J. H. Baxendale, F. Busi (Eds.): The Study of Fast Processes and Transient Species by Electron Pulse Radiolysis, NATO Adv. Study Inst. Series, Series C: Mathematical and Physical Sciences. D. Reidel Publ. Co., Dordrecht, Boston, London 1982. 637 Seiten, P

1983 ◽  
Vol 87 (11) ◽  
pp. 1100-1100
Author(s):  
J. Lilie
Keyword(s):  
Pulse Radiolysis ◽  
Electron Pulse ◽  
Transient Species ◽  
Physical Sciences

The Mechanism of Decay of the Radical HO—CH—CH2—OCOCH3 in Aqueous Solutions. A Conductometric Pulse Radiolysis Study

1976 ◽  
Vol 31 (7) ◽  
pp. 960-964 ◽  
Author(s):  
G. Koltzenburg ◽  
T. Matsushige ◽  
D. Schulte-Frohlinde
Keyword(s):  
Acetic Acid ◽  
Aqueous Solutions ◽  
Rate Constants ◽  
Pulse Radiolysis ◽  
Electron Pulse ◽  
Rate Determining Step ◽  
A Value

From conductivity changes following a 1 µs electron pulse applied to Ν2Ο saturated H2O or D2Ο solutions of acetic acid 2-hydroxyethyl esterthe rate constants of the monomolecular decay of the radical HO-ĊH-CH2-OCOCH3 (1) in H2O and of DO-ĊH-CH2-OCOCH3 in D2O were derived, reaction (1).A value of k1 of 5.5 · 105 s-1 ± 25%, at 22 to 24°C, independent of the above solvents and of pH (or pD) was obtained. It is concluded that the rate determining step of reaction (1) is the heterolytic fragmentation of the carbon acetate bond in 1 followed by formation of H+.

A Transient Intermediate in the Bimolecular Reaction of Hydrated Electrons

1972 ◽  
Vol 50 (13) ◽  
pp. 2059-2070 ◽  
Author(s):  
N. Basco ◽  
G. A. Kenney-Wallace ◽  
S. K. Vidyarthi ◽  
D. C. Walker
Keyword(s):  
Absorption Band ◽  
Extinction Coefficient ◽  
Pulse Radiolysis ◽  
Flash Photolysis ◽  
Bimolecular Reaction ◽  
Considerable Extent ◽  
Transient Species ◽  
Hydrated Electrons ◽  
Mean Lifetime ◽  
Transient Intermediate

Further studies are reported which attempt to identify the transient species (X) produced from hydrated electrons which may be photodissociated to re-form [Formula: see text] The method used involves the production of [Formula: see text] by u.v. flash photolysis of aqueous OH−/H2 solutions followed, after any specified delay, by a second and third photoflash of restricted wavelengths. Photoregeneration of [Formula: see text] is effected by light in the spectral range 320 to 400 nm, not at λ > 700 nm as earlier reported (1). The species X is much longer lived than [Formula: see text] having a mean lifetime of ∼5 ms at pH 11, but this is very dependent on the lifetime of [Formula: see text] in the system. Two conditions seem to be necessary in order to detect the presence of X, (i) [Formula: see text] must decay to a considerable extent through the bimolecular dimerisation reaction and (ii) the lifetime of [Formula: see text] with respect to all other reactions must be >ca. 200 μs. Thus it is not expected to be observable in most pulse radiolysis studies. Its extinction coefficient in that part of its absorption band which leads to photodissociation (320–400 nm) is estimated to average >2000 M−1 cm−1, may be as high as 6000 M−1 cm−1 at 347 nm but does not exceed 12 000 M−1 cm−1 at any wavelength. Its identity is discussed and it is concluded that X is probably the hydrated electron dimer, [Formula: see text] or a product formed there from by association with a cation.

Sign in / Sign up

Export Citation Format

Share Document