Radiolytic oxidation

The radioly tic behavior of a substituted picolinamide calix[6]arene, studied for the separation of actinides from lanthanides, was recently investigated by Mariani (263). For doses ranging from 0.014 to 0.055 MGy, the distribution ratios of both Am(III) and Ln(III) strongly increased, whereas after absorbed doses higher than 0.10 MGy, they decreased to values lower than those measured for nonirradiated samples. The selectivity for Am/Eu remained constant. Comparable experiments under a nitrogen atmosphere indicated the role of oxygen in the radiolysis, because the distribution ratios decreased by factors of 10 and 1.5-5 for Am-Eu and other lanthanides, respectively. The increase for lower doses was then explained by the formation of oxidized radiolytic products. No evidence of new products was obtained with the ESI-MS technique. 

Qin L, Tripathi G N R and Schuler R H 1987 Radiolytic oxidation of 1,2,4-benzenetriol an application of time-resolved resonance Raman spectroscopy to kinetic studies of reaction intermediates J. Chem. Phys. 

Many tracer chemicals are inherently unstable even as the unlabeled forms. Susceptibility of a chemical to hydrolysis, oxidation, photolysis, and microbiological degradation needs to be evaluated when designing suitable storage conditions for the labeled compound. Eactors that reduce radiolytic degradation, such as dispersal in solution, are apt to increase chemical degradation or instability. 

The simplest description of the reaction responsible for the radiolytic oxidation of graphite is ... 

Radiolytic oxidation alters most of the important properties of graphite, including strength, elastic modulus, work of fracture, thermal conductivity, permeability, and diffusivity but does not affect the thermal expansion coefficient or Poisson s ratio. The effects of radiolytic oxidation on the properties of a wide range of graphites have been studied in the U.K. [7,73,74] where it was found that, to a first approximation, they can be described by similar relationships ... 

It is well known that for a given weight loss, thermal oxidation of graphite causes a larger reduction in strength and elastic modulus than radiolytic oxidation. Pickup et al. [78] showed the decrement in dynamic elastic modulus, E, due to thermal oxidation fitted an exponential relationship ... 

Radiolytic oxidation is important to the design and operation of reactors because it adversely affects key graphite properties and, by removing moderator material, may bring about the need for increased fuel enrichment. As mentioned earlier, an inhibitor (methane) is added to the coolant to reduce radiolytic oxidation to acceptable levels. However, access of the inhibitor to the inner portions of the moderator brick must be assured. Two approaches have been adopted in the AGRs to provide this access. Vertical methane access holes are provided in the fuel bricks and in the later stations, Heysham II and Tomess, a pressure drop from outside to inside the brick was established to cause an enhanced flow through the brick. The amount of inhibitor added must be restricted, however, because the carbon inhibition reaction product deposits on the fuel pin and restricts heat transfer to the coolant, thus reducing reactor efficiency. 

In support of the development of graphite moderated reactors, an enormous amount of research has been conducted on the effects of neutron irradiation and radiolytic oxidation on the structure and properties of graphites. The essential mechanisms of these phenomena are understood and the years of research have translated into engineering codes and design practices for the safe design, construction and operation of gas-cooled reactors. 

Kelly, B.T., The effect of radiolytic oxidation on the graphite moderator brick strength in advanced gas-cooled reactors, Nucl. Energy, 1984, 24(3), 265 272. 

Birch, M., Schofield, P., Brocklehurst, J.E., Kelly, B.T., Harper, A. and Prior, H., The combined effects of fast neutron damage and radiolytic oxidation on the physical... 

The monoxides SeO and TeO have transient existence in flames but can not be isolated as stable solids. PoO has been obtained as a black, easily oxidized solid by the spontaneous radiolytic decomposition of the sulfoxide P0SO3. 

Ru(bipy)3 formed in this reaction is reduced by the sacrificial electron donor sodium ethylenediaminetetra-acetic acid, EDTA. Cat is the colloidal catalyst. With platinum, the quantum yield of hydrogenation was 9.9 x 10 . The yield for C H hydrogenation was much lower. However, it could substantially be improv l by using a Pt colloid which was covered by palladium This example demonstrates that complex colloidal metal catalysts may have specific actions. Bimetalic alloys of high specific area often can prepared by radiolytic reduction of metal ions 3.44) Reactions of oxidizing radicals with colloidal metals have been investigated less thoroughly. OH radicals react with colloidal platinum to form a thin oxide layer which increases the optical absorbance in the UV and protects the colloid from further radical attack. Complexed halide atoms, such as Cl , Br, and I, also react... 

Grootveld et al. (1994) employed this technique to investigate radiolytic, damage to biomolecules present in human body fluids. 7-Radiolysis of healthy or rheumatoid human serum (5.00 kGy) in the presence of atmospheric O2 gave rise to reproducible elevations in the concentration of NMR-detectable acetate, which are predominantly ascribable to the prior oxidation of lactate to pyruvate by OH radical followed by oxidative decarboxylation of pyruvate by radiolytically generated H2O2 and/or further OH radicals (Equations 1.7 and 1.8). 

Typical spectra obtained are shown in Fig. 1.2. Moreover, substantial radiolytically-mediated elevations in the concentration of serum formate, arising from the oxidation of carbohydrates present by OH radical, were also detectable. In addition to the above modifications, 7-radiolysis of inflammatory knee-joint synovial fluid generated an oligosaccharide species of low molecular mass derived from the radiolytic fragmentation of hyaluronate as outlined in the previous section dealing with oxidative damage to carbohydrates. The... 

The tautomeric product distribution has been a prerequisite for a further investigation aimed at predicting absorption properties of the transient semiquinones and quinones generated by pulse radiolytic oxidation of 2-4. The simulation of electronic absorption spectra has been computed using the TD-DFTapproach both in vacuum and in aqueous solution, using the large 6-311 + +G(2d,2p) basis set.19... 

It was suggested that Tc02 could be oxidized to TcO in high salinity oxygen-free water due to radiolytic effects [62], Lieser and Rauscher [63] showed that TcO could be reduced in natural ground water under anaerobic conditions. 

Adhikari, S., Kapoor, S., Chattopadhyay, S., and Mukheijee, T. 2000. Pulse radiolytic oxidation of P-carotene with halogenated alkylperoxyl radicals in a quaternary microemulsion Formation of retinal. Biophys. Chem. 88 111-117. 

The kinetically-stabilized complexes of the cage ligands normally yield redox reagents free of the exchange problems often associated with simple complexes. Indeed, the redox chemistry of the complexes shows a number of unusual features for example, saturated cages of the type mentioned in Chapter 3 are able to stabilize rare (monomeric) octahedral Rh(n) species (d7 electronic configuration) (Harrowfield etal., 1983). In a further study, radiolytical or electrochemical reduction of the Pt(iv) complexes of particular cages has been demonstrated to yield transient complexes of platinum in the unusual 3+ oxidation state (Boucher et al., 1983). 

Due to the high initiation rate and low (room) temperature, chains for oxidation of alkanes are short and many products are formed by disproportionation of peroxyl and hydroperoxyl radicals. The G values of the products of radiolytic oxidation of four alkanes are given in the following table [233] ... 

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