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

1977 ◽  
Vol 55 (11) ◽  
pp. 1996-2002 ◽  
Author(s):  
J. H. Baxendale
Keyword(s):  
Absorption Spectra ◽  
Pulse Radiolysis ◽  
Electron Pulse ◽  
Pulse Irradiation ◽  
Dilute Solutions ◽  
Solvated Electrons ◽  
Polar Liquids ◽  
Tert Butanol ◽  
Nonpolar Solvents ◽  
Existence Of Equilibria

Measurements of the conductivities following electron pulse irradiation of dilute solutions of ethanol, n-propanol, tert-butanol, or dimethyl sulphoxide in n-hexane, cyclohexane, or i-octane are quantitatively consistent with the existence of equilibria between electrons in the hydrocarbon and electrons solvated by dimers of the polar molecules. With dimethylformamide solutions in alkanes the equilibrium could be with the monomeric anion of the solute but this assignment is not unequivocal. Absorption spectra of es− in n-hexane solutions of ethanol and of tert-butanol have been obtained.

A pulse radiolysis study of solvated electrons in tert-butanol/water solutions

1986 ◽  
Vol 64 (8) ◽  
pp. 1548-1552
Author(s):  
Joanna Cygler ◽  
Norman V. Klassen ◽  
Carl K. Ross
Keyword(s):  
Experimental Data ◽  
Pulse Radiolysis ◽  
Oh Radicals ◽  
Solvated Electrons ◽  
Secondary Electrons ◽  
Water Solutions ◽  
Tert Butanol

Many solutes, added to water in amounts of a few mol%, cause an increase in the yield of solvated electrons (es−) measured by pulse radiolysis. A pulse radiolysis study of tert-butanol (tBuOH) in D2O has been carried out to investigate this phenomenon. Detailed measurements of the yield, measured as Gεmax(es−), and the deeay of solvated electrons were made at 6, 25, and 46 °C over the range 0–5mol% tBuOH. The maximum Gεmax(es−) occurs at about 1 mol% tBuOH, but the exact concentration depends on the temperature of the sample and the time after the pulse at which the measurement is made. Three factors are examined as contributing to the increased Gεmax(es−) in the presence of tBuOH and certain other solutes. They are (i) the change in viscosity produced by the added solute, (ii) the scavenging of OH radicals by the solute, thereby reducing the reaction of OH with es− and (iii) the possibility that the addition of the solute leads to an increase in the thermalization distance of the secondary electrons. It is concluded that effects (i) and (ii) are sufficient to explain the existing experimental data.

Dielectric Constants of Dilute Solutions of Polar Liquids in Nonpolar Solvents

1928 ◽  
Vol 31 (4) ◽  
pp. 653-671 ◽  
Author(s):  
J. D. Stranathan
Keyword(s):  
Dielectric Constants ◽  
Dilute Solutions ◽  
Polar Liquids ◽  
Nonpolar Solvents

The radiation chemistry of organic amides I. A pulse radiolysis study of solvated electrons and alkali-metal-electron species in cyclic amides

1989 ◽  
Vol 421 (1860) ◽  
pp. 169-178 ◽  
Keyword(s):  
Alkali Metal ◽  
Absorption Spectra ◽  
Pulse Radiolysis ◽  
Near Infrared ◽  
Radiation Chemistry ◽  
Alkali Metal Salts ◽  
Solvated Electrons ◽  
Electron Scavenger ◽  
Cyclic Amide ◽  
Metal Electron

Pulse radiolysis of the cyclic amides N -methylpyrrolidinone (NMP), N -ethylpyrrolidinone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI) and 1,3-dimethyl-2-oxo-hexahydropyrimidine (DMH) and the non-cyclic amide tetramethylurea (TMU) yielded absorption spectra in the near infrared that are attributed to solvated electrons. Addition of a variety of alkali-metal salts caused no detectable change in the absorption spectrum of e - s and no new absorptions attributable to alkali-metal anions were detected. The effect of dose on the decay of e - s in NMP was studied in detail. The yields of e - s in these amides were estimated by using trans -stilbene as an electron scavenger. Absorption spectra, which are not removed by saturation with N 2 O and CO 2 , are observed in the wavelength range 300-500 nm.

Absorption spectra of solvated electrons and radicals observed in the pulse radiolysis of cis and trans isomers of methylcyclohexanols and cyclopentanol to cyclooctanol

1991 ◽  
Vol 95 (16) ◽  
pp. 6259-6264 ◽  
Author(s):  
Noboru Fujisaki ◽  
Pascal Comte ◽  
Pierre P. Infelta ◽  
Tino Gaeumann
Keyword(s):  
Absorption Spectra ◽  
Pulse Radiolysis ◽  
Trans Isomers ◽  
Solvated Electrons ◽  
Cis And Trans Isomers ◽  
Cis And Trans

Temperature and density effects on the absorption maximum of solvated electrons in sub- and super-critical methanol

2010 ◽  
Vol 88 (10) ◽  
pp. 1026-1033 ◽  
Author(s):  
Y. Yan ◽  
M. Lin ◽  
Y. Katsumura ◽  
Y. Muroya ◽  
S. Yamashita ◽  
...  
Keyword(s):  
Optical Absorption ◽  
Absorption Maximum ◽  
Pulse Radiolysis ◽  
Electron Pulse ◽  
Density Range ◽  
Supercritical State ◽  
Solvated Electron ◽  
Solvated Electrons ◽  
Absorption Energy ◽  
Increasing Temperature

The optical absorption spectra of the solvated electron ([Formula: see text]) in sub- and super-critical methanol are measured by both electron pulse radiolysis and laser photolysis techniques, at temperatures in the range 220–270 °C. Over the density range studied (~0.45–0.59 g/cm3), the position of the absorption maximum ([Formula: see text]) of [Formula: see text] is found to shift only slightly to the red with decreasing density. In agreement with our previous work in water, at a fixed pressure, [Formula: see text] decreases monotonically with increasing temperature in passing through the phase transition at Tc (239.5 °C). By contrast, at a fixed density, [Formula: see text] exhibits a minimum as the solvent passes above the critical point into the supercritical state. These behaviors are discussed in terms of microscopic arguments based on the changes that occur in the methanol properties and methanol structure in the sub- and super-critical regimes. The effect of the addition of a small amount of water to the alcohol on the optical absorption energy of [Formula: see text] is also investigated.

Pulse Radiolysis of Tetraphenylcyclobutane in Hexamethylphosphoric Triamide Solution

1978 ◽  
Vol 33 (11) ◽  
pp. 1281-1284 ◽  
Author(s):  
S. Takamuku ◽  
B. Dinh-Ngoc ◽  
W. Schnabel
Keyword(s):  
Optical Absorption ◽  
Pulse Radiolysis ◽  
Electron Attachment ◽  
Radical Anions ◽  
Dissociative Electron Attachment ◽  
Dilute Solutions ◽  
Solvated Electrons ◽  
Hexamethylphosphoric Triamide ◽  
Attachment Process

r-1, c-2, t-3, t-4-tetraphenvlcyclobutane (TPCB) was irradiated in dilute solutions of hexamethylphosphoric triamide (HMPT) with 20 ns pulses of 16 MeV electrons. Solvated electrons (e-solv) produced during the radiolysis of HMPT react with TPCB with k = (6 ± 1) · 109 l/mol s. Simultaneously with the decay of the optical absorption of the solvated electrons, the formation of the absorption of t-stilbene (at 300 nm) and that of stilbene radical anions (at 500 nm) was observed. Thus, it is concluded th at TPCB is undergoing a dissociative electron attachment process e-solv + TPCB→t-St + t-St·̄̅. The lifetime of a possible intermediate (TPCB·̄̅) was estimated as being smaller than 10-9 s. The 100 eV yield of t-stilbene was determined as G(t-St) = 3.4.

Temperature and pressure dependence of the absorption spectra and decay kinetics of solvated electrons in ethanol from 22 to 250°C studied by pulse radiolysis

2005 ◽  
Vol 404 (4-6) ◽  
pp. 267-271 ◽  
Author(s):  
Z. Han ◽  
Y. Katsumura ◽  
M. Lin ◽  
H. He ◽  
Y. Muroya ◽  
...  
Keyword(s):  
Absorption Spectra ◽  
Pressure Dependence ◽  
Pulse Radiolysis ◽  
Decay Kinetics ◽  
Solvated Electrons ◽  
Temperature And Pressure ◽  
Kinetics Of
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