Pulse Radiolysis of Formamide and Formamide–Water Mixtures

1971 ◽  
Vol 49 (20) ◽  
pp. 3398-3401 ◽  
Author(s):  
D. C. Walker ◽  
S. C. Wallace
Keyword(s):  
Dielectric Constant ◽  
Absorption Spectrum ◽  
Absorption Band ◽  
Optical Absorption ◽  
Optical Absorption Spectrum ◽  
Pulse Radiolysis ◽  
Water Molecules ◽  
Pure Liquid ◽  
Solvated Electrons ◽  
Hydrated Electrons

From the optical absorption spectrum observed by a sub-nanosecond pulse radiolysis method it is concluded that irradiated pure liquid formamide (dielectric constant = 109) does not yield solvated electrons with lifetimes >10−11 s. In formamide–water mixtures the hydrated electron is formed in low yield and the position of the absorption band of eaq− is not altered by changing the composition. Apparently formamide reacts much more rapidly with thermalized electrons than it does with hydrated electrons. The latter may be formed in formamide–water mixtures due to aggregates of water molecules.

The Pulse Radiolysis of Dimethylsulfoxide and Binary Mixtures with Water

1973 ◽  
Vol 51 (13) ◽  
pp. 2195-2206 ◽  
Author(s):  
T. K. Cooper ◽  
D. C. Walker ◽  
H. A. Gillis ◽  
N. V. Klassen
Keyword(s):  
Dielectric Constant ◽  
Optical Properties ◽  
Absorption Band ◽  
Linear Relationship ◽  
Half Life ◽  
Pulse Radiolysis ◽  
Water Molecules ◽  
Solvated Electrons ◽  
Free Ion ◽  
Pure Dmso

The simultaneous interaction of solvated electrons with strongly solvating water molecules and weakly solvating dimethylsulfoxide (DMSO) molecules has been studied by pulse radiolysis. In all DMSO/H2O mixtures investigated the solvated electrons have a single absorption band with a maximum intermediate between that of pure DMSO (λmax > 1500 nm) and that of water (λmax = 720 nm). There is a nearly linear relationship between the photon energy of λmax and the bulk dielectric constant, indicating that the optical properties of solvated electrons in the mixtures are not dominated by the water. A minimum is observed in the variation of Gεmax with DMSO/H2O composition which may be associated with intermolecular structure. In mixtures containing > 0.2 mole fraction DMSO the solvated electrons have half-lives of 11–18 ns.The radiation produced oxidizing species in DMSO has a half-life of 1–4 µs and an absorption band centered at 600 nm. This species seems to be present in all DMSO/H2O mixtures.Pure DMSO gives a free-ion yield in the range 1.2 to 1.8, as determined separately for the oxidizing and reducing species by bromide and anthracene scavenging experiments respectively. This free-ion yield is in keeping with the dielectric constant of DMSO of 46. The yields in fully deuterated DMSO are ~30% higher than in the protonated material.

Article

1998 ◽  
Vol 76 (4) ◽  
pp. 411-413
Author(s):  
Yixing Zhao ◽  
Gordon R Freeman
Keyword(s):  
Absorption Spectrum ◽  
Optical Absorption ◽  
Temperature Dependence ◽  
Optical Absorption Spectrum ◽  
Infrared Light ◽  
Solvated Electron ◽  
Solvated Electrons ◽  
Tert Butanol ◽  
Solvent Dependence ◽  
Increasing Temperature

The energy and asymmetry of the optical absorption spectrum of solvated electrons, es- , change in a nonlinear fashion on changing the solvent through the series HOH, CH3OH, CH3CH3OH, (CH3)2CHOH, (CH3)3COH. The ultimate, quantum-statistical mechanical, interpretation of solvated electron spectra is needed to describe the solvent dependence. The previously reported optical spectrum of es- in tert-butanol was somewhat inaccurate, due to a small amount of water in the alcohol and to limitations of the infrared light detector. The present note records the remeasured spectrum and its temperature dependence. The value of the energy at the absorption maximum (EAmax) is 155 zJ (0.97 eV) at 299 K and 112 zJ (0.70 eV) at 338 K; the corresponding values of G epsilon max (10-22 m2 aJ-1) are 1.06 and 0.74. These unusually large changes are attributed to the abnormally rapid decrease of dielectric permittivity of tert-butanol with increasing temperature. The band asymmetry at 299 K is Wb/Wr = 1.8.Key words: optical absorption spectrum, solvated electron, solvent effects, tert-butanol, temperature dependence.

Is there any Correlation between the Mobility and the Absorption Spectra of Solvated Electrons in Polar Solvents?

2000 ◽  
Vol 214 (10) ◽  
Author(s):  
P. Krebs
Keyword(s):  
Absorption Spectrum ◽  
Optical Absorption ◽  
Absorption Spectra ◽  
Optical Absorption Spectrum ◽  
Chem Phys ◽  
Solvated Electrons ◽  
Polar Solvents ◽  
Excess Electrons

Some years ago Jay-Gerin and Ferradini attempted to establish a correlation between the optical absorption spectrum and the mobility of excess electrons in various polar solvents (J. Chem. Phys.

Sign in / Sign up

Export Citation Format

Share Document