Pulse radiolysis of aqueous cyanide solutions. Kinetics of the transient hydroxyl radical and hydrogen atom adducts and subsequent rearrangements

1976 ◽  
Vol 80 (14) ◽  
pp. 1549-1553 ◽  
Author(s):  
H. Buechler ◽  
R. E. Buehler ◽  
R. Cooper
1974 ◽  
Vol 29 (1-2) ◽  
pp. 86-88b ◽  
Author(s):  
Burkhard O. Wagner ◽  
Herbert Klever ◽  
Dietrich Schulte-Frohlinde

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*.


An apparatus for effecting flash photolysis in the vacuum ultra-violet region is described. Appreciable decompositions of water, carbon dioxide, acetylene, ethylene and methane were effected with a 2000 J flash of 30 p .s duration. A detailed study of water vapour photolysis has established that, in the primary step, at least 90 % of the dissociation leads to a hydrogen atom and a hydroxyl radical. The kinetics of the hydroxyl radical disappearance, following flash photolysis of water vapour in the presence of various third bodies, has been studied. The rate constant is faster in xenon than in helium and other similarities with the data on iodine atom recombination suggest the operation of a mechanism involving intermediate complex formation.


1995 ◽  
Vol 73 (12) ◽  
pp. 2137-2142 ◽  
Author(s):  
A.J. Elliot ◽  
M.P. Chenier ◽  
D.C. Ouellette

In this publication we report: (i) the rate constants for reaction of the hydrated electron with 1-hexyn-3-ol ((8.6 ± 0.3) × 108 dm3 mol−1 s−1 at 18 °C), cinnamonitrile ((2.3 ± 0.2) × 1010 dm3 mol−1 s−1 at 20 °C), and 1,3-diethyl-2-thiourea ((3.5 ± 0.3) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile and diethylthiourea, the temperature dependence up to 200 °C and 150 °C, respectively, is also reported; (ii) the rate constants for the reaction of the hydroxyl radical with 1-hexyn-3-ol ((5.5 ± 0.5) × 109 dm3 mol−1 s−1 at 20 °C), cinnamonitrile ((9.2 ± 0.3) × 109 dm3 mol−1 s−1 at 21 °C), and diethylthiourea ((8.0 ± 0.8) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile, the temperature dependence up to 200 °C is also reported; (iii) the rate constant for the hydrogen atom reacting with 1-hexyn-3-ol ((4.3 ± 0.4) × 109 dm3 mol−1 s−1 at 20 °C). Keywords: radiolysis, corrosion inhibitors, rate constants.


2008 ◽  
Vol 57 (6) ◽  
pp. 391-401 ◽  
Author(s):  
Michael S. Elovitz ◽  
Hilla Shemer ◽  
Julie R. Peller ◽  
K. Vinodgopal ◽  
Mano Sivaganesan ◽  
...  

1986 ◽  
Vol 240 (3) ◽  
pp. 897-903 ◽  
Author(s):  
L G Forni ◽  
R L Willson

Absolute rate constants for the reaction of NADH with thiyl free radicals derived from various sulphur-containing compounds of biological significance were measured by using the technique of pulse radiolysis. These and related reactions with phenoxyl free radicals are believed to occur through one-electron-transfer processes. Further evidence comes from studies with deuterated NADH. The results support the possibility that, in biochemical systems, thiols may act as catalysts linking hydrogen-atom and electron-transfer reactions.


2021 ◽  
pp. 128068
Author(s):  
Martin Walter ◽  
Gerald Geroldinger ◽  
Lars Gille ◽  
Stephan M. Kraemer ◽  
Walter D.C. Schenkeveld

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