Water, radiolytic reaction

Other than water, protein is the major constituent of meat averaging nearly 21% in heef or chicken meat, with fat varying fiom 4.6 to 11.0% in beef and fiom 2.7 to 12.6% in chickoi. The principal radiolytic reactions of aqueous solutions of aliphatic amino acids are reductive deamination and decarboxylation. Alanine yields NH3, pyruvic add, acetaldehyde, propionic acid, CO2, H2, and ethylamine (6). Sulfur-containing amino adds are espedally sensitive to ionizing radiation. Cysteine can be oxidized to cystine by the hydroxyl radical or it can react with the hydrated electron and produce... 

The radiolytic reaction, CO2 + C -> 2 CO, becomes a problem as the coolant temperature is increased in the C02-cooled reactor. It has been shown in the Windscale AGR (22) that this reaction can be adequately inhibited by the addition of methane to the coolant. Substantial amounts of carbon monoxide and water are formed as the result of methane reactions, and a purification system and dryer are required to clean the... 

Comparative studies are indeed effected especially for aqueous solutions. However, many important differences exist, and the existence of hydrated electrons in the products of water sonolysis are still controversial. In addition, many sonolyses occur primarily in the gas phase of the bubble, while radiolytic reactions occur in the solution. A major limitation, of importance for synthetic chemists, is that little is known concerning the basic aspects of cavitation in organic media, but the situation is still worse concerning their behavior under radiolysis. 

One of the most important parameters controlling iodine volatility is sump water pH not only will the I2 hydrolysis equilibrium and the iodine partition coefficient be affected by this parameter, but the product yields of radiolytic reactions and the extent of formation of organoiodine compounds as well. Because of the lack of practical experience, the sump water pH to be expected under severe accident conditions has to be calculated on the basis of assumed concentrations of potential sump water ingredients. In Table 7.17. (according to Beahm et al., 1992) an overview of substances to be expected in the sump water, which would effect a shift in solution pH either to lower or to higher values, is given. Besides these chemical substances, radiation may also affect sump water pH irradiation of trisodium phosphate solution (5.3 kGy/h) was reported to decrease the pH from an initial value of 9.0 to about 4.0 after 60 hours of irradiation (Beahm et al., 1992). It is obvious that in such a complicated system definition of the sump water pH to be expected in a real severe reactor accident is a difficult task. Nonetheless, a model for calculation has been developed by Weber et al. (1992). 

Packer and Richardson (1975) and Packer et al. (1980) made use of the fact that electrons can be generated in water by y-radiation from a 60Co source (Scheme 8-29) to induce a free radical chain reaction between diazonium ions and alcohols, aldehydes, or formate ion. It has to be emphasized that the radiolytically formed solvated electron in Scheme 8-29 is only a part of the initiation steps (Scheme 8-30) by which an aryl radical is formed. The aryl radical initiates the propagation steps shown in Scheme 8-31. Here the alcohol, aldehyde, or formate ion (RH2) is the reducing agent (i.e., the electron donor) for the main reaction. The process is a hydro-de-diazoniation. 

Unique radiolytical products (URP) in irradiated food are usually formed by the secondary reactions of water radicals, eh, H, and OH, and to a lesser extent by the direct action of radiation, especially for foods with considerable water content. Due... 

The second-order rate constant for the reaction of a hydrogen atom with a hydroxide ion to give an electron and water (hydrated electron) is 2.0 x 10 M s . The rate constant for the decay of a hydrated electron to give a hydrogen atom and hydroxide ion is 16M s. Both rate constants can be determined by pulse radiolytic methods. Estimate, using these values, the pA of the hydrogen atom. Assume the concentration of water is 55.5M and that the ionization constant of water is 10 M. 

Radioprotection. The processes of crosslinking and degradation observed in polymers irradiated in the pure state can also be observed in polymers irradiated in solution. The presence of a solvent can intervene in the reaction in several ways thus it allows increased polymer mobility, and some of the radiolytic products of the solvent may react with the polymer or with the polymer radicals, etc. The polymer-water system is of particular interest in that it provides a simple model for some radiobiological systems and can be analyzed far more readily. 

SCHEME 4.1 Schematics of radiolysis and reducing species. As a result of ionization of the water molecule, hydroxyl radicals and hydrated electrons are formed. The final radiolytic yield depends on the secondary reactions in spurs and on the presence of other compounds. See Refs 25,26,190, and 191 for the detailed discussion and references. Solvated electrons are mobile enough to escape spurs and to react with the heme protein complexes even at 77K. All other reactive products of radiolysis are immobilized in the solid solvent matrix, or trapped by radical quenchers. 

Water radiolysis is actually more complex than suggested by Eq. (2). A more complete series of reactions representing the radiolytic decomposition of water may be found in Table 1. 

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