent in our experimental conditions. Keywords: liquid hexane-1,2,6-triol, pulse radiolysis, linear accelerator and Febetron, solvated electron, optical absorption spectrum, kinetic properties, solvent viscosity, dose and temperature effects.

Pulse Radiolysis of Alkali Metal Solutions in Ethylamine

1973 ◽  
Vol 51 (17) ◽  
pp. 2975-2986 ◽  
Author(s):  
J. W. Fletcher ◽  
W. A. Seddon ◽  
F. C. Sopchyshyn
Keyword(s):  
Alkali Metal ◽  
Pulse Radiolysis ◽  
Electron Pair ◽  
Equilibrium Constants ◽  
Distinct Species ◽  
Complexing Agents ◽  
Crown Compounds ◽  
Solvated Electron ◽  
Sodium Potassium ◽  
Extinction Coefficients

Pulse radiolysis of solutions of alkali metal ethylamides in ethylamine shows the formation of three distinct species; the solvated electron es−, the alkali metal anion M−, and a species considered to be the cation–electron pair with stoichiometry M. The three species coexist in equilibrium in accord with the equations[Formula: see text]Studies of these solutions as a function of temperature, alkali metal concentration, and added complexing agents ("crown" compounds) show that es− and M have distinct absorption spectra with the former having a maximum ≥ 1800 nm. The latter exhibit maxima at 1400 nm for Na and K, ~1400 nm for Cs, and 1600–1700 nm for Li. The corresponding M− species were observed in sodium, potassium, and cesium solutions with absorption maxima at 680, 890, and 1100 nm, respectively.Rate and equilibrium constants for the formation of M and M− vary markedly with the nature of the alkali metal. Estimates for these constants along with the extinction coefficients for the various species are summarized and compared with data obtained in alkali metal solutions.

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