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.

Picosecond Pulse Radiolysis Studies. I. The Solvated Electron in Aqueous and Alcohol Solutions

1970 ◽  
Vol 53 (11) ◽  
pp. 4201-4210 ◽  
Author(s):  
M. J. Bronskill ◽  
R. K. Wolff ◽  
J. W. Hunt
Keyword(s):  
Pulse Radiolysis ◽  
Picosecond Pulse ◽  
Solvated Electron

Yield and properties of solvated electrons created by the γ radiolysis of hexamethylphosphorotriamide

1977 ◽  
Vol 55 (11) ◽  
pp. 1832-1835 ◽  
Author(s):  
M. C. Lebas ◽  
J. Sutton ◽  
A. M. Koulkes-Pujo
Keyword(s):  
Pulse Radiolysis ◽  
Total Yield ◽  
Solvated Electron ◽  
Solvated Electrons ◽  
Γ Rays

According to various authors, the value of the yield of the solvated electron in the pulse radiolysis of hexamethylphosphorotriamide (HMPT) varies from 1.2 to 2.4 and increases to 4.2 or 3.1 in the presence of NaBr. We exposed this compound to γ rays after purification and saturation with N2O. N2 was formed with a yield G(N2) = 4.4 ± 0.4. After elimination of a certain number of processes which might also lead to N2 formation, it was concluded that this G(N2) corresponds to the total yield of electrons. This value was confirmed by measuring G(Br−) obtained by radiolysis of HMPT with p-bromophenol as a scavenger. The yield of N2 remains constant whenever solutes generally known as good electron scavengers are added (H+, CH3COCH3, NO3−). An interpretation of the results leads to the suggestion of the formation of a dielectron in this medium.

Conductometric Pulse Radiolysis Study on the Reaction of the Solvated Electron with 5-Bromouracil in Aqueous Solutions at Different pH Values

1974 ◽  
Vol 29 (1-2) ◽  
pp. 86-88b ◽  
Author(s):  
Burkhard O. Wagner ◽  
Herbert Klever ◽  
Dietrich Schulte-Frohlinde
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Aqueous Solutions ◽  
Hydroxyl Radical ◽  
Rate Constant ◽  
Pulse Radiolysis ◽  
Solvated Electron ◽  
Ph Values

To study the reaction of the solvated electron with 5-bromouracil an aqueous solution has been examined by conductometric pulse radiolysis at pH values between 4.68 and 8.74. Alcohol was added to scavenge the hydrogen atom and the hydroxyl radical. G(Br—) = (2.64 ± 0.08)/100 eV was found to be independent of the pH. The mobility of the bromouracil mono-anion was measured to be (2.7 ± 0.2) 10-4 cm2 V-1 s-1 at 20°C, and the rate constant of reaction (3b) was determined to be k(H+ BrUr-) = (2.3 ± 0.2) 1010 I mole-1 s-1*.

Pulse Radiolysis of Liquid Deuterated Ammonia

1973 ◽  
Vol 51 (22) ◽  
pp. 3653-3661 ◽  
Author(s):  
William Arthur Seddon ◽  
John Wallace Fletcher ◽  
John Jevcak ◽  
Fred Charles Sopchyshyn
Keyword(s):  
Alkali Metal ◽  
Time Scale ◽  
Pulse Radiolysis ◽  
Equilibrium Mixture ◽  
Solvated Electron ◽  
Metal Amides ◽  
Initial Yield ◽  
Metal Electron

Pulse radiolysis of solutions of alkali metal amides in deuterated ammonia at −15 °C produces an initial absorption with a maximum at 1500 nm due to the solvated electron, eam−. This decays on a microsecond time scale giving a residual long lived absorption with a slightly broader spectrum and a maximum displaced to 1640 nm. We suggest the residual absorption is an equilibrium mixture of eam− and a metal–electron species. The initial decay of eam− is suppressed by scavenging ND2 and/or ND− radicals with dissolved D2 (1 atm) or NaBH4. Evidence is also obtained for the reaction ND− + D2 → eam−. It is estimated that k(eam− + ND2) and k(BH4− + ND2) = 2.5 × 1010 and 7 × 107 M−l s−1, respectively. Measurements of the initial yield in NH3 and ND3 give [Formula: see text]and 3.6 ± 0.4 molecules/100 eV, respectively.

Pulse Radiolysis Studies on the Temperature-Dependent Spectrum and the Time-Dependent Yield of Solvated Electron in Propane-1,2,3-triol

2009 ◽  
Vol 113 (44) ◽  
pp. 12193-12198 ◽  
Author(s):  
Mingzhang Lin ◽  
Haiying Fu ◽  
Isabelle Lampre ◽  
Vincent de Waele ◽  
Yusa Muroya ◽  
...  
Keyword(s):  
Pulse Radiolysis ◽  
Time Dependent ◽  
Solvated Electron ◽  
Temperature Dependent

Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

2009 ◽  
Vol 78 (12) ◽  
pp. 1157-1160 ◽  
Author(s):  
Takafumi Kondoh ◽  
Akira Asano ◽  
Jinfeng Yang ◽  
Kimihiro Norizawa ◽  
Kenji Takahashi ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Pulse Radiolysis ◽  
Solvated Electron ◽  
Species Effects ◽  
Ion Species
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