Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

International Nuclear Information System (INIS)

Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke

2000-01-01

The interaction of caffeic acid with e aq - , (CH 3 ) 2 (OH) CCH 2 · , CO 2 ·- , H · , ·OH and N 3 · radicals were studied by γ-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

Radiolysis of phenol in aqueous solution at elevated temperatures

International Nuclear Information System (INIS)

Miyazaki, Toyoaki; Katsumura, Yosuke; Lin Mingzhang; Muroya, Yusa; Kudo, Hisaaki; Taguchi, Mitsumasa; Asano, Masaharu; Yoshida, Masaru

2006-01-01

γ-Radiolysis and pulse radiolysis of phenol in aqueous solution up to supercritical condition have been carried out. G-values of phenol consumption and product formation have been determined. While dihydroxybenzenes were major products at room temperature, multi-ring compounds and benzene were formed above 300 deg. C. This indicates reaction mechanism was changed above 300 deg. C, where phenoxyl radical plays a predominant role. This is supported by the observation of phenoxyl radical in pulse radiolysis. In supercritical water, the G-values increased with decrease of density

γ-radiolysis of benzophenone in heptane solutions

International Nuclear Information System (INIS)

Melekhonova, I.I.; Romantsev, M.F.; Saraeva, V.V.

1979-01-01

The radiolysis mechanism of 8x10 -3 M solutions of benzophenon in heptane at 0 deg C and a dose of 3.8x10 20 eV/ml, is studied. The radiolysis products (benzpinacol and benzhydrol with alkyl substitution in aromatic ring) are isolated by the thin-layer chromatography. The identification of the products is performed using infrared and mass spectroscopy. The mechanism of the process is considered based on the reactions of a triplet state of benzophenon

Formation of clusters (ions solvated with products of radiolysis) during irradiation of certain chloralkanes in the condensed phase

International Nuclear Information System (INIS)

Sukhov, F.F.; Karatun, A.A.; Slovokhotova, N.A.

1983-01-01

Using the infrared spectroscopy method, the radiolysis of the 2-chloropropane and 2-chloro-2-methylpropane was investigated in various phase states and in argon matrix at 15 and 77 K. A conclusion is drawn that the reaction of the radiation dehydrochlorination in the chloralkanes investigated occurs under certain conditions in the vicinity of ions, mostly; as this takes place, unique clusters composed of radiolysis products, i.e. ions solvated with complexes of alkane and hydrogen chloride are being formed. (author)

Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

Energy Technology Data Exchange (ETDEWEB)

Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

2000-03-01

The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

Influence of chemisorption products of carbon dioxide and water vapour on radiolysis of tritium breeder

Energy Technology Data Exchange (ETDEWEB)

Zarins, Arturs, E-mail: arturs.zarins@lu.lv [University of Latvia, Institute of Chemical Physics, Kronvalda Boulevard 4, LV-1010 Riga (Latvia); Kizane, Gunta; Supe, Arnis [University of Latvia, Institute of Chemical Physics, Kronvalda Boulevard 4, LV-1010 Riga (Latvia); Knitter, Regina; Kolb, Matthias H.H. [Karlsruhe Institute of Technology, Institute for Applied Materials (IAM-WPT), 76021 Karlsruhe (Germany); Tiliks, Juris; Baumane, Larisa [University of Latvia, Institute of Chemical Physics, Kronvalda Boulevard 4, LV-1010 Riga (Latvia)

2014-10-15

Highlights: • Chemisorption products affect formation proceses of radiation-induced defects. • Radiolysis of chemisorption products increase amount of radiation-induced defects. • Irradiation atmosphere influence radiolysis of lithium orthosilicate pebbles. - Abstract: Lithium orthosilicate pebbles with 2.5 wt% excess of silica are the reference tritium breeding material for the European solid breeder test blanket modules. On the surface of the pebbles chemisorption products of carbon dioxide and water vapour (lithium carbonate and hydroxide) may accumulate during the fabrication process. In this study the influence of the chemisorption products on radiolysis of the pebbles was investigated. Using nanosized lithium orthosilicate powders, factors, which can influence the formation and radiolysis of the chemisorption products, were determined and described as well. The formation of radiation-induced defects and radiolysis products was studied with electron spin resonance and the method of chemical scavengers. It was found that the radiolysis of the chemisorption products on the surface of the pebbles can increase the concentration of radiation-induced defects and so could affect the tritium diffusion, retention and the released species.

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

Science.gov (United States)

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

Radiolysis of concentrated nitric acid solutions

International Nuclear Information System (INIS)

Nagaishi, R.; Jiang, P.Y.; Katsumura, Y.; Domae, M.; Ishigure, K.

1995-01-01

A study on electron pulse- and 60 Co γ-radiolysis of concentrated nitric acid and nitrate solutions has been carried out to elucidate the radiation induced reactions taking place in the solutions. Dissociation into NO 2 - and O( 3 P) was proposed as a direct action of the radiation on nitrate and gave the G-values were dependent on the chemical forms of nitrate: g s2 (-NO 3 - )=1.6 and g s2 (-HNO 3 )=2.2 (molecules/100eV). Based on the experimental yields of HNO 2 and reduced Ce IV , the primary yields of radiolysis products of water, g w , were evaluated to clarify the effects of nitrate on spur reactions of water in various nitrate solutions. (author)

A review of the radiolysis of methane

International Nuclear Information System (INIS)

Norfolk, D.J.

1975-08-01

The review had three objectives: to determine the yields of the primary products and to describe the sequence of reactions in which they take part; to ascertain the effect on these reactions of changes in the physical state of the methane and the quantum energy of the radiation, and of the presence of chemically inert sensitisers; and to identify the situation most similar to the adsorbed phase radiolysis of methane on alumina, and so to predict the likely radiolytic reactions in this system. The main primary product yields in methane gas under γ-irradiation are estimated to be G(CH 4 +) approximately 1.75, G(CH 3 +) approximately 1.46, G(CH 3 ) approximately 1.4 and G(CH 2 ) approximately 1.0. The situation most similar to adsorbed phase radiolysis is inert gas sensitised photolysis at energies below 12.6eV. In this system the major primary process is homolytic dissociation of methane to CH 3 +H. (author)

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins II reactions at side-chain loci in model systems

International Nuclear Information System (INIS)

Garrison, W.M.

1983-11-01

The major emphasis in radiation biology at the molecular level has been on the nucleic acid component of the nucleic acid-protein complex because of its primary genetic importance. But there is increasing evidence that radiation damage to the protein component also has important biological implications. Damage to capsid protein now appears to be a major factor in the radiation inactivation of phage and other viruses. And, there is increasing evidence that radiation-chemical change in the protein component of chromation leads to changes in the stability of the repressor-operator complexes involved in gene expression. Knowledge of the radiation chemistry of protein is also of importance in other fields such as the application of radiation sterilization to foods and drugs. Recent findings that a class of compounds, the α,α'-diaminodicarboxylic acids, not normally present in food proteins, are formed in protein radiolysis is of particular significance since certain of their peptide derivatives have been showing to exhibit immunological activity. The purpose of this review is to bring together and to correlate our present knowledge of products and mechanisms in the radiolysis of peptides, polypeptides and proteins both aqueous and solid-state. In part 1 we presented a discussion of the radiation-induced reactions of the peptide main-chain in model peptide and polypeptide systems. Here in part 2 the emphasis is on the competing radiation chemistry at side-chain loci of peptide derivatives of aliphatic, aromatic-unsaturated and sulfur-containing amino acids in similar systems. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis, and ESR spectroscopy are included

Radiolysis of groundwater in a repository for spent fuel - a literature survey

International Nuclear Information System (INIS)

Snellman, Margit

1989-06-01

This review on radiolysis considers both the fundamental mechanisms and theory involved in radiolysis of pure water and systems containing major species existing in repository conditions. The amount of different molecules and radicals formed in radiolysis of water is a complex function of the type of radiation and dose rate, pH and ionic strength of water. The principal effects of the species present in water are to scavenge the radiolytic intermediates and products producing new species and changing the yield of radical and molecular products. Of the metals (Cu, Fe) and inorganic ions (Cl - , HCO 3 - /CO 3 2- , NH 3 /NO 2 - ) considered, iron is the most important one and can participate in a number of reactions both with the primary and secondary radiolysis products and may effect both the H 2 and H 2 O 2 yield. For the estimation of the overall effect of radiolysis in the repository both calculations and supporting experimental work is needed

Identification of tetraphenylborate radiolysis products in a simulated feedstock for radioactive waste processing

International Nuclear Information System (INIS)

Eibling, R.E.; Bartlett, M.G.; Carlson, R.E.; Testino, S.A. Jr.; Kunkel, G.J.; Browner, R.F.; Busch, K.L.

1994-01-01

The first step towards immobilization of the soluble radioactive species in borosilicate glass is the addition of sodium tetraphenylborate (TPB) and sodium titanate to the radioactive aqueous solution. Initial studies of the TPB hydrolysis process have found that some component of the radiolysis mixture inactivates the Cu catalyst. The interaction of organic materials with the catalyst, and the subsequent interference with the hydrolysis process, would have presented problems with the use of the vitrification process. Prevention of the catalyst deactivation is obtained by washing the irradiated TPB precipitate in the Late Wash Facility prior to hydrolysis to remove the soluble radiolysis products. Identification of the organic radiolysis products, their distribution in the Late Wash Facility, and their interactions with the Cu catalyst has become an important analytical issue. To further investigate the reaction products of the TPB precipitation process, a simulated feedstock was created from compounds known to be present in the starting materials. This simulated feedstock was precipitated with sodium TPB and then exposed to Co-60 gamma radiation to simulate two years of additional storage time prior to the hydrolysis process. The irradiated product was divided into two parts, the filtered supernatant liquid and the precipitate slurry, which contains the TPB and the solid sodium titanate. Using gas chromatography/mass spectrometry, liquid secondary ion mass spectrometry, inductively coupled plasma/mass spectrometry, ion chromatography, and high performance liquid chromatography, over 50 organic and inorganic species have been identified in the aqueous portion of a simulated feedstock for TPB hydrolysis. The major organic species present are benzene, phenol, benzamide and a variety of substituted phenylphenols. The major inorganic species present are sodium, nitrite, and oxalate ions

Fenton-enhanced {gamma}-radiolysis of cyanuric acid

Energy Technology Data Exchange (ETDEWEB)

Varghese, Rani [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala (India); Aravind, Usha K. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala (India); Aravindakumar, Charuvila T. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala (India)]. E-mail: CT-Aravindakumar@rocketmail.com

2007-04-02

Degradation of cyanuric acid (OOOT), a stable end product of oxidative decomposition of atrazine, is investigated in a combined field of gamma radiolysis and fenton reaction. The reaction of hydroxyl radical ({center_dot}OH) at pH 6 was carried out by irradiating N{sub 2}O saturated aqueous solutions containing OOOT (1 x 10{sup -3} mol dm{sup -3}), and this resulted only a marginal degradation (20%). However, when the same reaction was carried out in the presence of varying concentrations of ferrous sulfate ((5-10) x 10{sup -5} mol dm{sup -3}), the decay of OOOT has been enhanced to more than 80%. This decay followed a first order kinetics. Nearly similar effects were observed with another triazine derivative, 2,4-dioxohexahydro-1,3,5-triazine (DHT). Two major reaction mechanisms are proposed for the enhanced decay of OOOT. The formation of unstable hydroxyl radical adducts from the reaction of {center_dot}OH which is the result of gamma radiolysis and the Fenton reaction (resulting from the reaction of the added Fe(II) and of the H{sub 2}O{sub 2} from the radiolysis of water), is proposed as the first mechanism. The second mechanism, which is likely the major contributor to degradation, is proposed as the reaction of a nucleophilic adduct, Fe(II)OOH, which could directly react with the electron deficient triazine ring. It is highlighted that such degradation reactions must be explored for the complete degradation of the byproducts of the oxidative decomposition of atrazine.

The effect of dissolved oxygen on water radiolysis behaviour

International Nuclear Information System (INIS)

Yakabuskie, P.A.; Joseph, J.M.; Wren, J.C.; Stuart, C.R.

2012-09-01

A quantitative understanding of the chemical or redox environments generated in water by ionizing radiation is important for material selection, development of maintenance programs, and safety assessments for water-cooled nuclear power reactors. The highly reactive radicals (·OH, ·H, ·e aq - , ·HO 2 , and ·O 2 - ) and molecular species (H 2 and H 2 O 2 ) generated by water radiolysis can compete in reactions with other dissolved compounds and impose changes to the system chemistry by altering the steady-state concentrations of water radiolysis products, which could impact the degradation of materials in contact with the aqueous phase. Understanding in detail how a given chemical additive changes the long-term radiolysis kinetics can help us to determine what chemistry control steps may be required to return the system to an optimal redox condition, and in turn, enhance the lifetime of reactor components. This study outlines the effect of dissolved oxygen gas, which could be introduced due to air ingress, on long-term water radiolysis behaviour. The effects of solution pH and initial dissolved O 2 concentration on the radiolytic production of molecular H 2 and H 2 O 2 have been investigated by performing experiments with three different O 2 concentrations at pH 6.0 and 10.6 under steady-state radiolysis conditions. The aqueous and gas phase analyses were performed using UV-Vis spectrophotometry and gas-chromatography equipped with electron capture and thermal conductivity detectors. The experimental results were compared with kinetic model calculations of steady-state radiolysis and were found to be in good agreement. The concentrations of water radiolysis products, H 2 O 2 and H 2 , were found to increase in the presence of dissolved oxygen, but the degree of increase was shown to depend on the solution pH. Furthermore, the steady-state concentration of H 2 did not increase as greatly as that of H 2 O 2 at either pH studied. The kinetic analyses have shown

Chemical behaviour of americium in natural aquatic solutions: Hydrolysis, radiolysis and redox reactions

International Nuclear Information System (INIS)

Stadler, S.; Kim, J.I.

1988-06-01

Hydrolysis and redox reactions of the Am(III) and Am(V) ions have been investigated in NaClO 4 and NaCl solutions as well as in natural saline groundwaters. The hydrolysis constants of Am(OH) n 3-n species and the solubility product of Am(OH) 3 (s) have been determined in 0.1 M NaClO 4 , 0.1 M NaCl and 0.6 M NaCl solutions. As observed in concentrated NaCl solutions (> 3 M), the α-radiation induces the radiolytic oxidation of the Cl - -ion to produce Cl 2 , HClO, ClO - and other oxidized species, which result in a strongly oxidizing medium. Consequently Am(III) is oxidized to Am(V). Under these conditions the hydrolysis constants of AmO 2 (OH) n 1-n species and the solubility product are also determined. The α-radiation induced radiolysis reactions in NaCl solution and the subsequent oxidation reaction of Am(III) have been systematically investigated by varying pH, NaCl concentration and specific α-activity. Also included in the investigation are a few selected groundwaters of relatively high salinity from the Gorleben aquifer systems. (orig.) [de

Pulse radiolysis studies of fast reactions in molecular systems. Progress report, November 1976--October 1977

International Nuclear Information System (INIS)

Dorfman, L.M.

1977-01-01

Results from research in the following two areas are given: formation, properties, and reactivity of molecular ionic species in irradiated liquid systems; and pulse radiolysis of elementary reactions in protein function

Self-Radiolysis of Tritiated Water: Experimental Study and Simulation

International Nuclear Information System (INIS)

Heinze, Sylver; Stolz, Thibaut; Ducret, Didier; Colson, Jean-Claude

2005-01-01

Radioactive decay of tritium contained in tritiated water leads to the production of gaseous helium and, through self-radiolysis, to the formation of molecular hydrogen and oxygen. For safety management of tritiated water storage, it is essential to be able to predict pressure increase resulting from this phenomenon. The present study aims to identify the mechanisms that take place in self-radiolysis of chemically pure liquid tritiated water. The evolution of the concentration of hydrogen and oxygen in the gas phase of closed vessels containing tritiated water has been followed experimentally. Simulation of pure water radiolysis has been carried out using data from the literature. In order to fit experimental results, simulation should take into account gas phase recombination reaction between hydrogen and oxygen. A simplified system has been extracted from the complete chemical system used to simulate radiolysis. This system allows identifying the basic mechanisms that are responsible for tritiated water self-radiolysis

Gas phase radiolysis and vacuum ultraviolet photolysis of heterocyclic organic compounds. Progress report, February 1, 1974--February 1, 1975

International Nuclear Information System (INIS)

Scala, A.A.; Salomon, D.; Colon, I.; D'Angona, J.

1975-01-01

In the γ radiolysis of tetrahydrofuran there are pronounced density effects in the pressure range from 0 to 50 Torr with the most important ion-pair yields decreasing as the pressure increases. The relative product yields of the radiolysis is compared with that of xenon photolysis. Possible mechanisms to explain the results obtained are discussed. The ion-pair yields from the γ radiolysis of the heterocyclic amines, ethylenimine, azetidine, pyrrolidine, and piperidine, are determined, and the pressure effects are evaluated. Reactions mechanisms are discussed. The vacuum ultraviolet photolysis products of thietane and tetrahydrothiophene are studied and compared with the γ radiolysis products. Reaction mechanisms are discussed. The status of the construction of a photoionization mass spectrometer and the measurement of the ionization efficiencies and extinction coefficients of organic compounds is reported. (U.S.)

The radiolysis of uracil in oxygenated aqueous solutions. A study by product analysis and pulse radiolysis

International Nuclear Information System (INIS)

Schuchnmann, M.N.; Sonntag, C. von

1983-01-01

Hydroxyl radicals are generated by the radiolysis of N 2 O-O 2 (4:1 v/v)-saturated aqueous solutions of uracil. They add to the 5,6-double bond of the substrate. These radicals are converted by oxygen into the corresponding peroxyl radicals (I) and (II), respectively. Peroxyl radical (I) undergoes a base-induced O 2 - elimination. As an intermediate 5-hydroxyisopyrimidine is formed which rearranges into isobarbituric acid and adds water forming 5,6-dihydro-5,6-dihydroxyuracil. Competing with this base-induced reaction of radical (I) there is a bimolecular decay of radicals (I) and (II). These processes become predominant at low pH. For this reason a strong pH dependence of G (products) is observed. The major products are (G values at pH 3 and 10 in parentheses) 5,6-dihydroxy-5,6-dihydrouracil (1.1; 2.4), isobarbituric acid (0; 1.2), N-formyl-5-hydroxyhydantoin (1.6; 0.2), 5-hydroxybarbituric acid (0.9; 0.2). 5-Hydroxybarbituric acid is formed in its keto form. Its deprotonation has been followed by pulse conductometry. Details of the reaction mechanism, e.g. the involvement of oxyl radicals in the bimolecular decay of (I) and (II), are discussed. (author)

Selectivity in dehydrodimerisation of amides: final product analysis from radiolysis in the liquid phase

International Nuclear Information System (INIS)

Dusaucy, A.C.; Tilquin, B.

1991-01-01

N,N-Dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) were irradiated with γ-rays and accelerated electrons (linac) in the liquid phase at different temperatures. Qualitative and quantitative analysis of the radiolysis products have been made by capillary GC. Effects of irradiation temperature and dose rate have revealed secondary mechanisms for the formation of the parent radicals. Irradiation in presence of N 2 O tends to reveal tonic reactions for the immediate formation of parent radicals. (author)

EPR and NMR detection of transient radicals and reaction products

International Nuclear Information System (INIS)

Trifunac, A.D.

1981-01-01

Magnetic resonance methods in radiation chemistry are illustrated. The most recent developments in pulsed EPR and NMR studies in pulse radiolysis are outlined with emphasis on the study of transient radicals and their reaction products. 12 figures

Study of water radiolysis in porous media

International Nuclear Information System (INIS)

Rotureau, Patricia

2001-08-01

The understanding of the production of H 2 in the radiolysis of water confined into pores of concrete is important for the disposal of radioactive waste. In order to describe the mechanisms of water radiolysis in such heterogeneous porous systems we have studied the behaviour under gamma radiation of water confined in porous silica glasses with pores going from 8 to 300 nm of diameter and meso-porous molecular sieves (MCM-41). The radiolytic yields of hydroxyl radicals, hydrated electron and dihydrogen, have been determined with respect to the pore size of materials. The increase of these radiolytic yields compared to those of free water allowed us to show a charge transfer from silica to confined water. On the other hand the kinetics of hydrated electron reactions measured by pulse radiolysis are not modified. (author) [fr

Electron paramagnetic resonance study of radicals formed by radiolysis at 77 K of nitroalkanes and of their solutions in organic glasses. Chromatography analysis of radiolysis products of nitromethane in ethanol solution in a vitreous medium

International Nuclear Information System (INIS)

Rosilio, C.

1969-01-01

With a view to explaining the formation of the final products resulting from the photolysis and the radiolysis of nitro-alkanes, we have attempted to identify the paramagnetic species formed as intermediates during the radiolysis. Our work has covered the structure and the reactivity of the radicals formed by 7 irradiation of the nitrogen containing derivatives at 77 K, and on the mechanism of formation and of disappearance of these radicals in the various matrices used. The radicals resulting from the removal of a hydrogen atom in the α position of the NO 2 group, and the radicals resulting from addition reactions on the nitrogen group characterized by an unpaired electron on the nitrogen have been identified, either during the radiolysis of pure nitroalkanes, or during the radiolysis of nitro-alkanes in solution in organic glasses at 77 K. A study has been made of the conformation and the movements of radicals in the matrices, and the mechanism of formation of the observed radicals produced generally by the capture by the nitro-alkanes of primary radiolysis species. The nitro-alkanes in ethanol solution can behave as traps both for electrons and for free radicals. The study of the radiolysis of nitro-alkanes in solution in a polar ethanol glass has been completed with chemical analyses on the final radiolysis products; it has been possible to deduce the capture efficiency of trapped electrons and of free radicals by nitro-alkanes in ethanol. For this we have determined the radio-chemical yields of hydrogen, acetaldehyde and glycol as a function of the capture agent concentration, for the nitro-methane-ethanol system. A mechanism for the disappearance of the observed radicals is proposed. (author) [fr

Gas phase pulse radiolysis

International Nuclear Information System (INIS)

Jonah, C.D.; Andong Liu; Mulac, W.A.

1987-01-01

Gas phase pulse radiolysis, a technique which can be used to study many different phenomena in chemistry and physics, is discussed. As a source of small radicals, pulse radiolysis is important to the field of chemistry, particularly to combustion and atmospheric kinetics. The reactions of 1,3-butadiene, allene, ethylene and acetylene with OH are presented. 52 refs., 1 fig., 1 tab

Formation and properties of radiation-induced defects and radiolysis products in lithium orthosilicate

Energy Technology Data Exchange (ETDEWEB)

Tiliks, J.E.; Kizane, G.K.; Supe, A.A.; Abramenkovs, A.A.; Tiliks, J.J. (Latvian Univ., Riga (Latvia)); Vasiljev, V.G. (Acad. A.A. Bochvar Inst. of Inorganic Materials, Moscow (USSR))

1991-12-01

Formation and properties of radiation-induced defects and radiolysis products in polycrystalline powders and ceramic pellets of Li{sub 4}SiO{sub 4} were studied under the effect of various types of ionizing irradiation ({gamma} quants, accelerated electrons, reactor irradiation), humidity, temperature, impurities in the samples, etc. The content of radiation defects and radiolysis products poorly depends on irradiation type, dose rate, admixture elements. The concentration of defects highly depends on the temperature of irradiation, humidity, granural size. Empirical dependence of radiolysis degree {alpha} on the dose was found: {alpha}=5x10{sup -2}xD{sup 0.5} for {gamma} and electron irradiation (T{sub rad}=300-350 K) and {alpha}=5x10{sup -3}xD{sup 0.5} for reactor radiation (T{sub rad}=700-800 K); {alpha} - matrix dissociation degree (in %); D - dose (in MGy). Colloidal lithium and silicon, lithium and silicon oxides, and O{sub 2} are the final products of radiolysis. Radiation-induced defects change tritium thermo-extraction parameters, deteriorate mechanical, thermo-physical and electric properties of ceramics. (orig.).

Redox reactions of tocopherol monoglucoside in aqueous solutions. A pulse radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Kapoor, S.; Mukherjee, T.; Nair, C.K.K. [Bhabha Atomic Research Centre, Mumbai (India); Kagiya, Tsutomu V. [Health Research Foundation, Kyoto (Japan)

2002-03-01

The reactions between tocopherol monoglucoside (TMG), a water-soluble vitamin-E derivative, with Br{sub 2}{sup {center_dot}}{sup -}, N{sub 3}{sup {center_dot}}, (SCN){sub 2}{sup {center_dot}}{sup -}, NO{sub 2}{sup {center_dot}}, OH{sup {center_dot}} and various halogenated peroxyl radicals were examined using a pulse radiolysis technique. The results demonstrate that TMG forms a stable phenoxyl radical at pH>6.8. The thus-formed phenoxyl radical shows pH-dependent decay kinetics and is disproportionated by 2nd order kinetics at pH2.3. It was observed that the TMG reactivity towards a halogenated peroxyl radical increases with the number of halogen atoms at the carbon atom having a peroxyl group. The reaction between the TMG phenoxyl radical and ascorbic acid was also examined using a pulse radiolysis technique. The results indicate that the TMG phenoxyl radical is repaired by ascorbate. Kinetic studies indicate that TMG may act as an antioxidant to repair free-radical damage to some biologically importnat compounds. The one-electron reduction potential for TMG was found to be 0.522 V{+-}0.06 vs. NHE. (author)

Radiolysis of uracil in oxygenated aqueous solutions. A study by product analysis and pulse radiolysis. [Gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Schuchnmann, M N; Sonntag, C von [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenchemie

1983-10-01

Hydroxyl radicals are generated by the radiolysis of N/sub 2/O-O/sub 2/ (4:1 v/v)-saturated aqueous solutions of uracil. They add to the 5,6-double bond of the substrate. These radicals are converted by oxygen into the corresponding peroxyl radicals (I) and (II), respectively. Peroxyl radical (I) undergoes a base-induced O/sub 2//sup -/ elimination. As an intermediate 5-hydroxyisopyrimidine is formed which rearranges into isobarbituric acid and adds water forming 5,6-dihydro-5,6-dihydroxyuracil. Competing with this base-induced reaction of radical (I) there is a bimolecular decay of radicals (I) and (II). These processes become predominant at low pH. For this reason a strong pH dependence of G (products) is observed. The major products are (G values at pH 3 and 10 in parentheses) 5,6-dihydroxy-5,6-dihydrouracil (1.1; 2.4), isobarbituric acid (0; 1.2), N-formyl-5-hydroxyhydantoin (1.6; 0.2), 5-hydroxybarbituric acid (0.9; 0.2). 5-Hydroxybarbituric acid is formed in its keto form. Its deprotonation has been followed by pulse conductometry. Details of the reaction mechanism, e.g. the involvement of oxyl radicals in the bimolecular decay of (I) and (II), are discussed.

Radiolysis of starch

International Nuclear Information System (INIS)

Raffi, J.; Saint-Lebe, L.; Berger, G.

1978-01-01

In the first part of the paper the results of work on the identification and determination of the gamma ( 60 Co) radiolysis products of maize starch are brought together and, wherever possible, a balance drawn up by chemical class. The second part of the paper deals with the main parameters governing radiolysis: dose, irradiation temperature and atmosphere, water content and the conditions under which the irradiated starch is stored. The third part, devoted to the mechanisms believed to be involved, contains the following conclusions: (a) the formation of radiation-induced products with a carbon skeleton probably results from a breaking of the -C-O-C- chains with rearrangement of the radicals and/or a reaction involving the water and the oxygen - the oxygen has an activating effect which does not fundamentally modify the mechanism, whereas the effect of the water is more complex and varies according to the product; (b) the formation of hydrogen peroxide probably implies the addition of atmospheric oxygen to the radiation-induced hydrogen atoms in the water or to the organic radicals obtained by abstraction of a hydrogen from the starch. Lastly, the different methods envisaged for confirming or improving the mechanistic hypotheses are discussed. (author)

Study of the selective abstration reaction of the hydrogen atom in the radiolysis and photolysis of alkane mixture at 77 K

International Nuclear Information System (INIS)

Guedes, S.M.L.

1979-01-01

The occurence of the selective abstraction reaction of the solute hydrogen atom by hydrogen atom produced during radiolysis or photolysis of the systems such as neopentane/cyclo-hexane/HI, neopentane/2,3 dimethylbutane, n-pentane/HI/cyclo-hexane and cyclo-hexane/HI/n-pentane, at 77 K is studied. Experiments have been undertaken on the kinetics nature of the active species, the H atom, during radiolysis and photolysis of the neopentane/cyclo-hexane/HI system at 77 K, presenting competitive reactions. Studies have also been made on the occurrence of the selective abstraction reaction in inverted systems, in which the concentrations of the components of a system are so much altered that the solute becomes the solvent and vice-versa, in the other system. By means of photolysis at 77 K, it has been observed that for the two systems constitued by the cyclo-hexane and n-pentane the selective abstraction reaction occurs. However, for radiolysis of that same two systems it has been observed that only the hydrogen atom abstraction reaction corresponding to the solvent occurs. (Author) [pt

gamma-radiolysis and pulse radiolysis of aqueous 4-chloroanisole

DEFF Research Database (Denmark)

Quint, R.M.; Park, H.R.; Krajnik, P.

1996-01-01

of oxygen leads to its addition on the hydroxpcyclohexadienyl radicals, k(OH-adduct + O-2) = 3.2 x 10(8) dm(3) mol(-1) s(-1). In airfree solution the reaction of H-atom with the substrate, k(H + 4-ClAn) = 1.2 x 10(9) dm(3) mol(-1) s(-1), results in H-adducts which decay in bimolecular reactions, 2k = 8.2 x...... 10(8) dm(2) mol(-1) s(-1). The rate constant for the reaction of the solvated electrons has been determined to k (e(aq)(-) + 4-CIAn) = 2 x 10(9) dm(2) mol(-1) s(-1). The absorption spectra of H- and OH-adducts were measured in the range of 280-450 nm. The products analysed by HPLC after T......-radiolysis in dependence of dose (100-600 Gy) are given for N2O-, air-, oxygen- and argon saturated neutral aqueous solutions. In conditions favoring the OH radical oxidation 4-chlorophenol, 4-methoxyphenol, 5-chloro-2-methoxyphenol and 2-chloro-5-methoxyphenol were determined as final products. In the presence of Ar...

Glycoside bond cleavage in the radiolysis of aqueous solutions of methylglycosides and disaccharides

International Nuclear Information System (INIS)

Shadyro, O.I.; Kisel', R.M.

2007-01-01

The kinetics of formation of methylglycoside and disaccharide radiolysis products resulting from the O-glycoside bond cleavage under the action of 137 Cs γ-radiation (0-2.5 kGy radiation doses, 0.28 Gy/s dose rate) was studied, and the yields of these products were determined. It was found that oxygen inhibits these processes. The findings suggest that the fragmentation reaction of C' 2 radicals plays an important role in the formation of carbohydrate degradation products in the radiolysis of aqueous carbohydrate solutions [ru

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold

2016-05-01

Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. It was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.

Pulse radiolysis of gases

International Nuclear Information System (INIS)

Nielsen, O.J.

1984-04-01

The pulse radiolysis equipment and technique are described and its relevance to atmospheric chemistry is discussed. Pulse radiolysis of a number of different chemical systems have been used to check the validity of the proposed mechanisms: 1) The hydrogen atom yield in the pulse radiolysis of H 2 was measured by four independent calibration techniques, using reactions of H with O 2 , C1NO, and HI. The H atom yield was compared with O 2 yields in pure O 2 and in O 2 /SF 6 mixtures which lead to a value G(H) = 17.6. The rate constants at room temperature of several reactions were determined. 2) OH radical reactions with tetraalkyllead at room temperature and with ethane, methane, and a series of C1- and F-substituted methanes at 300-400 K were studied. Arrhenius parameters, A and Esub(a), were determined for several reactions. The lifetime of Pb(CH 3 ) 4 and Pb(C 2 H 5 ) 4 in ambient air is estimated. CF 2 C1 2 was found to be a very efficient third body, M, in the reaction OH + OH + M arrow H 2 O 2 + M. 3) In the H 2 S systems the HS extinction coefficient at 3242 AA was determined to 9.5 x 10 2 cm -1 mol -1 . Four rate constants at room temperature were determined. (author)

Non-gaseous radiolysis products of 6-aminopenicillanic acid and potassium salt of benzylepenicillin

International Nuclear Information System (INIS)

Dziegielewski, J.; Jezowska-Trzebiatowska, B.; Siemion, I.Z.

1974-01-01

The radiolysis products of 6-aminopenicillanic acid (6-APA) and potassium salt of benzylpenicillin G, irradiated with γ-rays were separated by the extraction methods and chromatographically by the thin-layer method. On the basis of the IR and UV spectroscopic investigations as well as by the NMR and mass spectrometry methods of the radiolysis products, the paths of the radiation decomposition of 6-APA and of penicillin G were determined. (author)

GC-FTIR-MS analysis of volatile radiolytic products in the radiolysis of nitroaniline

International Nuclear Information System (INIS)

Kuruc, J.; Sahoo, M.K.; Kubinec, R.

1993-01-01

A good deal of products formed in the γ-radiolysis of isomeric nitroaniline solutions in carbon tetrachloride have been identified using GC-FTIR-MS technique. Tetrachloroethylene, chlorobenzene, hexachloroethane isomeric di-, tri- and tetrachlorobenzenes and chloroisocyanatobenzenes are among the important products formed in the radiolysis. Formation of dichlorobenzene is the result of ipso-substitution of both the nitro and aniline group by chlorine atom and the subsequent chloration of dichlorobenzene results in the formation of polychlorobenzenes. Chloroisocyanatobenzene is proposed to be the product arising from the interaction of dichlorocarbene and the nitro group of nitroaniline followed by chlorination of the resulting product, isocyanatobenzene. A 94% yield of undissolved 1,2-aminonitrobenzene chloride salt is obtained from the radiolysis of o-nitroaniline solution in carbon tetrachloride with a radiation yield of 1.83 molecules per 100 eV absorbed energy for an irradiation dose of 267 kGy. (author) 9 refs.; 3 figs.; 2 tabs

Study by γ radiolysis and pulsed radiolysis of the reactivity of the superoxide ion in the oxyhemoglobin-methemoglobin system

International Nuclear Information System (INIS)

Haristoy, Didier.

1976-01-01

γ radiolysis of aqueous solutions of methemoglobin (MetHb) in the presence of formate ions, shows that only 25% of the total protein is reduced in oxyhemoglobin (HbO 2 ) by superoxide ions O 2 - according to the reaction MetHb+O 2 - →HbO 2 . The result can be attributed neither to the reactions of O 2 - with HbO 2 , nor the oxidation of HbO 2 by H 2 O 2 produced in the radiolysis of water and by dismutation of O 2 - . Pulse radiolysis studies of this reaction strongly suggest the formation of a transient complex 'MetHbO 2 - ' during the reaction. In addition to the well known self-oxidation of HbO 2 , these results show the existence of an equilibrium between HbO 2 and MetHb+O 2 - . Such an equilibrium could give rise, 'in vivo' to a nearly steady concentration of superoxide ions which could initiate a reaction favoring oxidation by oxygen [fr

Pulse radiolysis and ab initio SCF MO studies of hydroxyl radical reactions with 2,2'-bipyridine and its complexes with transition metal ions

Energy Technology Data Exchange (ETDEWEB)

Maliyachel, A C

1984-01-01

In the present study, reactions of hydroxyl radical with 2,2'-bipyridine (bpy) and complexes of iron(II) and cobalt(III) containing 2,2'-bipyridine and/or cyanide as ligands have been investigated by pulse radiolysis and also by ab initio self-consistent field, molecular orbital (SCF MO) theoretical techniques for 2,2'-bipyridine and pyridines. In the pulse radiolysis experiments, the nascent products of hydroxyl radical reactions with these compounds have been characterized through their spectral and kinetic properties. All these reactions occur at near diffusion controlled rates to give transient products having absorption in the ultraviolet, visible and, in some cases, near-IR region. The primary reactions of OH are considered to take place by addition mechanisms in the cases of 2,2'-bipyridine, (Fe(bpy)/sub 3/)/sup 2 +/, (Fe(DMbpy)/sub 3/)/sup 2 +/ and (Co(bpy)/sub 3/)/sup 3 +/. With (Fe(pby)/sub 2/(CN)/sub 2/) and (Fe(bpy)(CN)/sub 4/)/sup 2 -/, both addition and charge transfer processes occur. The present study indicates that hydroxyl radical reactions with 2,2'-bipyridine can be considerably altered by complexation with metal ions such as iron(II) and cobalt(III), and the factors associated with this are discussed. In the second part of this work, ab initio SCF MO calculations have been performed for the reactions of OH with pyridine, pyridinium ion and 2,2'-bipyridine. Based on the calculated total energies for the various hydroxy radical products, the relative stability of OH addition products are found to be for pyridine, meta-C > N >> para-C > ortho-C; for pyridinium ion, meta-C >> para-C > ortho-C > N, and for 2,2'- bipyridine, C/sub 5/ > C/sub 6/ > C/sub 3/ > C/sub 4/ > N.

The investigation of the n-#betta#-radiolysis of nitrogen tetroxide under super-critical conditions

International Nuclear Information System (INIS)

Nesterenko, V.B.; Gvozdev, A.A.; Doroshkevich, V.N.; Nichipor, G.V.; Trubnikov, V.P.

1983-01-01

The yield of the 'irreversible' products of nitrogen tetroxide radiolysis has been determined in stainless steel ampoules in the field of the reactor mixed radiation; Radiolysis has been investigated in the range of temperatures 200 to 350 deg C, pressures 7.8 to 15.7 MPa and dose rates 48 and 162 W/kg. The measured primary yield of nitrogen atoms under nitrogen dioxide radiolysis is equal to 0.28 + 0.02 at/100 eV at 250 deg C. It is shown that in the investigated range of temperatures and pressures the yield of the 'irreversible' radiolysis products can be determined using the known kinetic data on the reactions of nitrogen atoms with molecules and assuming the primary yield of nitrogen atoms from nitrogen dioxide and nitric oxide equal to 0.28 and 4.5 at/100 eV respectively. (author)

Radiolysis of other organic compounds

International Nuclear Information System (INIS)

Pikaev, A.K.

1986-01-01

Peculiarities of radiolysis of organic halogen, phosphorus, sulfur and nitrogen (including amines, amides, nitriles et al.) compounds in liquid phase are discussed. Intermediate and stable finish products of radiolysis of the given compounds, properties and radiochemical yields of these products are considered

The synthesis and analysis of diuloses and deoxydiuloses with special reference to the radiolysis products of fructose

International Nuclear Information System (INIS)

Den Drijver, L.

1979-12-01

The exposure of fruit to γ-irradiation is a technique that is receiving increasing attention as a practical and economic preservation method. The analysis of irradiated fruit is necessary in order to identify and quantify possible mutagenic and toxic products formed during irradiation. Water and carbohydrates are the main components of fruit, the carbohydrates consisting mainly of mono- and disaccharides. An investigation of the radiolysis products of sugars, with special reference to hexosuloses and hexosdiuloses as possible toxic and/or mutagenic agents, formed the basis of the work described in this thesis. A number of diuloses formally derived from D-fructose was synthesized for mutagenicity tests and as standards for an investigation of the radiolysis products of D-fructose. High pressure liquid chromatography was used as analytical technique. The investigation represents the first application of the technique for the analysis of radiolysis products of sugars. It was succesfully applied to a study of the diuloses formed by the radiolysis of D-fructose in the presence of oxygen. The results obtained confirmed earlier work carried out with GC-MS as analytical technique. In addition, a previously unknown radiolysis product of D-fructose was identified as D-erythrohexos-2,3-diulose

Simultaneous action of external irradiation and products of air radiolysis

International Nuclear Information System (INIS)

Golikov, V.Ya.; Karklinskaya, O.N.; Mikhalev, V.P.; Vorotyntsev, A.P.; Kotov, N.N.

1977-01-01

To study the radiation damage due to the simultaneous effect of the acute ionizing radiation on the organism and the products of air radiolysis-ozone and nitrogen oxides, laboratory experiments were made. The scheme of the irradiation was the following: the acute dynamic effect (per hour) of X-rays at different doses, and nitrogen oxides and ozone with different concentrations. Male mice were exposed to irradiation (dose of 50-1000 rad, for 60 min.). Data obtained (mortality, survival, exponents of the peripheral blood) proved the radioprotective ability of the chemical agents under study. The radioprotective action was most pronounced at high concentrations. The fact proves that the mechanism of the simultaneous action of the products of air radiolysis and X-ray radiation is complex, and further efforts should be made at its investigation

Effect of nitrogen and oxygen on radiolysis of iodide solution

Energy Technology Data Exchange (ETDEWEB)

Karasawa, H; Endo, M [Hitachi Ltd., Power and Industrial System R+D Divisions, Ibaraki (Japan)

1996-12-01

The effect of nitrogen and oxygen on radiolysis of iodide solution was examined. Direct decomposition of nitrogen by {gamma}-radiation produced nitric acid to decrease a water pH. This resulted in the iodine formation in the radiolysis of iodide solution. Hydrogen peroxide was produced by the radiolysis of water containing oxygen. This worked a reducing agent to suppress the formation of iodine in the radiolysis of iodide solution. In the analytical model, fourteen iodine species were considered and reaction scheme consisted in 124 reactions. The analytical model could estimate the oxidation state of iodide ions. (author) 4 figs., 4 refs.

Electrons in water radiolysis

International Nuclear Information System (INIS)

Laverne, J.A.; Pimblott, S.M.

2006-01-01

The hydrated electron is the main reducing species produced in the radiolysis of water. Many studies have examined its reactivity using pulsed radiolysis techniques and competition kinetics. Data bases list hundreds of rate coefficients for reaction of the hydrated electron with substances ranging from inorganic ions like nitrate to biopolymers like DNA. Although the chemistry of the hydrated electron is often examined, its mechanism of formation and variation in yield are considerable less known, especially under extreme conditions such as in high temperature water or with heavy ion radiolysis. This work will examine various aspects of the radiation chemistry of the hydrated electron beginning with the generation of secondary electrons in primary energy loss events during the passage of ionizing radiation to the radiolytic yields of the hydrated electron produced by different types of radiation. Ion radiation is a 'white light source.' Energy losses range from the minimum excitation energy of the medium up to the kinematic maximum determined by the collision parameters. However, certain energy loss events are more probable than others. The dipole oscillator strength distributions of media essentially give the probability of energy loss events in collisions with no momentum transfer. Dipole oscillator distributions have been constructed from experimental data for a wide variety of materials including all the phases of water. Calculations using cross sections based on dipole oscillator distributions show that the most probable energy loss event in water is only about 20 eV with an average value closer to 60 eV. The preponderance of energy loss events of less than 100 eV means that many low energy electrons are formed by the passage of a single ion. Low energy electrons have short mean free paths and they remain in the vicinity of the primary energy loss events. The spatial distribution of these low energy electrons defines the radial track structure of the incident

Study of the radiolysis of water in porous media

International Nuclear Information System (INIS)

Rotureau, P.

2004-01-01

The understanding of the production of H 2 in the radiolysis of water confined into pores of concrete is important for the disposal of radioactive waste. In order to describe the mechanisms of water radiolysis in such heterogeneous porous systems we have studied the behaviour under gamma radiation of water confined in porous silica glasses with pores going from 8 to 300 nm of diameter and meso-porous molecular sieves (MCM-41). The radiolytic yields of hydroxyl radicals, hydrated electron and dihydrogen, have been determined with respect to the pore size of materials. The increase of these radiolytic yields compared to those of free water allowed us to show a charge transfer from silica to confined water. On the other hand the kinetics of hydrated electron reactions measured by pulse radiolysis are not modified. (author) [fr

Fundamental Aspects of Water Coolant Radiolysis

International Nuclear Information System (INIS)

Christensen, Hilbert

2006-04-01

The current state of knowledge of radiolysis in Light Water Reactors (LWR) is presented in this report. High-temperature data for rate constants and primary radiolysis yields have been collected and are shown in tables. Data from different sources have been compared and based on this recommended values have been selected. There is generally a good agreement between g-values for gamma-radiation at ambient temperature from different sources. There are larger discrepancies between results for primary yields from fast neutrons and also for g-values at reactor temperatures. Complete reaction mechanisms, including rate constants at reactor temperatures, from different sources are discussed and shown in tables. Experimentally determined activation energies are also shown, including the temperature range within which they have been determined. In normal cases rate constants at high temperature have been calculated from the rate constant at ambient temperature and the activation energy. Exceptions from this rule are shown and uncertainties have been discussed. The results of a number of radiolysis calculations, carried out for reactor temperatures, are also shown. The results of some sensitivity analyses are discussed. It has been shown that results from radiolysis calculations are rather sensitive to the rate constant ratio k(OH + H 2 )/(k(OH + H 2 O 2 ). The first reaction leads to recombination, whereas the last reaction leads to decomposition. In some cases reactions which are unimportant at ambient temperature may play a role at reactor temperatures. This may be the case for reactions with a low rate constant at ambient temperature in combination with a high activation energy

γ-radiolysis of dialkyl, alkyl-aryl and diaryl sulphones

International Nuclear Information System (INIS)

Bowmer, T.N.; O'Donnell, J.H.

1981-01-01

Dialkyl sulphones, RSO 2 R, have been considered as model compounds for the radiolysis of poly(olefin sulphone)s. They show preferential C-S scission and SO 2 elimination, attributable to the relatively low strengths of these bonds. Combination of the alkyl radicals, which are produced singly or in pairs according to whether one or two C-S scissions occur in one molecule, competes with hydrogen abstraction from sulphone molecules. The latter is favoured for single C-S scissions and as the size of the radical increases and hence its mobility decreases. An important degradation reaction in radiolysis is considered to be ionization to form the cation radical of the dialkyl sulphone, followed by a single C-S scission to produce the alkyl radical and the complementary alkyl sulphonyl cation, which may undergo scission of the remaining C-S bond to produce SO 2 . GC/MS studies of the volatile products from dimethyl sulphone have shown that radiolysis results in a complexity of fragmentation and combination reactions, involving scission of most bonds in the molecule. The variety of products has been confirmed using CD 3 SO 2 CD 3 . Radiation protection by aromatic substituents has been demonstrated and branched alkyls have been shown to give higher yields of alkanes and SO 2 than linear alkyls. (author)

Radiolysis of water at elevated temperatures. Pt. 3: Simulation of radiolytic products at 25 and 2500C under the irradiation with γ-rays and fast neutrons

International Nuclear Information System (INIS)

Sunaryo, Geni R.; Katsumura, Yosuke; Ishigure, Kenkichi

1995-01-01

The G-values of water decomposition products under the irradiations with γ-rays and fast neutrons up to 250 o C have been determined in previous studies. In order to clarify the characteristics of the determined G-values, computer simulations under the simplified conditions in nuclear reactors have been carried out. The recent G-values for γ-radiolysis reported by recent workers are almost equivalent from the point of simulations. On the contrary, G-values for fast neutron radiolysis give a significant influence to the result, which arises from the higher molecular yields and smaller radical yields of water decomposition in fast neutron radiolysis, and it has been revealed that the dose evaluation in the reaction is inevitably important. In addition, it was pointed out by the simulations that reverse reactions for H 2 + . OH → H . + H 2 O and e aq - + H + → . H, which can be neglected at room temperature, become important at higher temperatures. (author)

Alternative Energy: Production of H_2 by Radiolysis of Water in the Rocky Cores of Icy Bodies

International Nuclear Information System (INIS)

Bouquet, Alexis; Waite, J. Hunter; Glein, Christopher R.; Wyrick, Danielle

2017-01-01

We applied a model of radiolysis in earthly rock–water mixtures to several known or suspected ocean worlds: Enceladus, Ceres, Europa, Titania, Oberon, Pluto, and Charon. In this model, radiation emitted by the long-lived radionuclides ("4"0K, "2"3"2Th, "2"3"5U, and "2"3"8U) contained in the ordinary chondrite-like rocks is partly absorbed by the water permeating the material of each body’s core. The physical and chemical processes that follow release molecular hydrogen (H_2), which is a molecule of astrobiological interest. We compared the calculated production of H_2 by radiolysis in each body’s core to published estimates of production by serpentinization. This study presents production calculations over 4.5 Gyr for several values of rock porosity. We found that radiolysis can produce H_2 quantities equivalent to a few percent of what is estimated from serpentinization. Higher porosity, which is unlikely at the scale of a body’s entire core but possible just under the seafloor, can increase radiolytic production by almost an order of magnitude. The products of water radiolysis also include several oxidants, allowing for production of life-sustaining sulfates. Though previously unrecognized in this capacity, radiolysis in an ocean world’s outer core could be a fundamental agent in generating the chemical energy that could support life.

The application of radiolysis and analysis of influencing factors

International Nuclear Information System (INIS)

Xie Fang; Ha Yiming; Wang Feng

2008-01-01

As a branch of radiation technology, radiolysis technology has been developing in recent years. The update research and application of radiolysis is briefly reviewed. The radiolysis in reducing veterinary drug residues in food, processing plant sources products and environmental management are summaried. The influencing factors or the mechanism and radiolysis products are reviewed. (authors)

Application of chemiluminescence to the study of alpha, beta and gamma radiolysis of water

International Nuclear Information System (INIS)

Broudic, V.; Muzeau, B.; Jegou, C.; Bonnal, M.; Gavazzi, A.; Marques, C.

2004-01-01

In the frame of the French research program on the long-term behavior of spent nuclear fuel, experiments are conducted in ATALANTE to develop and validate models of spent fuel evolution in contact with an aqueous phase. One of the mechanisms that may govern intermediate or long-term alteration of the spent fuel matrix in a repository is the oxidizing dissolution by radiolysis products of water. Leaching experiments in de-aerated media requires the analysis of hydrogen peroxide, as a major product of water radiolysis, down to 10 -8 mol.L -1 . This work presents the results obtained using the chemiluminescence reaction of iso-luminol with H 2 O 2 , catalyzed by micro-peroxidase. Depending on the samples used, different types of radiolytic processes were studied: α radiolysis of water when leaching UO 2 pellets doped with alpha emitters, or γ radiolysis of water when leaching the same samples or spent fuel in a gamma field. Influences of operating conditions on the analytical results are discussed. (authors)

Effects of the radiolysis products of sennoside A on HepG2 and PC-3 cell

International Nuclear Information System (INIS)

Kim, Dong Ho; Jo, Min Ho

2016-01-01

Radiolysis of sennoside A was carried out by gamma irradiation and the anti-cancer activities of the radiolysis product were evaluated. An aqueous solution of sennoside A was exposed to 0.5-3 kGy of gamma irradiation and the radiolysis products were analyzed by HPLC. A fraction of radiolysis product (RLF) of sennoside A was isolated and the RLF was presumed as a rhein-8-β-D-glucoside. The anticancer effect of the RLF was compared with the sennoside and rhein using a in vitro assay system of human prostate cancer cells (PC-3) and human hepatoma HepG2 cells. The cell viability of PC-3 and HepG2 cell was significantly decreased to 12.4±1.2% and 32.4±2.1%, respectively, by the treatment of 0.6 μM of RLF. The sennoside A (range from 0 to 25 μM) had no cytotoxic effect on PC-3 and HepG2 cells, while the rhein had the effect on HepG2 cells with a LD_5_0 at 80 μM

Effects of the radiolysis products of sennoside A on HepG2 and PC-3 cell

Energy Technology Data Exchange (ETDEWEB)

Kim, Dong Ho; Jo, Min Ho [Research Division for Biotechnology, Korea Atomic Energy Research Institute, Jeongeup (Korea, Republic of)

2016-11-15

Radiolysis of sennoside A was carried out by gamma irradiation and the anti-cancer activities of the radiolysis product were evaluated. An aqueous solution of sennoside A was exposed to 0.5-3 kGy of gamma irradiation and the radiolysis products were analyzed by HPLC. A fraction of radiolysis product (RLF) of sennoside A was isolated and the RLF was presumed as a rhein-8-β-D-glucoside. The anticancer effect of the RLF was compared with the sennoside and rhein using a in vitro assay system of human prostate cancer cells (PC-3) and human hepatoma HepG2 cells. The cell viability of PC-3 and HepG2 cell was significantly decreased to 12.4±1.2% and 32.4±2.1%, respectively, by the treatment of 0.6 μM of RLF. The sennoside A (range from 0 to 25 μM) had no cytotoxic effect on PC-3 and HepG2 cells, while the rhein had the effect on HepG2 cells with a LD{sub 50} at 80 μM.

Study on the gamma radiolysis of poly (vinyl chloride). Application to the study on degradation by irradiation and leaching of industrial PVC

International Nuclear Information System (INIS)

Colombani, J.

2006-01-01

The works presented in this memory enter in the context of the management of plastic nuclear waste. This study was carried out on pure PVC and industrial PVC (formulated polymer). The radiolysis at high doses (up to 4 MGy) of pure PVC in anaerobic condition involves the formation of polyenyl radicals, polyenic sequences, hydrogen chloride and reactions of crosslinking. In aerobic condition, the radiolysis at high doses of pure PVC generates the formation of peroxyl radicals, hydrogen chloride, acid water, carboxylic acids, saturated or conjugated ketones and phenomena of scission. The production of HCl generated by irradiation of industrial PVC was carried out up to 40 MGy. The HCl formed by radiolysis is completely trapped by the calcic loads contained in industrial PVC and by the water produced by these reactions of trapping. A qualitative study on the formation of the products of radiolysis highlighted that the mechanisms of radiolysis of industrial PVC are different from those of pure PVC. This difference is due to the presence of additives belonging to the formulation of industrial PVC. The irradiation of plasticizers such as phthalic esters could induce the formation of radicals being able to react, by reaction of grafting, with the macro-radicals of PVC or with the polyenic sequences formed by radiolysis of PVC macromolecules. The results of leaching experiments tend to confirm this type of mechanism. (author)

Free radical reactions of hematoporphyrin: a pulse radiolysis study

International Nuclear Information System (INIS)

Ahmed, Mohammed; Guleria, Apurav; Singh, Ajay K.; Sarkar, S.K.

2011-01-01

Radiation chemistry of porphyrin derivatives has been given much attention in recent years. Although till date photo dynamic therapy (PDT) with Hematoporphyrin (HP) has already proved its effectiveness in the treatment of cancer, the molecular mechanisms by which this therapy-destroys tumour cells as well as its optimal physical parameters are still not fully understood. Thus it becomes necessary to understand the interaction of different free radicals with HP. Pulse radiolysis studies have been performed to understand the interaction of different free radicals with HP. The product formation along with bleaching and presence of a number of transients makes it difficult to pin point the mode and site of free radical attack. The radiation-induced formation of various transients (HP-OH, HO - , HP + ) in aqueous solution was investigated at various pHs by pulse radiolysis technique by means of N 3 , O - and CCl 3 O 2 radicals with and without triethyl-amine, under different dose conditions. The observed intermediates are characterized by their kinetic and spectroscopic data. The absorption spectrum of each transient could be differentiated from each other by their absorption maxima, extinction coefficients and kinetics. A clear indication of product formation has also been observed by employing continuous electron pulse and the solution shows a green coloration. It is conceivable that under certain conditions, similar transients may be produced when HP is used as a sensitizer in radiation chemotherapy of cancer patients. Our study may throw some light into the breakdown mechanism of haemoglobin to BV in addition to the understanding of free radical interaction of HP. (author)

Production of perhydroxy radical (HO2) and oxygen in the radiolysis of aqueous solution and the LET effects

International Nuclear Information System (INIS)

Imamura, Masashi

1987-01-01

This article aims to review the results concerning the production of perhydroxy radical (HO 2 ) and oxygen from irradiated aqueous solutions and the LET effects on these products, beginning with a brief introduction to the elementary primary processes in radiolysis of aqueous solution. Oxygen, if produced in the radiolysis of aqueous solution, may be considered responsible for the decreased oxygen enhancement ratio (OER) in biological systems exposed to high LET radiation. A Harwell's group has determined oxygen generated from aqueous ferrous solutions irradiated with heavy ions and concluded that the oxygen is a precursor of perhydroxy radicals. The LET-dependent yields for perhydroxy radical have been determined by LaVerne and Schuler; the analysis of their results sheds light into the reactions taking place in high-LET track cores. In conjunction with these results, the possible contributions to the LET effects are pointed out and discussed of the energetic secondary electrons ejected from the track core by knock-on collision with heavy ions and of the variation in the track core size with energy of the heavy particles. (author)

Alternative Energy: Production of H{sub 2} by Radiolysis of Water in the Rocky Cores of Icy Bodies

Energy Technology Data Exchange (ETDEWEB)

Bouquet, Alexis; Waite, J. Hunter [Department of Physics and Astronomy, University of Texas at San Antonio, San Antonio, TX (United States); Glein, Christopher R.; Wyrick, Danielle [Southwest Research Institute, Space Science and Engineering Division, San Antonio, TX (United States)

2017-05-01

We applied a model of radiolysis in earthly rock–water mixtures to several known or suspected ocean worlds: Enceladus, Ceres, Europa, Titania, Oberon, Pluto, and Charon. In this model, radiation emitted by the long-lived radionuclides ({sup 40}K, {sup 232}Th, {sup 235}U, and {sup 238}U) contained in the ordinary chondrite-like rocks is partly absorbed by the water permeating the material of each body’s core. The physical and chemical processes that follow release molecular hydrogen (H{sub 2}), which is a molecule of astrobiological interest. We compared the calculated production of H{sub 2} by radiolysis in each body’s core to published estimates of production by serpentinization. This study presents production calculations over 4.5 Gyr for several values of rock porosity. We found that radiolysis can produce H{sub 2} quantities equivalent to a few percent of what is estimated from serpentinization. Higher porosity, which is unlikely at the scale of a body’s entire core but possible just under the seafloor, can increase radiolytic production by almost an order of magnitude. The products of water radiolysis also include several oxidants, allowing for production of life-sustaining sulfates. Though previously unrecognized in this capacity, radiolysis in an ocean world’s outer core could be a fundamental agent in generating the chemical energy that could support life.

Gamma-radiolysis of benzosubstituted crown ethers

International Nuclear Information System (INIS)

Grigor'ev, E.I.; Nesterov, S.V.; Mikhalitsyna, O.V.; Trakhtenberg, L.I.; Myasoedova, T.G.

1992-01-01

The products of gamma-radiolysis of benzosubstituted crown ethers, which are distiguished by the size of polyether ring, and alkylsubstituted DB18C6 are studied by the methods of ESR and mass-spectrometry. A mechanism of the radiolysis of the radiolysis of the studied compounds in the solid phase is proposed. It is shown that the prinicple radiolysis process is the rupture of C-O bond resulting in the stabilization of H atoms from group -CH 2 - of polyether ring is realized with a lower probability

Gamma-radiolysis effects on leaching of nuclear fuel waste forms

International Nuclear Information System (INIS)

Tait, J.C.; Wilkin, D.L.; Hamon, R.F.

1986-06-01

Gamma-radiolysis experiments have been conducted on aqueous systems representative of those that might be found in a granite rock disposal vault for immobilized nuclear fuel recycle waste. Sealed capsules containing an air or an oxygen-free atmosphere, synthetic granite or chloride groundwaters, and components of the disposal system (granite, clay, metal containers and glass or glass-ceramic waste form) were irradiated by an external gamma field. Analysis of the gas phase showed the presence of H 2 gas in all capsules. Capsules containing graphite and air showed oxygen depletion. This depletion of O 2 is attributed to radiolytic reactions with iron species leached from the granite. Systems containing bentonite clay showed the production of CO 2 . A computer program, MAKSIMA-CHEMIST, was used to qualitatively predict the observed gas-phase composition by modelling the kinetics of the aqueous radiolysis reactions

Effects of Water Radiolysis in Water Cooled Reactors, NERI Proposal No.99-0010

International Nuclear Information System (INIS)

Pimblott, S.M.

2000-01-01

OAK B188 Effects of Water Radiolysis in Water Cooled Reactors, NERI Proposal No.99-0010. The aim of this project is to develop an experiment-and-theory based model for the radiolysis of nonstandard aqueous systems like those that will be encountered in the Advance Light Water reactor. Three aspects of the radiation chemistry of aqueous systems at elevated temperatures are considered in the project: the radiation-induced reaction within the primary track and with additives, the homogeneous production of H 2 O 2 at high radiation doses, and the heterogeneous reaction of the radiation-induced species escaping the track. The goals outlined for Phase 1 of the program were: the compilation of information on the radiation chemistry of water at elevated temperatures, the simulation of existing experimental data on the escape yields of e aq - , OH, H 2 and H 2 O 2 in γ radiolysis at elevated temperatures, the measurement of low LET and high LET production of H 2 O 2 at room temperature, the compilation of information on the radiation chemistry of water-(metal) oxide interfaces, and the synthesis and characterization the heterogeneous water-oxide systems of interest

Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

DEFF Research Database (Denmark)

Zona, Robert; Solar, Sonja; Getoff, Nikola

2010-01-01

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5−6.2)×109 dm3 mol−1 s−1, have been studied by pulse radiolysis in N2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320−340 nm. Their decay wa...... to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out....

Pulse radiolysis in model studies toward radiation processing

Energy Technology Data Exchange (ETDEWEB)

Sonntag, C Von; Bothe, E; Ulanski, P; Deeble, D J [Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany)

1995-10-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methyacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueos solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. (author).

Pulse radiolysis of 9,10-anthraquinone in methanol

International Nuclear Information System (INIS)

Mayer, J.; Krasiukianis, R.

1990-01-01

The reactions of anthraquinone with intermediates in methanol (e 2 - , . CH 2 O - , . CH 2 OH) were investigated using γ-radiolysis and pulse radiolysis method. The anthraquinone radical anions are reactive towards O 2 (ca 3 x 10 8 mol -1 dm 3 s -1 ) and can disproportionate giving corresponding dianion. (author)

Pulse radiolysis investigation of the reaction of the electronic adduct of bovine serum albumin with oxygen. Polychromatic kinetics of the reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

The method of pulse radiolysis was used to investigate the reaction of the electronic adduct of bovine serum albumin with oxygen. It was suggested that the disappearance of the electronic adduct of the protein occurs in the course of its interaction with oxygen adsorbed on the globular protein molecule

Pulse radiolysis study of the reactions of catechins with nitrogen dioxide

International Nuclear Information System (INIS)

Gebicki, Jerzy L.; Meisner, Piotr; Stawowska, Katarzyna; Gebicka, Lidia

2012-01-01

Nitrogen dioxide ( • NO 2 ), one of the oxidizing radicals formed in vivo is suspected to play a role in various pathophysiological processes. The reactions of • NO 2 with dietary catechins, the group of flavonoids present in high amounts in green tea and red wine, have been investigated by pulse radiolysis method. The kinetics of the reaction of • NO 2 with gallic acid have been also studied for comparison. The spectra of transient intermediates are presented. The rate constants of the reaction of • NO 2 with catechin, epigallocatechin, epigallocatechin gallate and gallic acid determined by the competition method with 2,2’-azinobis-(3-ethylbenzthiazoline-6-sulfonate) at pH 7.0 and room temperature have been found to be 0.9, 1.0, 2.3 and 0.5×10 8 M −1 s −1 , respectively. The values for catechins are among the highest reported for the reactions of • NO 2 with non-radical compounds. - Highlight: ► Reaction kinetics of catechins with · NO 2 is studied by the competition method. ► Catechins are excellent · NO 2 scavengers. ► Epigallocatechin gallate is the best · NO 2 scavenger among investigated catechins.

Pulse radiolysis study of reaction of bull serum albumin electron adduct with oxygen. Polychromatic kinetics of reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

By the method of pulse radiolysis the reaction of bull serum albumin electron adduct with oxygen is investigated. As pulsed radiation source electron linear accelerators with particle energy of 8.0 and 4.5 MeV and pulse time of 40 ns and 2.2 μs, respectively have been used. It is assumed that the disappearance of protein electron adduct occurs in the course of its interaction with oxygen adsorbed on protein globular molecule

Gamma radiolysis of the highly selective ligands CyMe_4BTBP and CyMe_4BTPhen: Qualitative and quantitative investigation of radiolysis product

International Nuclear Information System (INIS)

Schmidt, H.; Wilden, A.; Modolo, G.; Bosbach, D.; Santiago-Schuebel, B.; Hupert, M.; Svehla, J.; Gruner, B.; Ekberg, C.

2016-01-01

The highly selective nitrogen donor ligands CyMe_4BTBP and CyMe4_BTPhen where γ-irradiated under identical experimental conditions in 1-octanol with and without contact to nitric acid solution. Subsequently, solvent extraction experiments were carried out to evaluate the stability of the extractants against γ-radiation monitoring Am(III) and Eu(III) distribution ratios. Generally, decreasing distribution ratios with increasing absorbed dose were detected for both molecules. Furthermore, qualitative mass spectrometric analyses were performed and ligand concentrations were determined by HPLC-DAD after irradiation to investigate the radiolysis mechanism. An exponential decrease with increasing absorbed dose was observed for both ligands with a faster rate for CyMe_4BTPhen. Main radiolysis products indicated the addition of one or more diluent molecules (1-octanol) to the ligand via prior production of α-hydroxy-octyl radicals from diluent radiolysis. The addition of nitric acid during the irradiation lead to a remarkable stabilization of the system, as the extraction of Am(III) and Eu(III) did not change significantly over the whole examined dose range. Quantification of the remaining ligand concentration on the other hand showed decreasing concentrations with increasing absorbed dose. The stabilization of D values is therefore explained by the formation of 1-octanol addition products which are also able to extract the studied metal ions. (authors)

The reaction set, rate constants and g-values for the simulation of the radiolysis of light water over the range 20 deg to 350 deg C based on information available in 2008

International Nuclear Information System (INIS)

Elliot, A.J.; Bartels, D.M.

2009-08-01

An understanding of the aqueous radiolysis-induced chemistry in nuclear reactors is an important key to the understanding of materials integrity issues in reactor systems. Significant materials and chemistry issues have emerged in Pressurized Water Reactors (PWR), Boiling Water Reactors (BWR) and CANDU reactors that have required a detailed understanding of the radiation chemistry of the coolant. For each reactor type, specific computer radiolysis models have been developed to gain insight into radiolysis processes and to make chemistry control adjustments to address the particular issues. The objective of this report is to compile and review the radiolysis data now available and, where possible, correct the reported g-values and rate constants to provide a recommendation for the best values to use in high temperature modelling of light water radiolysis up to 350 o C. With a few exceptions, the review has been limited to those reactions that occur in slightly acid and slightly alkaline solutions, e.g., it does not address reactions involving the oxide radical anion, O - , or ionized forms of hydrogen peroxide, HO 2 - , beyond their acid-base equilibria reactions. However, a few reactions have been included where the rate constant for a reaction involving O - is significantly larger than the corresponding hydroxyl radical reaction rate constant and thus can influence the chemistry below the pK A of the hydroxyl radical. (author)

Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

International Nuclear Information System (INIS)

Fagerstroem, K.

1993-01-01

The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

Contribution to the study of gamma radiolysis of 2-furyl butyl or substituted phenyl ketones in isopropanol

International Nuclear Information System (INIS)

El Dessouky Aly, M.M.

1982-03-01

The following ketones: 2-furyl butyl ketone (I), 2 furyl phenyl ketone (II), 2-furyl p-methylphenyl ketone (III) and 2-furyl p-methoxyphenyl ketone (IV) were synthesised and characterised. The yields of hydrogen and methane obtained during radiolysis of the mixtures ketones (I to IV)-2-propanol were determined. These yields are always lower than with pure 2-propanol. Radiolysis products for ketones (I) and (II) are studied. Analysis of radiolitical products were conducted by gas chromatography. Effect of radiation dose and ketone concentration is determined. Reaction mechanisms are studied [fr

Pulse radiolysis study of egg white

International Nuclear Information System (INIS)

Micic, O.I.; Josimovic, L.; Markovic, V.

1978-01-01

Radiolytic processes in egg white in intervals of 0.1μs to several seconds have been studied by the pulse radiolysis technique. The formation and decay of short-lived intermediates and their absorption spectra were observed under varied experimental conditions. The results show that intermediates are produced predominantly in reactions of radicals formed in water radiolysis with egg white proteins. The intermediates decay mainly in the first-order intermolecular processes, though the mechanism of transformations is very complex. (author)

Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

International Nuclear Information System (INIS)

Zakurdaeva, O.A.; Nesterov, S.V.; Moscow State Univ.; Feldman, V.I.

2013-01-01

Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH 3 (CH 2 ) 6 C circle HOH and interior-type alkyl R 1 C circle HR 2 OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH 2 -C circle H- and acyclic -C circle H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

Energy Technology Data Exchange (ETDEWEB)

Zakurdaeva, O.A.; Nesterov, S.V. [Russian Academy of Sciences, Moscow (Russian Federation). Enikolopov Institute of Synthetic Polymer Materials; Moscow State Univ. (Russian Federation). Dept. of Chemistry; Feldman, V.I. [Moscow State Univ. (Russian Federation). Dept. of Chemistry

2013-03-01

Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH{sub 3}(CH{sub 2}){sub 6}C {sup circle} HOH and interior-type alkyl R{sub 1}C {sup circle} HR{sub 2}OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH{sub 2}-C {sup circle} H- and acyclic -C {sup circle} H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

Modelling the radiolysis of RSG-GAS primary cooling water

Science.gov (United States)

Butarbutar, S. L.; Kusumastuti, R.; Subekti, M.; Sunaryo, G. R.

2018-02-01

Water chemistry control for light water coolant reactor required a reliable understanding of radiolysis effect in mitigating corrosion and degradation of reactor structure material. It is known that oxidator products can promote the corrosion, cracking and hydrogen pickup both in the core and in the associated piping components of the reactor. The objective of this work is to provide the radiolysis model of RSG GAS cooling water and further more to predict the oxidator concentration which can lead to corrosion of reactor material. Direct observations or measurements of the chemistry in and around the high-flux core region of a nuclear reactor are difficult due to the extreme conditions of high temperature, pressure, and mixed radiation fields. For this reason, chemical models and computer simulations of the radiolysis of water under these conditions are an important route of investigation. FACSIMILE were used to calculate the concentration of O2 formed at relatively long-time by the pure water γ and neutron irradiation (pH=7) at temperature between 25 and 50 °C. This simulation method is based on a complex chemical reaction kinetic. In this present work, 300 MeV-proton were used to mimic γ-rays radiolysis and 2 MeV fast neutrons. Concentration of O2 were calculated at 10-6 - 106 s time scale.

Simulation of the inhibition of water α-radiolysis via H2 addition

International Nuclear Information System (INIS)

Lertnaisat, Phantira; Katsumura, Yosuke; Mukai, Satoru; Umehara, Ryuji; Shimizu, Yuichi; Suzuki, Masashi

2014-01-01

The continuous formation of H 2 , O 2 , and H 2 O 2 observed in water during α-radiolysis may be suppressed by the addition of H 2 above the threshold hydrogen concentration (THC). Using the FACSIMILE simulation code, water radiolysis was reproduced in order to determine the THC and clarify the mechanism at room temperature. Using the reaction set and rate constants reported by Ershov and Gordeev together with the primary yields for water decomposition products generated using 12 MeV α-particles, the THC was found to be 165 μM. Further simulation results clearly showed that the value of THC is strongly dependent on the reaction set and rate constants. In addition, a possible mechanism involving a chain reaction governed by the two reactions OH + H 2 → H + H 2 O and H + H 2 O 2 → OH + H 2 O was proposed. Furthermore, the same inhibition effect was found when a high-temperature simulation (300degC) was performed, but the concentration range and THC were much smaller than the values obtained at room temperature. The importance of the reverse reaction OH + H 2 → H + H 2 O was also investigated. (author)

Gamma radiolysis of the highly selective ligands CyMe{sub 4}BTBP and CyMe{sub 4}BTPhen: Qualitative and quantitative investigation of radiolysis product

Energy Technology Data Exchange (ETDEWEB)

Schmidt, H.; Wilden, A.; Modolo, G.; Bosbach, D. [Forschungszentrum Juelich GmbH, Institute of Energy and Climate Research IEK-6: Nuclear Waste Management, 52425 Juelich (Germany); Santiago-Schuebel, B.; Hupert, M. [Forschungszentrum Juelich GmbH, Central Institute for Engineering, Analytics - ZEA-3, 52425 Juelich (Germany); Svehla, J.; Gruner, B. [Institute of Inorganic Chemistry, Academy of Sciences, Hlavni 1001, 25068 Husinec-Rez (Czech Republic); Ekberg, C. [Department of Chemical and Biochemical Engineering, Chalmers University of Technology, 41296 Gothenburg (Sweden)

2016-07-01

The highly selective nitrogen donor ligands CyMe{sub 4}BTBP and CyMe4{sub B}TPhen where γ-irradiated under identical experimental conditions in 1-octanol with and without contact to nitric acid solution. Subsequently, solvent extraction experiments were carried out to evaluate the stability of the extractants against γ-radiation monitoring Am(III) and Eu(III) distribution ratios. Generally, decreasing distribution ratios with increasing absorbed dose were detected for both molecules. Furthermore, qualitative mass spectrometric analyses were performed and ligand concentrations were determined by HPLC-DAD after irradiation to investigate the radiolysis mechanism. An exponential decrease with increasing absorbed dose was observed for both ligands with a faster rate for CyMe{sub 4}BTPhen. Main radiolysis products indicated the addition of one or more diluent molecules (1-octanol) to the ligand via prior production of α-hydroxy-octyl radicals from diluent radiolysis. The addition of nitric acid during the irradiation lead to a remarkable stabilization of the system, as the extraction of Am(III) and Eu(III) did not change significantly over the whole examined dose range. Quantification of the remaining ligand concentration on the other hand showed decreasing concentrations with increasing absorbed dose. The stabilization of D values is therefore explained by the formation of 1-octanol addition products which are also able to extract the studied metal ions. (authors)

Pulse radiolysis of bilirubin in aqueous solution

International Nuclear Information System (INIS)

Barber, D.J.W.; Richards, J.T.

1977-01-01

A pulse radiolysis study of bilirubin, the breakdown product of heme, has been made. In aqueous solution at pH 12, short-lived transient spectra have been obtained for reaction of bilirubin with e/sub aq//sup -/ and OH. Bimolecular rate constants for these reactions have been measured, namely, k/sub BR+e/sub aq//sup -/ equals 9.5 x 10 9 M -1 sec -1 and k/sub BR+OH/ equals 3.45 x 10 9 M -1 sec -1 , and the spectrum of a long-lived product resulting from decay of the bilirubin-OH adduct has been obtained. In addition, solute destruction by OH has been investigated in detail. The transient absorption spectrum for reduction of bilirubin with the H atom at neutral pH has been measured. By measuring the rate of reaction with e/sub aq//sup -/ in the presence of bovine serum albumin (BSA), the mode of binding of bilirubin to this biologically important compound has been studied

Regularities of radiolysis of carbon dioxide adsorbed on Zeokar-2 catalyst

International Nuclear Information System (INIS)

Rustamov, V.R.; Kurbanov, M.A.; Kerimov, V.K.; Musaeva, P.F.

1982-01-01

Kinetics of CO formation, effect of dose rate and adsorbed water on CO yield during heterogeneous gamma-radiolysis of CO 2 have been studied. Radiation-chemical yields of the products are determined. The mechanism of reactions is discussed. It is shown that the catalyst plays the role of acceptor of active intermediate particles (O - and others) and acts as a chemical reagent

Gamma-radiolysis of organic compounds and alpha-radiolysis of water

International Nuclear Information System (INIS)

Christensen, H.

1978-09-01

This KBS-report is a collection of five technical reports. Various radiolytic problems in connection with the disposal of high-active waste are dealt with. The English titles of the five reports are: 1) Radiolysis of fulvic acids; 2) Radiolysis of organic compounds in bentonite; 3) α-radiolysis of water during the disposal of fuel without reprocessing; 4) Radiolysis of water during the disposal of unreprocessed spent fuel. Oxidation by hydrogen peroxide; 5) Formation and decomposition of hydrogen peroxide by α-radiolysis. These reports (in Swedish) are attached as Appendices A-E. (author)

Pulse radiolysis of anthraquinone dye aqueous solution

International Nuclear Information System (INIS)

Perkowski, J.; Gebicki, J.L.; Lubis, R.; Mayer, J.

1988-01-01

Pulse radiolysis of argon flushed aqueous solutions of 10 -5 -10 -4 mol dm -3 anthraquinone dye (C.I. Acid Blue 62) gives rise to the transients originated from the reactions of e - aq , OH and H. The rate constants of these reactions are determined. (author)

Pulse radiolysis of 6-aminophenalenone ethanolic solutions

International Nuclear Information System (INIS)

Semenova, G.V.; Kartasheva, L.I.; Ryl'kov, V.V.; Pikaev, A.K.

1986-01-01

Intermediates of 6-aminophenalenone radiolytic transformations in ethanol are investigated using pulse radiolysis method (5 and 8 MeV energy electrons, pulse duration is 2.3 μs and 15 ns respectively). Constants of reaction rate of e s and α-ethanolic radical with dye are measured (they are equal to (9.3±1.0)x10 9 and (1.1±0.2)x10 8 l/(molxs) respectively); optical and kinetic characteristics of products of their interaction are investigated. Mechanism of radiolytic transformations of this dye is proposed

Pulse radiolysis studies of iron(I) in aqueous solutions

International Nuclear Information System (INIS)

Nenadovic, M.T.; Micic, O.I.; Muk, A.A.

1980-01-01

The absorption spectrum and decay kinetics of the products of the reactions of iron(II) ions with hydrated electrons and hydrogen atoms have been studied in aqueous solution using pulse-radiolysis techniques. Iron(I) is formed by reaction with hydrated electrons and its absorption spectrum is reported and discussed. The formation of molecular hydrogen by reaction of Fe + with water is suppressed by other solutes present in the solutions. In acidic solutions containing [SO 4 ] 2- , the intermediates formed in the reaction with H atoms decay by a first-order process and produce molecular hydrogen, but the rate of their decay does not depend only on the oxonium ion concentration but also on intermolecular rearrangement in the [FeSO 4 -H] complex. (author)

Selecting ethanol as an ideal organic solvent probe in radiation chemistry γ-radiolysis of acetone-ethanol system and acetophenone-ethanol system

International Nuclear Information System (INIS)

Jin Haofang; Wu Jilan; Fang Xingwang; Zhang Xujia

1995-01-01

Radiolysis of acetone-ethanol solution and acetophenone-ethanol solution has been studied in this work. The dependences of G values of the final γ radiolysis products such as H 2 . 2,3-butanediol and acetaldehyde on additive concentration in liquid ethanol have been obtained. There are two kinds of new final products, isopropanol and 2-methyl-2,3-butanediol are detected in irradiated acetone-ethanol solution. As for acetophenone-ethanol system, more new final products are found. In addition, experiments of pulse radiolysis upon acetophenone-ethanol solution have also been performed. The absorption spectrum with λ max at 315nm and 440nm is observed, which is assigned to ketyl radical ion C 6 H 5 (CH 3 )CO - . And the reaction mechanism of the two systems is proposed respectively with a moderate success. (author)

Radiolysis characterization of chloramphenicol in powder and in eye ointment

International Nuclear Information System (INIS)

Hong, L.; Altorfer, H.R.

2005-01-01

The effects of γ-radiation sterilization on chloramphenicol, in both pure powder state and petrolatum eye ointment, were investigated with high performance liquid chromatography. The content of chloramphenicol decreases by 1.0% in powder state and by 1.2% in eye ointment at the reference radiation dose of 25 kGy. The profile of chloramphenicol radiolysis products in powder state differs from that in eye ointment. It was found that microenvironment of chloramphenicol molecule is a key factor governing the radiolysis of chloramphenicol in powder state. Solvent residues in chloramphenicol powder could change the radiolysis behavior of chloramphenicol. The solvents, having good solubility for chloramphenicol, promote radiolytic hydrolysis of chloramphenicol, but the converses do not. Inert gas purging or diffusion by exposing in absorbent is efficient method to prevent chloramphenicol powder from radiolysis. The influence of the presence of oxygen was explored. Oxygen plays a role of scavenger and diminishes radiolysis of chloramphenicol. It was found that Nactyl-L-cysteine can protection chloramphenicol in eye ointment from radiolysis. Hydrophobic radiolysis products of chloramphenicol were observed in eye ointment part. Using scavengers and lower irradiation can be strategies to resist radiolysis of chloramphenicol in petrolatum eye ointment. (author)

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

International Nuclear Information System (INIS)

Erben-Russ, Michael; Bors, Wolf; Saran, Manfred

1987-01-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N 2 O/O 2 -saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N 2 O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N 3 with rate constants exceeding 10 9 dm 3 mol -1 s -1 . Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10 7 dm 3 mol -1 s-? 1 ), with aroxyl radicals to form covalent adducts (> 10 8 dm 3 mol -1 s -1 ), as well as for their bimilecular decay (3.0 x 10 8 dm 3 mol -1 s -1 ). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution. (author)

Measurement of the hydrogen yield in the radiolysis of water by dissolved fission products

International Nuclear Information System (INIS)

Sauer, M.C. Jr.; Hart, E.J.; Flynn, K.F.; Gindler, J.E.

1976-04-01

Hydrogen from the radiolysis of water by dissolved fission products is stripped from the solution and collected by bubbling CO 2 through the solution. Quantitative measurements of the G value for hydrogen show that the yield is essentially the same as would be obtained by external gamma radiolysis of nonradioactive solutions of the same chemical composition. The hydrogen yield can be enhanced by addition of a hydrogen-atom donor, such as formic acid, to the solution. The yield of hydrogen from fission-waste solutions is discussed with respect to the question of whether it represents a significant energy source

Radiolysis of benzyl alcohol in aqueous solution by external gamma-irradiation

International Nuclear Information System (INIS)

Ikebuchi, Hideharu; Kido, Yasumasa; Urakubo, Goro

1977-01-01

Radiolysis of 0.05% aqueous solution of benzyl alcohol with 60 Co γ-rays ranging from 1 x 10 4 to 7 x 10 5 rad was investigated, in order to presume the change of it contained in radiopharmaceuticals. For both O 2 free and oxygenated solutions, an approximately linear relationship holds between the retaining benzyl alcohol and dose in the range from 1 x 10 5 to 7 x 10 5 rads. The G(-M) values of benzyl alcohol calculated from the relation were 2.34 in the absence and 1.92 in presence of oxygen. In the presence of oxygen, a main product was benzaldehyde and its G value was 0.87. In the absence of oxygen, the main products of the radiolysis were dibenzyl, benzyl phenylcalbinol and hydrobenzoin, which were regarded as the radical-reaction products of PhCH 2 and PhCHOH, and the yield of benzaldehyde was negligible. Irrespective of the presence of oxygen, o- and p-hydroxylated products of benzyl alcohol were found only in small quantity. (auth.)

Some mechanisms which may reduce radiolysis

Energy Technology Data Exchange (ETDEWEB)

Neretnieks, I; Faghihi, M. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Chemical Engineering

1991-08-01

In this report two mechanisms which may considerably decrease the rate of radiolysis are studied. The first main effect is that capillary forces in the very fine pores of the bentonite which surround the canisters do not permit the release of water if there is a gas over pressure inside the canister. As long as there is gas inside the canister the gap will partly be gas filled and the alpha-particles will have less water to radiolyze. Because some hydrogen will be dissolved and will escape by diffusion, a rate of radiolysis will be maintained which balances the rate of diffusion. This in turn will be influenced by the geometry of the diffusion path. The size of the hole in the copper canister seems to be one of the critical items which determine the escape of the hydrogen and thus the rate of radiolysis. The other main effect which will reduce the radiolysis is the accumulation of the corrosion products in the gap. This reduces the water content in the gap. Consequently there will be less water which can be radiolyzed. The presence of corrosion products which have a higher density than water will also consume the energy of the alpha-particles faster. Both effects seem to, independently, have a potential of reducing the rate of radiolysis by a few order of magnitude.

Some mechanisms which may reduce radiolysis

International Nuclear Information System (INIS)

Neretnieks, I; Faghihi, M.

1991-08-01

In this report two mechanisms which may considerably decrease the rate of radiolysis are studied. The first main effect is that capillary forces in the very fine pores of the bentonite which surround the canisters do not permit the release of water if there is a gas over pressure inside the canister. As long as there is gas inside the canister the gap will partly be gas filled and the alpha-particles will have less water to radiolyze. Because some hydrogen will be dissolved and will escape by diffusion, a rate of radiolysis will be maintained which balances the rate of diffusion. This in turn will be influenced by the geometry of the diffusion path. The size of the hole in the copper canister seems to be one of the critical items which determine the escape of the hydrogen and thus the rate of radiolysis. The other main effect which will reduce the radiolysis is the accumulation of the corrosion products in the gap. This reduces the water content in the gap. Consequently there will be less water which can be radiolyzed. The presence of corrosion products which have a higher density than water will also consume the energy of the alpha-particles faster. Both effects seem to, independently, have a potential of reducing the rate of radiolysis by a few order of magnitude

Determination of radiolysis products in gamma-irradiated multilayer barrier food packaging films containing a middle layer of recycled LDPE

International Nuclear Information System (INIS)

Chytiri, Stavroula; Goulas, Antonios E.; Badeka, Anastasia; Riganakos, Kyriakos A.; Petridis, Dimitrios; Kontominas, Michael G.

2008-01-01

Volatile and non-volatile radiolysis products and sensory changes of five-layer food packaging films have been determined after gamma irradiation (5-60 kGy). Barrier films were based on polyamide (PA) and low-density polyethylene (LDPE). Each film contained a middle buried layer of recycled LDPE or 100% virgin LDPE (control samples). Data showed that a large number of radiolysis products were produced such as hydrocarbons, alcohols, carbonyl compounds, carboxylic acid. These compounds were detected in the food simulant after contact with all films even at the lower absorbed doses of 5 and 10 kGy. The type and concentration of radiolysis products increased progressively with radiation dose, while no new compounds were detected as a result of the presence of recycled LDPE. In addition, irradiation dose appears to influence the sensory properties of table water in contact with films

Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

Science.gov (United States)

Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

2017-11-22

Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

γ radiolysis of thymine in oxygen-free aqueous solution in the presence of electron affinic radiosensitizers: identification of stable products

International Nuclear Information System (INIS)

Cadet, J.; Guttin-Lombard, M.; Teoule, R.

1976-01-01

Radiosensitizers react with nucleic radicals by addition and by electron transfer reactions. A study has been made of the steady-state γ radiolysis of 1 mM thymine in oxygen-free aqueous solutions containing different classes of radiosensitizing drugs: N-oxyl-free radicals (TAN and TMPN), quinones (menadione and naphthoquinone), nitroheterocyclic compounds (metronidazole and 5-nitro-2-furoic acid) and N-ethylmaleimide. Two classes of thymine degradation products were isolated by thin-layer chromatography and characterized by spectroscopic measurements. The main products, irrespective of radiosensitizers, resulting from oxidation reaction were identified as the cis and trans isomers of 5,6-dihydroxy-5, 6-dihydrothymine, N-pyruvyl-N'-formylurea, 6-hydroxy-5,6-dihydrothymine and 5-hydroxy-5,6-dihydrothymine. In the experimental conditions used only N-oxyls and to a lesser extent NEM reacted with 5-hydroxy-5,6-dihydrothymine-6-yl radical, giving stable covalently-bonded addition products with a high yield. TAN showed a higher binding ability with respect to TMPN, which is in good agreement with the rate-constants previously reported for these bimolecular reactions. (author)

Radiolysis of dodecane--tributylphosphate and nitrous oxide solutions

International Nuclear Information System (INIS)

Razvi, J.

1978-01-01

The chemical effects of 60 Co gamma irradiation on the nuclear fuel reprocessing solvents tributylphosphate (TBP) and dodecane were studied. Nitrous oxide, with concentrations in the range 20 mM to 140 mM, was used as the standard for competition kinetics. Solutions of TBP (with electron fractions of 0.025, 0.05, 0.1 and 0.3) in dodecane were irradiated. Primary gaseous products (non-condensible at 77K) in the radiolysis were nitrogen and hydrogen. Liquid products observed were the dimer, dodecanone, dodecanol, and fragmentation products C 5 -C 11 and C 17 -C 20 . Acid products from TBP were dibutylphosphate (DBP) and monobutylphosphate (MBP). All yields were determined both as a function of TBP and nitrous oxide concentrations. Kinetic analysis of nitrogen yields from dodecane--N 2 O radiolysis gave, G(total scavengable primary species) = 6.7 molecules/100 eV. Yields of dodecane liquid products could not be analyzed quantitatively due to the complex spectrum of products. In dodecane--N 2 O solutions, the dimer showed insignificant changes in yields and product distributions, indicating formation of additional dodecyl radicals in the presence of nitrous oxide. In dodecane--TBP mixtures, dimer yields reduced significantly as did the products from carbon--carbon bond cleavage. The addition of nitrous oxide to the binary mixture caused the dimer yield to increase, confirming formation of C 12 H 25 radicals by nitrous oxide reactions

Pulse radiolysis of rhodamine dye solutions

International Nuclear Information System (INIS)

Kucherenko, E.A.; Kartasheva, L.I.; Pikaev, A.K.

1982-01-01

Applying the method of pulse radiolysis (5 MeV electrons) a study was made on intermediate products of rhodamine B radiolytic transformations in neutral aqueous and ethanol solutions. Rate constants of reactions of esub(aq) and OH with the dye (they are equal to (2.2+-0.3)x10 10 and (2.1+-0.3)x10 10 e/molxs, accordingly) as well as optical and kinetic characteristics of esub(aq), OH and H interaction products were measured. The nature of these products is concluded. It was found that in ethanol solutions the semirecovered form - electroneutral radical of rhodamine B - was the only intermediate product. It arises during the interaction of the dye with esub(s) (k=(9.2+-1.2)x10 9 e/molxs) and α-et hananol radical (k=(1.1+-0.1)x10 8 l/molxs). Properties of this product were investigated

Effects of seawater components on radiolysis of water at elevated temperature

International Nuclear Information System (INIS)

Wada, Yoichi; Tachibana, Masahiko; Ishida, Kazushige; Ota, Nobuyuki; Shigenaka, Naoto; Inagaki, Hiromitsu; Noda, Hiroshi

2014-01-01

Effects of seawater components on radiolysis of water at elevated temperature have been studied with a radiolysis model in order to evaluate influence on integrity of materials used in an ABWR. In 2011, seawater flowed into a wide part of the nuclear power plant system of the Hamaoka Nuclear Power Station Reactor No. 5 owned by Chubu Electric Power Co., Inc. after condenser tubes broke during the plant shutdown operation. The reactor water temperature was 250°C and its maximum Cl − concentration was ca. 450 ppm when seawater was mixed with reactor water. In order to clarify effects of the sea water components on radiolysis of water at elevated temperature, a radiolysis model calculation was conducted with Hitachi's radiolysis analysis code 'SIMFONY'. For the calculation, the temperature range was set from 50 to 250°C with 50°C increments and the gamma dose rate was set at 60 Gys −1 to see the effect of gamma irradiation from fuels under shutdown conditions. Concentrations of radiolytic species were calculated for 10 5 s. Dilution ratio of seawater was changed to see the effects of concentration of seawater components. Reaction rate constants of the Cl − , Br − , HCO 3 − , and SO 4 2− systems were considered. The main radiolytic species were predicted to be hydrogen and oxygen. Hydrogen peroxide of low concentration was produced in seawater-mixed water at elevated temperatures. Compared with these main products, concentrations of radiolytic products originating from chloride ion and other seawater components were found to be rather low. The dominant product among them was ClO 3 − and its concentration was found to be below 0.01ppm at 10 5 s. Then, during the plant shutdown operation, the harmful influence from radiolytic species originating from seawater components on integrity of fuel materials must be smaller than that of chloride ion which is the main ionic species in seawater. (author)

Pulse radiolysis of solutions of trans-stilbene

International Nuclear Information System (INIS)

Langan, J.R.; Salmon, G.A.

1982-01-01

On pulse radiolysis of solutions of trans-stilbene (t-St) in THF the radical-anion of t-St is formed by reaction of e - sub(s) with t-St. The transient absorption spectrum observed with lambdasub(max) at 500 and 720 nm is attributed to the unassociated St - . The subsequent decay of the radical-anion is accounted for by reaction with the counter-cation of THF formed on radiolysis and with radiolytically generated radicals; rate constants for these processes are estimated. Addition of sodium tetrahydridoaluminate (NAH) results in the radical-anion being associated with Na + as a contact ion-pair and a shift of lambdasub(max) to 490 nm. In the presence of the lithium salt the absorption spectrum of the radical-anion reverts to 500 nm. On pulse radiolysis of solutions containing NAH the main reaction forming St - is that of (Na + , e - sub(s))ion pairs with t-St. In addition there is a delayed formation of St - over a period of microseconds. The presence of tetrahydridoaluminate salts also greatly enhances the stability of St - and at high doses per pulse little decay was observed over 700 μs. The variation of G(St - ) with [NAH] was studied and was found to attain a plateau value of 2.0 at the higher concentrations. (author)

A pulse radiolysis study of the formation and reactions of reduced metal EDTA complexes

International Nuclear Information System (INIS)

Buitenhuis, R.

1977-01-01

The construction of a computerized pulse radiolysis system with available means appropriate for the wavelength interval between 300 and 1000 nm is described. The investigation of the radiolysis of aqueous solutions of EDTA complexes in the presence of alcohols is discussed

Computer modeling of inhibition of α-radiolysis of water by H2 addition (9. International Workshop on Radiolysis, Electrochemistry and Materials Performance)

International Nuclear Information System (INIS)

Lertnaisat, Phantira; Katsumura, Yosuke; Mukai, Satoru; Umehara, Ryuji; Shimizu, Yuichi; Suzuki, Masaru

2012-09-01

It is known that α-radiolysis of water produces H 2 gas continuously. The addition of H 2 to water inhibits the water decomposition; H 2 evolution. In order to suppress the water decomposition, 25 cc H 2 STP/kg-H 2 O is added to the coolant water in PWR. However, the exact inhibition mechanism is still not made clear yet. In this project, the chemical kinetic simulation program, so called FASCIMILE, was used to reproduce the suppression of α-radiolysis of water by H 2 addition. By using three important factors; the decomposition (G-value), the reaction set and rate constants, and the dose rate, it is found that without hydrogen addition, the simulation shows the almost linear increase of molecular products; H 2 , H 2 O 2 , and O 2 . Nevertheless, as the additional hydrogen is added to the system, this behaviour of linear increase is shifted to longer time period. And up to certain concentration, the linear increase behaviour is completely suppressed and the molecular products reach the steady state condition at early time period and much lower concentration. The minimum concentration of H 2 which could completely suppress the decomposition of water is called Critical Hydrogen Concentration (CHC) and it is dose rate dependent value. The CHC is found to be dependent on the reaction set and rate constants. The simulation results show that the CHC at room temperature and dose rate of 1 kGy/s of the simulation done by using reaction set and rate constants obtained from Ershov et al. and AECL report 2009 are 165μM and 146 μM, respectively. From the change of the behaviour of molecular products after reaching the CHC, the possible mechanism is proposed. First, the OH radical are formed via the reaction of H + H 2 O 2 → OH + H 2 O and e - aq + H 2 O 2 → OH+OH - . Then OH, which normally will react with H 2 O 2 to produced HO 2 , will react with the additional H 2 , which produce H to continue the chain reaction. The relation of chain reaction to the suppression of

Non-gaseous radiolysis products of procaine benzylpenicillin and Na salt 3-ortho-chloro-5-methyl-4-isoxasolyl penicillin

International Nuclear Information System (INIS)

Dziegielewski, J.; Jezowska-Trzebiatowska, B.

1974-01-01

Radiolysis products of procaine benzylpenicillin and Na salt 3-ortho-chlorophenyl-5-methyl-4-isoxasolyl penicillin were isolated and spectroscopic studies were made over the NMR, IR, UV and mass spectrometric ranges. On the basis of the results obtained, the bond breakage sites resulting from irradiation were determined and the modes of radiolysis decomposition were suggested. Irradiation of penicillins has been found to result in decomposition of the β-lactam and thiazolidine rings. Besides, decarboxylation of penicillins and bond cleavages within the amide group were observed as well as dehydrogenation and abstraction of simple hydrocarbons. The role of procaine and crystallization water in the radiolysis of penicillins was determined. (author)

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Erben-Russ, M.; Bors, W.; Saran, M.

1987-09-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N/sub 2/O/O/sub 2/-saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N/sub 2/O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N/sub 3/ with rate constants exceeding 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/. Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10/sup 7/ dm/sup 3/ mol/sup -1/ s-./sup 1/), with aroxyl radicals to form covalent adducts (> 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/), as well as for their bimilecular decay (3.0 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution.

Radiolysis of water in the vicinity of passive surfaces

International Nuclear Information System (INIS)

Moreau, S.; Fenart, M.; Renault, J.P.

2014-01-01

Highlights: • HO° production through water radiolysis is enhanced near metal surfaces. • Hastelloy and Stainless steel surfaces can also produce HO° radicals through hydrogen peroxide activation. • There is a deficit in solvated electron production compared to hydroxyl radicals near metal surfaces. - Abstract: Porous metals were used to describe the water radiolysis in the vicinity of metal surfaces. The hydroxyl radical production under gamma irradiation was measured by benzoate scavenging in water confined in a 200 nm porous Ni base alloy or in Stainless steel. The presence of the metallic surfaces changed drastically the HO° production level and lifetime. The solvated electron production was measured via glycylglycine scavenging for Stainless steel and was found to be significantly smaller than hydroxyl production. These observations imply that interfacial radiolysis may deeply impact the corrosion behavior of the SS and Ni based alloys

Radiolysis products and sensory properties of electron-beam-irradiated high-barrier food-packaging films containing a buried layer of recycled low-density polyethylene.

Science.gov (United States)

Chytiri, S D; Badeka, A V; Riganakos, K A; Kontominas, M G

2010-04-01

The aim was to study the effect of electron-beam irradiation on the production of radiolysis products and sensory changes in experimental high-barrier packaging films composed of polyamide (PA), ethylene-vinyl alcohol (EVOH) and low-density polyethylene (LDPE). Films contained a middle buried layer of recycled LDPE, while films containing 100% virgin LDPE as the middle buried layer were taken as controls. Irradiation doses ranged between zero and 60 kGy. Generally, a large number of radiolysis products were produced during electron-beam irradiation, even at the lower absorbed doses of 5 and 10 kGy (approved doses for food 'cold pasteurization'). The quantity of radiolysis products increased with irradiation dose. There were no significant differences in radiolysis products identified between samples containing a recycled layer of LDPE and those containing virgin LDPE (all absorbed doses), indicating the 'functional barrier' properties of external virgin polymer layers. Sensory properties (mainly taste) of potable water were affected after contact with irradiated as low as 5 kGy packaging films. This effect increased with increasing irradiation dose.

Pulse radiolysis of porphyrin and ferriporphyrin solutions in 2-propanol-carbon tetrachloride systems. Protonation and ligand exchange kinetics

International Nuclear Information System (INIS)

Brault, D.; Neta, P.

1983-01-01

Pulse radiolysis of aqueous and nonaqueous 2-propanol-acetone-carbon tetrachloride mixtures has been investigated by means of conductivity measurements and spectrophotometry. In these solvent mixtures, a pulse of hydrochloric acid originating from either primary events of solvent radiolysis or from further reactions of carbon tetrachloride with radicals derived from 2-propanol and acetone, is produced within ca 100 nanoseconds. Further production of hydrochloric acid occurs as a result of chain reactions involving hydrogen abstraction by CCl 3 or CCl 3 O 2 radicals. These latter radicals appear to be much more reactive and are likely to be involved in the reaction unless the solutions have been thoroughly deoxygenated. Protonation Reactions of porphyrins and ferriporphyrins, which do not react rapidly with the above radicals, were followed by means of spectrophotometric measurements. In turn, these reactions may be used to monitor hydrochloric acid formation. Spectrophotometric measurements on porphyrins corroborate conductivity results, although a quantitative comparison is not feasible because of differences in solvent properties. 6 figures

Chromatographic studies of gamma radiolysis products of phenols in methanolic solution

International Nuclear Information System (INIS)

Cordeiro, P.J.M.

1989-10-01

The radiolytic effects on phenolic compounds (catechol, resorcinol, hydroquinone and pyrogallol), under different doses of gamma irradiation, were studied. The results shown that the radiolytic effects are independent of the irradiation doses with almost all compounds formed from the solvent radiolysis. Analysis of the resulting products were carried out by High Performance Liquid Chromatography and Capillary Gas Chromatography. The quantification of these compounds was made by mass spectrometry. (author)

Radiolysis of N-acetyl amino acids as model compounds for radiation degradation of polypeptides

International Nuclear Information System (INIS)

Garrett, R.W.; Hill, D.J.T.; Ho, S.Y.; O'Donnell, J.H.; O'Sullivan, P.W.; Pomery, P.J.

1982-01-01

Radiation chemical yields of (i) the volatile radiolysis products and (ii) the trapped free radicals from the γ-radiolysis of the N-acetyl derivatives of glycine, L-alanine, L-valine, L-phenylalanine and L-tyrosine in the polycrystalline state have been determined at room temperature (303 K). Carbon dioxide was found to be the major molecular product for all these compounds with G(CO 2 ) varying from 0.36 for N-acetyl-L-tyrosine to 8 for N-acetyl-L-valine. There was evidence for some scission of the N-Csub(α) bond, indicated by the production of acetamide and the corresponding aliphatic acid, but the deamination reaction was found to be of much lesser importance than the decarboxylation reaction. A protective effect of the aromatic ring in N-acetyl-L-phenylalanine and in N-acetyl-L-tyrosine was indicated by the lower yields of volatile products for these compounds. The yields of trapped free radicals were found to vary with the nature of the amino acid side chain, increasing with chain length and chain branching. The radical yields were decreased by incorporation of an aromatic moiety in the side chain, this effect being greater for the tyrosyl side chain than for the phenyl side chain. The G(R) values showed a good correlation with G(CO 2 ) indicating that a common reaction may be involved in radical production and carbon dioxide formation. (author)

Mechanisms of transformation of the antioxidant kaempferol into depsides. Gamma-radiolysis study in methanol and ethanol.

Science.gov (United States)

Marfak, A; Trouillas, P; Allais, D P; Calliste, C A; Cook-Moreau, J; Duroux, J L

2003-09-01

In this study, we irradiated the antioxidant kaempferol in ethanol and methanol solutions with gamma rays at doses ranging from 0.2-20 kGy. NMR and ES-MS spectroscopy were used to identify radiolysis products. Two depsides, [2-[(4'-hydroxybenzoyl)oxy]-4,6-dihydroxyphenyl](oxo) methyl acetate and [2-[(4'-hydroxybenzoyl)oxy]-4,6-dihydroxyphenyl](oxo) ethyl acetate, were the major compounds of kaempferol degradation in methanol and in ethanol, respectively. Other products formed in low concentrations were identified as [4-hydroxyphenyl](oxo) methyl acetate, [4-hydroxyphenyl](oxo) ethyl acetate, and depside [2-[(4'-hydroxybenzoyl)oxy]-4,6-dihydroxyphenyl](oxo) acetic acid. The formation of the latter was observed in both solvents. We propose degradation mechanisms that suggest that (.)CH(2)OH and CH(3)(.)CHOH, produced by solvent radiolysis, react with the 3-OH kaempferol group because of its high H-donor capacity. pi-Electron delocalization in the flavonoxy formed after the first H-transfer leads to C-ring opening and consequently to the formation of depsides. G calculation of the degradation products and of (.)CH(2)OH and CH(3)(.)CHOH radicals confirmed the proposed mechanism of kaempferol radiolysis. The rate constants for the reaction between kaempferol and these free radicals were also calculated. Formation of depside has also been observed in many studies of the oxidation of flavonoids; those studying human metabolism have suggested similar redox transformation of flavonols. The antioxidant activities of radiolysis products were evaluated and compared to those of kaempferol.

Fast reactions of organic anion radicals with organic halides in hexamethylphosphoric triamide studied by pulse radiolysis

International Nuclear Information System (INIS)

Honda, Eiji; Tokuda, Masao; Yoshida, Hiroshi; Ogasawara, Masaaki

1987-01-01

Fast reactions of diethyl fumarate anion radical (DEF - ) and fluorenone anion radical (Fl - ) with various organic halides (RX) in hexamethylphosphoric triamide have been studied by means of ns pulse radiolysis at room temperature. Reactions of acetophenone anion radical were also studied for comparison. It was found that the reaction rate of Fl - was subject to the steric and resonance effects of R groups of RX in accord with the classical concept of S N 2 reactions: the rate constant was reduced by 2 orders of magnitude by the steric effect when R was changed from ethyl to bulky isopropyl or t-butyl, and it was still large by the resonance effect of R even if R was changed from ethyl to an allyl or a benzyl group. While the reaction rate of DEF - was not much affected when R was changed to more bulky groups, the rate constant was correlated to the reduction potential of RX. The results were interpreted in terms of a VB correlation diagram approach or rate-equilibrium relationship within a framework of S N 2 reactions. (author)

Gamma radiolysis of C6F6, product formation

International Nuclear Information System (INIS)

Sagert, N.H.; LeBlanc, J.C.; Wood, D.D.; Kremers, W.; Westmore, J.B.; Buchannon, W.D.

1991-01-01

The γ radiolysis of perfluorobenzene (PFB) has been studied at a dose rate of about 26 Gy·s -1 and at total doses up to 10 5 Gy. Radiolyses were carried out in fluorine-passivated nickel cells in the absence of air. There were no significant gas yields, but higher molecular weight products were observed and characterized by combined gas chromatography and mass spectrometry (GC/MS). The yield of all polymers totalled 1.7 molecules of PFB consumed for each 100 eV absorbed. This result is comparable to yields measured by earlier workers at much higher doses and dose rates. (author)

The effect of temperature on radiolysis of iodide ion diluted aqueous solutions

International Nuclear Information System (INIS)

Gorbovitskaya, T.; Tiliks, J.

1996-01-01

In order to investigate the radiolysis of iodine containing aqueous solutions a flow type facility - Iodine Thermoradiation Facility (ITF) has been designed. It has a possibility to irradiate aqueous solutions in the steel vessel with 60 Co γ-rays and continuously (on line) to analyze the products of radiolysis both in liquid and in gaseous phases. By means of ITF the formation of I ox (I 2 + I 3 - + HOI), IO 3 - , H 2 O 2 was studied in 10 -5 - 10 -3 mol/dm 3 CsI aqueous solutions by their radiolysis at dose rate 4.5 kGv/h for six hours in region of temperatures from 313 to 404 K. Under similar conditions, some experiments in glass ampoules were also performed. The steady-state concentrations of I ox and IO 3 - decreased with increasing temperature as linear function of inverted temperature. The effect decreased with decreasing concentration of iodide ion. As the result, at high temperatures (T≥380 K) the steady-state concentration of I ox does not depend essentially on the iodide ion initial concentration. Molecular iodine (I 2 ) released from the solution was the main radiolysis product in gaseous phase. Its steady-state concentration increased with increasing temperature because of iodine solubility in the water and decreased at the same time because the radiolytic iodine concentrations decreased. Therefore the most volatility of irradiated 10 -3 and 10 -4 M CsI solutions was observed at the temperature about 350 K. The volatility of 10 -5 M solutions gradually decreased with increasing temperature. The experimental data were explained on the base of the hypothesis that the reaction between I 2 and radiolytic H 2 O 2 was the limit one determining the temperature dependence of I ox and IO 3 - steady-state concentrations. Its activation energy was estimated to be 27,5 kcal.mol -1 . The temperature dependence for reaction (IO - + H 2 O 2 ) was also estimated. (author) 8 figs., 1 tab., 17 refs

Production of oxidants from α-radiolysis in the South Devon deposit

International Nuclear Information System (INIS)

Christensen, H.

2001-08-01

The maximum production of H 2 O 2 caused by α-radiolysis of water in the close vicinity of uranium-containing nodules found at the South Devon site has been estimated. The integrated α-doses from decay of U-238 and U-235 from the time of mineralization until today have been calculated. Calculations have been carried out for three different times: 140, 170, and 240 Myear. The maximum production from one nodule (diameter 4 cm) under 240 Myear was estimated to be 0.075 mole H 2 O 2 (= 2.5 g). For a number of causes, discussed in the report, the actual production will probably be much lower

One-electron oxidations of ferrocenes: a pulse radiolysis study

International Nuclear Information System (INIS)

Faraggi, Moshe; Weinraub, Dany; Broitman, Federico; DeFelippis, M.R.; Klapper, M.H.

1988-01-01

Using the pulse radiolysis technique we have studied the oxidation by various inorganic radicals of four water soluble ferrocene derivatives, hydroxyethyl, dimethylaminomethyl, monocarboxylic acid and dicarboxylic acid. We report the second order rate constants for these reactions, the stabilities and spectral properties of the ferrocinium products, and the electrochemically determined ferrocinium/ferrocene redox potentials. We also present preliminary estimates of tyrosine and tryptophan radical redox potentials obtained with the dicarboxylic acid ferrocene derivative as reference, and we discuss the relationship between redox potential differences and the reactivities of the ferrocenes with the inorganic radicals. (author)

Breaking time-resolution limits in pulse radiolysis

International Nuclear Information System (INIS)

Yang Jinfeng; Kondoh, Takafumi; Norizawa, Kimihiro; Yoshida, Yoichi; Tagawa, Seiichi

2009-01-01

Pulse radiolysis, which is a time-resolved stroboscopic method based on ultrashort electron pulse and ultrashort analyzing light, is widely used for the study of the chemical kinetics and radiation primary processes or reactions. Although it has become possible to use femtosecond-pulse electron beam and femtosecond laser light in pulse radiolysis, the resolution is limited by the difference in group velocities of the electrons and the light in sample. In this contribution, we introduce a concept of equivalent velocity spectroscopy (EVS) into pulse radiolysis and demonstrate the methodology experimentally. In EVS, both the electron and the analyzing light pulses precisely overlap at every point in the sample and throughout the propagation time by rotating the electron pulse. The advance allows us to overcome the resolution degradation due to the different group velocity. We also present a method for measuring the rotated angle of the electron pulse and a technique for rotating the electron pulse with a deflecting cavity.

Development of a new picosecond pulse radiolysis system by using a femtosecond laser synchronized with a picosecond linac. A step to femtosecond pulse radiolysis

Energy Technology Data Exchange (ETDEWEB)

Yoshida, Yoichi; Yamamoto, Tamotsu; Miki, Miyako; Seki, Shu; Okuda, Shuichi; Honda, Yoshihide; Kimura, Norio; Tagawa, Seiichi [Osaka Univ., Ibaraki (Japan). Inst. of Scientific and Industrial Research; Ushida, Kiminori

1997-03-01

A new picosecond pulse radiolysis system by using a Ti sapphire femtosecond laser synchronized with a 20 ps electron pulse from the 38 MeV L-band linac has been developed for the research of the ultra fast reactions in primary processes of radiation chemistry. The timing jitter in the synchronization of the laser pulse with the electron pulse is less than several picosecond. The technique can be used in the next femtosecond pulse radiolysis. (author)

Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

DEFF Research Database (Denmark)

Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

1996-01-01

The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...

Radiolysis of anthraquinone dyes in aqueous solutions

International Nuclear Information System (INIS)

Vysotskaya, N.A.; Bortun, L.N.; Ogurtsov, N.A.; Migdalovich, E.A.; Revina, A.A.; Volodko, V.V.; AN SSSR, Moscow. Inst. Ehlektrokhimii)

1986-01-01

The commercial anthraquinone dyes (Dark Blue, Light Blue, Green) in aqueous solutions were shown to be decoloured and degrade under the action of ionizing radiation. The degree of decolouration and degradation of aromatic rings was found to increase in presence of oxygen. Hydroxyl radicals were shown to play the key role in the degradation of the dyes under irradiation. The radiolysis intermediate products were studied using the pulse radiolysis technique. (author)

Volatile and non-volatile radiolysis products in irradiated multilayer coextruded food-packaging films containing a buried layer of recycled low-density polyethylene.

Science.gov (United States)

Chytiri, S; Goulas, A E; Badeka, A; Riganakos, K A; Kontominas, M G

2005-12-01

The effects of gamma-irradiation (5-60 kGy) on radiolysis products and sensory changes of experimental five-layer food-packaging films were determined. Films contained a middle buried layer of recycled low-density polyethylene (LDPE) comprising 25-50% by weight (bw) of the multilayer structure. Respective films containing 100% virgin LDPE as the buried layer were used as controls. Under realistic polymer/food simulant contact conditions during irradiation, a large number of primary and secondary radiolysis products (hydrocarbons, aldehydes, ketones, alcohols, carboxylic acids) were produced. These compounds were detected in the food simulant after contact with all films tested, even at the lower absorbed doses of 5 and 10 kGy (approved doses for food preservation). The type and concentration of radiolysis products increased progressively with increasing dose. Generally, there were no significant differences in radiolysis products between samples containing a buried layer of recycled LDPE and those containing virgin LDPE (all absorbed doses), indicating the good barrier properties of external virgin polymer layers. Volatile and non-volatile compounds produced during irradiation affected the sensory properties of potable water after contact with packaging films. Taste transfer to water was observed mainly at higher doses and was more noticeable for multilayer structures containing recycled LDPE, even though differences were slight.

Current state of knowledge in radiolysis effects on spent fuel corrosion

International Nuclear Information System (INIS)

Christensen, H.; Sunder, S.

1998-09-01

Literature data on the effect of water radiolysis products on spent fuel oxidation and dissolution have been reviewed. Effects of γ-radiolysis, α-radiolysis and dissolved O 2 or H 2 O 2 in unirradiated solutions have been discussed separately. Also the effect of carbonate in γ-irradiated solutions and radiolysis effects on leaching of spent fuels have been reviewed. In addition a radiolysis model for calculation of corrosion rates of UO 2 , presented previously, has been discussed. The model has been shown to give a good agreement between calculated and measured corrosion rates in the case of γ-radiolysis and in unirradiated solutions of dissolved oxygen or hydrogen peroxide. The model has failed to predict the results of α-radiolysis. In a recent study it was shown that the model gave a good agreement with measured corrosion rates of spent fuel exposed in deionized water

Pulse radiolysis of ethanolic solutions of rhodamine dyes

International Nuclear Information System (INIS)

Kartasheva, L.I.; Kucherenko, E.A.; Kozlov, A.S.; Pikaev, A.K.

1983-01-01

The primary products of radiolytical transformations of rhodamine 6G, rhodamine B, rhodamine 3B and rhodamine 110 in ethanolic solutions were studied by pulse radiolysis method under various conditions. It was found that the semireduced form of a dye was the only intermediate product of such transformations in ethanolic solutions of all dyes. It was shown that this species was formed by interaction of the dye with esub(s) - and CH 3 CHOH. The properties of this species were investigated and the rate constants of respective reactions for each dye were determined. It was found that nature and position of a substituent in the molecule of the dye have an effect on the rate of formation of the semi-reduced form. (author)

A model for radiolysis of water and aqueous solutions of H2, H2O2 and O2

International Nuclear Information System (INIS)

Ershov, B.G.; Gordeev, A.V.

2008-01-01

Kinetic model for the radiolysis of pure water describing the formation of H 2 , H 2 O 2 and O 2 and the radiation chemical transformations of aqueous solutions containing these compounds over a broad range of concentrations, pH, absorbed doses and dose rates is proposed and substantiated. The model includes a set of chemical reactions with optimized rate constants and the radiation chemical yields of radiolysis products. The model applicability to the description of the whole set of data on the radiation chemical transformations of water and aqueous solutions of H 2 , H 2 O 2 and O 2 is demonstrated

The formation of hydrogen in the radiolysis of water in closed volumes

International Nuclear Information System (INIS)

Kabakchi, S.A.; Lebedeva, I.E.

1984-01-01

By applying the sum total of the elementary reactions involving short-lived particles it is possible to fairly accurately calculate the kinetics of hydrogen formation and of its separation from water, and also to calculate the accumulation of hydrogen peroxide and oxygen during radiolysis of pure water and water solutions at room temperature. This paper describes a semi-empirical method to calculate the kinetics of hydrogen formation for certain cases encountered in nuclear power production. (author)

Chemical evolution studies: the radiolysis and thermal decomposition of malonic acid

International Nuclear Information System (INIS)

Cruz-Castaneda, J.; Negron-Mendoza, A.; Heredia, A.; Ramos-Bernal, S.; Villafane-Barajas, S.; Frias, D.; Colin-Garcia, M.

2015-01-01

In the context of chemical evolution a simulation of a hydrothermal vent was performed. The thermolysis and radiolysis of malonic acid in aqueous solution were studied. The thermolysis was done by heating the samples (95 deg C) and radiolysis using gamma radiation. Products were identified by gas chromatography and gas chromatography-mass spectrometry. The thermal treatment produced acetic acid and CO 2 . The radiolysis experiments yield carbon dioxide, acetic acid, and di- and tricarboxylic acids. A theoretical model of the chemical process occurring under irradiation was developed; this was able to reproduce formation of products and the consumption of malonic acid. (author)

Early stages of methanol radiolysis from data of photoelectron spectroscopy and mass spectrometry

International Nuclear Information System (INIS)

Kalyazin, E.P.; Kovalev, G.V.

1982-01-01

Comparison of data on photoelectron spectroscopy and mass spectrometry permits to conclude that 4 types of molecular ions CH 3 O + H, H + CH 2 OH, H 3 C + OH and CH 3 O + H are initial products of methanol radiolysis. They start four parallel lines of methanol transformations. Mass spectrum of methanol can be evaluated according to the structural formula of methanol molecule. Composition of radiolysis products of gaseous methanol correlate satisfactorily with its mass spectrum. Reasons for the difference in compositions of radiolysis products of liquid and gaseous methanol are discussed

The effect of temperature on radiolysis of iodide ion diluted aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Gorbovitskaya, T; Tiliks, J [Latvia Univ., Lab. of Radiation Chemistry, Riga (Latvia)

1996-12-01

To investigate the radiolysis of iodine containing aqueous solutions a flow type facility (ITF) has a possibility to irradiate aqueous solutions in the steel vessel with {sup 60}Co {gamma}-rays and continuously (on line) to analyze the products of radiolysis both in liquid and in gaseous phases. By means of ITF the formation of I{sub ox} (I{sub 2} + I{sub 3}{sup -} + HOI), IO{sub 3}{sup -}, H{sub 2}O{sub 2} was studied in 10{sup -5} - 10{sup -3} mol/dm{sup 3} CsI aqueous solutions by their radiolysis at dose rate 4.5 kGv/h for six hours in region of temperatures from 313 to 404 K. Some experiments in glass ampoules were also performed. The steady-state concentrations of I{sub ox} and IO{sub 3}{sup -} decreased with increasing temperature as linear function of inverted temperature. The effect decreased with decreasing concentration of iodide ion. As the result, at high temperatures (T{>=}380 K) the steady-state concentration of I{sub ox} does not depend essentially on the iodide ion initial concentration. Molecular iodine (I{sub 2}) released from the solution was the main radiolysis product in gaseous phase. Its steady-state concentration increased with increasing temperature because of iodine solubility in the water and decreased at the same time because the radiolytic iodine concentrations decreased. Therefore the most volatility of irradiated 10{sup -3} and 10{sup -4}M CsI solutions was observed at the temperature about 350 K. The volatility of 10{sup -5}M solutions gradually decreased with increasing temperature. The experimental data were explained on the base of the hypothesis that the reaction between I{sub 2} and radiolytic H{sub 2}O{sub 2} was the limit one determining the temperature dependence of I{sub ox} and IO{sub 3}{sup -}steady-state concentrations. Its activation energy was estimated to be 27,5 kcal.mol{sup -1}. The temperature dependence for reaction (IO{sup -} + H{sub 2}O{sub 2}) was also estimated. (author) 8 figs., 1 tab., 17 refs.

Study of the radiolysis of tetracycline hidrochloride in aerated aqueous solutions

International Nuclear Information System (INIS)

Guedes, S.M.L.; Vasconcellos, M.B.A.

1983-01-01

The radiolysis of tetracycline hydrochloride (TC) was studied in neutral, acid and alkaline aerated solutions, by electron spin resonance spectroscopy at 77K. The paramagnetic species observed are: H.; OH.; HO 2 .; e - trapped and impurity radical. The reaction mechanism shows that the solute reacts with the solvent before the radiolysis and produces H + ions, as a consequence of the ionization of tricarbonylmethane group. The H + ions react with the e - from the radiolysis of water and produce HO 2 in the presence of O 2 . The interaction of TC with the alkaline solvent favours the interaction between gamma rays and solute. The products formed in the interaction of solute with the solvent before the radiolysis, as a consenquence of the ionization of TC, according to the pH of the solution, are of fundamental importance in the interaction of gamma rays with the solute. A crude estimate of the average distance that the e - is able to travel through solvent molecules before its capture by the solute was obtained in these 0.1N, 0.5N and 1.0N NaOH aqueous solutions. Until [TC] - travels more in solutions that contain less [NaOH]. In higher [TC] the e - travels through 680 solvent molecules. In order to explain the selective capture of the e3- by solute molecules, a simple model is suggested based on the existence of channel walls of solvent molecules where the electrical atraction betwwed Na + and e - influences the collision frequency and the energy loss. (Author) [pt

Comparison of the linear energy transfer effect in the radiolysis of cyclopentane, cyclohexane and cyclooctane

International Nuclear Information System (INIS)

Wojnarovits, L.; La Verne, J.A.

1998-01-01

In the radiolysis of cyclopentane, cyclohexane and cyclooctane, changing the irradiating particles from γ-rays to heavy ions, there are indications for the increase of the proportion of the H atom forming reaction at the expense of the reactions leading to H 2 molecule elimination and to radical production without participation of H atoms. This shift is attributed to changes in charge recombination with the increasing LET from basically geminate recombination to predominantly cross combination. The iodine scavenging results are similar in the three systems which is attributed to the basically diffusion controlled character of the competing reactions. (author)

Free-radical coupling, cleavage, and redox reactions in 60Co γ radiolysis of aqueous methyl acetate. Effects of additives

International Nuclear Information System (INIS)

Bernath, T.; Parsons, G.H. Jr.; Cohen, S.G.

1975-01-01

Reaction of methyl acetate with e - /sub aq/ may lead to CH 3 C(O )OCH 3 (I - ), CH 3 C(OH)OCH 3 (II), and CH 3 CO (IIA), and with .OH and H. to .CH 2 CO 2 CH 3 (III), and to CH 3 CO 2 CH 2 . (IV). Methyl acetate is consumed, G = --3.5, and the loss is decreased by formate which scavenges .H and .OH, and increased by N 2 O which converts e - /sub aq/ to .OH. Hydrogen is formed, G = 1.1, and this is decreased by scavengers for H., and increased by H + which converts e - /sub aq/ to H.. In radiolysis of 0.027 M methyl acetate, 1.5 x 10 22 ev/l., radical combination products are: ethylene diacetate (CH 3 CO 2 CH 2 CH 2 OCOCH 3 ) (EDA), G = 0.48, from IV + IV; methyl β-acetoxypropionate (CH 3 CO 2 CH 2 CH 2 CO 2 CH 3 ) (MAP), G = 0.28, from IV + III; dimethyl succinate (DMS), G = 0.05, from III + III; and a mixture of methyl acetoacetate and acetonyl acetate (MAA and AA), (MAS and AA), G = 0.07. Biacetyl is not observed. β-Mercaptopropionic acid, 0.0005 M, prevents formation of coupling products, as it reduces radicals III and IV, and thiyl radical oxidizes radical II back to methyl acetate. Other sources of .OH, Fenton's reagent and H 2 O 2 -uv, lead to EDA, MAP, and DMS with a high IV/III ratio. H. preferentially attacks acyl C--H; .OH preferentially attacks alkoxyl C--H. Yields of radicals involved in formation of coupling products and acetic acid are estimated: G(II and IIA) = 1.2; G(III) = 1.4; G(IV) = 1.7. Part of the radicals, G approximately 1.6, regenerate methyl acetate by self-repair reduction of IV and III by II. Deuterium is introduced into methyl acetate during radiolysis in D 2 O. (U.S.)

Study on radiolysis products of N,N,N',N'-tetrabutyl-3-oxa-pentanediamide. Pt.1: Qualitative and quantitative analysis of dibutylamine

International Nuclear Information System (INIS)

Zhang Xiaolan; Shanghai Univ., Shanghai; Bao Borong; Shanghai Univ., Shanghai; Yang Yanqin; Ye Guoan; Zhang Xianye

2005-01-01

The study on radiolysis products of gamma-irradiated N,N,N',N'-tetrabutyl-3-oxa-pentane-diamide (TBOPDA) is very useful towards the extractant stability. IR and headspace solid-phase microextraction combined with gas chromatography/mass spectrometry (SPME-GC/MS) are used in the research. By comparisons with standard substances, dibutylamine and N,N-dibutylformamide are comfirmed to be the major radiolysis products. The influences of irradiation on TBOPDA and dibutylamine are quantitated by using headspace SPME-GC and HPLC. According to the experiment results, the possible ways of degradation are also proposed. (authors)

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

Energy Technology Data Exchange (ETDEWEB)

Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

1981-02-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

International Nuclear Information System (INIS)

Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

1981-01-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

Diffusion-kinetic theories for LET effects on the radiolysis of water

International Nuclear Information System (INIS)

Pimblott, S.M.; LaVerne, J.A.

1994-01-01

Diffusion-kinetic methods are used to investigate the effects of incident particle linear energy transfer (LET) on the radiolysis of water and aqueous solutions. Chemically realistic deterministic diffusion-kinetic calculations examining the scavenging capacity dependences of the scavenged yield of e aq - and of OH demonstrate that the scavenged yields are related to the underlying time-dependent kinetics in the absence of the scavenger by a simple Laplace transform relationship. This relationship is also shown to link the effect of an e eq - scavenger on the formation of H 2 with the time dependence of H 2 production in the absence of the scavenger. The simple Laplace relationship does not work well when applied to H 2 O 2 formation in high-LET particle tracks even though such a relationship is valid with low-LET particles. It is found that while the secondary reaction of H 2 O 2 with e aq - can be neglected in low-LET particle radiolysis, it is of considerable significance in the tracks produced by high-LET particles. The increased importance of this reaction with increasing LET is the major reason for the failure of the Laplace relationship for H 2 O 2 . 55 refs., 9 figs., 2 tabs

Verification of computer code for calculation of coolant radiolysis in the VVER reactor core with regard for boiling in its upper part

Energy Technology Data Exchange (ETDEWEB)

Arkhipov, O.P.; Kabakchi, S.A. [OKB Gidropress, Podolsk, Moscow (Russian Federation)

2010-07-01

Code Bora for WWER coolant radiolysis calculation considering single jets boiling in the reactor core top part is developed on the basis of computer codes MOPABA-H2 (radiolysis of aqueous solutions) and SteamRad (radiolysis of vapor). Physico-chemical processes taking place in boiling core coolant are complex and diversified. Still, for the solution of certain problems their simulation can be simplified. The approach of reasonable simplification was used for development of code Bora: mathematical model assumed is purposed for simulation of phenomena only in the area of interest; the number of simulated chemical reactions and particles shall be reasonably minimum; complexity of interphase mass transfer calculation procedure shall be adequate to actually available accuracy of modeling. The analysis of new experimental initial yields of water radiolysis products data and kinetic parameters of elementary chemical reactions with their participation has been carried out. Some changes have been introduced in the mechanism of liquid water and aqueous solutions of ammonia radiolysis have been significantly revised on the basis of this analysis. Examples of the calculations provided for code Bora verification are presented. Despite of very simple simulation of interphase mass transfer, Bora allows to obtain average chemical composition of two-phase coolant at BWR core outlet with the accuracy sufficient for engineering calculations. The report also presents the results of two-phase coolant chemical composition test calculation for reactor core top part coolant boiling in pressurized water reactor. (author)

Current state of knowledge of water radiolysis effects on spent nuclear fuel corrosion

International Nuclear Information System (INIS)

Christensen, H.; Sunder, S.

2000-07-01

Literature data on the effect of water radiolysis products on spent-fuel oxidation and dissolution are reviewed. Effects of gamma radiolysis, alpha radiolysis, and dissolved O 2 or H 2 O 2 in unirradiated solutions are discussed separately. Also, the effect of carbonate in gamma-irradiated solutions and radiolysis effects on leaching of spent fuel are reviewed. In addition, a kinetic model for calculating the corrosion rates of UO 2 in solutions undergoing radiolysis is discussed. The model gives good agreement between calculated and measured corrosion rates in the case of gamma radiolysis and in unirradiated solutions containing dissolved oxygen or hydrogen peroxide. However, the model fails to predict the results of alpha radiolysis. In a recent study , it was shown that the model gave good agreement with measured corrosion rates of spent fuel exposed in deionized water. The applications of radiolysis studies for geologic disposal of used nuclear fuel are discussed. (author)

Detecting the formation of products of radiolysis of tryptophan in foods rich in protein and irradiated with γ rays

International Nuclear Information System (INIS)

Kleeberg, K.K.; Wickern, B. van; Simat, T.J.; Steinhart, H.

1999-01-01

N-formyl kynurenine (NFK), OIA and the four hydroxytryptophan isomers (4-, 5-, 6- and 7-OH-TRP) were found as the major radiolysis products in γ-ray irradiated solutions containing tryptophan, in tripeptides and lysozyme. Their identification was achieved by enzymatic hydrolysis with pronase E under mild conditions (40 C, 30-60 min), applying electrochemical methods and RP-HPLC and uv fluroscence methods. Highly significant dissimilarity of results was shown for all the radiolysis products found in the specimens irradiated with 1.3 or 5 kGy and in non-irradiated samples. For release of the radiolysis products from protein-rich foods (egg white, white chicken meat, North Sea shrimps), a two-stage enzymatic hydrolytic process was developed, using proteinase K and carboxypeptidase A for egg white and chicken meat, and proteinase K and pronase E for the shrimps. The four OH-TRP isomers could be detected and quantified in all specimens. The contents varied from 0.02 to 1.97 mg/kg of proteine. Significant deviation of results between irradiated and non-irradiated specimens of egg white and chicken meat could be detected as from an applied dose of 3 kGy. In the shrimps, deviations were evident only at applied doses of 5 kGy. (orig./CB) [de

OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products-A gamma radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Krimmel, Birgit; Swoboda, Friederike [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Reznicek, Gottfried [Department of Pharmacognosy, Althanstrasse 14, A-1090 Vienna (Austria)

2010-12-15

The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH{sub 3} by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

Gamma radiolysis of C 6F 6, product formation

Science.gov (United States)

Sagert, Norman H.; LeBlanc, Jacques C.; Wood, Donald D.; Kremers, Walter; Westmore, John B.; Buchannon, Wayne D.

The γ radiolysis of perfluorobenzene (PFB) has been studied at a dose rate of about 26 Gy · s -1 and at total doses up to 10 5 Gy. Radiolyses were carried out in fluorine-passivated nickel cells in the absence of air. There were no significant gas yields, but higher molecular weight products were observed and characterized by combined gas chromatography and mass spectrometry (GC/MS). These higher molecular weight products included decafluorobiphenyl (DFBP), but more highly fluorinated dimers were produced with higher yields. Higher oligomers were formed in significant yields, and the trimer was especially prominent. Polymers with molar masses up to and exceeding 1500 (which corresponds to octamers) were observed by GC/MS, although their yields were small. The yield of all polymers totalled 1.7 molecules of PFB consumed for each 100 eV absorbed. This result is comparable to yields measured by earlier workers at much higher doses and dose rates.

Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

DEFF Research Database (Denmark)

Langer, S.; Ljungström, E.; Ellermann, T.

1995-01-01

UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

Picosecond radiolysis of ionic liquids

International Nuclear Information System (INIS)

Funston, A.M.; Wishart, J.F.; Neta, P.; Lall, S.I.; Engel, R.

2003-01-01

Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in nuclear fuel and waste processing, energy production, improving the efficiency and safety of industrial chemical processes, and pollution prevention. Ionic liquids are completely nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. An understanding of the radiation chemistry of ionic liquids is important for development of their applications in radioactive material processing and for the application of pulse radiolysis techniques to the general study of chemical reactivity in ionic liquids. Kinetic studies with a picosecond electron accelerator, such as the BNL Laser-Electron Accelerator Facility (LEAF), allow one to observe primary radiation products and their reactions on short time scales. For example, the solvated electron lifetime in neat methyltributylammonium bis(trifluoromethylsulfonyl)imide is ∼300 ns and its absorption maximum is ∼1400 nm. Kinetic studies of primary radiolytic products and their reactivities will be described for several types of ionic liquids. Supported in part by the U.S. Department of Energy, Division of Chemical Sciences, Office of Basic Energy Sciences, under contract DE-AC02-98-CH1088

The radiolysis of lithium oxide ceramics

Energy Technology Data Exchange (ETDEWEB)

Tiliks, J; Supe, A; Kizane, G; Tiliks, J Jr [Latvia Univ., Riga (Latvia). Dept. of Chemistry; Grishmanov, V; Tanaka, S

1998-03-01

The radiolysis of Li{sub 2}O ceramics exposed to accelerated electrons (5 MeV) at 380 K was studied in the range of high absorbed doses up to 250 MGy. The formation of radiation defects (RD) and radiolysis products (RP) was demonstrated to occur simultaneously in the regions of (1) the regular crystalline lattice and (2) an enhanced content of the intrinsic defects and impurities. The production of the electronic RD and RP is more efficient in the region of the defected lattice than that at the site of the regular crystalline lattice. However, the stability of RD and RP formed in the region of the intrinsic defects is far less than those produced at the crystalline lattice, since most of the first mentioned RD and RP disappears with irradiation dose due to the radiation stimulated recombination. By this means the enhanced quantity of RD and RP is localized in the Li{sub 2}O ceramics irradiated to absorbed dose of 40-50 MGy, and hence this can influence the tritium release parameters. As soon as the intrinsic defects have been consumed in the production of RD and RP and the recombination of unstable electronic RD and RP takes place (at dose of {approx}100 MGy), the radiolysis of Li{sub 2}O ceramics occurs only at the crystalline lattice. Furthermore, the concentration of RD and RP increases monotonically and tends to the steady-state level. (author)

Laser Flash Photolysis and Pulse Radiolysis of Iodate and Periodate in Aqueous Solution

DEFF Research Database (Denmark)

Kläning, U K; Sehested, Knud; Wolff, Thomas

1981-01-01

photolysis study of IeVI and I0VI suggests that the predominant IeVI and I0VI species formed are IO42– and IO3 at 3 12. Redox reactions of the iodine(VI) species are fast compared with interconversion among the various iodine(VI) species......Species containing iodine in oxidation state six are formed by photolysis and radiolysis of aqueous iodate and periodate solutions in the following reactions: IO3–+ O–→ IO42–; IO3–+ OH → IO3; IVII+ eaq–→ IeVI and IVII [graphic omitted] I0VI+ O–(or OH). The present pulse radiolysis and laser flash...

Products of aqueous vitamin B5 (pantothenic acid) formed by free radical reactions

International Nuclear Information System (INIS)

Schittl, H.; Quint, R.M.; Getoff, N.

2007-01-01

The radiolysis of aqueous vitamin B5 (pantothenic acid) has been investigated under various experimental conditions. The highest vitamin degradation (G=3.22) was observed in solutions saturated with N 2 O, where 90% OH radicals are operating. As final products, the following were established: aldehydes, carboxylic acids and ammonia. Their yield strongly depends on the presence/absence of air as well as on N 2 O (used to convert e aq - into OH) and was determined as a function of absorbed radiation dose. HPLC-analysis showed that in all media, a main product is formed, having the highest yield in aerated solutions. Based on the chemical analysis, it appears that the OH radicals are most involved in the degradation process. A precise sequence of the reaction steps could not be given presently, because of the implication of many simultaneous reactions

Analysis of low-molecular weight radiolysis products in extracts of gamma-irradiated polymers by gas chromatography and high-performance liquid chromatography

International Nuclear Information System (INIS)

Buchalla, Rainer; Begley, Timothy H.; Morehouse, Kim M.

2002-01-01

Estimating exposure to radiolysis products of polymers is an important part of the regulatory evaluation of packaging materials for use in food irradiation. However, as Koni Grob recently put it, the comprehensive analysis of migrants is a challenge. This paper discusses some of the analytical difficulties and presents results obtained with extracts of irradiated polystyrene and polyamide-6. The results indicate that headspace or thermal desorption techniques may, in some instances, lead to an overestimation of radiolysis product concentrations. It is concluded that validated analytical methods and a better understanding of the underlying radiation chemistry would greatly facilitate the safety assessment of irradiated packaging materials

Radiolysis of aqueous solutions of ammonium bicarbonate over a large dose range

International Nuclear Information System (INIS)

Draganic, Z.D.; Draganic, I.G.; Negron-Mendoza, A.; Navarro-Gonzales, R.; Albarran-Sanchez, M.G.; Sehested, K.

1986-12-01

0 2 -free aqueous solutions of 0.05 mol dm -3 ammonium bicarbonate were studied after receiving various doses of 60 Co gammas (0.001-170 Mrd) or krd pulses of 10 MeV electrons. Formate, oxalate, formaldehyde and an unidentified polymer (M w 14000-16000 daltons) were found to be the main radiolytic products. A large initial yield of formate in the γ-radiolysis, G(HCOO - ) = 2.2, is due to the reaction CO 2 - + HCO 3 - ↔ HC00 - + CO 3 - . The efficiency of organic synthesis within the large dose range studied is low and is explained by efficient pathways to the reformation of bicarbonate, where the reaction CO 2 - + CO 3 - is particurlarly significant. Computer fitting of the data obtained in the γ-radiolysis and by pulsed electron beam experiments gives k(CO 2 - + HCO 3 - ) = (2 ± 0.4)x10 3 dm 3 mol -1 s -1 , k(CO 2 - + CO 3 - ) = (5 ± 1)x10 7 dm 3 mol -1 s -1 , k(NH 2 + = HCO 3 - ) 4 dm 3 mol -1 s -1 and k(NH 2 + CO 3 - ) = (1.5 ± 0.5)x10 9 dm 3 mol -1 s -1 . (author)

The bimolecular reaction of radiolysis product of hydrated electron at temperature up to 473K; Reaksi bimolekular antar produk radiolisis elektron terhidrasi pada temperatur hingga 473K

Energy Technology Data Exchange (ETDEWEB)

Sunaryo, G R [Reactor Safety Technology Research Centre, National Atomic Energy Agency, Serpong (Indonesia)

1996-06-01

Rate constant from the bimolecular reaction of hydrated electron was determined by using radiolysis method. The methanol solution with concentration of 5 x 10{sup -2} dm{sup 3} mol{sup -1} was used as a scavenger of H and OH radicals. The pH was kept by adding the buffer solution of 1.0 x 10{sup -3} dm{sup 3} mol{sup -1} Na{sub 2}HPO{sub 4} + 1.0 x 10{sup 4} dm{sup 3} mol{sup -1} NaH{sub 2}PO{sub 4}. The irradiation was done by using the electron beam which come from linear accelerator 28 MeV with pulse width 10ns and dose of 80 Gy per pulse. The absorbance of hydrated electron was observed at wavelength of 824 nm. By using the kinetic equation the rate reaction constants were obtained. The bimolecular reaction of hydrated electron increase with temperature up to 423K. The activation energy was 19.3 kJ mol{sup -1} and the 2 k (298K) was 1.1 x 10{sup 10} dm{sup 3} mol{sup -1}. Then this bimolecular reaction decrease at temperature higher than 423K and the rate reaction constant at 473K almost similar with that at 298K. (author)

Gamma radiolysis of alkaline aqueous solutions of neptunium and plutonium ions

International Nuclear Information System (INIS)

Pikaev, A.K.; Gogolev, A.V.; Shilov, V.P.

1998-01-01

Full text: The paper is a brief review of data obtained by the authors from the study on redox reactions of neptunium and plutonium ions upon γ radiolysis of their aerated alkaline aqueous solutions. It includes the information on radiolytic reduction of Np(V), Np(VI) and Pu(VI) ions under various experimental conditions. It was found that the values of Np(VI) and Pu(VI) reduction yields do not depend on alkali concentration. The values considerably increase in the presence of some organic compounds (EDTA and formate were investigated). The formation of the Np(V) peroxo complex was observed in the γ radiolysis of alkaline aqueous solutions of Np(VI) and Np(V) in the presence of nitrate. The mechanism of radiolytic redox reactions of the ions is discussed in some detail

Free radicals generated by radiolysis of aqueous solutions

International Nuclear Information System (INIS)

Schwarz, H.A.

1981-01-01

The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

Pulse Radiolysis of Aqueous Solutions of Aniline and Substituted Anilines

Energy Technology Data Exchange (ETDEWEB)

Christensen, H C

1971-07-01

The primary reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals with aniline and the aniline cation in aqueous solutions have been studied by the technique of pulse radiolysis and by determination of end products after y-radiolysis. Hydrogen atoms and hydrated electrons react with aniline under formation of the cyclohexadienyl type radical with absorption maximum at 355 nm and an extinction coefficient of 4100/M/cm. A similar radical formed by reaction of hydrogen atoms with the aniline cation has its absorption maximum at 31 0 nm and an extinction coefficient of 3200/M/cm. Hydrogen atoms react with the acid and neutral forms of aniline with rate constants of (1.3 +- 0.2 ) x 109/M/s and (2.9 +- 0.7) x 109/M/s, respectively. OH radicals react with aniline with a rate constant of (1.4 +- 0.3) x 1010/M/s under formation of the cyclohexadienyl radical with absorption maximum at 355 nm and the anilino radical with absorption maxima at 300 and 400 nm. The cyclohexadienyl radical decayed in a first order process with a rate constant of 1.4 x 105/s by elimination of NH{sub 3}, whereas the anilino radical disappeared in a second order reaction under formation of hydrazobenzene. O- radicals react with aniline at pH 13.3 with a rate constant of (3.1 +- 0.6) x 109 under formation of anilino radicals. The reaction of OH radicals with the aniline cation produced the anilino radical cation with a rate constant of (4.8 +- 0.8) x 109 . The absorption maximum was placed at 415 nm, The cyclohexadienyl type radical with absorption maximum at 350 nm was also found in aqueous solutions of 2-amino-1,3-dimethylbenzene but was not formed in solutions of N,N' -dimethylaniline

Pulse Radiolysis of Aqueous Solutions of Aniline and Substituted Anilines

International Nuclear Information System (INIS)

Christensen, H.C.

1971-01-01

The primary reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals with aniline and the aniline cation in aqueous solutions have been studied by the technique of pulse radiolysis and by determination of end products after y-radiolysis. Hydrogen atoms and hydrated electrons react with aniline under formation of the cyclohexadienyl type radical with absorption maximum at 355 nm and an extinction coefficient of 4100/M/cm. A similar radical formed by reaction of hydrogen atoms with the aniline cation has its absorption maximum at 31 0 nm and an extinction coefficient of 3200/M/cm. Hydrogen atoms react with the acid and neutral forms of aniline with rate constants of (1.3 ± 0.2 ) x 10 9 /M/s and (2.9 ± 0.7) x 10 9 /M/s, respectively. OH radicals react with aniline with a rate constant of (1.4 ± 0.3) x 10 10 /M/s under formation of the cyclohexadienyl radical with absorption maximum at 355 nm and the anilino radical with absorption maxima at 300 and 400 nm. The cyclohexadienyl radical decayed in a first order process with a rate constant of 1.4 x 10 5 /s by elimination of NH 3 , whereas the anilino radical disappeared in a second order reaction under formation of hydrazobenzene. O - radicals react with aniline at pH 13.3 with a rate constant of (3.1 ± 0.6) x 10 9 under formation of anilino radicals. The reaction of OH radicals with the aniline cation produced the anilino radical cation with a rate constant of (4.8 ± 0.8) x 10 9 . The absorption maximum was placed at 415 nm, The cyclohexadienyl type radical with absorption maximum at 350 nm was also found in aqueous solutions of 2-amino-1,3-dimethylbenzene but was not formed in solutions of N,N' -dimethylaniline

Primary processes during water radiolysis

International Nuclear Information System (INIS)

Pikaev, A.K.

1980-01-01

Briefly reviewed are investigations of primary process mechanism taking place during radiolysis of water and similar systems, executed by direct and indirect methods. A conclusion is made on the important role of the water structure during radiolysis of aqueous solutions of some substances. A necessity to take account of this factor during consideration of radiolysis theoretical models is pointed out

Radiolysis and radiosterilization of drugs

International Nuclear Information System (INIS)

Zeegers, F.; Crucq, A.S.; Gibella, M.; Tilquin, B.

1993-01-01

Can the absence of increased toxicological danger in irradiated foods be applied with confidence to drugs. The World Health Organization stated that up to 10 kGy there is no toxicological hazard. However, even if the irradiated drugs meet official standards, it would have to be established that any traces of radiolysis product formed are not toxic. All the tests from PHARMACOPEIA are not appropriate to detect the radiolysis and new physicochemical tests have to be used. Chromatographic detection of the radiosterilization of antibiotics may be advantageously used when the pharmaceuticals are not radio-resistant. The main obstacle to practical application is the low sensitivity of the detectors in liquid-liquid chromatography, a re-irradiation of the suspected samples will be necessary after preliminary chromatographic studies. 8 figs

Formation of carbonyl compounds in radiolysis of ethylene glycol in methanol

International Nuclear Information System (INIS)

Bezborodova, S.G.; Vetrov, V.S.; Kalyazin, E.P.; Korolev, V.M.; Salamatov, I.I.

1977-01-01

Radiolysis of diluted solutions of ethylene glycol has been investigated. It is shown that acetaldehyde, glycol aldehyde and formaldehyde are the main products of radiolysis of methanol solutions of ethylene glycol. Acetaldehyde and glycol aldehyde yields increase in radiolysis of methanol solutions of ethylene glycol with an increase of the original concentration of ethylene glycol and a temperature rise of radiolysis. Formaldehyde yields increase with the ethylene glycol concentration but decrease with a temperature rise (the formation of formaldehyde from methanol is taken into account). A mechanism of radiation-chemical transformations of ethylene glycol in methanol is explained. It is concluded that the main directions of ethylene glycol decomposition, detected in water solutions of ethylene glycol, are also realized in methanol solutions. However, a role of different directions of decomposition depends on the medium

Products of aqueous vitamin B5 (pantothenic acid) formed by free radical reactions

Energy Technology Data Exchange (ETDEWEB)

Schittl, H. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria); Quint, R.M. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria); Getoff, N. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria)]. E-mail: nikola.getoff@univie.ac.at

2007-10-15

The radiolysis of aqueous vitamin B5 (pantothenic acid) has been investigated under various experimental conditions. The highest vitamin degradation (G=3.22) was observed in solutions saturated with N{sub 2}O, where 90% OH radicals are operating. As final products, the following were established: aldehydes, carboxylic acids and ammonia. Their yield strongly depends on the presence/absence of air as well as on N{sub 2}O (used to convert e{sub aq} {sup -} into OH) and was determined as a function of absorbed radiation dose. HPLC-analysis showed that in all media, a main product is formed, having the highest yield in aerated solutions. Based on the chemical analysis, it appears that the OH radicals are most involved in the degradation process. A precise sequence of the reaction steps could not be given presently, because of the implication of many simultaneous reactions.

Radiolysis of aqueous solutions of ammonium bicarbonate over a large dose range

International Nuclear Information System (INIS)

Draganic, Z.D.; Negron-Mendoza, A.; Vujosevic, S.I.; Navarro-Gonzales, R.; Albarran-Sanchez, M.G.

1991-01-01

Oxygen-free aqueous solutions of 0.05 mol dm -3 ammonium and sodium bicarbonate were studied after receiving various doses of 60 Co gammas (0.01-400 kGy) or 0.5-20 Gy pulses of 10 Mev electrons. Formate and oxalate were found to be the main radiolytic products, in addition to trace amounts of formaldehyde and an unidentified polymer. A large initial yield of formate in the γ-radiolysis, G(HCOO - ) = 2.2, is due to the reaction COO - + HCO 3 - ↔ HCOO - +CO 3 - . The efficiency of organic synthesis within the large dose range studied is low and is explained by efficient pathways leading to the reformation of bicarbonate, where the reaction COO - + CO 3 - is particularly significant. (author)

GC-FTIR-MS analysis of volatile products in the radiolysis of nitrobenzene-carbon tetrachloride solution

International Nuclear Information System (INIS)

Kuruc, J.; Sahoo, M.K.; Kuran, P.

1993-01-01

A number of volatile products formed in the gamma-radiolysis of nitrobenzene-carbon tetrachlorine solution have been identified using a GC-FTIR-MS technique. The conditions for separation of the products have been described. HCL, COCl 2 chlorobenzene, chloro- and dichloronitrobenzene, isomeric di-, tri- and tetrachlorobenzene, hexachloroethane, tetrachloroethylene, α,α,α-trichloromethylbenzene, chloro-and dichloroisocyanatobenzene, and other chloroderivatives are among the important products formed. Ipso-substituion of the nitro group as well as hydrogen atom by chlorine atom and Cl 3 free radical is noticed. It is proposed that chloroisocyanatobenzene is formed as the result of interaction of dichlorocarbene and nitrobenzene. (orig.)

Radiolysis study of the radical-like action mechanisms of an antioxidant: Sulfarlem

International Nuclear Information System (INIS)

Ruimy-Ifrah, Pascale

1989-01-01

Sulfarlem or p-anisyldithiolthione (ADT) is a sulfured heterocyclic compound which exhibits antioxidant properties. This work presents the quantitative study of the mono-electronic exchange mechanisms involved in this action. This study has been performed by gamma radiolysis and pulse radiolysis. The gamma radiolysis of ADT aerated ethanolic solutions has shown that O 2 . and RO 2 . radicals are not reactive towards ADT. In return, ADT is an efficient scavenger of R . radicals; the rate constant of this reaction being k (ADT + R . ) = 6.7 x 10 4 mol -1 .l.s -1 . The pulse radiolysis experiments allowed the characterization of ADT reduction by the solvated electron (k (e solv - + ADT) = 2.3 x 10 10 mol -1 .l.s -1 ), the determination of the absorption spectrum of the reduced species A . (maximum wavelength = 580 nm) and the rate constant of its evolution (k (A . + A . ) = 5.7 x 10 8 mol -1 .l.s -1 ). An analogous study has been performed with ADO, an ADT oxidized derivative, which appeared to be a less efficient free radicals scavenger. (author) [fr

The effects of water radiolysis on the corrosion and stress corrosion behavior of type 316 stainless steel in pure water

International Nuclear Information System (INIS)

Wyllie, W.E. II; Duquette, D.J.; Steiner, D.

1994-11-01

In the ITER Conceptual Design Activity, water will be used as coolant for the major reactor components, which will be made of solution-annealed 316 SS. A concern is that the radiolysis products may increase the stress corrosion cracking (SCC) susceptibility of 316 SS. The corrosion and stress corrosion of 316 SS was observed under irradiated and nonirradiated conditions. Gamma irradiation produced a 100 mV potential shift in the active direction, probably from the polarizing effect of reducing radiolysis products. The irradiation also resulted in nearly an order of magnitude increase in the passive current density of 316 SS, probably from increased surface reaction rates involving radiolysis products as well as increased corrosion rates; however the latter was considered insignificant. Computer simulations of pure water radiolysis at 50, 90, and 130 C and dose rates of 10 18 -10 24 were performed; effects of hydrogen, argon, and argon + 20% oxygen deaeration were also studied. Slow strain rate suggest that annealed and sensitized 316 SS was not suscepible to SCC in hydrogen- or argon-deaerated water at 50 C. Modeling of irradiated water chemistry was performed. Open circuit potential of senstizied and annealed 316 SS had a shift of 800 mV in the noble (positive) direction. Steady-state potentials of -0.180 V for sensitized 316 SS wire and -0.096 V vs Hg/HgSO 4 for annealed 316 SS wire were independent of oxygen presence. The -0.180 V shift is likely to promote SCC

Radiolysis of carbohydrates as studied by ESR and spin-trapping—II. Glycerol- d8 xylitol, dulcitol, d-sorbitol and d-mannitol

Science.gov (United States)

Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.

Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.

Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Zona, Robert [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Sehested, Knud; Holcman, Jerzy [RISO National Laboratory Environmental Science and Technology Department, DK-4000, Roskilde (Denmark)

2010-05-15

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k({sup c}entre dotOH+substrates)=(4.5-6.2)x10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, have been studied by pulse radiolysis in N{sub 2}O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2k=(1-9)x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}. In the presence of N{sub 2}O/O{sub 2} the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O{sub 2})=(2-4)x10{sup 7} dm{sup 3} mol{sup -1} s{sup -1}, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N{sub 2}O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only approx60% of {sup c}entre dotOH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

Selective hydrogen atom abstraction by hydrogen atoms in photolysis and radiolysis of alkane mixtures at 770 K

International Nuclear Information System (INIS)

Miyazaki, T.; Kinugawa, K.; Eguchi, M.; Guedes, S.M.L.

1977-01-01

Selective hydrogen atom abstraction reaction by H atoms, has been found in Isobutane, 2,2,3,3-tetramethylbutane(TMB), cyclopropane matrices besides neopentane matrix. The selective hydrogen atom abstraction reaction in neopentane-isobutane mixture is affected by the difference of kinetic energies of H atoms. The reaction occurs more favorably with decreasing the kinetic energy of H atoms. Competitive reaction between c-C 6 H 12 and Hi for H atoms has been studied in the radiolysis and photolysis of neo-C 5 H 12 HI mixture at 77 K. The rate constants of these reactions in neopentane matrix are quite different from these of thermal H atom reaction, but similar to those of hot H atom reaction. Importance of the selective hydrogen atom abstraction reaction by H atoms is pointed out in the radical formation in the radiolysis of pure TMB at 77 K [pt

Gamma-radiolysis of dimethyl sulfoxide. II. Radiolysis yields and possible mechanisms

International Nuclear Information System (INIS)

Gutierrez, M. C.; Barrera, R.

1978-01-01

As result of quantitative studies on gamma-radiolysis of DMSO at a dose range of 90-850 Mrads, constant G values have been obtained for the following radiolysis compounds: G(-DMSO) - 6.7 ±0.2; G(dimethyl sulphide) - 3.4 ±0.3; G(methane) - 0,75 ± 0.04; G(dimethyl disulphide) -0.33 ±0,03; G(tri methylsulphonium methanesulphonate) - 0.26 ± 0,01; G(methyl methanethiosulphonate) - 0,25 ±0.02; G(dimethyl sulphona)-0.21±0.02; G(H 2 )-0.18±0.02; and G(propane)--0.0092±0.0007. Initial G values have been obtained for other identified compounds: Gi(ethane)-0,46; Gi(CO)-0.052; and Gi(CO 2 )-0.030. Possible mechanisms on the radiolysis process are proposed. (Author) 17 refs

Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

DEFF Research Database (Denmark)

Holcman, Jerzy; Sehested, Knud

1975-01-01

The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

Radiolysis of n-dodecane and its physical property change based on the dose in one pass through a reference high active (HA) column

International Nuclear Information System (INIS)

Ikeda, Hidematsu; Suzuki, Atsuyuki

1998-01-01

The radiolysis of n-dodecane which is used both as diluent and as scrub solution and its physical property change were studied by irradiation from a 60 Co γ-source under the relative condition of the HA column in Purex process. First, the radiation exposure of organic phase in one pass through the HA columns were calculated by using the reference HA columns. Then, the radiolysis of the commercial n-dodecane without purification was investigated under the several dose conditions based on the absorption in one pass through the reference HA columns. A large variety of additional n-alkane degradation products was observed and they were increased with dose. The G-value in lower exposure was a high yield, and the absolute G-value decreased with increasing radiation exposure to 1.01 W·h/l. Several expected inferable species from previous literature and three schemes for both principal radiolysis products and reaction of n-dodecane were suggested. These chemical products were probably formed in open system with gamma rays. The physical property change was also performed, and the effect of decomposition products on its change was small but not ignored. The annular with nozzle plates column diminished the absorbed dose in comparison with the other combination columns. (author)

Pulse radiolysis studies of the interaction of tea polyphenol derivatives with oxidizing OH adduct of thymine

International Nuclear Information System (INIS)

Jiang Yue; Li Hucheng; Yao Side; Zuo Zhihua; Wang Zailan; Zhang Jiashan; Lin Nianyun

1996-01-01

The electron transfer reactions between oxidizing OH adduct of thymine with tea polyphenol derivatives has been investigated by pulse radiolysis. The tea polyphenol derivatives are identified as good antioxidants for reduction of oxidizing OH adducts of thymine. From buildup kinetic analysis of radical phenoxyl product, the rate constants for reactions of the N 3 radical with tea polyphenol derivatives have been determined to be (8-9) x 10 9 dm 3 /mol s, while the rate constants of electron transfer from tea polyphenol derivatives to oxidizing OH adducts of thymine was obtained to be around 10 9 dm 3 /mol s. Copyright direct C 1996 Elsevier Science Ltd

Interaction study of water radiolysis products with Crotalus durissus terrificus miotoxin

International Nuclear Information System (INIS)

Silva, Murilo Casare da

2008-01-01

Ionizing radiation has been satisfactorily employed for venoms detoxification. In this report, the radiation was employed to verify the effects caused by the radiolysis products of water on the Crotamine, toxin purified from Crotalus durissus terrificus venom. These effects were analyzed using some substances called 'scavengers', those substances competes for specific reactive species hindering them to act on the toxins molecules. In order to study the possible structural damages caused on the toxins, circular dichroism, fluorescence, nuclear magnetic resonance, amino acids analysis and intravital microscopy were employed. Our results indicate that ionizing radiation caused structure alterations, mainly, in secondary and tertiary structure of crotamine. In the irradiated crotamine, was not possible to determine tridimensional structure. And the crotamine toxic effect was removed by ionizing radiation. (author)

Electron spin resonance of spin-trapped radicals of amines and polyamines. Hydroxyl radical reactions in aqueous solutions and. gamma. radiolysis in the solid state

Energy Technology Data Exchange (ETDEWEB)

Mossoba, M.M.; Rosenthal, I.; Riesz, P. (National Cancer Inst., Bethesda, MD (USA))

1982-06-15

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H/sub 2/O/sub 2/ and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ..gamma..-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the ..cap alpha..-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H/sub 2/O/sub 2/ in the dark. ..gamma..-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the ..cap alpha..-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine.

Effect of radiation parameters on the formation of radiolysis products in meat and meat substances

International Nuclear Information System (INIS)

Merritt, C. Jr.; Angelini, P.; Graham, R.A.

1978-01-01

Analytical chemical methods, employing gas and liquid chromatography for separation and mass spectrometry for identification, have been used to study the formation of radiolysis products in various meats such as beef and pork and in fats and proteins derived from meat. In this study the dependency of the amount of product formed in beef is evaluated as a function of various parameters such as radiation dose, dose rate, temperature of irradiation, precursor concentration, and various other factors. Statistical analysis of data accumulated from a large number of samples is provided by means of a laboratory automation computer. The significance of the data is assessed with particular regard to the wholesomeness of the irradiated product

Pulse radiolysis of Triton X-100 aqueous solution

International Nuclear Information System (INIS)

Perkowski, J.; Mayer, J.

1990-01-01

Pulse radiolysis of deaerated aqueous solutions of 4 · 10 -5 -2.4 · 10 -3 mol · dm -3 Triton X-100 gives rise to a transient species originating from the reactions of OH radicals and H atoms. The rate constants of these reactions were found to be 8.8 · 10 9 mol -1 · dm 3 · s -1 and 1.25 · 10 9 mol -1 · dm 3 · s -1 , respectively, for Triton X-100 concentrations below CMC. The corresponding transient species were found to decay according to second order kinetics. The mechanism of the reactions, including concentration effects is discussed. (author) 18 refs.; 3 figs

Pulse radiolysis of catalase in solution: Pt. 1

International Nuclear Information System (INIS)

Gebicka, Lidia; Metodiewa, Diana; Gebicki, J.L.

1989-01-01

The time-course of absorption changes of oxygen-saturated solutions of bovine-liver catalase after pulse radiolysis have been studied. The rate constant of formation of Compound I due to the reaction of catalase with hydrogen peroxide has been estimated to be 2.0 x 10 7 dm 3 mol -1 s -1 . Radiation generated super-oxide radicals reduce Compound I to Compound II with a rate constant of 5.0 x 10 6 dm 3 mol -1 s -1 . The formation of Compound III in the direct reaction of O 2 - with catalase has also been observed. (author)

Computer modeling of inhibition of α-radiolysis of water by H2 addition (NPC 2012 conference)

International Nuclear Information System (INIS)

Lertnaisat, Phantira; Katsumura, Yosuke; Mukai, Satoru; Umehara, Ryuji; Shimizu, Yuichi; Suzuki, Masaru

2012-09-01

It is known that α-radiolysis of water produces H 2 gas continuously. The addition of H 2 to water inhibits the water decomposition; H 2 evolution. In order to suppress the water decomposition, 25 cc H 2 STP/kg-H 2 O is added to the coolant water in PWR. However, the exact inhibition mechanism is still not made clear yet. In this project, the chemical kinetic simulation program, so called FASCIMILE, was used to reproduce the suppression of α-radiolysis of water by H 2 addition. By using three important factors; the decomposition (G-value), the reaction set and rate constants, and the dose rate, it is found that without hydrogen addition, the simulation shows the almost linear increase of molecular products; H 2 , H 2 O 2 , and O 2 . Nevertheless, as the additional hydrogen is added to the system, this behaviour of linear increase is shifted to longer time period. And up to certain concentration, the linear increase behaviour is completely suppressed and the molecular products reach the steady state condition at early time period and much lower concentration. The minimum concentration of H 2 which could completely suppress the decomposition of water is called Critical Hydrogen Concentration (CHC) and it is dose rate dependent value. The CHC is found to be dependent on the reaction set and rate constants. The simulation results show that the CHC at room temperature and dose rate of 1 kGy/s of the simulation done by using reaction set and rate constants obtained from Ershov et al. and AECL report 2009 are 165μM and 146μM, respectively. From the change of the behaviour of molecular products after reaching the CHC, the possible mechanism is proposed. First, the OH radical are formed via the reaction of H + H 2 O 2 → OH + H 2 O and e - aq + H 2 O 2 → OH+OH - . Then OH, which normally will react with H 2 O 2 to produced HO 2 , will react with the additional H 2 , which produce H to continue the chain reaction. The relation of chain reaction to the suppression of

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

International Nuclear Information System (INIS)

Mincher, B.J.; Groenewold, G.S.; Mezyk, S.P.

2016-01-01

The organophosphorus amide octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) is proposed for use in fuel cycle separations as a group actinide/lanthanide extractant. Alternative compounds such as the mono-amides and diglycol amides (DGAs) proposed for actinide and/or actinide/lanthanide extraction also contain the amidic functional group, but do not contain the CMPO aromatic or phosphoryl groups. Their radiation stability is in the order mono-amides > CMPO > DGA for irradiation under similar conditions. Although they produce similar radiolysis products, the kinetics of degradation for CMPO are completely different than for the other amides. CMPO degradation occurs in a zero-order fashion, and the -G-value for the change in [CMPO] is much lower when in the presence of acid. The DGAs and mono-amides degrade with pseudo-first-order kinetics and are not protected by acidity. Possible mechanistic reasons for the differences between CMPO and the other amides are discussed, as are the effects of the diluent and metal complexation on CMPO free radical reaction rates. Finally, it is also shown that α-irradiation has much less adverse effects on CMPO degradation than β/γ irradiation, both with respect to -G-values, and radiolysis product generation. (authors)

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Mincher, B.J.; Groenewold, G.S. [Idaho National Laboratory, PO Box 1625, Idaho Falls, ID 83415 (United States); Mezyk, S.P. [California State University at Long Beach, Long Beach, CA 90840 (United States)

2016-07-01

The organophosphorus amide octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) is proposed for use in fuel cycle separations as a group actinide/lanthanide extractant. Alternative compounds such as the mono-amides and diglycol amides (DGAs) proposed for actinide and/or actinide/lanthanide extraction also contain the amidic functional group, but do not contain the CMPO aromatic or phosphoryl groups. Their radiation stability is in the order mono-amides > CMPO > DGA for irradiation under similar conditions. Although they produce similar radiolysis products, the kinetics of degradation for CMPO are completely different than for the other amides. CMPO degradation occurs in a zero-order fashion, and the -G-value for the change in [CMPO] is much lower when in the presence of acid. The DGAs and mono-amides degrade with pseudo-first-order kinetics and are not protected by acidity. Possible mechanistic reasons for the differences between CMPO and the other amides are discussed, as are the effects of the diluent and metal complexation on CMPO free radical reaction rates. Finally, it is also shown that α-irradiation has much less adverse effects on CMPO degradation than β/γ irradiation, both with respect to -G-values, and radiolysis product generation. (authors)

Pulse Radiolysis of Adrenaline in Acid Aqueous Solutions

DEFF Research Database (Denmark)

Gohn, M.; Getoff, N.; Bjergbakke, Erling

1976-01-01

Pulse radiolysis of adrenaline in acid aqueous solutions (pH 1–3) was carried out. The rate constants for the reactions of adrenaline with H and OH were determined: k(H + adr.) = (0·9±0·1) × 109 dm3 mol−1s−1; k(OH + adr.) = (1·65±0·15) × 1010 dm3 mol−1s−1. The H-adduct of adrenaline has two λmax...

Gamma-radiolysis of aqueous solutions of methyl orange and chrysoidine

International Nuclear Information System (INIS)

Khabarov, V.N.; Kozlov, L.L.; Panchenkov, G.M.

1980-01-01

Radiation-chemical bleaching of azo dyes of methyl orange and chrysoidine in aqueous and aqueous-alcoholic solutions under the effect of γ-radiation of 60 Co is studied. The effect of different additions and pH value of medium upon radiolysis of azo dyes is investigated. Radiation-chemical yields of the bleaching are determined. Quantitative connection between the initial yields of water radiolysis products and radiation yields of the bleaching of azo dyes is established. On the basis of the results obtained the most probable mechanism of methyl orange and chrysoidine bleaching is suggested

Pulse radiolysis studies of proline-ninhydrin complex

Energy Technology Data Exchange (ETDEWEB)

Barik, A; Priyadarsini, K I [Radiation and Photochemistry Division, Behabha Atomic Research Centre, Trombay, Mumbai (India); Prabhakar, K R; Veerapur, V P; Unnikrishnan, M K [Department of Pharmacology, Manipal College of Pharmaceutical Sciences (India)

2006-07-01

Proline-Ninhydrin (PN) complex has earlier been reported by us to be an excellent free radical scavenger and also examined for in vitro and in vivo radioprotection. Here we present mechanism of reaction of PN complex with hydroxyl ({sup .}OH) radicals and other oxidants and compared the results with proline and ninhydrin independently. PN complex was prepared by mixing in 1:1 stoichiometric ratio of proline and ninhydrin in a ball mill at 40 degree C and purified by crystallisation. Parent absorption spectra of PN complex show peak at 300 nm and 304 nm with a ground state pK{sub a} of 9.3. The reaction of {sup .}OH radical and other one-electron oxidants were studied using 7 MeV electron pulses from LINAC and the dose determined by aerated KSCN dosimeter. {sup .}OH radical reaction with PN studied at pH 6.8 produced a transients having broad absorption band at 400 nm. The reaction of {sup .}OH with PN complex was found to be dependent on the pH of the solution, at pH > 8 the transient absorption band shifted to 360 nm. The pK{sub a} of the transient was measured by following these absorption changes with varying the pH from 2 to 11 to be 6.9. OH radical reactions with the organic substrates is non-selective in nature and in order to establish the nature of the transient absorption band, pulse radiolysis studied were carried out with specific one electron oxidants, SO{sub 4}{sup .-} radical and Cl{sub 2}{sup .-} radical, which showed the transient absorption band with maximum at 440 nm and 350 nm respectively, indicating that the reaction {sup .}OH with PN complex at pH 7 is not by oxidation but by addition reaction to the aromatic ring. The reaction of H atom with PN complex was carried out in presence of tert-butanol at pH 1. The transient showed similar spectrum as observed with reaction OH radical reaction. As the H atom proceeds through mostly abstraction reaction, the transient formed by H atom and OH radical at low pH produces H atom abstracted species of the

Pulse radiolysis study of the intermediates formed in ionic liquids. Intermediate spectra in the p-terphenyl solution in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide

International Nuclear Information System (INIS)

Grodkowski, J.; Kocia, R.; Mirkowski, J.

2006-01-01

Room temperature ionic liquids (Il) are non-volatile,and non-flammable and serve as good solvents for various reactions, mainly for g reen processing . To understand the effect of these solvents on the chemical reactions, the rate constants of several elementary reactions in ionic liquids have been studied by the pulse radiolysis technique. In this study, the formation of intermediates derived from p-terphenyl (Tp) in the ionic liquid methyl tributylammonium bis[(trifluoromethyl)sulfonyl] imide (R 4 NNTf 2 ) solutions have been studied by pulse radiolysis as a part of broader studies concerning CO 2 reduction. The registered spectra can be explained by CO 2 reaction with solvated and dry electrons thus eliminating one path of TP ·- formation. Some TP ·- are formed by reaction of excited TP *- states with Tea. Direct reactions involving Tp, TP ·- , CO 2 and CO 2 ·- are too slow to be observed in pulse radiolysis time scale

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

The fate of primary cations in radiolysis of alkanes as studied by ESR

International Nuclear Information System (INIS)

Iwasaki, M.; Toriyama, K.; Nunome, K.

1983-01-01

The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

Gamma-radiolysis of methanol solutions of Mo(CO)/sub 6/ at room temperature

Energy Technology Data Exchange (ETDEWEB)

Dziegielewski, J O; Gil, R; Glowacki, P [Uniwersytet Slaski, Katowice (Poland)

1982-02-04

Radiation decomposition yields of Mo(CO)/sub 6/ in methanol solutions saturated with argon, N/sub 2/O and in alkaline solutions saturated with argon were measured. The results indicate the interaction of Mo(CO)/sub 6/ with esub(s)sup(-) and CH/sub 2/O/sup -/. The rate constants for these reactions were calculated to be 1.65x10/sup 9/ l x mol/sup -1/ x s/sup -1/ and 2.76x10/sup 7/ l x mol/sup -1/ x s/sup -1/, respectively. On the basis of the spectrophotometrical measurements in the UV-VIS and IR ranges, the stable products of radiolysis were determined.

Radiolysis of simple quaternary ammonium salt components of Amberlite resin

International Nuclear Information System (INIS)

Dhiman, Surajdevprakash B.; LaVerne, Jay A.

2013-01-01

The radiation chemical yields of gaseous products, H 2 and CH 4 , in the radiolysis of dry methylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, tetramethylammonium chloride and benzyl trimethylammonium chloride by γ-rays and 5 MeV helium ions have been investigated. Some of these amines are the different components of the quaternary ammonium resin Amberlite, which is a strongly basic anion exchange resin based on a polystyrene divinylbenzene copolymer. Molecular hydrogen yields with γ-radiolysis range from a high of 4.43 molecules per 100 eV for trimethylammonium chloride to 0.07 and 0.05 molecules per 100 eV for tetramethylammonium chloride and benzyl trimethylammonium chloride, respectively. Yields of methane gas are generally negligible except for trimethylammonium chloride and tetramethylammonium chloride, 0.26 and 0.02 molecules per 100 eV, respectively. Isotopic labeling studies suggest that the first step in H 2 production is the breakage of the N-H bond followed by abstraction of H · atom from the methyl groups. EPR analysis shows the formation of both N and C centered radicals. A comparison is made between the radiolysis of Amberlite and its various components

Kinetics of the gas-phase tritium oxidation reaction

International Nuclear Information System (INIS)

Failor, R.A.

1989-01-01

Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

Study of the effect of water radiolysis on zirconolite dissolution

International Nuclear Information System (INIS)

Tribet, M.

2007-09-01

conditions (solid irradiation or not). The behaviour of Ti and Zr is enhanced (about 100 times) in presence of complexing species such as fluoride ions. Nevertheless, the alteration remains very weak, even in presence of complexing species and is sorely observable on the solid surface. Elementary releases are first kinetically controlled: if we base on Nd releases, the dissolution under radiolytic conditions is about 5 orders of magnitude higher than out of radiolysis. However, this kinetic step is shorter, a couple of hours, compared to a couple of days out of radiolysis. When there is only water radiolysis, a thermodynamic step is then observed as soon as the leachate is saturated in respect to the Zr and Ti hydroxides phases: elemental releases then become constant. When the solid is also irradiated, colloids are observed, although the leachate is not saturated in respect with hydroxides phases. The formation of these colloids could arise from chemical equilibriums modification induced by ionizations occurring in the solid during its irradiation. The radiolytic production of H 2 O 2 is lower than predicted by the calculated primary yield, because of the consumption of H 2 O 2 or its precursors by chemical reactions involving others radiolytic species such as H2 or the aqueous electron. (author)

Alpha Radiolysis of Sorbed Water on Uranium Oxides and Uranium Oxyfluorides

Energy Technology Data Exchange (ETDEWEB)

Icenhour, A.S.

2003-09-10

The radiolysis of sorbed water and other impurities contained in actinide oxides has been the focus of a number of studies related to the establishment of criteria for the safe storage and transport of these materials. Gamma radiolysis studies have previously been performed on uranium oxides and oxyfluorides (UO{sub 3}, U{sub 3}O{sub 8}, and UO{sub 2}F{sub 2}) to evaluate the long-term storage characteristics of {sup 233}U. This report describes a similar study for alpha radiolysis. Uranium oxides and oxyfluorides (with {sup 238}U as the surrogate for {sup 233}U) were subjected to relatively high alpha radiation doses (235 to 634 MGy) by doping with {sup 244}Cm. The typical irradiation time for these samples was about 1.5 years, which would be equivalent to more than 50 years irradiation by a {sup 233}U sample. Both dry and wet (up to 10 wt % water) samples were examined in an effort to identify the gas pressure and composition changes that occurred as a result of radiolysis. This study shows that several competing reactions occur during radiolysis, with the net effect that only very low pressures of hydrogen, nitrogen, and carbon dioxide are generated from the water, nitrate, and carbon impurities, respectively, associated with the oxides. In the absence of nitrate impurities, no pressures greater than 1000 torr are generated. Usually, however, the oxygen in the air atmosphere over the oxides is consumed with the corresponding oxidation of the uranium oxide. In the presence of up to 10 wt % water, the oxides first show a small pressure rise followed by a net decrease due to the oxygen consumption and the attainment of a steady-state pressure where the rate of generation of gaseous components is balanced by their recombination and/or consumption in the oxide phase. These results clearly demonstrate that alpha radiolysis of either wet or dry {sup 233}U oxides will not produce deleterious pressures or gaseous components that could compromise the long-term storage of

A pulse radiolysis study of emulsion polymerization

International Nuclear Information System (INIS)

McAskill, N.A.

1976-01-01

The emulsion polymerisation of slightly water soluble monomers such as styrene occurs initially in micelles of surfactant swollen with monomer and later in larger particles consisting of polymer swollen with monomer and stabilized with an outer layer of surfactant. There is considerable controversy on whether the reaction sites of polymerization are inside or on the surface of the particle or micelle. The relative amounts of micelle and particles present at various stages of the polymerization are also nuclear. In the present study the OH radical formed by pulse radiolysis has been used as a probe to investigate the site of solubilization of styrene in various surfactant micelles. Two products can be distinguished by UV spectrometry, a benzyl type radical formed by OH addition to the side chain of styrene and a cyclohexadienyl type radical formed by addition to the ring. Wide differences in the relative amounts of each product were observed suggesting that in some surfactants the styrene ring is buried inside the micelle whilst in other systems the styrene appears to be so solubilized at the interface leaving both the ring and the side chain open to attack by the OH radical. (author)

Radiolysis of polytetrafluoroethylene

International Nuclear Information System (INIS)

Ferreira, Max Passos; Ferreira, Roberta Viana; Verly, Rodrigo Moreira

2007-01-01

Polytetrafluoroethylene is a linear polymer with structure: -[-CF 2 -CF 2 -] n -. Due to its singular properties, it is ideal for use at high temperatures and in chemically aggressive environments. It is extremely sensitive to ionizing radiation and is quickly degraded. PTFE radiolysis has been extensively studied. However, despite the many published papers, its degradation mechanism remains much uncertain. The degradation of polytetrafluoroethylene by γ irradiation yields perfluorinated carboxylic acids, olefin mixtures, and paraffins with different molecular weights. This process is a new alternative for the synthesis of aliphatic perfluorinated compounds used as intermediates for obtaining special products such as fluoro surfactants, electrical materials, special products for the textile industry, etc. PTFE scraps were irradiated with a uniform source of 60 Co gamma rays in oxygen atmosphere with a dose of 3 MGy. The radiolysis of PTFE yielded a water soluble material (probably fluorinated hydrocarbons with low molecular weight and main chains with 10-20 carbon atoms) and a water insoluble brittle polymeric material. Spectroscopy analysis in the infrared region of irradiated and non-irradiated PTFE were carried out. X-ray diffractometry pointed to changes in the crystalline structure of PTFE; scanning electron microscopy indicated alterations in samples irradiated under different conditions. Mass spectrometry was also used to identify the compounds formed after sample irradiation. Comparison of irradiated and non-irradiated FTIR spectra showed the formation of bands at 3450 cm -1 , associated with the O-H stretching, and at 1631 cm -1 , associated with the C=O stretching. The bands are characteristic of carboxylic acid, which indicates its formation in irradiated PTFE. (author)

Pulse radiolysis for the study of lead salt solutions

International Nuclear Information System (INIS)

Breitenkamp, M.

1976-01-01

The Pb + ions are produced from Pb 2 + in lead perchlorate solutions by reduction with hydrated electrons, and the absorption spectrum of this ion has been measured together with a time differential observation in the micro- and millisecond range of the disparation of these ions from the solution in the presence of different substances. For these studies the method of pulsed radiolysis has been applied, detecting the short lifed intermediate reaction products by optical absorption and electric conductivity measurements. First an attempt has been made to produce the Pb + ions also by reduction of Pb 2 + with H-atoms. If Pb + and H is produced simultaneously in an aqueous solution the reaction Pb + + H -> PbH + can occur. The absorption spectrum of the short lifed species PbH + has been studied together with the second order evanescence. In addition Pb 2 + has been reduced by i-propanol radicals at high Pb 2 + concentrations. The second order evanescence has been observed and the rate constant of the reaction 2Pb + -> Pb + Pb 2 + has been measured. The Pb 2 + ions can also be reduced by CO 2- radicals, which are formed in the presence of formiate. The observations can be interpreted by the assumption of the primary reaction Pb 2 + + CO 2- -> PbCO 2+ . the spectrum of the product PbCO 2+ has been measured. A second order reaction of PbCO 2+ is observed with a resulting unstable particle of the structure Pb 2 CO 2 2 + . Finally the oxidation of Pb + by the OH-radical and by hydrogen peroxide has been studied. (orig./HK) [de

Radiolysis in nature: Evidence from the Oklo natural reactors

International Nuclear Information System (INIS)

Curtis, D.B.; Gancarz, A.J.

1983-02-01

An examination of the mineralogy of the reactor zones at Oklo shows that they have been significantly altered. The rocks immediately adjacent to these zones are also mineralogically modified with respect to normal uranium bearing rocks. The mineralogic changes appear to be the consequence of radiation damage, changes in the bulk chemistry of the system and increased temperatures. Chemical changes were the consequence of convectively circulating fluids that transported elements in and out of the rocks. There were also changes in the electrochemical conditions in the rocks. These changes can most reasonably be attributed to oxidizing and reducing species produced by the radiolysis of water. We have calculated radiation doses and examined the production of radiolysis products in the fluid phase which lead to the following conclusions: 1) There was a net reduction of iron, probably associated with a net increase in total iron in the rocks of the reactor zones. The reduction of iron was most likely the result of hydrogen produced by the radiolysis of water. 2) Commensurate with the iron reduction, there was an oxidation of uranium and multivalent fission products, resulting in their transport out of the reactor zone. 3) Approximately 10 percent of the uranium and various proportions of these fission products were removed and redeposited in rocks within a few meters of the reactor zones. 4) The calculated radiation doses from alpha radiation and the inferred hydrogen production suggest an effective radiation yield of 0.06 molecules of hydrogen per 100 eV of energy imparted to the fluid phase. Considering radiation from both alpha and beta sources, the G value for hydrogen production is reduced to 0.01 to 0.002 molecules H 2 /100 eV. (author)

Radiolysis of Aqueous Benzene Solutions

Energy Technology Data Exchange (ETDEWEB)

Christensen, H

1964-05-15

Aerated and deaerated aqueous solutions of benzene have been irradiated with {sup 60}Co {gamma}-rays. The products of radiolysis in deaerated, unbuffered or acid, solutions were phenol, biphenyl, hydrogen and in acid solutions also hydrogen peroxide with the following yields: G(phenol) = 0. 37 (0. 37), G(biphenyl) = 1.3 (1.7), G(H{sub 2}) = 0.44 (0. 43) and G(H{sub 2}O{sub 2}) = 0 (0.60), the figures in brackets giving the results for acid solutions. The results are shown to agree with the conclusion that k(e{sup -}{sub aq} + H{sub 2}O{sub 2}) >> k(H + H{sub 2}O{sub 2}). Furthermore, the results indicate that a competition takes place between the reactions: 2 C{sub 6}H{sub 6}OH {center_dot} -> dimer -> biphenyl. C{sub 6}H{sub 7} {center_dot} + C{sub 6}H{sub 6}OH {center_dot} -> dimer -> biphenyl. The yields in aerated, unbuffered or acid, solutions were: G(phenol) = 2.1 (2.3), G(biphenyl) = 0 (0), and G(H{sub 2}O{sub 2}) = 2.2 (3.1), the figures in brackets being valid for acid solutions. The ratio k(H + C{sub 6}H{sub 6})/k(H + O{sub 2}) was 1.4x10{sup -2}. The results indicate that peroxides, or more probably hydroperoxides, take part in the reactions. After the addition of Fe{sup 2+} or Fe{sup 3+} to aerated acid solutions G(phenol) was increased to 6.6 and 3.4 respectively. Oxygen was consumed more rapidly in the presence of Fe. Reaction mechanisms are discussed.

Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

International Nuclear Information System (INIS)

Mieden, O.J.

1989-01-01

In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

IL 14: Radiolysis of water confined in nano-porous materials

International Nuclear Information System (INIS)

Renault, J.P.; Pommeret, S.; Musat, R.; Le Caer, S.; Alam, M.; Mialocq, J.C.

2010-01-01

Radiolysis of water in nano-porous media has raised a lot of interest and involved research in the recent years, with respect to concerns arising from the storage of nuclear waste. In the civil nuclear industry, storing for a long time nuclear wastes requires safety evaluations in order to test the durability of the materials involved. Among these materials, concrete and clays are a complex heterogeneous material that traps important quantities of interstitial water. Irradiation that arises from the nuclear wastes stored in these materials may lead to the radiolysis of the interstitial water, and the formation of radiolytic products, such as H 2 , O 2 or H 2 O 2 that may cause the breaking or the corrosion of the confining matrix. This communication will describe the possible impacts of confinement on the radiolysis of water. We will especially discuss the current knowledge about the evolution of radiolytic yields of primary species (hydroxyl radical, dihydrogen, aqueous electron) as a function of the degree of confinement and of the nature of the confining material. SEM picture of a nano-porous gold sample used to study the radiolysis of confined water The yield enhancement observed in many cases revealed original energy and charge transfer phenomena that we tried to decipher. (authors)

Multi-Scale Modelling of the Gamma Radiolysis of Nitrate Solutions

OpenAIRE

Horne, Gregory; Donoclift, Thomas; Sims, Howard E.; M. Orr, Robin; Pimblott, Simon

2016-01-01

A multi-scale modelling approach has been developed for the extended timescale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages; radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modelling. The first three components model...

Impact of β- radiolysis and transient products on irradiation-enhanced corrosion of zirconium alloys

International Nuclear Information System (INIS)

Lemaignan, C.

1992-01-01

An analysis has been undertaken of the various cases of local enhancement of the corrosion rate of zirconium alloys under irradiation. It is observed that in most cases a strong emission of energetic β - is present leading to a local energy desorption rate higher than the core average. This suggests that the local transient radiolytic oxidising species produced in the coolant by the β - particles could contribute to corrosion enhancement, by increasing the local corrosion potential. This process is applicable to the local enhanced corrosion found in front of stainless steels structural parts, due to the contribution of Mn, in front of Pt inserts and Cu-rich cruds. It explains also the irradiation corrosion enhancement of Cu-rich Zr alloys. Enhanced corrosion around neutron absorbing material is explained similarly by pair production from conversion of high energy capture photons in the cladding, leading to energetic electrons. The same process was found to be active with other highly ionising species like α in Ni-rich alloys and fission products in homogeneous reactors. This mechanism, applicable for an explanation of localised irradiation-enhanced corrosion, is proposed to be extended to the reactor core, where the general enhancement of Zr-alloy corrosion under irradiation would be due to the general radiolysis. It suggests that care should be taken to avoid any source of β - emission or other ionising species in the reactor core that could give an increase of energy deposition rate for radiolysis. Also the corrosion testing conditions for the materials to be used in reactors have to be relevant to the radiolytic environments found in the reactor cores. (orig.)

Hydrogen peroxide kinetics in water radiolysis

Science.gov (United States)

Iwamatsu, Kazuhiro; Sundin, Sara; LaVerne, Jay A.

2018-04-01

The kinetics of the formation and reaction of hydrogen peroxide in the long time γ- radiolysis of water is examined using a combination of experiment with model calculations. Escape yields of hydrogen peroxide on the microsecond time scale are easily measured with added radical scavengers even with substantial amounts of initial added hydrogen peroxide. The γ-radiolysis of aqueous hydrogen peroxide solutions without added radical scavengers reach a steady state limiting concentration of hydrogen peroxide with increasing dose, and that limit is directly proportional to the initial concentration of added hydrogen peroxide. The dose necessary to reach that limiting hydrogen peroxide concentration is also proportional to the initial concentration, but dose rate has a very small effect. The addition of molecular hydrogen to aqueous solutions of hydrogen peroxide leads to a decrease in the high dose limiting hydrogen peroxide concentration that is linear with the initial hydrogen concentration, but the amount of decrease is not stoichiometric. Proton irradiations of solutions with added hydrogen peroxide and hydrogen are more difficult to predict because of the decreased yields of radicals; however, with a substantial increase in dose rate there is a sufficient decrease in radical yields that hydrogen addition has little effect on hydrogen peroxide decay.

Risk analysis for a radiolysis gas detonation in an in-pile loop with supercritical water

International Nuclear Information System (INIS)

Zeiger, T.; Raque, M.; Kuznetsov, M.; Redlinger, R.; Schulenberg, T.

2012-01-01

The SCWR (supercritical water reactor) -FQT project is a cooperation between European and Chinese partners aimed to test the fuel SCWR elements under reactor conditions. In the frame of this work the risk of radiolysis gas production in the active range of the test track was assessed. The radiolysis gas could accumulate in an emergency cooling system with stagnating coolant. The ignition of this radiolysis gas could cause pressure peaks that are able to damage the primary coolant circuit. Pressure increase and deformations in case of ignition of accumulated gas were investigated. As piping material the Ti stabilized austenitic steel 08Ch18N10T was assumed, the simulation was performed using the ANSYS code. The results show that pipes without significant wall thickness enhancement cannot withstand the radiolysis gas detonation.

Temporal behavior of hydrated electron studied up to 400 deg. C by ultrafast pulse radiolysis and Monte Carlo calculation

International Nuclear Information System (INIS)

Katsumura, Yosuke; Muroya, Yusa; Lin, Mingzhang; Yu, Yan; Mehran, Mostafavi; Sanguanmith, Sunuchakan; Meesungnoen, Jintana; Jay-Gerin, Jean-Paul

2012-09-01

Pulse radiolysis is a very powerful and unique method to observe the transient species and to determine their yields and has been widely used up to now. Since the radiation-induced reactions at elevated temperatures are accelerated, precise measurement becomes difficult by the conventional pulse radiolysis systems. Then, a higher time resolved pulse radiolysis system is highly expected. Recently, an ultrafast pulse radiolysis system has been developed in the University of Tokyo and applied to water radiolysis at elevated temperatures [1]. Temporal behavior of the hydrated electron at elevated temperatures up to 400 deg C has been detected. The time dependent behavior of hydrated electron at elevated temperatures were detected and the latest version of the Monte Carlo simulation code developed at University of Sherbrooke was applied to reproduce the experimental results. From the simulation, it was made clear that the thermalization distance becomes smaller with increasing temperature. In addition, in supercritical water, the initial yield is significantly dependent on density (pressure), which is consistent with our previous evaluation. (authors)

Chemical reactions induced by fast neutron irradiation

International Nuclear Information System (INIS)

Katsumura, Y.

1989-01-01

Here, several studies on fast neutron irradiation effects carried out at the reactor 'YAYOI' are presented. Some indicate a significant difference in the effect from those by γ-ray irradiation but others do not, and the difference changes from subject to subject which we observed. In general, chemical reactions induced by fast neutron irradiation expand in space and time, and there are many aspects. In the time region just after the deposition of neutron energy in the system, intermediates are formed densely and locally reflecting high LET of fast neutrons and, with time, successive reactions proceed parallel to dissipation of localized energy and to diffusion of the intermediates. Finally the reactions are completed in longer time region. If we pick up the effects which reserve the locality of the initial processes, a significant different effect between in fast neutron radiolysis and in γ-ray radiolysis would be derived. If we observe the products generated after dissipation and diffusion in longer time region, a clear difference would not be observed. Therefore, in order to understand the fast neutron irradiation effects, it is necessary to know the fundamental processes of the reactions induced by radiations. (author)

Pulse radiolysis of water by energetic heavy ion

International Nuclear Information System (INIS)

Taguchi, M.; Sugo, Y.; Iwamatsu, K.; Yamaguchi, M.; Katsumura, Y.

2011-01-01

Complete text of publication follows. Water radiolysis is a fundamental process governing radiation effects in various aspects. Degree of water molecule decomposition depends on the type and LET (Linear Energy Transfer) value of radiations. However, the degradation of water molecules by α-particle has not been clearly understood. In this study, we aimed to clarify the reaction behavior of the groundwater induced by of α-particles from high-level radioactive waste (HLW) in the geological disposal environment. α-radiolysis of water was investigated by use of high energy helium ions accelerated by the AVF cyclotron in TIARA facility, JAEA/Takasaki. The pulsed He ion irradiation technique and online time resolved absorbance measurement system was investigated for direct observation of chemical reactions of transient species produced by irradiations. Hydroxyl (OH) radical is the most important species for reactions in aqueous samples because of its high reactivity and formation yield. NaCl was selected as a probe reagent for the OH radical produced by the irradiation with He ion, and dissolved in pure water. Because 50 MeV He ion has the penetration range at 1.5 mm in water, the sample cell has the thickness of 2 mm, and 50 μm glass windows on the top and bottom for preventing energy loss of the incident ions and measuring the absorbance. The transient absorbance was recorded for the aqueous NaCl solutions using semiconductor LASER diode at 375 nm as a probe light source. ClOH - was formed by the reaction of the OH radical with Cl - . The absorbance of ClOH - increased within the irradiation pulse width, and then decreased gradually. The formation yield of ClOH - which was estimated from the peak absorbance value, increased with the solute concentration. Precise analyses of chemical reactions occurred in track will be discussed at the presentation. This study is a part of the project on geological disposal funded by the Ministry of Economy, Trade and Industry, Japan

ECP evaluation by water radiolysis and ECP model calculations

Energy Technology Data Exchange (ETDEWEB)

Hanawa, S.; Nakamura, T.; Uchida, S. [Japan Atomic Energy Agency, Tokai-mura, Ibaraki (Japan); Kus, P.; Vsolak, R.; Kysela, J. [Nuclear Research Inst. Rez plc, Rez (Czech Republic)

2010-07-01

In-pile ECP measurements data was evaluated by water radiolysis calculations. The data was obtained by using an in-pile loop in an experimental reactor, LVR-15, at the Nuclear Research Institute (NRI) in Czech Republic. Three types of ECP sensors, a Pt electrode, an Ag/AgCl sensor and a zirconia membrane sensor containing Ag/Ag{sub 2}O were used at several levels of the irradiation rig at various neutron flux and gamma rates. For water radiolysis calculation, the in-pile loop was modeled to several nodes following their design specifications, operating conditions such as flow rates, dose rate distributions of neutron and gamma-ray and so on. Concentration of chemical species along the water flow was calculated by a radiolysis code, WRAC-J. The radiolysis calculation results were transferred to an ECP model. In the model, anodic and cathodic current densities were calculated with combination of an electrochemistry model and an oxide film growth model. The measured ECP data were compared with the radiolysis/ECP calculation results, and applicability the of radiolysis model was confirmed. In addition, anomalous phenomenon appears in the in-pile loop was also investigated by radiolysis calculations. (author)

Effects of dissolved species on radiolysis of diluted seawater

International Nuclear Information System (INIS)

Hata, Kuniki; Hanawa, Satoshi; Kasahara, Shigeki; Motooka, Takafumi; Tsukada, Takashi; Muroya, Yusa; Yamashita, Shinichi; Katsumura, Yosuke

2014-01-01

Fukushima Daiichi Nuclear Power Plants (NPPs) experienced seawater injection into the cores and fuel pools as an emergent measure after the accident. After the accident, retained water has been continuously desalinized, and subsequently the concentration of chloride ion (Cl"-) has been kept at a lower level these days. These ions in seawater are known to affect water radiolysis, which causes the production of radiolytic products, such as hydrogen peroxide (H_2O_2), molecular hydrogen (H_2) and molecular oxygen (O_2). However, the effects of dissolved ions relating seawater on the production of the stable radiolytic products are not well understood in the diluted seawater. To understand of the production behavior in diluted seawater under radiation, radiolysis calculations were carried out. Production of H_2 is effectively suppressed by diluting by up to vol10%. The concentrations of oxidants (H_2O_2 and O_2) are also suppressed by dilution of dissolved species. The effect of oxidants on corrosion of materials is thought to be low when the seawater was diluted by less than 1 vol% by water. It is also shown that deaeration is one of the effective measure to suppress the concentrations of oxidants at a lower level for any dilution conditions. (author)

Studies on radiolysis of amino acids, (3)

International Nuclear Information System (INIS)

Oku, Tadatake

1978-01-01

For the purpose of investigating the radiolysis of amino acids and the safeness to radiation, the radiolytic mechanism and radio-sensitivity of sulfur-containing amino acids in aqueous solution in the presence of air or in the atmosphere of nitrogen were studied. Aqueous solutions of L-methionine, cysteine (both 1mM) and L-cystine (0.3mM) were irradiated with γ-ray of 60 Co at the dose of 4.2 - 2,640 x 10 3 rad. The amino acids and the radiolytic products were determined with an amino acid analyzer. The volatile sulfur compounds formed from γ-irradiated methionine were estimated by a flame photometric detector-gas chromatograph. From the results obtained, G values of the radiolysis of sulfur-containing amino acids and the products were calculated, and the radiolytic mechanisms of methionine, cysteine and cystine were proposed. The radio-sensitivity of sulfur-containing amino acids was shown as follows: cysteine (C3-SH) > methionine (C5, -SCH 3 ) > cystine (C 6 , -S-S-). Off-flavor development from γ-irradiated methionine when oxidizing agent was added was less than that when reducing agent was added. (Kobatake, H.)

Nitrogen oxidative activation in the radiolysis process of dioxide hydrocarbon composition, oxygen-nitrogen over 3-d transition metals

International Nuclear Information System (INIS)

Rustamov, V.R.; Garibov, A.A.; Kerimov, V.K.; Aliyev, S.M.; Nasirova, Kh.Y.

2004-01-01

The radiochemical process of nitrogen fixation in carbon dioxide, oxygen-nitrogen composition in 3-d metal (iron, nickel) was studied. Bifunctional character of surface's role in the generation of radiolysis products was postulated: a) Chemisorption's of molecular ions (N 2 + , CO 2 + , O 2 + ) on the surface of metal and their dissociative neutralization. b) Coordination of nitrogen and carbon oxide being generated in nitrosyl and carbonyl-nitrosyl complex of iron and nickel. Total yield of the products is over the rang 6,4†7,5, to explain radiolysis' what contribution of only neutral products is impossible. Evidently in the generation of final products, defined contribution brings in molecular ions N 2 + (N + ) and CO 2 + . Interaction character of these ions with nickel proposes the formation of the relation between unpaired electrons N 2 + and CO 2 + with unfilled d-sub level of this metals with the nickel nitride generation [N i -N=N + ] and binding energy in ion diazotate decreases to twice. The yield of nitrogen dioxide on radiolysis of the air gave G NO2 =0,8±0,2 molecule/100eV which is proper to the date in the literature. Kinetic curve appears rapidly in the saturation. Air radiolysis over iron gave the following results: G NO 2 = 2,75 ± 0,25, G N 2 O = 9,0 ± 1,0 molecule/100eV. Thus total yield of radiolysis products is Σ G = 10,5 ± 12,0 molecule/100eV. (author)

Nitrogen oxidative activation in the radiolysis process of dioxide hydrocarbon composition, oxygen-nitrogen over 3-D transition metals

International Nuclear Information System (INIS)

Rustamov, V.R.; Garibov, A.A.; Kerimov, V.K.; Aliyev, S.M.; Nasirova, Kh.Y.

2004-01-01

Full text: The radiochemical process of nitrogen fixation in carbon dioxide, oxygen-nitrogen composition in 3-d metal (iron, nickel) was studied. Bifunctional character of surface's role in the generation of radiolysis products was postulated: a) Chemisorption's of molecular ions (N 2 + , CO 2 + , O 2 + ) on the surface of metal and their dissociative neutralization. b) Coordination of nitrogen and carbon oxide being generated in nitrosyl and carbonyl-nitrosyl complex of iron and nickel. Total yield of the products is over the rang 6,4†7,5, to explain radiolysis' what contribution of only neutral products is impossible. Evidently in the generation of final products, defined contribution brings in molecular ions N 2 + (N + ) and CO 2 + . Interaction character of these ions with nickel proposes the formation of the relation between unpaired electrons N 2 + and CO 2 + with unfilled d-sub level of this metals with the nickel nitride generation [N i -N=N + ] and binding energy in ion diazotate decreases to twice. The yield of nitrogen dioxide on radiolysis of the air gave G NO2 =0,8±0,2 molecule/100eV which is proper to the date in the literature. Kinetic curve appears rapidly in the saturation. Air radiolysis over iron gave the following results: G NO 2 = 2,75 ± 0,25, G N 2 O = 9,0 ± 1,0 molecule/100eV. Thus total yield of radiolysis products is Σ G = 10,5 ± 12,0 molecule/100eV

Summary of TRUEX Radiolysis Testing Using the INL Radiolysis Test Loop

Energy Technology Data Exchange (ETDEWEB)

Dean R. Peterman; Lonnie G. Olson; Rocklan G. McDowell; Gracy Elias; Jack D. Law

2012-03-01

The INL radiolysis and hydrolysis test loop has been used to evaluate the effects of hydrolytic and radiolytic degradation upon the efficacy of the TRUEX flowsheet for the recovery of trivalent actinides and lanthanides from acidic solution. Repeated irradiation and subsequent re-conditioning cycles did result in a significant decrease in the concentration of the TBP and CMPO extractants in the TRUEX solvent and a corresponding decrease in americium and europium extraction distributions. However, the build-up of solvent degradation products upon {gamma}-irradiation, had little impact upon the efficiency of the stripping section of the TRUEX flowsheet. Operation of the TRUEX flowsheet would require careful monitoring to ensure extraction distributions are maintained at acceptable levels.

Pulse radiolysis study on several fluoroquinolones

Energy Technology Data Exchange (ETDEWEB)

Zhang Peng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Graduate University of Chinese Academy of Science, Beijing 100049 (China); Yao Side [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Li Haixia; Song Xiyu; Liu Yancheng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Graduate University of Chinese Academy of Science, Beijing 100049 (China); Wang Wenfeng, E-mail: wangwenfeng@sinap.ac.c [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China)

2011-04-15

Reactions of several fluoroquinolones (FQs), including enoxacin, norfloxacin, and ciprofloxacin, with various reactive species such as e{sub aq}{sup -}, N{sup {center_dot}}{sub 3}, and {sup {center_dot}O}H are investigated by pulse radiolysis techniques. The FQ radical anions formed in the reactions of FQs with e{sub aq}{sup -} could either be protonated or deprotonated, and the absorption of FQ radical anions was located around 370 nm. The absorption of the neutral radicals produced in the protonation, and the radical dianions produced in the deprotonation of FQ radical anions were located in the 500-750 nm region. The FQ radical cations formed in the reactions of FQs with N{sub 3}{sup {center_dot}} showed an absorption band around 360 nm. Due to the strong bleaching below 350 nm, the absorption maxima ({lambda}{sub max}) of FQ radical anions, and the {lambda}{sub max} of FQ radical cations were not confirmed. The absorption of the FQ radical anions and cations was clearly pH dependent. Under neutral conditions, the reaction rate constants of FQs with e{sub aq}{sup -} and {sup {center_dot}O}H, which are diffusion controlled, were determined.

In honour of N. Yngve Öhrn: surveying proton cancer therapy reactions with Öhrn's electron nuclear dynamics method. Aqueous clusters radiolysis and DNA-base damage by proton collisions

Science.gov (United States)

Mclaurin, Patrick M.; Privett, Austin J.; Stopera, Christopher; Grimes, Thomas V.; Perera, Ajith; Morales, Jorge A.

2015-02-01

Proton cancer therapy (PCT) utilises high-energy H+ projectiles to cure cancer. PCT healing arises from its DNA damage in cancerous cells, which is mostly inflicted by the products from PCT water radiolysis reactions. While clinically established, a complete microscopic understanding of PCT remains elusive. To help in the microscopic elucidation of PCT, Professor Öhrn's simplest-level electron nuclear dynamics (SLEND) method is herein applied to H+ + (H2O)3-4 and H+ + DNA-bases at ELab = 1.0 keV. These are two types of computationally feasible prototypes to study water radiolysis reactions and H+-induced DNA damage, respectively. SLEND is a time-dependent, variational, non-adiabatic and direct-dynamics method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction. Additionally, our SLEND + effective-core-potential method is herein employed to simulate some computationally demanding PCT reactions. Due to these attributes, SLEND proves appropriate for the simulation of various types of PCT reactions accurately and feasibly. H+ + (H2O)3-4 simulations reveal two main processes: H+ projectile scattering and the simultaneous formation of H and OH fragments; the latter process is quantified through total integrals cross sections. H+ + DNA-base simulations reveal atoms and groups displacements, ring openings and base-to-proton electron transfers as predominant damage processes. The authors warmly dedicate this SLEND investigation in honour of Professor N. Yngve Öhrn on the occasion of his 80th birthday celebration during the 54th Sanibel Symposium in St. Simons' Island, Georgia, on February 16-21, 2014. Associate Professor Jorge A. Morales was a former chemistry PhD student under the mentorship of Professor Öhrn and Dr Ajith Perera took various quantum chemistry courses taught by Professor Öhrn during his chemistry PhD studies. Both Jorge and Ajith look back to those great times of their scientific formation under

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

Science.gov (United States)

Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

2007-05-01

Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

Redox chemistry of orange I and orange II: a pulse radiolysis study

International Nuclear Information System (INIS)

Yadav, P.; Sharma, K.K.; Rao, B.S.M.; O'Neill, P.; Oakes, J.; Batchelor, S.N.

2004-01-01

The relative reactivities of different tautomeric forms of model azo dyes (Orange I and Orange II) with oxidising and reducing radicals are investigated using pulse radiolysis technique. The rate of the reaction of N 3 with Orange I is diffusion controlled and the order of the reactivity among the tautomers is common ion > hydrazone > azo, whereas a reverse trend was seen in the reaction of e aq . The reducing alcohol radicals react with Orange II with k values in the range (1-3) x 10 9 dm 3 mol -1 s -1 . The relevant reaction mechanism is discussed. (author)

LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

Energy Technology Data Exchange (ETDEWEB)

Slegers, Catherine [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)]. E-mail: catherine.slegers@skynet.be; Maquille, Aubert [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Deridder, Veronique [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Sonveaux, Etienne [Unite de Chimie Pharmaceutique et de Radiopharmacie, Universite Catholique de Louvain, Brussels (Belgium); Habib Jiwan, Jean-Louis [Laboratoire de Spectrometrie de Masse, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Tilquin, Bernard [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)

2006-09-15

E-beam and gamma products from the radiolysis of aqueous solutions of ({+-})-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of ({+-})-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed.

Pulse radiolysis studies on DNA-Binding radioprotectors

International Nuclear Information System (INIS)

Anderson, R.F.

1996-01-01

Full text: Hoechst 33342 and newly-synthesised analogues exhibit radioprotective activity in cultured cells and in vivo, as described in accompanying abstracts. These minor groove binding ligands bind at discreet sites in DNA, characterised by 3 to 4 consecutive AT base pairs, and DNA sequencing studies have shown focussed radioprotection at these binding sites. There is evidence that the bound ligands also confer more 'global' protection including the intervening DNA between the binding sites. The observed focussed radioprotection could be explained by H-atom donation from the ligand to radiation-induced carbon-centred deoxyribosyl radicals, but this mechanism is unlikely to account for the global radioprotection. We now report pulse radiolysis studies on another possible mechanism, namely reduction of transient radiation-induced oxidising species on DNA by the ligand, which is consistent with the report of reduction of G + by TMPD. Oxidation of deoxyguanosine (dG) by Br 2 - , produced by radiolysis of Br- in N 2 0-saturated solutions, in the presence of Hoechst 33342 results in the appearance of a transient ligand species which is kinetically resolvable from that obtained from direct oxidation of Hoechst 33342 by Br 2 - . A plot of reaction rate versus ligand concentration indicates that the rate constant for reduction of G + is approximately 3 x 10 8 dm 3 M -1 sec -1 . Similar experiments with DNA, rather than dG, also revealed a transient species corresponding to oxidation of the ligand, but the absolute rate of oxidation was considerably slower for the DNA-bound ligand compared to that for oxidation of the free ligand by G+. These results are clearly consistent with the proposed mechanism of radioprotection by Hoechst 33342 and its analogues, moreover, pulse radiolysis may provide a very useful endpoint for screening new analogues, as a preliminary to radiobiological evaluation

Radiolysis of Ca14CO3

International Nuclear Information System (INIS)

Sanchez, M.G.A.

1986-01-01

The partition-ion exclusion chromatography is evaluated to analyse non-ionic organic compounds obtained from radiolysis of high specific activity Ca 14 CO 3 . The Ca 14 CO 3 was irradiated by β - decay of carbon-14 or by γ rays from a cobalt-60 source. The crystals were dissolved for qualitative and quantitative analysis of the radiolytic products. Formic and oxalic acids were produced in high yields. Glyoxylic, acetic and glycolic acids, formaldehyde and methanol were produced in low yields. Quantitative determination was carried out by liquid scintillation spectroscopy and the chemical yields (G-values) were calculated for the products. Mechanisms of product formation are proposed based on thermal annealing experiments. (Author) [pt

Pulse radiolysis studies of bergenin, an isocoumarin polyphenolic derivative

International Nuclear Information System (INIS)

Singh, Umang; Srinivasan, R.; Barik, A.; Priyadarsini, K.I.

2008-01-01

Bergenin, a polyphenolic isocoumarin derivative, isolated from medicinal plant Caesalpinia digynae, has been subjected for OH and oxidizing radical reactions using pulse radiolysis technique coupled with absorption detection. OH radicals cause multiple reactions, producing transients absorbing with maxima at 440 nm and 500 nm. By comparing the spectra and decay kinetics with that produced by N 3 radicals, the species absorbing at 440 nm is assigned to phenoxyl type radical and the one absorbing at 500 nm to be a hydroxyl-radical adduct, which has been found to be reducing in nature. Bergenin also reacts with peroxyl radicals, with rate constants of 4.2 x 10 6 M -1 s -1 . (author)

Pulse radiolysis studies of bergenin, an isocoumarin polyphenolic derivative

Energy Technology Data Exchange (ETDEWEB)

Singh, Umang; Srinivasan, R; Barik, A; Priyadarsini, K I [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

2008-01-15

Bergenin, a polyphenolic isocoumarin derivative, isolated from medicinal plant Caesalpinia digynae, has been subjected for OH and oxidizing radical reactions using pulse radiolysis technique coupled with absorption detection. OH radicals cause multiple reactions, producing transients absorbing with maxima at 440 nm and 500 nm. By comparing the spectra and decay kinetics with that produced by N{sub 3} radicals, the species absorbing at 440 nm is assigned to phenoxyl type radical and the one absorbing at 500 nm to be a hydroxyl-radical adduct, which has been found to be reducing in nature. Bergenin also reacts with peroxyl radicals, with rate constants of 4.2 x 10{sup 6} M{sup -1}s{sup -1}. (author)

Femtosecond pulse radiolysis based on photocathode electron accelerator

International Nuclear Information System (INIS)

Yoshida, Y.; Yang, Jinfeng; Kondoh, T.; Kozawa, T.; Tagawa, S.

2006-01-01

Pulse radiolysis is a powerful tool for studying chemical kinetics and primary processes or reactions of radiation chemistry. In the pulse radiolysis, a short electron beam, which is almost produced by radio-frequency (RF) electron linear accelerator with energy from a few MeV to a few tens MeV, is used as an irradiative source. The electron-induced reactions or phenomena in matter are analyzed by a short-pulse analyzing light (e.g. synchronized lasers) with the time-resolved stroboscopic technique. The time resolution of pulse radiolysis is not only dependent on the electron bunch length, the analyzing light pulse width, the time jitter between the electron bunch and the analyzing light, but also determined by degradation due to the velocity difference between light and the electron in the sample because of the refractive index. In order to improve the time resolution into femtosecond time region, we have develop a new pulse radiolysis based on a concept of 'Equivalent Velocity Spectroscopy (EVS)' to avoid the degradation of the time resolution caused by the velocity difference between the light and the electron beam in sample. In EVS as shown in Fig.1, a femtosecond electron beam produced by a photocathode electron linear accelerator was used, and a synchronized femtosecond laser was used as the analyzing light source. The electron beam and the laser light were injected into sample with an angle (θ), which is determined by the refractive index (n) of the sample. The electron bunch was also rotated with a same angle to make an overlap of the electron bunch with the laser pulse. The degradation of the time resolution caused by the velocity difference between the light and the electron beam can be calculated as g(L)=L[n/c-1/(vcos θ)], where L is the optical path length and v is the velocity of the electron in sample (we can assume v=c for a few tens MeV electron beam).We can thus obtained g(L)=0 by adjusting the incident angle to cos θ=1/n. However, the rotation

Pulse radiolysis - new approaches to the classical technique

Energy Technology Data Exchange (ETDEWEB)

Zagorski, Z P [Institute of Nuclear Research, Warsaw (Poland)

1973-01-01

The present status of classical pulse radiolysis is described as well as trends in the further development of this technique (the investigation of radiolysis with nano- and picoseconds time resolution, new optica and electrochemical methods of intermediate species detection). The attention is concentrated on experimental difficulties of particular versions and the achievements are reviewed critically. This paper is the background for experiments being performed in the Institute of Nuclear Research on new techniques of pulse radiolysis.

Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

International Nuclear Information System (INIS)

Bisby, R.H.; Tabassum, N.

1988-01-01

The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k 2 ) of (2.2 ± 0.4) x 10 9 M -1 sec -1 . In alkaline solutions the radical deprotonates with a pK of 11.1 ± 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 ± 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10 6 M -1 sec -1 at pH7 and 2.7 x 10 8 M -1 sec -1 at pH 11.3 were obtained. The reaction of O 2 with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed. (author)

Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Bisby, R H; Tabassum, N

1988-07-15

The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k/sub 2/) of (2.2 +- 0.4) x 10/sup 9/ M/sup -1/ sec/sup -1/. In alkaline solutions the radical deprotonates with a pK of 11.1 +- 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 +- 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10/sup 6/ M/sup -1/ sec/sup -1/ at pH7 and 2.7 x 10/sup 8/ M/sup -1/ sec/sup -1/ at pH 11.3 were obtained. The reaction of O/sub 2/ with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed.

LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

International Nuclear Information System (INIS)

Slegers, Catherine; Maquille, Aubert; Deridder, Veronique; Sonveaux, Etienne; Habib Jiwan, Jean-Louis; Tilquin, Bernard

2006-01-01

E-beam and gamma products from the radiolysis of aqueous solutions of (±)-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of (±)-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed

Favism inducing agents: a pulse radiolysis study of isouramil and convicine

International Nuclear Information System (INIS)

Chevion, M.; Ilan, Y.A.

1980-01-01

Isouramil and covicine, substances implicated in precipitating favic crises in glucose-6-phosphate dehydrogenase deficient individuals, have been studied in N 2 O-saturated aqueous solutions by pulse radiolysis, and the kinetics of the reactions of both substances with OH radicals were determined. The products of these reactions are addition intermediates absorbing above 330 nm. The decay of the intermediate(s) formed in the isouramil reaction is a biphasic one, while the decay of the corresponding intermediate for the convicine reaction is characterized by a single constant. By analogy to uracil, it is suggested that the OH radical is added to the double bond at either positions 5 or 6 of the pyrimidine ring forming two different intermediates. Each of these intermediates loses a molecule of water indicated by the observed biphasic decay reaction. For convicine on the other hand, position 5 is blocked by the O-gucosidic bond and the addition of the OH radical could take place only at position 6. Thus, a single intermediate is formed and its decay is a single-phase one. It has been shown that although free radicals could not be detected in the course of the reactions between isouramil and oxygen or with cellular components by electron paramagnetic resonance, isouramil can participate in a uni-electron transfer reacton and can form relatively stable intermediates. Thus, it is speculated that in the red blood cells isouramil could give rise to deleterious free radicals

Gamma radiolysis of aqueous solution of ascorbic acid

International Nuclear Information System (INIS)

Loyola V, V.M.; Azamer B, J.A.; Laviada C, A.; Luna V, P.

1977-01-01

A preliminary study of the gamma radiolysis of a 1.13 x 10 -4 Maqueous solution of ascorbic acid is presented. It was found that dehydroascorbic acid was the principal product at doses of about 75 Krad. An increase in the dehydroascorbic acid concentration rangins from 5 to 40% was obtained, these values depend mainly on the initial ascorbic acid concentration. (author)

Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

DEFF Research Database (Denmark)

Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

1996-01-01

was studied with SF6 pressures of 5-1000 mbar at 298 K. Comparative studies were carried out by monitoring the decay kinetics of NO2 at 445 nm using pressures of 100-1000 mbar at 295 and 341 K. The observed pressure dependence is represented in terms of a fall-off curve with the following values......The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics...

Electron inductive effects in the radiolysis of substituted phenylboronic acid solutions

International Nuclear Information System (INIS)

Brown, B.J.; Fitch, P.G.; Sangster, D.F.

1976-01-01

The pulse radiolysis of aqueous solutions of phenylboronic acid PhB(OH) 2 and its m-nitro and m-amino derivatives has been investigated. The transient optical absorption spectra indicate the presence of three intermediate species absorbing with independent maxima at 297, 317 and 400 nm. The 297-nm band has been assigned to the anion formed in an electron capture reaction, i.e. PhB(OH) 2 +epsilonsub(aq) - → PhB(OH) 2 - and the 317-nm band to cyclohexadienyl radicals formed from OH and H attack on OhB(OH) 2 . Hydroxyphenylboronic acid has been identified as the major stable radiation product. For each of the systems studied the respective yield and reactivity of observed intermediate species can be interpreted relative to the inductive effects of substituent groups in agreement with the Hammett relationship. (author)

Reactivity of OH and O– with aqueous methyl viologen studied by pulse radiolysis

DEFF Research Database (Denmark)

Solar, Sonja; Solar, Wolfgang; Getoff, Nikola

1985-01-01

The behaviour of aqueous MV2+ towards oxidizing radicals (OH and O–) has been investigated in the pH range from 6 to 14 by means of pulse radiolysis. A semi-linear optimization method was applied for resolving the complex reaction mechanism. In the pH range from 6 to 8 the rate constant for attac...

Kinetics of the addition reaction of methyl radicals with nitric oxide studied by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Jodkowski, J.T.; Ratajczak, E.; Sillesen, A.

1993-01-01

The reaction CH3 + NO (+ M) --> CH3NO ( + M) was initiated by pulse radiolysis of acetone/nitric oxide mixtures and the kinetics of methyl radicals was studied by time-resolved infrared absorption spectroscopy. The rate constant was found to be strongly pressure dependent in the range of p (M) = 6.......5-150 mbar at 298 K with M = acetone as the third body. The experimental results are represented in terms of a fall-off curve centered at 37 mbar with limiting high- and low-pressure rate constants of k(rec,infinity) = (6.6 +/- 0.9) x 10(9) x (T/300)0.6 M-1 s-1 and k(rec,0)/[M] = (4.4 +/- 0.4) x 10(12) x (T...

Chemical kinetics and reaction mechanism

International Nuclear Information System (INIS)

Jung, Ou Sik; Park, Youn Yeol

1996-12-01

This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

Ligand exchange reactions of the heme group in hemoglobin and myoglobin as studied by pulse radiolysis

International Nuclear Information System (INIS)

Raap, I.A.

1978-01-01

In this thesis, the kinetic aspects of the ligand exchange reactions of hemoglobin are studied using the pulse radiolysis technique, in particular, the reactions of hydrated electrons with methemoglobin. A hitherto unobserved transient state of the heme group is observed which appears immediately after the rapid reduction process. The absorption spectrum of this new species has the characteristics of a ferrous low-spin state and can therefore be ascribed to the formation of a hemochrome non-equilibrium state. The subsequent relaxation of this intermediate structure into a deoxy-conformation is dependent on the amount of proton activity in the solution and on the presence of organic and inorganic phosphate anions. The final absorption spectrum of the heme group is shown to correspond to a ferrous high-spin state in the relaxed quaternary conformation. This is in agreement with the kinetics observen the binding of carbon monoxide and oxygen to partially reduced methemoglobin. At reduction degrees of methemoglobin as well as of valncy 8ybrids where there is an important contribution from species with two reduced subunits, the binding of carbon monoxide to hemoglobin occurs with on-rate constants characteristic for the tensed quaternary conformation. It is argued that this conformational change of hemoglobin (the R-to-T transition) takes place very rapidly, which suggests the participation of an activated relaxed conformation. In addition, it is found that there is a distinct heterogeneity in the binding of oxygen to partially reduced methemoglobin even at low degrees of reduction

Investigation of free-radical processes in low temperature radiolysis of copolymers of ethylene with styrene

International Nuclear Information System (INIS)

Mal'tseva, A.P.; Golikov, V.P.; Leshchenko, S.S.; Karpov, V.L.; Muromtsev, V.I.

1977-01-01

Free radical processes during γ-radiolysis of statistical ethylene-styrene copolimers (ESC) have been investigated. The presence of styrene links in the ESC has been shown to reduce both radical yields and their reaction ability as compared with low density polyethylene irradiated under the same conditions. The character of radical processes in ESC sighificantly depends both on styrene concentration in them and on the dose absorbed. The most pronounced decrease in radical yield is found in the copolymer having 5 mol % styrene. This effect seems to be caused by the accumulation in the irradiated copolymer of products which are capable of more effective dissipation of absorbed energy than only styrene links alone

Novel system for pulse radiolysis with multi-angle light scattering detection (PR-MALLS) - concept, construction and first tests

Science.gov (United States)

Kadlubowski, S.; Sawicki, P.; Sowinski, S.; Rokita, B.; Bures, K. D.; Rosiak, J. M.; Ulanski, P.

2018-01-01

Time-resolved pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is an effective method for rapidly generating free radicals and other transient species in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. When used for polymer solutions, pulse radiolysis can be coupled with light-scattering detection, creating a powerful tool for kinetic and mechanistic analysis of processes like degradation or cross-linking of macromolecules. Changes in the light scattering intensity (LSI) of polymer solutions are indicative of alterations in the molecular weight and/or in the radius of gyration, i.e., the dimensions and shape of the macromolecules. In addition to other detection methods, LSI technique provides a convenient tool to study radiation-induced alterations in macromolecules as a function of time after the pulse. Pulse radiolysis systems employing this detection mode have been so far constructed to follow light scattered at a single angle (typically the right angle) to the incident light beam. Here we present an advanced pulse radiolysis & multi-angle light-scattering-intensity system (PR-MALLS) that has been built at IARC and is currently in the phase of optimization and testing. Idea of its design and operation is described and preliminary results for radiation-induced degradation of pullulan as well as polymerization and crosslinking of poly(ethylene glycol) diacrylate are presented. Implementation of the proposed system provides a novel research tool, which is expected to contribute to the expansion of knowledge on free-radical reactions in monomer- and polymer solutions, by delivering precise kinetic data on changes in molecular weight and size, and thus allowing to formulate or verify reaction mechanisms. The proposed method is

Generalized model for the radiolysis of groundwaters: bicarbonate chemistry and influences

International Nuclear Information System (INIS)

Nicolosi, S.L.

1987-01-01

A groundwater radiolysis model has been developed at Battelle-Columbus which is applicable to groundwaters containing bicarbonate species. The model consists of a chemical mechanism which describes interactions between groundwater species and radiolytic species. Due to the chemical kinetics nature of the model, elementary reactions can be added to extend its range of applicability to other groundwaters. This paper describes the chemical kinetics and influences of bicarbonate species in the model. 23 references, 2 tables

Development of hydrogen oxidizing bacteria using hydrogen from radiolysis or metal corrosion

International Nuclear Information System (INIS)

Libert, M.F.; Sellier, R.; Marty, V.; Camaro, S.

2000-01-01

The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H 2 production in a bituminized nuclear waste environment were simulated in the present study: - H 2 production by iron corrosion under anaerobic conditions was simulated by adding 10% of H 2 in the atmosphere; - H 2 production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H 2 in water allows the growth of hydrogen oxidizing bacteria leading to: - CO 2 and N 2 production; - H 2 consumption; - lower NO 3 - concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO 3 - release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H 2 instead of hydrocarbons. (authors)

Radical Cations and Acid Protection during Radiolysis

Energy Technology Data Exchange (ETDEWEB)

Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2016-09-09

Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO₃. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

Radical Cations and Acid Protection during Radiolysis

International Nuclear Information System (INIS)

Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.

2016-01-01

Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

Radiolysis of methylene blue studied by ESR

International Nuclear Information System (INIS)

Contineau, M.; Iliescu, C.; Ciureanu, M.

1983-01-01

Electron spin resonance spectra have been used to gain information on the mechanism of radiolysis of aqueous solutions of methylene blue. The identity and behaviour of the semiquinone radicals formed as intermediate reduction products were discussed for strongly acid and for alcaline solutions. In order to obtain information on the radiolytic mechanism in strongly acidic media, irradiation was performed in the presence of various types of scavengers: sodium formate, glucose, succinic acid, hydroquinone and D,L-α alanine. (author)

Testing requirements for SCWR radiolysis

International Nuclear Information System (INIS)

Guzonas, D.; Stuart, C.; Jay-Gerin, J.-P.; Meesungnoen, J.

2010-01-01

The Generation IV supercritical water-cooled reactor (SCWR) designs under consideration would operate at ∼430-625 o C and 25 MPa, i.e., well beyond the thermodynamic critical point of water. Supercritical (light/heavy) water (SCW)-cooled reactors would enable thermodynamic cycle efficiencies as high as ∼44% (versus ∼33% for existing water reactors), thus generating lower-cost electricity. The purpose of this report is to survey the literature on SCW radiolysis, describe the recent modeling performed at the Universite de Sherbrooke, and to broadly outline the testing required to develop a benchmarked SCW radiolysis model. (author)

Influence of irradiation and radiolysis on the corrosion rates and mechanisms of zirconium alloys

International Nuclear Information System (INIS)

Verlet, Romain

2015-01-01

The nuclear fuel of pressurized water reactors (PWR) in the form of uranium oxide UO 2 pellets (or MOX) is confined in a zirconium alloy cladding. This cladding is very important because it represents the first containment barrier against the release of fission products generated by the nuclear reaction to the external environment. Corrosion by the primary medium of zirconium alloys, particularly the Zircaloy-4, is one of the factors limiting the reactor residence time of the fuel rods (UO 2 pellets + cladding). To optimize core management and to extend the lifetime of the fuel rods in reactor, new alloys based on zirconium-niobium (M5) have been developed. However, the corrosion mechanisms of these are not completely understood because of the complexity of these materials, corrosion environment and the presence of radiation from the nuclear fuel. Therefore, this thesis specifically addresses the effects of radiolysis and defects induced by irradiation with ions in the matrix metal and the oxide layer on the corrosion rate of Zircaloy-4 and M5. The goal is to separate the influence of radiation damage to the metal, that relating to defects created in the oxide and that linked to radiolysis of the primary medium on the oxidation rate of zirconium alloys in reactor. 1) Regarding effect of irradiation of the metal on the oxidation rate: type dislocation loops appear and increase the oxidation rate of the two alloys. For M5, in addition to the first effect, a precipitation of fines needles of niobium reduced the solid solution of niobium concentration in the metal and ultimately in the oxide, which strongly reduces the oxidation rate of the alloy. 2) Regarding the effect of irradiation of the oxide layer on the oxidation rate: defects generated by the nuclear cascades in the oxide increase the oxidation rate of the two materials. For M5, germination of niobium enriched zones in irradiated oxide also causes a decrease of the niobium concentration in solid solution

Picosecond pulse radiolysis studies to understand the primary processes in radiolysis

International Nuclear Information System (INIS)

Jonah, C.D.; Lewis, M.A.

1984-01-01

The use of pulse radiolysis to learn about processes which occur before the beginning of chemical times is discussed. Two examples, the distance distribution of positive and negative ions in hydrocarbons, and the state of the dry electron are discussed in detail

Picosecond pulse radiolysis studies to understand the primary processes in radiolysis

Energy Technology Data Exchange (ETDEWEB)

Jonah, C.D.; Lewis, M.A.

1984-01-01

The use of pulse radiolysis to learn about processes which occur before the beginning of chemical times is discussed. Two examples, the distance distribution of positive and negative ions in hydrocarbons, and the state of the dry electron are discussed in detail.

The pulse radiolysis of Decaborane-14 solutions

International Nuclear Information System (INIS)

Brown, B.J.; Sangster, D.F.

1976-01-01

Results for the pulse radiolysis of B 10 H 14 in selected solvent systems are reported. In polar solvents the solvated electron is rapidly scavenged by B 10 H 14 with k or approximately equal to 2 x 10 10 1. mol -1 s -1 . In H 2 O, CH 3 OH and C 2 H 5 OH a transient optical absorption (G x epsilon approximately 10 4 1. mol. -1 cm -1 ) attributed to boranyl radicals is observed. A lower yield is observed in aqueous acid and hydrocarbon solutions and in the presence of electron scavengers. The results are consistent with an electron scavenging reaction leading to formation of a boranyl radical. (author)

Characterisation and activation of catalysts for recombination of radiolysis gas

International Nuclear Information System (INIS)

Bolz, Michael; Koehler, Jan; Schorle, Rolf; Helf, Achim

2011-01-01

Radiolysis gas is produced by radiolysis of cooling water during the operation of boiling water reactors. Small amounts of radiolysis gas can accumulate at dead ends of pipes in the water-steam circuit. Under certain conditions, it can accumulate even to higher concentrations. To avoid these accumulations, small catalysts are built in. As part of a diploma thesis, the catalysts were analysed and characterised. (orig.)

Radiolysis of titanium potassium oxalate in aqueous solution. [. gamma. rays

Energy Technology Data Exchange (ETDEWEB)

Bundo, Y; Ono, I [Industrial Research Inst. of Kanagawa Prefecture, Yokohama (Japan); Ogawa, T

1975-01-01

The dissolution state of titanium potassium oxalate in aqueous solution is different according to the pH. The yellowish brown titanium complex produced by the reaction of titanium potassium oxalate and hydrogen peroxide seems to be different in its structure according to the pH. Considering these points, gamma-ray irradiation was carried out on the sample by dissolving titanium potassium oxalate in purified water under the conditions of oxygen saturation and nitrogen saturation, and the relation between irradiation dose and the production of titanium complex was determined. On the basis of the experimental result, the mechanism of forming hydrogen peroxide was presumed. The radiation source used was 2,000 Ci of /sup 60/Co. For photometric analysis, a 139 type photoelectric spectrophotometer of Hitachi Ltd. was used. From the experimental results, in neutral water, titanium potassium oxalate exists in the state that two oxalic acid ions are coordinated to titanyl ion, while in case of the pH lowered by the addition of sulfuric acid, it can exist in the state that one oxalic acid ion is coordinated to titanyl ion. The yield of hydrogen peroxide produced by irradiating titanium potassium oxalate aqueous solution with gamma-ray is the sum of the molecular product from water and the radiolysis product from titanium potassium oxalate.

On the radiolysis of concentrated alkaline and calcium-nitrate solutions

International Nuclear Information System (INIS)

Kiwi, J.T.; Daniels, M.

1978-01-01

Previous studies have shown that more nitrite is produced than can reasonably be accounted for by an indirect radiolysis mechanism based on the radical products of radiolysed water. Further results on the relative roles of indirect effect and direct effect (a chemical transformation in the solute due to its energy absorption) are presented. Major products are nitrite, peroxide and oxygen and yields can be accounted for using the electron fraction model. (author)

Radiolysis of dilute aqueous solutions of cesium iodide

International Nuclear Information System (INIS)

Gorbovitskaya, T.I.; Galinkin, D.L.; Kants, L.K.; Tiliks, Yu.E.; Kotelkin, I.M.; Luzanova, L.M.

1993-01-01

Study of physical-chemical processes in the NPP containment by severe accident is carried out. Radiolysis of reactor cooling water containing iodine and cesium radionuclides penetrated therein in the course of accident is considered as of such processes. Role of ionizing radiation in the process of formation and release of ecologically hazardous volatile forms of radioiodine from reactor water into environment is studied. Experiments on radiolysis of CsI diluted water solutions are carried out. The data obtained were used for clarification of radiolysis mechanism for iodine-containing water system, enabling forecast of iodine behaviour in the course of the accident. 5 refs., 4 figs., 1 tab

Mathematical modeling of water radiolysis in the Syrian MNSR reactor

International Nuclear Information System (INIS)

Soukieh, M.

2009-11-01

Because it is difficult to measure the concentration of the radiolytic species in reactors under operating conduction, they must be estimated by computer simulation techniques. This study discusses the mathematical modeling of water radiolysis modeling of the MNSR nuclear reactor cooling water. The mathematical model comprising of 13 differential equations describe 55 chemical reactions of radiolytic species e - a q H + , OH - , H, H 2 , OH, HO 2 , O 2 , HO - 2 , O - , O - 2 , O - 3 . The mathematical model have been tested and it shows a good agreement of the computed values in this work with the results cited in references [1,18] in case of only γray irradiation of pure water with dose rate of 1.18x10 19 eV/L s. The neutron fluxes and dose rates at the interface of cladding-water for the different fuel rings in the MNSR core are determined using MCNP-4C code. In addition, the time dependent of the radiolytic specie concentrations were estimated for max. and min. dose rates and at temperature of 20 degree centigrade in the MNSR. The radiolytic specie concentrations reach the steady sate after about 200-400 s. The radiolytic specie concentrations order of H 2 , O 2 , H 2 O 2 were about ppb. Also this study shows the possibility of suppressed the water radiolysis reactions by adding hydrogen to the MNSR reactor cooling water. (author)

Pulse radiolysis study on temperature and pressure dependence of the yield of solvated electron in methanol from room temperature to supercritical condition

International Nuclear Information System (INIS)

Han, Zhenhui; He, Hui; Lin, Mingzhang; Muroya, Yusa; Katsumura, Yosuke

2012-09-01

A new concept of nuclear reactor, supercritical water-cooled reactor (SCWR), has been proposed, which is based on the success of the use of supercritical water (SCW) in fossil fuel power plants for more than three decades. This new concept reactor has advantages of higher thermal conversion efficiency, simplicity in structure, safety, etc, and it has been selected as one of the reactor concepts for the next generation nuclear reactor systems. In these reactors, the same as in boiling water reactors (BWR) and pressurized water reactors (PWR), water is used not only as a coolant but also as a moderator. It is very important to understand the behavior of the radiolysis products of water under the supercritical condition, since the water is exposed to a strong radiation field under very high temperature condition. Usually, in order to predict the concentrations of water decomposition products with carrying out some kinds of computer simulations, knowledge of the temperature and/or pressure dependent G-values (denoting the experimentally measured radiolytic yields) as well as of the rate constants of a set of reactions becomes very important. Therefore, in recent years, two groups from Argonne National Laboratory and The University of Tokyo, simultaneously conducted two projects aimed at obtaining basic data on radiolysis of SCW. However, it is still lack of reliable radiolytic yields of water decomposition products in very high temperature region. As we known, the properties of solvated electrons in polar liquid are very helpful for our understanding how they play a central role in many processes, such as solvation and reducing reactions. The solvated electron can also be used as a probe to determine the dynamic nature of the polar liquid systems. Comparing to water, the primary alcohols have much milder critical points, for example, for water and methanol, the critical temperature and pressure are 374 deg. C and 22.1 MPa and 239.5 deg. C and 8.1 MPa, respectively

Effect of cation nature of Cl2- yields in pulse radiolysis of alkali metal chloride aqueous solutions

International Nuclear Information System (INIS)

Kabakchi, S.A.; Zansokhova, A.A.; Pikaev, A.K.

1975-01-01

A study is made of the amount of Cl 2 - formed during a pulsating radiolysis of potassium, rubidium and cesium chlorides in aqueous solutions saturated with air. An equation is presented relating the yield of Cl 2 - and the concentration of the starting materials. Various mechanisms describing the radiolysis of neutral aqueous solutions of the chlorides are proposed. The observed effect of the cation on the efficiency of Cl 2 - formations favours the mechanism according to which Cl 2 - forms through the reaction of Cl - ion with a ''hole''. Due to charge migration in the conductivity zone the electron transfer reaction either goes steadily by jumps. As a result of the interaction between the ''hole'' and water [H 3 O + ...OH] a complex is formed from a hydrogen ion and OH radical, which are united trhough the hydrogen bond. Disturbance of the hydrogen bond structure should increase the probability of disintegration of the complex

Radiolysis of concentrated solutions. 2. Pulse and #betta#-radiolysis studies of direct and indirect effects in lithium iodide solutions

International Nuclear Information System (INIS)

Hadjadj, A.; Julien, R.; Pucheault, J.; Ferradini, C.; Hickel, B.

1982-01-01

In the preceding study of the radiolysis of concentrated aqueous LiCl solutions, one of the hypotheses used to explain the apparent inefficacy of Cl 2- formation by the direct effect was that molecular chlorine, not detectable by spectrophotometry, could be formed during the early stages of water radiolysis. Such an hypothesis is confirmed here for pulse and #betta#-radiolysis of concentrated aqueous neutral LiI solutions. Indeed, it is shown that, 10 ns after the pulse, molecular iodine, detected as I 3- , is formed with a yield that increases with the LiI concentration. The experimental results yields values of 4.8 and 7.3 respectively for the indirect and direct effects of total oxidation G/sub I 2- / + 2G/sub I 3- /. This last high value is discussed

Radiolysis of hydrocarbons in liquid phase (Modern state of problem)

International Nuclear Information System (INIS)

Saraeva, V.V.

1986-01-01

Problems of ionizing radiation effect on hydrocarbons and hydrocarbon systems in a liquid phase are considered. Modern representations on the mechanism of hydrocarbon radiolysis are presented. Electron moderation and ion-electron pair formation, behaviour of charged particles, excited states, radical formation and their reactions are discussed. Behaviour of certain hydrocarbon classes: alkanes, cyclic hydrocarbons, olefines, aromatic hydrocarbons as well as different hydrocarbon mixtures is considered in detail. Radiation-chemical changes in organic coolants and ways of increasing radiation resistance are considered. Polyphenyl compounds are noted to be most perspective here

Aspects of the physics and chemistry of water radiolysis by fast neutrons and fast electrons in nuclear reactors

Energy Technology Data Exchange (ETDEWEB)

McCracken, D.R. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Tsang, K.T. [Atomic Energy of Canada Limited, Mississauga, Ontario (Canada); Laughton, P.J

1998-09-01

Detailed radiation physics calculations of energy deposition have been done for the coolant of CANDU reactors and Pressurized Water Reactors (PWRs). The geometry of the CANDU fuel channel was modelled in detail. Fluxes and energy-deposition rates for neutrons, recoil ions, photons, and fast electrons have been calculated using MCNP4B, WIMS-AECL, and specifically derived energy-transfer factors. These factors generate the energy/flux spectra of recoil ions from fast-neutron energy/flux spectra. The energy spectrum was divided into 89 discrete ranges (energy bins).The production of oxidizing species and net coolant radiolysis can be suppressed by the addition of hydrogen to the coolant of nuclear reactors. It is argued that the net dissociation of coolant by gamma rays is suppressed by lower levels of excess hydrogen than when dissociation is by ion recoils. This has consequences for the modelling of coolant radiolysis by homogeneous kinetics. More added hydrogen is required to stop water radiolysis by recoil ions acting alone than if recoil ions and gamma rays acted concurrently in space and time. Homogeneous kinetic models and experimental data suggest that track overlap is very inefficient in providing radicals from gamma-ray tracks to recombine molecular products in ion-recoil tracks. An inhomogeneous chemical model is needed that incorporates ionizing-particle track structure and track overlap. Such a model does not yet exist, but a number of limiting cases using homogeneous kinetics are discussed. There are sufficient uncertainties and contradictions in the data relevant to the radiolysis of reactor coolant that the relatively high CHC's (critical hydrogen concentration) observed in NRU reactor experiments (compared to model predictions) may be explainable by errors in fundamental data and understanding of water radiolysis under reactor conditions. The radiation chemistry program at CRL has been focused to generate quantitative water-radiolysis data in a

Studies on oxidative radiolysis of ibuprofen in presence of potassium persulfate

International Nuclear Information System (INIS)

Paul, Jhimli; Naik, D.B.; Bhardwaj, Y.K.; Varshney, Lalit

2014-01-01

The radiolysis of ibuprofen (IBP), a model pharmaceutical compound, was studied by gamma irradiation in an aqueous solution in the presence and absence of potassium persulfate (K 2 S 2 O 8 ). The extent of mineralization was investigated by measuring the UV–visible spectra, decrease in the chemical oxygen demand (COD) and the total organic carbon (TOC) content of aqueous IBP solution at different doses. The gamma radiolysis, in the presence of K 2 S 2 O 8 , required much lesser dose compared to in the absence of K 2 S 2 O 8 for the same extent of mineralization of aqueous IBP solution. The pulse radiolysis of IBP was carried out under different radiolytic conditions to understand the mechanism of efficient mineralization of IBP during gamma radiolysis in the presence of K 2 S 2 O 8 . It was found that unlike · OH radical, SO 4 ·− radical preferentially produces benzyl type of radicals via the formation of the benzene radical cation. The results concluded that the gamma radiolysis in presence of K 2 S 2 O 8 could be one of the efficient advanced oxidation processes for degradation of pharmaceutical compounds present in the aqueous solution. - Highlights: • The radiolysis of aqueous solution of Ibuprofen (IBP) was investigated. • The COD and TOC content decreased significantly in presence of K 2 S 2 O 8 . • Pulse radiolysis studies revealed the mechanism of mineralization of IBP. • The presence of K 2 S 2 O 8 increased the efficiency of gamma radiolysis

Radiolysis of poly(acrylic acid) in aqueous solution

Science.gov (United States)

Ulanski, Piotr; Bothe, Eberhard; Hildenbrand, Knut; Rosiak, Janusz M.; von Sonntag, Clemens

1995-02-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CHCH(CO 2H)- (β-radicals) and -CH 2C(CO 2H)- (α-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of α-radicals from model systems. The β-radicals convert slowly into α-radicals ( k = 0.7 s -1 at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10 -2 mol dm -3 chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 × 10 -2s -1 was observed. Oxygen reacts with PAA-radicals with k = 3.1 × 10 8 dm 3 mol -1 s -1 at pH 3.5 and k = 1.0 × 10 8 dm 3 mol -1 s -1 at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones.

Formation of stable radicals during perfluoroalkane radiolysis

International Nuclear Information System (INIS)

Allayarov, S.R.; Demidov, S.V.; Kiryukhin, D.P.; Mikhajlov, A.I.; Barkalov, I.M.

1984-01-01

Accumulation and stabilization kinetics of perfluoroalkyls during α-radiolysis ( 60 Co) of perfluoralkanes (PFA) in a wide temperature range for different PFA fractions differing in the average molecular weight, is investigated. It is noted that low temperature (PFA) radiolysis (77 K) is of a linear nature of accumulation of stabilized radicals up to doses of approximately 700 KGy. In the case of PFA radiolysis at 300 K radiation yields of stable radicals are somewhat lower than at 47 K and at doses of 200-300 KGy, their accumulation ceases. It is shown that kinetics of formation and accumulation of stable radicals does not depend on molecular mass and PFA fraction viscosity. Perfluoroalkyl stability is explained by intra molecular conformation spheric insulation of the free valency. Perfluoroalkyl stability in different PFA fractions in a wide time range in different media is investigated

Proton Pulse Radiolysis

Energy Technology Data Exchange (ETDEWEB)

Christensen, H C; Nilsson, G; Reitberger, T; Thuomas, K A

1973-03-15

A 5 MeV proton accelerator (Van de Graaff) has been used for pulse radiolysis of a number of organic gases and the transient spectra obtained from the alkanes methane, ethane, propane, n-butane and neopentane have tentatively been assigned to alkyl radicals. Some methodological aspects of this new technique are discussed

Spent fuel reaction - the behavior of the ε-phase over 3.1 years

International Nuclear Information System (INIS)

Finn, P.A.; Hoh, J.C.; Wolf, S.F.

1996-01-01

The release fractions of the five elements in the ε-phase ( 99 Tc, 97 Mo, Ru, Rh, and Pd) as well as that of 238 U are reported for the reaction of two oxide fuels (ATM-103 and ATM-106) in unsaturated tests under oxidizing conditions. The 99 Tc release fractions provide a lower limit for the magnitude of the spent fuel reaction. The 99 Tc release fractions indicate that a surface reaction might be the rate controlling mechanism for fuel reaction under unsaturated conditions and the oxidant is possibly H 2 O 2 , a product of alpha radiolysis of water

Radiolysis of water confined in zeolites 4A: application to tritiated water storage

International Nuclear Information System (INIS)

Frances, Laetitia

2014-01-01

Self-radiolysis of tritiated water (HTO) adsorbed in zeolites 4A shows differences compared to free-bulk water radiolysis. We studied the roles of zeolites on that. We took special care with the influence of water loading ratio. We first exposed zeolites to external irradiations, reproducing selectively the dose or the dose rate measured in the case of tritiated water storage. This strategy enables the characterising of the samples after their irradiation since they are not contaminated by tritium. Those experiments revealed the high stability of zeolites 4A. We used a second approach which consisted in studying the precise case of self-radiolysis of tritiated water, in order to obtain radiolytic yields representative of HTO storage. The comparison between the quantities of gas released when zeolites are exposed to the three different sources that we used (electrons accelerated at 10 MeV, γ released by radioactive decay of 137 Cs and β - released by radioactive decay of tritium) revealed the strong influence of the dose rate. Moreover, whatever the irradiation source, zeolites 4A first favour hydrogen release and secondarily oxygen release too. On the contrary, zeolites favour next a recombination between those radiolytic products, with a dependence on their water loading ratio. Several processes are discussed to explain such a phenomena, not noticed during the free-bulk water radiolysis. (author) [fr

The reactivity of the electron formed in the radiolysis of aerated alkaline aqueous solutions containing tetracycline hydrochloride, at 77 Ksup(+)

International Nuclear Information System (INIS)

Guedes, S.M.L.; Vasconcellos, M.B.A.

1986-01-01

The radiolysis of tetracycline hydrochloride dissolved in aerated alkaline aqueous solutions containing 0.1, 0.5 and 1M NaOH at 77 K, followed by ESR is reported. The rate constants for the reactions between the electron and physical or chemical traps which are present in these solutions are calculated. The reactivity of electrons that are formed in the radiolysis of water decreases in the following proportions: physical traps: chemical traps: molecules of water (4.8x10sup(14) : 6.5x10sup(8) : 1.0). The electrons react preferentially with the solute instead of the solvent. (author)

Gamma radiolysis effects on leaching behavior of ceramic materials for nuclear fuel waste immobilization containers

International Nuclear Information System (INIS)

Onofrei, M.; Raine, D.K.; Hocking, W.H.; George, K.; Betteridge, J.S.

1986-01-01

The leaching behavior of ceramic materials for nuclear fuel waste immobilization containers, under the influence of a moderate gamma dose rate (4 Gy/h), has been investigated. Samples of Al/sub 2/O/sub 3/, stabilized ZrO/sub 2/, TiO/sub 2/, cermet (70% Al/sub 2/O-30% TiC), porcelain (with high Al/sub 2/O/sub 3/ content), and concrete (with sulfate-resisting portland cement plus silica fume) have been leached in Standard Canadian Shield Saline Solution (SCSSS), and SCSSS plus clay and sand (components of the disposal system), at 100 0 and 150 0 C for 231 and 987 days, respectively. Leaching solutions were analyzed and the surfaces of the leached samples were investigated by scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy and secondary ion mass spectrometry. Radiolysis did not appear to enhance the leaching, with or without bentonite and sand in the system. Analysis of the gas phase from sealed capsules showed O/sub 2/ depletion and production of CO/sub 2/ in all experiments containing bentonite. The decrease in O/sub 2/ is attributed to the leaching from the clay of Fe(II) species, which can participate in redox reactions with radicals generated by radiolysis. The CO/sub 2/ is produced from either the organic or inorganic fraction in the bentonite

Pulse radiolysis study of supercritical water-G-value measurement up to 450 degree C

International Nuclear Information System (INIS)

Katsumura, Y.

2006-01-01

It is widely recognized that the understanding of water radiolysis at elevated temperatures is inevitably important in the field of water chemistry in light water reactors because water radiolysis is closely related to many subjects such as hydrogen water chemistry (H 2 injection), SCC (stress corrosion cracking), dose accumulation and so on. This situation would also be applied to the future reactor using supercritical water (>374 C, 22.1MPa) as a coolant, so called supercritical water-cooled reactor (SCWR). Therefore, it is important to investigate water radiolysis of supercritical water. In 1989 Prof. Oka, University of Tokyo, proposed the SCWR as a future reactor and done much design study. This reactor has many advantages such as high energy efficiency, applicability of experience accumulated in light water reactors and supercritical fissile plant, and compact structure. In 2002 the Department of Energy in USA has selected the SCWR as one of the six Generation IV reactors and fundamental research has started in different countries as a national or an international project. In the present research G-values of water radiolysis have been measured by using a pulse radiolysis method up to 450 degree C to obtain the fundamental data relevant to the development of the SCWR. In supercritical water, the pressure controls the density of water easily and it was found that the G-values are strongly dependent not only on temperature but also on density in supercritical water. After presentation of experimental method and its difficulties, temperature and density dependent G-values of water decomposition products in supercritical water would be summarized. (authors)

Heavy water radiolysis and chemistry control of the Fugen Nuclear Power Station

International Nuclear Information System (INIS)

Ibuki, Y.; Kitabata, T.; Kato, T.

1989-01-01

A computer analysis for heavy water radiolysis clarified the mechanism of the heavy water radiolysis rate change with impurities in the heavy water and cover gas, helium. The mechanism is supported by over ten years' operational data of the heavy water radiolysis in the Fugen nuclear power station. (author)

Radiolysis of pyridoxine (vitamin B6) in aqueous solution under different conditions

International Nuclear Information System (INIS)

Albarran, Guadalupe; Ramirez-Cahero, Fernando; Aliev, Roustam

2008-01-01

Aqueous solutions of pyridoxine (1 mM) without or with additive of K 3 [Fe(CN) 6 ] (2.5 mM) were gamma-irradiated at different doses and dose rate of 2.16 kGy/h in the absence of air, in the presence of air or by their saturation with N 2 O. The radiolytic products were analyzed with HPLC, mass spectrometry and UV spectroscopy. 2,4,5-Trihydroxymethyl-3-pyridinol, pyridoxal, isopyridoxal and 6-hydroxypyridoxine were formed by radiolysis in the absence of K 3 [Fe(CN) 6 ], and their concentrations were much higher in samples saturated with N 2 O. Pyridoxi-3,6-quinone was found by radiolysis under all the above-mentioned conditions but only in the presence of K 3 [Fe(CN) 6 ]. Besides, the pyridoxal formation increased in the presence of this oxidizing agent. G values of pyridoxal formation and pyridoxine degradation were quantified. Some details of the radiolytic product formation were discussed

Muon radiolysis affected by density inhomogeneity in near-critical fluids.

Science.gov (United States)

Cormier, P J; Alcorn, C; Legate, G; Ghandi, K

2014-04-01

In this article we show the significant tunability of radiation chemistry in supercritical ethane and to a lesser extent in near critical CO2. The information was obtained by studies of muonium (Mu = μ(+)e(-)), which is formed by the thermalization of positive muons in different materials. The studies of the proportions of three fractions of muon polarization, PMu, diamagnetic PD and lost fraction, PL provided the information on radiolysis processes involved in muon thermalization. Our studies include three different supercritical fluids, water, ethane and carbon dioxide. A combination of mobile electrons and other radiolysis products such as (•)C2H5 contribute to interesting behavior at densities ∼40% above the critical point in ethane. In carbon dioxide, an increase in electron mobility contributes to the lost fraction. The hydrated electron in water is responsible for the lost fraction and decreases the muonium fraction.

Development of subpicosecond pulse radiolysis system

CERN Document Server

Kozawa, T; Miki, M; Yamamoto, T; Suemine, S; Yoshida, Y; Tagawa, S

2000-01-01

The highest time resolution of the pulse radiolysis had remained about 30 ps since the late 1960s. To make clear the primary processes in the radiation chemistry and physics within 30 ps, we developed a stroboscopic pulse radiolysis system for the absorption spectroscopy with the time resolution of 2.0 ps (10-90% rise time). The time resolution of 2.0 ps was estimated from the time-dependent behavior of the hydrated electrons. The system consists of a subpicosecond electron linac as an irradiation source, a femtosecond laser as an analyzing light and a jitter compensation system.

Monte Carlo simulation of chemistry following radiolysis with TOPAS-nBio

Science.gov (United States)

Ramos-Méndez, J.; Perl, J.; Schuemann, J.; McNamara, A.; Paganetti, H.; Faddegon, B.

2018-05-01

Simulation of water radiolysis and the subsequent chemistry provides important information on the effect of ionizing radiation on biological material. The Geant4 Monte Carlo toolkit has added chemical processes via the Geant4-DNA project. The TOPAS tool simplifies the modeling of complex radiotherapy applications with Geant4 without requiring advanced computational skills, extending the pool of users. Thus, a new extension to TOPAS, TOPAS-nBio, is under development to facilitate the configuration of track-structure simulations as well as water radiolysis simulations with Geant4-DNA for radiobiological studies. In this work, radiolysis simulations were implemented in TOPAS-nBio. Users may now easily add chemical species and their reactions, and set parameters including branching ratios, dissociation schemes, diffusion coefficients, and reaction rates. In addition, parameters for the chemical stage were re-evaluated and updated from those used by default in Geant4-DNA to improve the accuracy of chemical yields. Simulation results of time-dependent and LET-dependent primary yields Gx (chemical species per 100 eV deposited) produced at neutral pH and 25 °C by short track-segments of charged particles were compared to published measurements. The LET range was 0.05–230 keV µm‑1. The calculated Gx values for electrons satisfied the material balance equation within 0.3%, similar for protons albeit with long calculation time. A smaller geometry was used to speed up proton and alpha simulations, with an acceptable difference in the balance equation of 1.3%. Available experimental data of time-dependent G-values for agreed with simulated results within 7%  ±  8% over the entire time range; for over the full time range within 3%  ±  4% for H2O2 from 49%  ±  7% at earliest stages and 3%  ±  12% at saturation. For the LET-dependent Gx, the mean ratios to the experimental data were 1.11  ±  0.98, 1.21  ±  1.11, 1.05�

Pulse radiolysis study of the reduction mechanism of an antitumor antibiotic, mitomycin C

International Nuclear Information System (INIS)

Machtalere, G.; Houee-Levin, C.; Gardes-Albert, M.; Ferradini, C.; Hickel, B.

1988-01-01

Mitomycin C is a quinonic antitumor metabolized in vivo by one-electron reduction. We have studied the mechanism of the one-electron reduction of this drug by pulse radiolysis using C00 .- free radicals as reductants. Semiquinonic and hydroquinonic intermediates are formed. The hydroquinonic form undergoes a methanol elimination leading to a transient which can disappear in one of two ways: by either internal redox reaction or hydrolysis of the aziridine. 17 refs [fr

Pulse radiolysis of adrenaline in acid aqueous solutions

International Nuclear Information System (INIS)

Gohn, M.; Getoff, N.; Bjergbakke, E.

1976-01-01

Pulse radiolysis of adrenaline in acid aqueous solutions (pH 1 to 3) was carried out. The rate constants for the reactions of adrenaline with H and 0H were determined: k(H + adr.) = (0.9 +- 0.1) x 10 9 dm 3 mol -1 s -1 ; k(0H + adr.) = (1.65 +- 0.15) x 10 10 dm 3 mol -1 s -1 . The H-adduct of adrenaline has two lambdasub(max), at 280 and 355 nm, with epsilon 280 = 420 m 2 mol -1 and epsilon 355 = 390 m 2 mol -1 , which disappears according to a first order reaction, k 1 = 1.4 x 10 3 s -1 . The spectra formed by 0H attack was assigned to the corresponding benzoxy radical with absorption maxima at 285 and 365 nm and epsilon 285 = 620 m 2 mol -1 and epsilon 365 = 105 m 2 mol -1 . Due to the overlapping of the intermediates, no decay kinetics could be obtained. (author)

Gamma-radiolysis of some glycoproteins in dilute aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Nagrani, S

1981-01-01

A study has been made of the radiation-induced damage of some glycoproteins in dilute aqueous solutions. By use of specific radical scavengers, the roles of the individual free radicals, formed by ..gamma..-radiolysis, in causing damage has been assessed. The most effective radical in causing damage to human and porcine glycopolypeptide is the OH radical. The structure of the different blood group glycopolypeptides determines the sensitivity towards the free radical attack. The glycopolypeptide shows depolymerization and a characteristic absorption at approximately 270 nm due to the formation of additional products on irradiation. Chemical changes of the irradiated glycopolypeptide solutions revealed significant damage to the oligosaccharide chain and the polypeptide core of the glycopolypeptide. The radiation-induced inactivation of another glycoprotein, external yeast invertase, due to different radical species at pH 7.0 decreases in the following order: ea-barq > OH radical > (SCN) radical/sub 2//sup -/ > Br radical/sub 2//sup -/. The structure of this enzyme, accounts for the mechanism of enzyme inactivation and the relative damage of carbohydrate and amino acid residues. The irradiated enzyme solutions show significant changes in their electrophoretic behaviour on cellogel electrophoresis due to the formation of radiolysis products, which also show characteristic absorption maxima at approximately 275 nm. (author).

Electron paramagnetic resonance study of radicals formed by radiolysis at 77 K of nitroalkanes and of their solutions in organic glasses. Chromatography analysis of radiolysis products of nitromethane in ethanol solution in a vitreous medium; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux

Energy Technology Data Exchange (ETDEWEB)

Rosilio, C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1968-05-01

With a view to explaining the formation of the final products resulting from the photolysis and the radiolysis of nitro-alkanes, we have attempted to identify the paramagnetic species formed as intermediates during the radiolysis. Our work has covered the structure and the reactivity of the radicals formed by 7 irradiation of the nitrogen containing derivatives at 77 K, and on the mechanism of formation and of disappearance of these radicals in the various matrices used. The radicals resulting from the removal of a hydrogen atom in the {alpha} position of the NO{sub 2} group, and the radicals resulting from addition reactions on the nitrogen group characterized by an unpaired electron on the nitrogen have been identified, either during the radiolysis of pure nitroalkanes, or during the radiolysis of nitro-alkanes in solution in organic glasses at 77 K. A study has been made of the conformation and the movements of radicals in the matrices, and the mechanism of formation of the observed radicals produced generally by the capture by the nitro-alkanes of primary radiolysis species. The nitro-alkanes in ethanol solution can behave as traps both for electrons and for free radicals. The study of the radiolysis of nitro-alkanes in solution in a polar ethanol glass has been completed with chemical analyses on the final radiolysis products; it has been possible to deduce the capture efficiency of trapped electrons and of free radicals by nitro-alkanes in ethanol. For this we have determined the radio-chemical yields of hydrogen, acetaldehyde and glycol as a function of the capture agent concentration, for the nitro-methane-ethanol system. A mechanism for the disappearance of the observed radicals is proposed. (author) [French] Dans le but d'expliquer la formation des produits finals formes au cours de la photolyse et la radiolyse des nitroalcanes, nous nous sommes proposes d'identifier les especes paramagnetiques se formant intermediairement au cours de la radiolyse. Notre

Electron paramagnetic resonance study of radicals formed by radiolysis at 77 K of nitroalkanes and of their solutions in organic glasses. Chromatography analysis of radiolysis products of nitromethane in ethanol solution in a vitreous medium; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux

Energy Technology Data Exchange (ETDEWEB)

Rosilio, C. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1968-05-01

With a view to explaining the formation of the final products resulting from the photolysis and the radiolysis of nitro-alkanes, we have attempted to identify the paramagnetic species formed as intermediates during the radiolysis. Our work has covered the structure and the reactivity of the radicals formed by 7 irradiation of the nitrogen containing derivatives at 77 K, and on the mechanism of formation and of disappearance of these radicals in the various matrices used. The radicals resulting from the removal of a hydrogen atom in the {alpha} position of the NO{sub 2} group, and the radicals resulting from addition reactions on the nitrogen group characterized by an unpaired electron on the nitrogen have been identified, either during the radiolysis of pure nitroalkanes, or during the radiolysis of nitro-alkanes in solution in organic glasses at 77 K. A study has been made of the conformation and the movements of radicals in the matrices, and the mechanism of formation of the observed radicals produced generally by the capture by the nitro-alkanes of primary radiolysis species. The nitro-alkanes in ethanol solution can behave as traps both for electrons and for free radicals. The study of the radiolysis of nitro-alkanes in solution in a polar ethanol glass has been completed with chemical analyses on the final radiolysis products; it has been possible to deduce the capture efficiency of trapped electrons and of free radicals by nitro-alkanes in ethanol. For this we have determined the radio-chemical yields of hydrogen, acetaldehyde and glycol as a function of the capture agent concentration, for the nitro-methane-ethanol system. A mechanism for the disappearance of the observed radicals is proposed. (author) [French] Dans le but d'expliquer la formation des produits finals formes au cours de la photolyse et la radiolyse des nitroalcanes, nous nous sommes proposes d'identifier les especes paramagnetiques se formant intermediairement au cours de la

Radiolysis study of actinide complexing agent by irradiation with helium ion beam

International Nuclear Information System (INIS)

Sugo, Yumi; Taguchi, Mitsumasa; Sasaki, Yuji; Hirota, Koichi; Kimura, Takaumi

2009-01-01

α-Radiolysis of N,N,N',N'-tetraoctyldiglycolamide (TODGA) in n-dodecane was investigated by the irradiation with helium ion beam provided by a tandem accelerator. The radiation chemical yield for the degradation of TODGA by helium ion beam irradiation was less than that by γ-rays irradiation. It is considered that the radical cations of n-dodecane, which contribute to the charge transfer reaction with the TODGA molecules, decrease by recombination in track by high LET radiations such as α-particles.

Modelling 'steady-state' water radiolysis in nuclear reactors: status of the reaction set, rate constants and g-Values for 20o - 350oC

International Nuclear Information System (INIS)

Elliot, J.

2010-01-01

This paper gives a review of water radiolysis in reactor circuits. The discussion is illustrated with experimental results from the radiolysis of water under high temperature, high dose conditions in a re-circulating water loop in a reactor. It also gives the status of the database for modeling radiation chemistry under power reactor conditions.

The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

International Nuclear Information System (INIS)

Miyazaki, Tetsuo

1991-01-01

The formation of olefin cations in the radiolysis of 2,3-dimethylbutane (DMB) was studied by ESR at 4.2 and 77 K. When a DMB-SF 6 mixture is γ-irradiated at 77 K, tetramethylethylene (TME) cations are formed remarkably. The formation of the TME cations, however, is suppressed at 4.2 K. When the DMB-SF 6 mixture is γ-irradiated at 4.2 K and then warmed to 77 K, TME cations are formed by thermal annealing. The TME cations are not formed by a charge transfer to olefinic impurities or olefinic products in radiolysis, but by H 2 elimination from parent DMB cations in the ground state. The remarkable formation of olefin cations at 77 K corresponds to the large yields of unsaturated dimers in the radiolysis of DMB at 77 K. The suppression of olefin cation formation at 4.2 K corresponds to the low yields of unsaturated dimers in the radiolysis of DMB at 4.2 K. (author)

Gamma-radiolysis of dimethyl sulfoxide. II. Radiolysis yields and possible mechanisms; Gamma-Radiolisis del dimetilsulfoxido II. Rendimientos radioloticos y posibles mecanismos

Energy Technology Data Exchange (ETDEWEB)

Gutierrez, M C; Barrera, R

1978-07-01

As result of quantitative studies on gamma-radiolysis of DMSO at a dose range of 90-850 Mrads, constant G values have been obtained for the following radiolysis compounds: G(-DMSO) - 6.7 {+-}0.2; G(dimethyl sulphide) - 3.4 {+-}0.3; G(methane) - 0,75 {+-} 0.04; G(dimethyl disulphide) -0.33 {+-}0,03; G(tri methylsulphonium methanesulphonate) - 0.26 {+-} 0,01; G(methyl methanethiosulphonate) - 0,25 {+-}0.02; G(dimethyl sulphona)-0.21{+-}0.02; G(H{sub 2})-0.18{+-}0.02; and G(propane)--0.0092{+-}0.0007. Initial G values have been obtained for other identified compounds: Gi(ethane)-0,46; Gi(CO)-0.052; and Gi(CO{sub 2})-0.030. Possible mechanisms on the radiolysis process are proposed. (Author) 17 refs.

A study of solute transport of radiolysis products in crud and its effects on crud growth on PWR fuel pin

Energy Technology Data Exchange (ETDEWEB)

Joe, Justin H. [BNF Consulting (United States); Kim, Seung Jun, E-mail: skim@lanl.gov [Mechanical and Thermal Engineering Group (AET-1), Los Alamos National Laboratory (United States); Jones, Barclay G. [Department of Nuclear Plasma Radiological Engineering, University of Illinois Urbana-Champaign (United States)

2016-04-15

Highlights: • We model a 3-D numerical solute transport within crud deposit on PWR fuel pin. • Source term effect from radiolysis yield and recombination is minimal. • Lower crud porosity leads substantially higher concentration of solutes. • Thicker crud deposit generates substantially higher concentration of solutes. • High concentration of radiolysis species (H{sub 2}, O{sub 2}, and H{sub 2}O{sub 2}) can be directly related to corrosion issues on fuel cladding. - Abstract: This research examines the concentration of radiolysis species (H{sub 2}, O{sub 2}, and H{sub 2}O{sub 2}) over the porous crud layer using a three dimensional time dependent solute transport model. A Monte Carlo random walk technique is adopted to simulate the transport behavior of the different species with various parametric studies of source term, crud thickness, and crud porosity. Particularly, this model employs a system of coupled mass transport and chemical interactions as the source term, which makes the problem non-linear. It is demonstrated that a negligible effect on radiolysis species concentrations change due to the consideration of source term. The crud thickness and porosity effect on the concentration distributions are notably observed. In general, higher concentration starts from the intersection of the heating surface with the chimney wall from the beginning and it reaches the equilibrium state within tens of seconds. The concentration profiles of the radiolysis species H{sub 2}, O{sub 2}, and H{sub 2}O{sub 2} can be directly related to corrosion issues. The direct application of this study to nuclear engineering research is to aid in the design of reactors with higher performance without experiencing an Axial Offset Anomaly (AOA), an unexpected measured shift in axial power distribution from predicted values.

A study of solute transport of radiolysis products in crud and its effects on crud growth on PWR fuel pin

International Nuclear Information System (INIS)

Joe, Justin H.; Kim, Seung Jun; Jones, Barclay G.

2016-01-01

Highlights: • We model a 3-D numerical solute transport within crud deposit on PWR fuel pin. • Source term effect from radiolysis yield and recombination is minimal. • Lower crud porosity leads substantially higher concentration of solutes. • Thicker crud deposit generates substantially higher concentration of solutes. • High concentration of radiolysis species (H 2 , O 2 , and H 2 O 2 ) can be directly related to corrosion issues on fuel cladding. - Abstract: This research examines the concentration of radiolysis species (H 2 , O 2 , and H 2 O 2 ) over the porous crud layer using a three dimensional time dependent solute transport model. A Monte Carlo random walk technique is adopted to simulate the transport behavior of the different species with various parametric studies of source term, crud thickness, and crud porosity. Particularly, this model employs a system of coupled mass transport and chemical interactions as the source term, which makes the problem non-linear. It is demonstrated that a negligible effect on radiolysis species concentrations change due to the consideration of source term. The crud thickness and porosity effect on the concentration distributions are notably observed. In general, higher concentration starts from the intersection of the heating surface with the chimney wall from the beginning and it reaches the equilibrium state within tens of seconds. The concentration profiles of the radiolysis species H 2 , O 2 , and H 2 O 2 can be directly related to corrosion issues. The direct application of this study to nuclear engineering research is to aid in the design of reactors with higher performance without experiencing an Axial Offset Anomaly (AOA), an unexpected measured shift in axial power distribution from predicted values.

Radiolysis of pyridoxine (vitamin B{sub 6}) in aqueous solution under different conditions

Energy Technology Data Exchange (ETDEWEB)

Albarran, Guadalupe [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Mexico 04510, D.F. (Mexico)], E-mail: albarran@nucleares.unam.mx; Ramirez-Cahero, Fernando; Aliev, Roustam [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Mexico 04510, D.F. (Mexico)

2008-05-15

Aqueous solutions of pyridoxine (1 mM) without or with additive of K{sub 3}[Fe(CN){sub 6}] (2.5 mM) were gamma-irradiated at different doses and dose rate of 2.16 kGy/h in the absence of air, in the presence of air or by their saturation with N{sub 2}O. The radiolytic products were analyzed with HPLC, mass spectrometry and UV spectroscopy. 2,4,5-Trihydroxymethyl-3-pyridinol, pyridoxal, isopyridoxal and 6-hydroxypyridoxine were formed by radiolysis in the absence of K{sub 3}[Fe(CN){sub 6}], and their concentrations were much higher in samples saturated with N{sub 2}O. Pyridoxi-3,6-quinone was found by radiolysis under all the above-mentioned conditions but only in the presence of K{sub 3}[Fe(CN){sub 6}]. Besides, the pyridoxal formation increased in the presence of this oxidizing agent. G values of pyridoxal formation and pyridoxine degradation were quantified. Some details of the radiolytic product formation were discussed.

Density dependence of the radiolysis yields of primary species from fast neutron-irradiated supercritical water at 400 {sup o}C

Energy Technology Data Exchange (ETDEWEB)

Butarbutar, S.L. [Universite de Sherbrooke, Sherbrooke, QC (Canada); National Nuclear Energy Agency, BATAN, Tangerang Selatan, Banten (Indonesia); Meesungnoen, J. [Universite de Sherbrooke, Sherbrooke, QC (Canada); Guzonas, D.A.; Stuart, C.R. [Atomic Energy of Canada Limited, Chalk River, ON (Canada); Jay-Gerin, J-P [Universite de Sherbrooke, Sherbrooke, QC (Canada)

2014-07-01

A reliable understanding of radiolysis processes in supercritical water (SCW)-cooled reactors is crucial to developing chemistry control strategies that minimize corrosion and the transport of both corrosion products and radionuclides. Chemistry control is one of the most important factors to keep the integrity of materials from degradation processes and also to reduce out-of-core radiation fields and worker dose. However, directly measuring the chemistry in reactor cores is difficult due to the extreme conditions of high temperature and pressure and mixed neutron and γ-radiation fields that are not compatible with normal chemical instrumentation. Thus, chemical models and computer simulations are an important route of investigation for predicting the detailed radiation chemistry of the coolant in a SCW reactor and the consequences for materials. Surprisingly, there is only limited information on the fast neutron radiolysis of water at high temperatures, and no experimental data are yet available on the radiolysis yields for fast neutron irradiation of SCW. In this work, Monte Carlo simulations were used to predict the G-values for the primary species e{sup -}{sub aq}, H{sup •}, H{sub 2}, {sup •}OH, and H{sub 2}O{sub 2} formed from the radiolysis of pure, deaerated SCW (H{sub 2}O) by 2-MeV mono-energetic neutrons at 400 {sup o}C as a function of water density in the range of ~0.15-0.6 g/cm{sup 3}. The 2-MeV neutron was taken as representative of a fast neutron flux in a reactor. For light water, the moderation of these neutrons after knock-on collisions with water molecules generated mostly recoil protons of 1.264, 0.465, 0.171, and 0.063 MeV having linear energy transfer (LET) values of ~3.3, 6.5, 10.4, and 11.4 keV/μm at 0.15 g/cm{sup 3}, and ~13.3, 26, 42, and 46 keV/μm at 0.6 g/cm{sup 3}, respectively. Neglecting oxygen ion recoils and assuming that the most significant contribution to the radiolysis came from these first four recoil protons, the fast

Radiolysis of poly(acrylic acid) in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Ulanski, P [Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany); [Politechnika Lodzka, Lodz (Poland); Bothe, E; Hildenbrand, K; Sonntag, C von [Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany); Rosiak, J M [Politechnika Lodzka, Lodz (Poland)

1995-10-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CH-CH(CO{sub 2}H)- ({beta}-radicals) and -CH{sub 2}-C(CO{sub 2}H)-({alpha}-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of {alpha}-radicals from model systems. The {beta}-radicals convert slowly into {alpha}-radicals (k = 0.7s {sup -1} at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10{sup -2} mol dm{sup -3} chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 x 10{sup -2}s{sup -1} was observed. Oxygen reacts with PAA-radicals with k = 3.1 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 3.5 and k = 1.0 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones. (Author).

Experiments about the integrity of BWR relief pipes in postulated radiolysis gas combustion. Scenario No.2. Minor steam leakages without any lowering of the water level

International Nuclear Information System (INIS)

Friedrich, A.; Grune, J.; Sempert, K.; Stern, G.; Kuznetsov, M.; Redlinger, R.; Breitung, W.; Franke, T.

2008-01-01

The experiments described in this article were performed to study this comprehensive radiolysis gas scenario: - The relief pipe is filled completely with radiolysis gas (2H 2 +O 2 ). - After opening of the S and R valve, the radiolysis gas is compressed adiabatically by the incoming steam without mixing. - Roughly at the point of peak pressure in the relief pipe (20 bar) the radiolysis gas ignites. This dynamic scenario was studied in steady-state model experiments with a test pipe which corresponds to the relief pipes installed in KKP-1 in terms of materials, dimensions, and manufacturing control. The initial conditions and boundary conditions of the experiments were conservative. In the course of the tests, the maximum dynamic strain and the residual plastic deformation of the test pipe were measured via the transient detonation load. The maximum dynamic strain measured was 0.75%, the maximum residual plastic strain reached 0.15%. The pipe suffered no other deformation above and beyond this slight plastic strain. The radiolysis gas detonation was simulated very well numerically. Using the calculated pressure loads in a structural dynamics model also showed good agreement with the measured maximum dynamic pipe strains. In this way, the experimental findings were confirmed theoretically. The experiments and the calculations showed that postulated radiolysis gas reactions during pressure relief cannot jeopardize the integrity of the relief pipe. (orig.)

Pulse radiolysis studies of mangiferin: A C-glycosyl xanthone isolated from Mangifera indica

International Nuclear Information System (INIS)

Mishra, B.; Priyadarsini, K.Indira; Sudheerkumar, M.; Unnikrishhnan, M.K.; Mohan, H.

2006-01-01

Pulse radiolysis technique has been employed to study the reaction of different oxidizing and reducing radicals with mangiferin. The reaction of · OH radical showed the formation of transient species absorbing in 380-390 and 470-480 nm region. The reaction with specific one-electron oxidants (N 3 · , CCl 3 O 2 · ) also showed the formation of similar transient absorption bands and is assigned to phenoxyl radicals. The pK a values of the transient species have been determined to be 6.3 and 11.9. One-electron oxidation potential of mangiferin at pH 9 has been found to be 0.62 V vs. NHE. The reaction of e aq - showed the formation of transient species with λ max at 340 nm, which is assigned to the ketyl anion radical formed on addition of e aq - at carbonyl site. Reactions of one-electron oxidised mangiferin radicals with ascorbic acid have also been studied

Pulse radiolysis studies of mangiferin: A C- glycosyl xanthone isolated from Mangifera indica

Science.gov (United States)

Mishra, B.; Priyadarsini, K. Indira; Sudheerkumar, M.; Unnikrishhnan, M. K.; Mohan, H.

2006-01-01

Pulse radiolysis technique has been employed to study the reaction of different oxidizing and reducing radicals with mangiferin. The reaction of rad OH radical showed the formation of transient species absorbing in 380-390 and 470-480 nm region. The reaction with specific one-electron oxidants (N 3rad , CCl 3O 2rad ) also showed the formation of similar transient absorption bands and is assigned to phenoxyl radicals. The p Ka values of the transient species have been determined to be 6.3 and 11.9. One-electron oxidation potential of mangiferin at pH 9 has been found to be 0.62 V vs. NHE. The reaction of e aq- showed the formation of transient species with λmax at 340 nm, which is assigned to the ketyl anion radical formed on addition of e aq- at carbonyl site. Reactions of one-electron oxidised mangiferin radicals with ascorbic acid have also been studied.

Technical Report for a Study on the Mechanism and Control of Non-Enzymatic Browning Reaction in Gamma-Irradiated Food

Energy Technology Data Exchange (ETDEWEB)

Byun, Myung Woo; Lee, Ju Woon; Kim, Jae Hun

2007-01-15

Gamma irradiation leads to a non-enzymatic browning reaction (carbonyl -amine reaction) in an aqueous system similar to those induced in a heated one. This reaction may influence the changes of the color in irradiated foods. The intensity of the reaction was dependent on the type of the sugar, if the occurrence is by irradiation or by heating. There was a difference in the browning reaction between irradiation and heating. Although no browning was observed in the heated solution of the non-reducing sugar, the formation of colored products was observed in the irradiated sucrose-lysine solution. It could be explained on the basis that irradiation promotes the breakdown of the glycosidic linkages of the disaccharide, sucrose and the produce of a reducing power. The high molecular weight melanoidin (> MW 12,000-14,000 Da) was produced by gamma irradiation from the non-enzymatic browning reaction between glucose and glycine. The structure of melanoidin was similar to melanodin from heat processing. The results suggested that gamma-irradiation occurred the non-enzymatic browning reaction that is similar the reaction by heat processing. Non-enzymatic browning reaction during gamma-irradiation processing was greatly influenced by pH and medium of reaction system. The brown color development of irradiated sugar solutions with and without glycine is more increased in buffer system especially with alkaline pH than DDW. When food is irradiated, off-color such as browning can be produced due to the non-enzymatic browning reaction and it is influenced by other ions and/or pH of system. This suggests that the browning of irradiated food might be retarded by lowering the pH of the system. Gamma-irradiation produce the free radical and the radiolysis products of sugar and glycine and then they may be condensed to colored products during post-irradiation. However, when the food is irradiated in frozen state, the production of free radical and radiolysis product is inhibited and it

Technical Report for a Study on the Mechanism and Control of Non-Enzymatic Browning Reaction in Gamma-Irradiated Food

International Nuclear Information System (INIS)

Byun, Myung Woo; Lee, Ju Woon; Kim, Jae Hun

2007-01-01

Gamma irradiation leads to a non-enzymatic browning reaction (carbonyl -amine reaction) in an aqueous system similar to those induced in a heated one. This reaction may influence the changes of the color in irradiated foods. The intensity of the reaction was dependent on the type of the sugar, if the occurrence is by irradiation or by heating. There was a difference in the browning reaction between irradiation and heating. Although no browning was observed in the heated solution of the non-reducing sugar, the formation of colored products was observed in the irradiated sucrose-lysine solution. It could be explained on the basis that irradiation promotes the breakdown of the glycosidic linkages of the disaccharide, sucrose and the produce of a reducing power. The high molecular weight melanoidin (> MW 12,000-14,000 Da) was produced by gamma irradiation from the non-enzymatic browning reaction between glucose and glycine. The structure of melanoidin was similar to melanodin from heat processing. The results suggested that gamma-irradiation occurred the non-enzymatic browning reaction that is similar the reaction by heat processing. Non-enzymatic browning reaction during gamma-irradiation processing was greatly influenced by pH and medium of reaction system. The brown color development of irradiated sugar solutions with and without glycine is more increased in buffer system especially with alkaline pH than DDW. When food is irradiated, off-color such as browning can be produced due to the non-enzymatic browning reaction and it is influenced by other ions and/or pH of system. This suggests that the browning of irradiated food might be retarded by lowering the pH of the system. Gamma-irradiation produce the free radical and the radiolysis products of sugar and glycine and then they may be condensed to colored products during post-irradiation. However, when the food is irradiated in frozen state, the production of free radical and radiolysis product is inhibited and it

Pulse radiolysis

International Nuclear Information System (INIS)

Greenshields, H.; Seddon, W.A.

1982-03-01

This supplement to two bibliographies published in 1970 and 1972 lists 734 references to the literature of pulse radiolysis, arranged under eight broad subject headings. The references were compiled by searching Biological Abstracts, Chemical Abstracts, Nuclear Science Abstracts and the Weekly List of Papers in Radiation Chemistry issued by the Radiation Chemistry Data Center of Notre Dame University. Full bibliographic data is given for papers published in the period 1971 to 1974. A personal author index listing more than 600 authors and a similar number of co-authors is included

Radiolysis effects on polyethylene terephtalate

International Nuclear Information System (INIS)

Zaharescu, Traian; Ciuprina, Florin

2005-01-01

The effects of high energy exposure of polyethylene terephtalate, the main electrical insulator for the conduction bars in alternative current generators, is presented. For comparison γ-irradiation was performed in distilled water and air at various doses, up to about 200 kGy. The dependencies of current on time for radiation processed PET sheets allow to depict the variation in the resistivity values as a measure of chemical changes in polyethylene terephtalate macromolecules. The comparison between the evolution of currents in irradiated specimens and spectral analysis bring about a light on the accumulation of radiolysis product in PET matrix. The high energy exposure of PET in air causes an increase of final value of current, while similar experiments in water produces a contrary effect. Some considerations of degradation mechanism are presented

Radiolysis of Reactive AZO Dyes in Aqueous Solution

International Nuclear Information System (INIS)

Bagyo, Agustin NM; Winarti-Andayani; Hendig-Winarno; Ermin-Katrin; Soebianto, Yanti S

2004-01-01

The effects of radiation on aerated reactive dye solutions i.e Cibacron Violet, Cibacron Orange and Cibacron Yellow solutions have been studied. Parameters analysis were the change of pH after radiation, the change of absorption, degradation products and effects of pH on the radiolysis. The uv-vis absorption of solutions were observed before and after irradiation. pH variation was done from pHs 3, 5, 7, 9 and 12. Irradiation was done at doses of 0, 2, 4, 6, 8 and 10 kGy with dose rate of 5 kGy/h and was determined by a Fricke dosimeter. HPLC with UV detector was used to analyze the degradation products. Oxalic acid was the main degradation product and small amount of succinic acid was also detected. (author)

Influence of radiolytic products on the chemistry of uranium VI in brines

International Nuclear Information System (INIS)

Lucchini, J-F.; Reed, D.T.; Borkowski, M.; Rafalski, A.; Conca, J.

2004-01-01

In the near field of a salt repository of nuclear waste, ionizing radiations can strongly affect the chemistry of concentrated saline solutions. Radiolysis can locally modify the redox conditions, speciation, solubility and mobility of the actinide compounds. In the case of uranium VI, radiolytic products can not only reduce U(VI), but also react with uranium species. The net effect on the speciation of uranyl depends on the relative kinetics of the reactions and the buildup of molecular products in brine solutions. The most important molecular products in brines are expected to be hypochlorite ion, hypochlorous acid and hydrogen peroxide. Although U(VI) is expected not to be significantly affected by radiolysis, the combined effects of the major molecular radiolytic products on the chemistry of U(VI) in brines have not been experimentally established previously. (authors)

Radiolysis of liquid ammonia in the presence of isopropylalcohol

Energy Technology Data Exchange (ETDEWEB)

Dessouki, A M

1973-09-01

The effects of variation of dose on the various yields resulting from gamma -irradiation of liquid ammonia and ammoniacal solutions containing isopropanol and N/sub 2/O, NH/sub 4/Cl, NaNO/sub 3/, CH/sub 3/I , Fe (III) or benzophenone were investigated. The G-Values of the primary products resulting from the gamma -radiolysis of ammoniacal solutions containing isopropanol are reported. The G-value of the free electron was calculated and found to be 2.1. Additionally (auth)

Study of the influence of radiolysis on the stability of plutonium III. Application to a heterogeneous medium formed by a nitric solution of ferrous ions and an organic solution of trilauryl-ammonium nitrate

International Nuclear Information System (INIS)

Fourmaux, J.M.

1980-01-01

The objective of this research thesis is to study the behaviour of plutonium 238 in media which are commonly used to isolate it from other elements such as neptunium and fission products created during the neutron irradiation of the neptunium 237 isotope. As plutonium 238 purification processes are all based on redox reaction, it is essential to know the influence of radiolysis on the redox behaviour, and on the distribution coefficients of this isotope in solutions used during its separation from the neptunium 237 isotope. Therefore, it is necessary to study the influence of radiolysis on the stability of plutonium with an oxidation III level. As this extraction is performed by an organic solvent (trilauryl-ammonium nitrate), this study addresses the behaviour of plutonium in an emulsion formed by this solvent and the nitric aqueous solution previously adjusted in terms of Fe 2+ ions. After a brief recall of bibliographical generalities related to radiolysis, the author presents and comments the Nernst law in the case of a two-phase system (emulsion), and reports the use of this law to obtain the plutonium potential-distribution coefficient relationship. The last part reports experimental data

A computerized pulse radiolysis system

International Nuclear Information System (INIS)

Eriksen, T.E.; Lind, J.; Reitberger, T.

1976-01-01

A computer based pulse radiolysis system for gathering and handling of transient optical absorption and electric conductivity data is presented. The system has been developed around a Biomation 8100 transient recorder and a PDP 11/40 (Digital Equipment Corp) computer. (author)

Radiolysis of Aqueous Toluene Solutions

International Nuclear Information System (INIS)

Christensen, H.C.; Gustafson, R.

1971-04-01

Aqueous toluene solutions have been irradiated with Co γ-rays. In unbuffered solutions the various cresol isomers are formed in a total yield of 0.45, 0.87 and 0.94 molecules/100 eV absorbed energy in argon-, N 2 O- and air - saturated solutions, respectively. The yields are reduced in acid (pH 3) solutions (G 0.14, 0.14 and 0.52, respectively) but the reduction is compensated by the formation of 1,2-di-phenylethane in yields of 0.49 and 1.60 in argon- and N 2 O-saturated solutions, respectively. Benzyl radicals are formed through an acid catalysed water elimination reaction from the initially formed hydroxymethylcyclohexadienyl radical. Phenyltolylmethanes, dimethylbiphenyls and partly reduced dimers are also formed during the radiolysis. Hydrogen is formed in the same yield as the molecular yield, g(H 2 ). Xylene isomers and benzene are formed in trace quantities. The most remarkable effects of the addition of Fe(III) ions to deaerated acid toluene solutions are the formation of benzyl alcohol and benzaldehyde and an increase in the yield of 1,2-diphenylethane

Spectral studies of intermediate species formed in one-electron reactions of bovine liver catalase at room and low temperatures. A comparison with peroxidase reactions

International Nuclear Information System (INIS)

Metodiewa, D.; Dunford, H.B.

1992-01-01

The reactions of native bovine catalase with superoxide and solvated electrons have been investigated using three different methods for generating these reducing substrates: γ-radiolysis of oxygenated or deaerated buffer solutions in the presence of an OH radical scavenger; either xanthine or acetaldehyde with xanthine oxidase; and low-temperature (77 K) γ-radiolysis of buffered ethylene glycol/water solutions with subsequent annealing of samples at 183 K. (Author)

Radiation induced Maillard reactions (the kinetic of colour formation during heating)

International Nuclear Information System (INIS)

Tegota, A.; Bachman, S.

1998-01-01

The results are presented of the investigation of the effect of ionizing radiation from 60 Co on the acceleration of the Maillard reactions in a model system containing an aqueous solution of fructose (F) at 0.03 mol/dm 3 and alanine (Ala) at 0.01 mol/dm 3 . Solutions of F/Ala irradiated with 5 to 30 kGy at a dose rate 1.4 Gy/s were then heated for a few hours at different temperatures: 400, 600, 800, and 1000 deg C. The colour intensity of the solutions was measured via their absorbance at 450 nm. The reaction constant estimates increased with increasing radiation dose and temperature. The activation energy of colour development determined over the range of 600 deg C to 1000 deg C decreased with dose from 70.6 kJ/mol for 5 kGy to 60.7 kJ/mol for 30 kGy. The results confirmed the formation of carbonyl products from fructose radiolysis and their participation in the acceleration of the non-enzymatic browning reactions. The aldehyde products formed from the amino acids as a result of the Strecker degradation are responsible for the formation of odour typical of the Maillard reaction during heating. The changes in the F and Ala concentrations during irradiation of the solutions were proportional to the radiation dose. The radiation yield of fructose and alanine decomposition was G = 2.6 and 0.22, respectively. In the irradiated solutions of F/Ala, serine has been found, which has not been mentioned so far as a product of alanine radiolysis. The study demonstrates the influence of radiation and acceleration of the Maillard reaction during subsequent heating at 400 deg C up to 1000 deg C of systems containing reducing sugars and amino acids. It should be taken under consideration in the studies on introducing radiation technology of food products preservation connected with further thermal treatment

Radiolysis ob benzene, toluene and phenol aqueous solutions utilizing high energy electron beam

International Nuclear Information System (INIS)

Gonzalez Vanderhaghen, D.E.

1998-01-01

In a search for solutions to environmental pollution problems, radiolysis has proved to be an innovative technique for the removal of organic chemical pollutants in aqueous solution. Radiolysis has shown many advantages over many other techniques, as highly reactive species formed in water by ionizing radiation oxidize organic pollutants breaking down organic molecules to final simple products by oxidation to carbon dioxide and water in a complete oxidation. Our work consisted in doing some experiments in radiolysis with simulated polluted water to help us understand this technique and also develop, in a near future, a project for large scale water treatment. Our project includes the application of a Pelletron type Mexican made Electron Accelerator, which will affirm its capability and usefulness in performing investigation in this field of study. Experiments consisted in treating benzene, toluene and phenol aqueous solutions with an Electron Beam (0.48-0.55 MeV; 24 μA). Two concentrations were used for each compound: 5 and 20 ppm (mg/l) for benzene and toluene; 10 and 50 ppm for phenol. Solutions were prepared with pure, mineral free water and two different p H (5.9), in order to study the effect of concentration and p H on removal efficiency, but avoiding the interference of radical scavengers. Results obtained coincide with the ones reported by Cooper, Nickelsen and Kurucz; highly efficient removal was achieved for benzene (>99.8%), toluene (>98.0%) and phenol (>88%). There was no visible important effect of p H on radiolysis efficiency for benzene nor toluene, phenol however, showed lower removal efficiency in acidic conditions. Concentration of aqueous solutions, nevertheless, did show an important effect at low doses for phenol. Results obtained reveal the importance of this technique in water pollution control and water remedial as expressed by Cooper, Nickelsen and Kurucz, who have studied radiolysis of organic compounds and apply this technique in water

3D analysis of the gas dynamic loads in the KKB containment resulting from combustion of radiolysis gas

International Nuclear Information System (INIS)

Kotchourko, A.; Breitung, W.; Dorofeev, S.; Ohlmeyer, H.

2003-01-01

The radiolysis gas explosion in the KKB power plant was recalculated in 3D simulations as followed: The total energy released was limited as far as possible. - Pressure generation and dispersion across the containment was calculated for three different initial energies. - Loads in the near field were simulated assuming the most probable total energy (about 14 MJ) and using three different models of the explosion process. The calculation with direct simulation of detonation inside the tube provided realistic results, according to the authors. - Transient local pressure and temperature loads were recorded in specified local points and evaluated in further damage analyses. The results showed that modern 3D flow and combustion calculations provide valuable information on pressure and temperature loads resulting from radiolysis gas reactions in big complex safety containments. (orig.) [de

Study of the mechanism of the gamma radiolysis of saccharose and its derivatives in aqueous or solid phase. Study by spin trapping

International Nuclear Information System (INIS)

Triolet, J.

1991-01-01

Powder or aqueous solutions of saccharose, deoxysaccharose and fructanes are irradiated. Radicals created during gamma radiolysis are converted into sugar-nitroxide radicals by reaction with 2 methyl 2 nitroso-propane. They are stable enough to be studied in solution by electron paramagnetic resonance (EPR) coupled or not to high performance liquid chromatography. EPR spectra obtained are simulated with the Voyons program for the determination of spectrocopic characteristics of trapped species. The study of glucosides, disaccharides and sugar labelled with carbon 13 allows to suggest a chemical structure for 5 out of the 7 species trapped during saccharose radiolysis. Influence of irradiation conditions is studied and mechanisms are proposed [fr

Reaction of Br/sub 3/. /sup 2 -/ with 2-deoxy-D-ribose. A preferred attack at C-1

Energy Technology Data Exchange (ETDEWEB)

Parsons, B J; Schulte-Frohlinde, D; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenchemie

1978-06-01

In the photolysis of 5-bromouracil containing DNA Br atoms are expected intermediates. In order to evaluate the possible site of attack of the Br atom at the sugar moiety of DNA the reaction of 2-deoxy-D-Ribose with the Br atom (complexed with two bromide ions) was investigated. Hydroxyl radicals generated by the radiolysis of N/sub 2/O saturated aqueous solutions were converted into Br/sub 3/./sup 2 -/-radicals by 1 M bromide ions. Br/sub 3/./sup 2 -/-reacts with 2-deoxy-D-ribose (k = 3.7 x 10/sup 4/M/sup -1/s/sup -1/, pulse radiolysis). The major product is 2-deoxy-D-erythro-pentonic acid (G = 2.4, ..gamma..-radiolysis). It is formed by hydrogen abstraction from C-1 and oxidation of this radical by other radicals. An alternative route via the radical at C-2 is neglible. It follows that Br/sub 3/./sup 2 -/ reacts preferentially at C-1 of 2-deoxy-D-ribose.

Radiolysis and corrosion aspects of the aqueous self-cooled blanket concept

International Nuclear Information System (INIS)

Bruggeman, A.; Snykers, M.; Bogaerts, W.F.; Waeben, R.; Embrechts, M.J.; Steiner, D.

1989-01-01

Corrosion and radiolysis aspects of the Aqueous Self-Cooled Blanket concept, proposed as a potential shielding breeding blanket for near term fusion devices and fusion reactors, have been investigated. On the basis of preliminary results for selected aqueous solutions of lithium compounds, no particular corrosion problems have been revealed for the low-temperature concept envisaged for NET and radiolysis effects might be controlled by appropriate countermeasures. For the reactor-relevant high-temperature concept particular attention has to be paid to intergranular stress-corrosion and to the synergistic radiolysis-corrosion effects. Further information is needed from tests performed in relevant operational conditions. (orig.)

Gas generation by self-radiolysis of tritiated waste materials

International Nuclear Information System (INIS)

Tadlock, W.E.; Abell, G.C.; Steinmeyer, R.H.

1980-01-01

Studies simulating the effect of self-radiolysis in disposal packages containing tritiated waste materials show hydrogen to be the dominant gas-phase product. Pressure buildup and gas composition over various tritiated octane and tritiated water samples are designed to give worst case results. One effect of tritium fixation agents is to reduce pressure buildup. The results show that development of explosive gas mixtures is unlikely and that maximum pressure buildup in typical Mound Facility waste packages can be expected to be <0.25 MPa

Measurement of HOx· production rate due to radon decay in air

International Nuclear Information System (INIS)

Ding, Huiling.

1993-08-01

Radon in indoor air may cause the exposure of the public to excessive radioactivity. Radiolysis of water vapor in indoor air due to radon decay could produce (·OH and HO 2 ·) that may convert atmospheric constituents to compounds of lower vapor pressure. These lower vapor pressure compounds might then nucleate to form new particles in the indoor atmosphere. Chemical amplification was used to determine HO x · production rate in indoor air caused by radon decay. Average HO x · production rate was found to be (4.31±0.07) x 10 5 HO x · per Rn decay per second (Bq) 3.4 to 55.0% at 22C. This work provided G (HO x ·) -value, 7.86±0.13 No./100 eV in air by directly measuring [HO x ·] formed from the radiolysis procedure. This G value implies that HO x · produced by radon decay in air might be formed by multiple processes and may be result of positive ion-molecule reactions, primary radiolysis, and radical reactions. There is no obvious relation between HO x · production rate and relative humidity. A laser-induced fluorescence (LIF) system has been used for ·OH production rate measurement; it consists of an excimer laser, a dye laser, a frequency doubler, a gaseous fluorescence chamber, and other optical and electronic parts. This system needs to be improved to eliminate the interferences of light scattering and artificial ·OH produced from the photolysis of O 3 /H 2 O

Effect of radiolysis on long-term corrosion system formed on low-alloy steels

International Nuclear Information System (INIS)

Badet, H.

2013-01-01

In France, for nuclear waste management, it is planned to build a storage device with a barrier system composed of steel container. Corrosion is evaluated for the safety of anoxic storage over the long term. With radiation, water radiolysis generates oxidizing and reducing species that can change the corrosion. Three aspects are developed in this thesis. The first concerns iron coupon samples experimented in carbonate deaerated water and subjected to gamma irradiation. It is shown that irradiation can increase corrosion rates within the parameters of dose. Identified crystalline phases are little changed with irradiation. Solution chemistry shows a decrease in pH with dose related to iron. Organic species are identified. The second axis is archaeological analogues irradiation with an old corrosion products layer. Structural analysis verified the phase stability with radiolysis, only the newly formed products changes. The third axis is a kinetic simulation approach. It checks the pH drop under irradiation. Taken together, these results allow us to provide new data for the anoxic corrosion under irradiation. (author) [fr

Dibromine radical anion reactions with heme enzymes

International Nuclear Information System (INIS)

Gebicka, L.; Gebicki, J.L.

1996-01-01

Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs

Peculiarities of heterogeneous radiolysis of carbon dioxide in the presence of aluminium oxide

International Nuclear Information System (INIS)

Rustamov, V.R.; Kurbanov, M.A.; Kerimov, V.K.; Musaeva, P.F.

1982-01-01

The effect of ν-radiation dose rate, reaction temperature and treatment of aluminium oxide on the yield of CO at radiolysis of CO 2 /ν-Al 2 O 3 heterogeneous system has been investigated. The measurements have been carried out at 0.55 and 5.5 Gr/s dose rates in 40-300 deg C temperature range. Kinetic curves of CO accumulation are characterized by the saturation region at 0.15-0.2 MG 2 doses. In such a way, the dependence of CO yeild on the dose attests that the reaction of radiation annealing of defects occurs in Al 2 O 3 and that decreases the efficiency of CO 2 decomposition. The rise of temperature from 40 to 300 deg results in the decrease of CO 2 yield and in 100-200 range it is manifested more markedly. This fact is conditioned by the increase of reaction rates leading to the decrease of CO 2 decomposition rate as the temperature rises. The reaction mechanism is discussed

Radiolysis of concentrated solutions. 1. Pulse and γ radiolysis studies of direct and indirect effects in LiCl solutions

International Nuclear Information System (INIS)

Pucheault, J.; Ferradini, C.; Julien, R.; Deysine, A.; Gilles, L.; Moreau, M.

1979-01-01

This study of the radiolysis of concentrated aqueous LiCl solutions enables the relative contributions of the direct and indirect effects to be evaluated as a function of Cl - concentration and also permits an evaluation of the role of Cl - in the early stages of water radiolysis. Radicalar and molecular yields G/sub Cl 2 - /, G/sub OH/, G//sub e//sub aq/ - / + G/sub H/, G/sub H 2 O 2 /, and G/sub H 2 / are determined for all concentrations employed, and the material balance is verified. The main conclusions concerning the apparent inefficacy of the direct effect and the importance of OH scavenging in spurs are discussed

Reduction of a dimeric tantalum(III) compound in acetonitrile solution by pulse radiolysis

International Nuclear Information System (INIS)

Koulkes-Pujo, A.-M.; Le Motais, B.; Hubert-Pfalzgraf, L.G.

1986-01-01

The reduction of the compound [Ta 2 Cl 6 (4Me-py) 4 ] (4Me-py 4-methylpyridine), having a metal-metal double bond, has been achieved by pulse radiolysis in dry oxygen-free acetonitrile. The reduction occurs by CH 3 CN - which leads to a transient species assigned to a tantalum dimer in a 2.5 oxidation state. The spectrum of this species has been established. It decays by a first-order process to give a new transient species which in turn decays more slowly by a second-order reaction. (author)

Influence of acetylacetonates of 3d-metals on the γ radiolysis of benzene

International Nuclear Information System (INIS)

Zatonskii, S.V.; Makhlyarchuk, V.V.; Morozova, L.N.

1986-01-01

This paper investigates the formation of diphenyl and phenylcyclohexadiene in the radiolysis of benzene in the presence of the following acetylacetonates: Cr (AA) 3 , Mn (AA) 2 .2H 2 O, Mn (AA) 3 , Fe (AA) 2 .2H 2 O, Fe (AA) 3 , Co (AA) 3 . It was found that bisacetylacetonatocobalt (II) lowers the radiation chemical yields of the dimers to a substantial degree. It was suggested that the effect is caused by a reaction of addition of free radicals, arising under the action of radiation, to the central ion of the chelate

Photochemistry of CS2/Cl complexes-combined pulse radiolysis-laser flash photolysis studies

International Nuclear Information System (INIS)

Sumiyoshi, Takashi; Nakayama, Masayoshi; Fujiyoshi, Ryoko; Sawamura, Sadashi

2006-01-01

Complexes of chlorine atoms and carbon disulfide (CS 2 ) were produced by pulse radiolysis of CS 2 in halocarbons and photochemical reactions were studied by laser flash photolysis. Excitation of CS 2 /Cl complexes resulted in rapid and permanent photobleaching. The photobleaching of CS 2 /Cl complexes is due to intermolecular chlorine atom abstraction in CCl 4 with a quantum yield of 0.04, while that ascribed to hydrogen atom abstraction in 1,2-dichloroethane has a quantum yield of 0.21. The effects of additives are discussed based on the bond dissociation energy

The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature

DEFF Research Database (Denmark)

Lundström, T.; Christensen, H.; Sehested, K.

2001-01-01

The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1) and the activa......The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1...

Kinetics of hydrogen isotope exchange reactions

International Nuclear Information System (INIS)

Gold, V.; McAdam, M.E.

1975-01-01

Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

Study of growth mechanism of conducting polymers by pulse radiolysis

International Nuclear Information System (INIS)

Coletta, Cecilia

2016-01-01

Today conductive polymers have many applications in several devices. For these reasons they have received much attention in recent years. Despite intensive research, the mechanism of conducting polymers growth is still poorly understood and the methods of polymerization are limited to two principal ways: chemical and electrochemical synthesis. On the other hand, the complex properties of polymers can be controlled only if a good knowledge of polymerization process is acquired. In this case, it is possible to control the process during the synthesis (functionalization, hydrophilicity, chain length, doping level), and consequently to improve the conductive properties of the synthesized polymers. Water radiolysis represents an easy and efficient method of synthesis comparing to chemical and electrochemical polymerization routes. It enables the polymerization under soft conditions: ambient temperature and pressure, without any external dopant. Among all conductive polymers, poly(3, 4-ethylenedioxy-thiophene) (PEDOT, a derivative of poly-thiophene) and poly-Pyrrole (PPy) have gained some large scale applications for their chemical and physical proprieties. The aim of the present work was the synthesis of PEDOT and PPy in aqueous solution and the study of their growth mechanism by pulsed radiolysis. Thanks to the electron accelerator ELYSE, the use of pulsed radiolysis coupled with time-resolved absorption spectroscopy allowed to study the kinetics of polymerization. The first transient species involved in the mechanism were identified by time resolved spectroscopy and the rate constants were determined. First, the reaction of hydroxyl radicals onto EDOT and Py monomers was studied, as well as the corresponding radiation induced polymerization. Then, the study was transposed to others oxidizing radicals such as CO3 .- , N 3 . and SO 4 .- at different pHs. This approach allowed to check and to highlight the influence of oxidizing species onto the first transient species

Pulse radiolysis studies of mangiferin: A C-glycosyl xanthone isolated from Mangifera indica

Energy Technology Data Exchange (ETDEWEB)

Mishra, B. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Priyadarsini, K.Indira [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)]. E-mail: kindira@apsara.barc.ernet.in; Sudheerkumar, M. [College of Pharmaceutical Sciences, Kasturba Medical College, Manipal 576119 (India); Unnikrishhnan, M.K. [College of Pharmaceutical Sciences, Kasturba Medical College, Manipal 576119 (India); Mohan, H. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

2006-01-15

Pulse radiolysis technique has been employed to study the reaction of different oxidizing and reducing radicals with mangiferin. The reaction of {sup {center_dot}}OH radical showed the formation of transient species absorbing in 380-390 and 470-480 nm region. The reaction with specific one-electron oxidants (N{sub 3} {sup {center_dot}}, CCl{sub 3}O{sub 2} {sup {center_dot}}) also showed the formation of similar transient absorption bands and is assigned to phenoxyl radicals. The pK {sub a} values of the transient species have been determined to be 6.3 and 11.9. One-electron oxidation potential of mangiferin at pH 9 has been found to be 0.62 V vs. NHE. The reaction of e{sub aq} {sup -} showed the formation of transient species with {lambda} {sub max} at 340 nm, which is assigned to the ketyl anion radical formed on addition of e{sub aq} {sup -} at carbonyl site. Reactions of one-electron oxidised mangiferin radicals with ascorbic acid have also been studied.

Radiolysis of chitosan derivatives exhibiting antimutagenic activity

International Nuclear Information System (INIS)

Aleksandrova, V.A.; Kuzina, S.I.; Shilova, I.A.; Mikhajlov, A.I.

2006-01-01

The radiolysis of antimutagens extracted from natural biopolymer chitosan was studied by the EPR. The radiolysis of test samples of biopolymers and gallic acid was performed in vacuum at 77 K using a 60 Co γ-radiation source, with radiation doses 50 kGy. It was shown that addition of gallic acid (2 mol %) to quaternized chitosan results in a 2.5-fold decrease in the radiation-chemical yield of radicals and a nearly complete inhibition of the formation of ion radicals. Gallic acid units likely play the role of a stabilizer that protects the polycation from radiation damage and, hence, the structure of the cationogenic units from changes, thereby improving the antimutagenic properties of the system [ru

Radiolysis effects in sub-cooled nucleate boiling

International Nuclear Information System (INIS)

Dickinson, S.; Henshaw, J.; Tuson, A.; Sims, H.E.

2002-01-01

A hydrogen depleted region may form in the water during bubble formation when boiling occurs in a PWR. This would arise from stripping of gases into the steam phase. The depleted water may then become oxidising due to radiolysis forming H 2 O 2 . The presence of radiolytic oxidising conditions is one of the mechanisms proposed to explain deposits formed in Axial Offset Anomalies. This work describes a model that has been developed to examine this behaviour. The model deals with bubble growth and material transport as well as the radiolysis chemistry. The model simulates diffusion of species through the gas/liquid boundary layer. The appropriate mass conservation equations for this problem are described and the results of their numerical solution discussed. This model indicates the importance of the assumed boundary conditions on the results of the calculations. These boundary conditions are discussed in detail and the most appropriate ones for the actual reactor situation are outlined. The conclusion of this modelling study is that at normal PWR operating conditions of 40 cc H 2 (STP) kg -1 it is unlikely that radiolysis in a subcooled boiling region would be important. The situation is more ambiguous at the 1 to 5 cc H 2 (STP) kg -1 range. (author)

Radiolysis effects in sub-cooled nucleate boiling

Energy Technology Data Exchange (ETDEWEB)

Dickinson, S.; Henshaw, J.; Tuson, A.; Sims, H.E. [AEA Technology (United Kingdom)

2002-07-01

A hydrogen depleted region may form in the water during bubble formation when boiling occurs in a PWR. This would arise from stripping of gases into the steam phase. The depleted water may then become oxidising due to radiolysis forming H{sub 2}O{sub 2}. The presence of radiolytic oxidising conditions is one of the mechanisms proposed to explain deposits formed in Axial Offset Anomalies. This work describes a model that has been developed to examine this behaviour. The model deals with bubble growth and material transport as well as the radiolysis chemistry. The model simulates diffusion of species through the gas/liquid boundary layer. The appropriate mass conservation equations for this problem are described and the results of their numerical solution discussed. This model indicates the importance of the assumed boundary conditions on the results of the calculations. These boundary conditions are discussed in detail and the most appropriate ones for the actual reactor situation are outlined. The conclusion of this modelling study is that at normal PWR operating conditions of 40 cc H{sub 2} (STP) kg{sup -1} it is unlikely that radiolysis in a subcooled boiling region would be important. The situation is more ambiguous at the 1 to 5 cc H{sub 2} (STP) kg{sup -1} range. (author)

Pulse radiolysis studies of model membranes

International Nuclear Information System (INIS)

Heijman, M.G.J.

1984-01-01

In this thesis the influence of the structure of membranes on the processes in cell membranes were examined. Different models of the membranes were evaluated. Pulse radiolysis was used as the technique to examine the membranes. (R.B.)

Effectiveness of quenchers to reduce radiolysis of (111)In- or (177)Lu-labelled methionine-containing regulatory peptides. Maintaining radiochemical purity as measured by HPLC.

Science.gov (United States)

de Blois, Erik; Chan, Ho Sze; Konijnenberg, Mark; de Zanger, Rory; Breeman, Wouter A P

2012-01-01

An overview how to measure and to quantify radiolysis by the addition of quenchers and to maintain Radio-Chemical Purity (RCP) of vulnerable methionine-containing regulatory peptides is presented. High RCP was only achieved with a combination of quenchers. However, quantification of RCP is not standardized, and therefore comparison of radiolabelling and RCP of regulatory peptides between different HPLC-systems and between laboratories is cumbersome. Therefore we suggest a set of standardized requirements to quantify RCP by HPLC for radiolabelled DTPA- or DOTA-peptides. Moreover, a dosimetry model was developed to calculate the doses in the reaction vials during radiolabelling and storage of the radiopeptides, and to predict RCP in the presence and absence of quenchers. RCP was measured by HPLC, and a relation between radiation dose and radiolysis of RCP was established. The here described quenchers are tested individually as ƒ(concentration) to investigate efficacy to reduce radiolysis of radiolabelled methionine-containing regulatory peptides.

Temperature impact on the primary radiolysis yields concerning the hydrous electron

International Nuclear Information System (INIS)

Baldacchino, G.; Vigneron, G.; Pommeret, St.

2005-01-01

We have studied the impact of temperature on the water radiolysis formation rate of the hydrous electron in presence of selenate di-anion SeO 4 2+ . We have used a high temperature (up to 500 Celsius degrees) optical cell coupled to the electron accelerator Alienor. It appears that the capture of the hydrous electron by selenate follows an Arrhenius law till the sub-critical range, beyond this range the kinetics of the reaction seems more erratic. We have also studied the capture of the hydrous electron by methyl-viologen (MV 2+ ) at 20 and 380 Celsius degrees. It seems that at high temperature more hydrous electrons are produced, it might be interpreted as a consequence of the shift toward the right of the following equilibrium reaction: OH - + H . ↔ e - (aq) + H 2 O. All these results need to be confirmed. (A.C.)

Aliphatic alkenes and alkynes

International Nuclear Information System (INIS)

Cserep, Gy.

1981-01-01

This chapter describes the decomposition of aliphatic alkenes and alkynes by radiolysis, concentrating on results published after 1968. The radiolysis of individual compounds, product yields and possible mechanisms of radiation chemical reactions are discussed in detail. The radiolysis of mixtures of aliphatic alkenes is also investigated. General information on decomposition and some condensation reactions is also presented. (Auth./C.F.)

Pulse radiolysis in model studies toward radiation processing

Science.gov (United States)

Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

1995-02-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect

Radiolytic oxidation of propane: computer modeling of the reaction scheme

International Nuclear Information System (INIS)

Gupta, A.K.; Hanrahan, R.J.

1991-01-01

The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

Radiolysis of Aqueous Toluene Solutions

Energy Technology Data Exchange (ETDEWEB)

Christensen, H C; Gustafson, R

1971-04-15

Aqueous toluene solutions have been irradiated with Co gamma-rays. In unbuffered solutions the various cresol isomers are formed in a total yield of 0.45, 0.87 and 0.94 molecules/100 eV absorbed energy in argon-, N{sub 2}O- and air - saturated solutions, respectively. The yields are reduced in acid (pH 3) solutions (G = 0.14, 0.14 and 0.52, respectively) but the reduction is compensated by the formation of 1,2-di-phenylethane in yields of 0.49 and 1.60 in argon- and N{sub 2}O-saturated solutions, respectively. Benzyl radicals are formed through an acid catalysed water elimination reaction from the initially formed hydroxymethylcyclohexadienyl radical. Phenyltolylmethanes, dimethylbiphenyls and partly reduced dimers are also formed during the radiolysis. Hydrogen is formed in the same yield as the molecular yield, g(H{sub 2}). Xylene isomers and benzene are formed in trace quantities. The most remarkable effects of the addition of Fe(III) ions to deaerated acid toluene solutions are the formation of benzyl alcohol and benzaldehyde and an increase in the yield of 1,2-diphenylethane

Radiolysis studies of uranyl nitrate solution in nitric acid medium

International Nuclear Information System (INIS)

Siri, Sandra; Mondino, Angel V.

2005-01-01

The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

Biomarkers on Europa: Unique signatures produced by radiolysis?

Science.gov (United States)

Carlson, R. W.; Hand, K. P.

A promising habitat for life is Jupiter's moon Europa, with its likely ocean under a young, active surface. Europa orbits in the heart of Jupiter's powerful magnetosphere and suffers intense energetic particle bombardment, producing both good and bad aspects for astrobiology at Europa. Ionizing radiation can produce oxidants that could support a radiation-driven ecology as proposed by Chyba. On the other hand, biomolecular evidence for oceanic life that may be emplaced on the surface is rapidly altered by radiation, perhaps complicating astrobiological searches for evidence of life. We are studying the radiolytic degradation of molecular biomarkers in ice at Europa temperatures by studying both simple organics and more complex biomolecules, including microorganisms. High energy (1-100 keV) electron irradiation is employed and the products are analyzed using infrared spectroscopy, thermal desorption mass spectroscopy, and laser desorption/ionization mass spectroscopy. Hydrocarbon radiolysis yields carbon dioxide and methane which can escape the system and results in the net loss of carbon. Aliphatic molecules with C=O bonds are formed and thought to be mainly polymethylene oxides. When heated, they polymerize to form brown, high-molecular-weight refractory residues with linear, spherical, and ring- shaped macrostructures, typically many tens of micrometers in size. Laser desorption mass spectra of the residues are not overly complex and are different for each initial species. Radiolysis of microorganisms shows the destruction of amine, amide, methyl, and methylene groups, and production of carbon dioxide, carbon monoxide, nitriles, and isocyanates. Mass spectra of irradiated B. pumilus spores are different and surprisingly less complex than those of unirradiated spores. It is possible that unique, diagnostic biosignatures may exist in mass spectra of irradiated microorganisms.

Studies on radiolysis of amino acids, 1

International Nuclear Information System (INIS)

Oku, Tadatake

1977-01-01

In order to elucidate the radiolysis of amino acid, peptide, protein and enzyme, the radiolytic mechanisms of neutral amino acids (glycine, L-alanine, L-valine, L-leucine, L-isoleucine, L-serine, and L-threonine) and acidic amino acids (L-aspartic acid, L-glutamic acid and DL-amino-n-adipic acid) were studied in the presence of air or in the atmosphere nitrogen. An aqueous solution of 1 mM. of each amino acid was sealed in a glass ampoule under air or nitrogen. Irradiation of amino acid solutions was carried out with γ-rays of 60 Co at doses of 4.4-2,640x10 3 rads. The amino acids and the radiolytic products formed were determined by ion-exchange chromatography. From the results of determining amino acids and the radiolytic products formed and their G-values, the radiolytic mechanisms of the amino acids were discussed. (auth.)

Structural characterisation of degradation products formed upon di-n-butyl phthalate radiolysis by high-performance liquid chromatography electro-spray tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Tintaru, A.; Charles, L. [Univ Aix Marseille 1, CNRS, Lab Chim Provence Spectrometries Appl Chim Struct, UMR 6264, F-13397 Marseille (France); Univ Aix Marseille 2, CNRS, Lab Chim Provence Spectrometries Appl Chim Struct, UMR 6264, F-13397 Marseille (France); Labed, V. [CEA Marcoule, DTCD SPDE L2ED, F-30207 Bagnols Sur Ceze (France)

2010-07-01

Complete text of publication follows: Structural characterisation of 15 degradation products, formed upon di-n-butyl phthalate (DBP) radiolysis, has been achieved using a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) coupling. The dissociation behaviour of protonated DBP was first established to be further used to characterise structural deviation in the degradation products. Based on accurate mass measurements, compounds shown by HPLC-MS analysis were all found to be DBP oxidation products, amongst which various sets of isomers could be distinguished. Collision-induced dissociation experiments performed on each electro-sprayed molecule first allowed unambiguous definition of the location of the additional oxygen atoms; that is, in the alkyl branch or on the aromatic ring. Although location of the oxygen atom in the alkyl branches could not always be precisely determined, relative abundances of some product ions allowed oxygenated functions to be identified

Design guideline to prevent the pipe rupture by radiolysis gases in BWR steam piping

International Nuclear Information System (INIS)

Inagaki, T.; Miyagawa, M.; Ota, T.; Sato, T.; Sakata, K.

2009-01-01

In late 2001, pipe rupture accidents due to fast combustion of radiolysis gas occurred in Japan and elsewhere's BWR power plants. TENPES began to set up the guideline as action to such a new problem to prevent accumulation and combustion of radiolysis gas in BWR steam piping. And then, the first edition of guideline was published in October 2005. Afterwards, the experimental study about combustion/detonation of radiolysis gas have been continued. And in March 2007, TENPES published a revised edition of the guideline. This is the report of the revised edition of that guideline. According to this guideline, it became possible to design BWR's steam piping to prevent accumulation of radiolysis gas. (author)

Study of the radiolysis of tetracycline hydrochloride in powder form, in aqueous solutions and in benzyl alcohol, at 77K, by electron paramagnetic resonance spectroscopy

International Nuclear Information System (INIS)

Guedes, S.M.L.

1984-01-01

The radiolysis of tetracycline hydrochloride in powder form, dissolved in benzyl alcohol and in acid, neutral and alkaline aerated aqueous solutions at 77K is studied by electron paramagnetic resonance spectroscopy. Mechanisms of reactions that occur in the radiolysis of these systems are proposed and some aspects of the reactions that occurs with electrons and with hydrogen atoms at 77K are investigated, since tetracycline hydrochloride captures both paramagnetic species. Also discussed is the influence of some factors in the migration of these species at 77K, such as: the position of solutes, the crystalline structure of the solvent, the kinetic energy of the species and the angle of incidence in the channeling. The rate constants for the reaction between the electron and physical and chemical traps which are present in the alkaline aerated aqueous solutions, at 77k, are calculated. The values found are, respectively: k=9.6 x 10 15 1 mol -1 s -1 and k= 1.8 x 10 10 1 mol -1 s -1 . (Author) [pt

Pulse radiolysis studies of liquid heavy water at temperatures up to 250 degrees C

International Nuclear Information System (INIS)

Stuart, C.R.; Ouellette, D.C.; Elliot, A.J.

2002-09-01

This report documents the rate constants and associated activation energies for the reactions of the primary radical species, e aq - , ·OD and ·D, which are formed during the radiolysis of heavy water within the temperature range 20 to 250 o C. These heavy-water data have been compared with the corresponding information for light water. These kinetic data form part of the database that is required to model the aqueous radiation chemistry that occurs within the core of the heavy water cooled and moderated CANDU reactor. (author)

Pulse radiolysis studies of liquid heavy water at temperatures up to 250 degrees C

Energy Technology Data Exchange (ETDEWEB)

Stuart, C.R.; Ouellette, D.C.; Elliot, A.J

2002-09-01

This report documents the rate constants and associated activation energies for the reactions of the primary radical species, e{sub aq}{sup -}, {center_dot}OD and {center_dot}D, which are formed during the radiolysis of heavy water within the temperature range 20 to 250 {sup o}C. These heavy-water data have been compared with the corresponding information for light water. These kinetic data form part of the database that is required to model the aqueous radiation chemistry that occurs within the core of the heavy water cooled and moderated CANDU reactor. (author)

A study of low-energy ion induced radiolysis of thiol-containing amino acid cysteine in the solid and aqueous solution states

Energy Technology Data Exchange (ETDEWEB)

Ke Zhigang [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Huang Qing, E-mail: huangq@ipp.ac.c [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Dang Bingrong [Institute of Modern Physics, Chinese Academy of Sciences, 509 Nanchang Road, Lanzhou 730000 (China); Lu Yilin [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China); Department of Physics, Anhui University, Hefei 230031 (China); Yuan Hang; Zhang Shuqing; Yu Zengliang [Key Laboratory of Ion Beam Bio-engineering, Institute of Plasma Physics of Chinese Academy of Sciences, 350 Shushanhu Road, P.O. Box 1126, Hefei 230031 (China)

2010-09-15

The radiolysis of cysteine under plasma discharge and irradiation of low-energy ion beam was investigated. The damage of cysteine in aqueous solution under discharge was assessed via the acid ninhydrin reagent and the yield of cystine produced from the reaction was analyzed by FTIR. In addition, the generation of hydrogen sulfide was also identified. The destruction of solid cysteine under low-energy ion beam irradiation was estimated via monitoring IR bands of different functional groups (-SH, -NH{sub 3}, -COO{sup -}) of cysteine, and the production of cystine from ion-irradiated solid cysteine after dissolution in water was also verified. These results may help us to understand the inactivation of sulphydryl enzymes under direct and indirect interaction with the low-energy ion irradiation.

Gamma radiolysis of aliphatic sulfur compounds in aqueous solutions. A study to contribute to the analysis of the end products of the OH radical-induced oxidation of aliphatic mercaptanes, sulfides, and disulfides

International Nuclear Information System (INIS)

Weiss, J.

1982-01-01

By identifying and determining numerous hitherto unknown end products, the study in hand contributes to a better insight into the radiation chemical processes occurring in OH radical-induced oxidation of aliphatic sulfur compounds. An extraction method has been developed for the qualitative and quantitative analysis of end products in aqueous solution in order to determine these compounds down to the level of trace amounts. Separation of endproducts is achieved by means of gas chromatography and high-pressure liquid chromatography, subsequent identification by GC-MS analysis. Aliphatic mercaptanes are oxidized by OH radicals to thiyl radicals which after combination can be detected as disulfide. At high radiation doses, secondary reactions will lead to polysulfides of which the homologues could first be prepared as the pure substance. The end products of the γ-radiolysis of aliphatic thioethers are determined to be dithia compounds, symmetrical or asymmetrical disulfides, or polysulfides, depending on the thioethers. With some end products, the radiation chemical yield is found to be a function of the absorbed dose so that material balances are impossible. Intermediate thiyl, α-alkyl mercaptoalkyl or alkyl radicals can be captured by tetramethyl ethylene, cyclohexene or p-benzoquinone, and can then be identified as the relevant adducts. (orig./RB) [de

Influence of radiolysis on UO2 fuel matrix dissolution under disposal conditions. Literature Study

International Nuclear Information System (INIS)

Ollila, K.

2011-05-01

The objective of this study was to examine the recent published literature on the influence of water radiolysis on UO 2 fuel matrix dissolution under the disposal conditions. The α radiation is considered to be dominating over the other types of radiations at times longer than 1000 years. The presence of the anaerobic corrosion products of iron, especially of hydrogen, has been observed to play an important role under radiolysis conditions. It is not possible to exclude gamma/beta radiolysis effects in the experiments with spent fuel, since there is not available a fuel over 100 years old. More direct measurements of α radiolysis effects have been conducted with α doped UO 2 materials. On the basis of the results of these experiments, a specific activity threshold to observe α radiolysis effects has been presented. The threshold is 1.8 x 10 7 to 3.3 x 10 7 Bq/g in anoxic 10 -3 M carbonate solution. It is dependent on the environmental conditions, such as the reducing buffer capacity of the conditions. The results of dissolution rate measurements at VTT with 233 U-doped UO 2 samples in 0.01 to 0.1 M NaCl solutions under anoxic conditions did not show any effect of α radiolysis with doping levels of 5 and 10% 233 U (3.2 x 10 7 and 6.3 x 10 7 Bq/g). Both Fe 2+ and hydrogen can act as reducing species and could react with oxidizing radiolytic species. Fe 2+ concentrations of the order of 10 -5 M can decrease the rate of H 2 O 2 production. Low dissolution rates, 2 x 10 -8 to 2 x 10 -7 /yr, have been measured in the presence of metallic Fe with 5 and 10% 233 U-doped UO 2 in 0.01 to 1 M NaCl solutions. The tests with isotope dilution method showed precipitation phenomena of U to occur during dissolution process. The concentrations of dissolved U were extremely low (≤ 8.4 x 10 -11 M). No effects of -radiolysis could be seen. It is difficult to distinguish the effects of metallic Fe, Fe 2+ or hydrogen in these tests. Hydrogen could also act as a reducing agent

Redox reaction studies by nanosecond pulse radiolysis

International Nuclear Information System (INIS)

Moorthy, P.N.

1979-01-01

Free radicals are formed as intermediates in many chemical and biochemical reactions. An important type of reaction which they can undergo is a one electron or redox process. The direction and rate of such electron transfer reactions is governed by the relative redox potentials of the participating species. Because of the generally short lived nature of free radicals, evaluation of their redox potentials poses a number of problems. Two techniques are described for the experimental determination of the redox potentials of short lived species generated by either a nanosecond electron pulse or laser flash. In the first method, redox titration of the short lived species with stable molecules of known redox potential is carried out, employing the technique of fast kinetic spectrophotometry. Conversely, by the same method it is also possible to evaluate the one electron redox potentials of stable molecules by redox titration with free radicals of known redox potential produced as above. In the second method, electrochemical reduction or oxidation of the short lived species at an appropriate electrode (generally a mercury drop) is carried out at different fixed potentials, and the redox potential evaluated from the current-potential curves (polarograms). Full description of the experimental set up and theoretical considerations for interpretation of the raw data are given. The relative merits of the two methods and their practical applicability are discussed. (auth.)

Radiolysis in cement-based materials ; application to radioactive waste-forms

International Nuclear Information System (INIS)

Bouniol, P.

2014-01-01

Cement-based materials appear to be an original environment with respect to radiolysis, due to their intrinsic complexity (porous, multiphasic and evolutional medium) or their very specific physico-chemical conditions (hyper-alkaline medium with pH ≥ 13, high content in calcium) or by the fact of numerous couplings existing between different phenomenologies. At the level of a radioactive cemented wasteform, a high degree of complexity is reached, in particular if the system communicates with the atmosphere (open system allowing regulation of the pressures but also the admission of O 2 , strong reactive with regards to radiolysis). Then, the radiolysis description exceeds widely the only one aspect of the decomposition of alkaline water under irradiation and makes necessary a global phenomenological approach. In this context, some 'outlying' phenomena, highly coupled with radiation chemistry, have to be taken into account because they contribute to deeply modify the net result of the radiolysis: radioactive decay of multiple αβγ emitters with filiation, phase changes (for example H 2 aq → H 2 gas) within the pores, gas transport by convection (Darcy law) and by diffusion (Fick law), precipitation/dissolution of solid phases, effect of the ionic strength and the temperature, disturbances connected to the presence of some solutes with redox potentialities (iron, sulphur). The integration work carried out on the previous points leads to an operational model (DOREMI) allowing the estimate of H 2 amounts produced by radiolysis in different cemented radioactive waste-forms. As the final expression of the model, numerical simulations constitute a relevant tool of expertise and prospecting, contributing to accompany the thought on radiolysis in cement matrices in general and in cemented waste-forms in particular. Starting from different examples, simulations can be so used in order to test some hypotheses or illustrate the greatest influence of gas transport, dose

Coolant radiolysis studies in the high temperature, fuelled U-2 loop in the NRU reactor

International Nuclear Information System (INIS)

Elliot, A.J.; Stuart, C.R.

2008-06-01

An understanding of the radiolysis-induced chemistry in the coolant water of nuclear reactors is an important key to the understanding of materials integrity issues in reactor coolant systems. Significant materials and chemistry issues have emerged in Pressurized Water Reactors (PWR), Boiling Water Reactors (BWR) and CANDU reactors that have required a detailed understanding of the radiation chemistry of the coolant. For each reactor type, specific computer radiolysis models have been developed to gain insight into radiolysis processes and to make chemistry control adjustments to address the particular issue. In this respect, modelling the radiolysis chemistry has been successful enough to allow progress to be made. This report contains a description of the water radiolysis tests performed in the U-2 loop, NRU reactor in 1995, which measured the CHC under different physical conditions of the loop such as temperature, reactor power and steam quality. (author)

Tritium release reduction and radiolysis gas formation

Energy Technology Data Exchange (ETDEWEB)

Batifol, G.; Douche, Ch.; Sejournant, Ch. [CEA Valduc, 21 - Is-sur-Tille (France)

2008-07-15

At CEA Valduc, the usual tritiated waste container is the steel drum. It allows good release reduction performance for middle activity waste but in some cases tritium outgassing from the waste drums is too high. It was decided to over-package each drum in a tighter container called the over-drum. According to good safety practices it was also decided to measure gas composition evolution into the over-drum in order to defect hydrogen formation over time. After a few months, a significant release reduction was observed. Additionally there followed contamination reduction in the roof storage building rainwater. However hydrogen was also observed in some over-drums, in addition to other radiolysis products. Catalyst will be added to manage the hydrogen risk in the over-drums. (authors)

Accumulation of radiation defects and products of radiolysis in lithium orthosilicate pebbles with silicon dioxide additions under action of high absorbed doses and high temperature in air and inert atmosphere

Science.gov (United States)

Zarins, A.; Supe, A.; Kizane, G.; Knitter, R.; Baumane, L.

2012-10-01

One of the technological problems of a fusion reactor is the change in composition and structure of ceramic breeders (Li4SiO4 or Li2TiO3 pebbles) during long-term operation. In this study changes in the composition and microstructure of Li4SiO4 pebbles with 2.5 wt% silicon dioxide additions, fabricated by a melt-spraying process, were investigated after fast electron irradiation (E = 5 MeV, dose rate up to 88 MGy h-1) with high absorbed dose from 1.3 to 10.6 GGy at high temperature (543-573 K) in air and argon atmosphere. Three types of pebbles with different diameters and grain sizes were investigated. Products of radiolysis were studied by means of FTIR and XRD. TSL and ESR spectroscopy were used to detect radiation defects. SEM was used to investigate structure of pebbles. Experiments showed that Li4SiO4 pebbles with a diameter of 500 μm had similar radiation stability as pebbles with diameter <50 μm which were annealed at 1173 K for 128 h in argon and air atmosphere. As well as determined that lithium orthosilicate pebbles with size 500 (1243 K 168 h) and <50 μm (1173 K 128 h) have a higher radiation stability in air and argon atmosphere than pebbles with size <50 μm (1073 K 1 h). Degree of decomposition α10.56 of the lithium orthosilicate pebbles at an absorbed dose of 10.56 GGy in air atmosphere is 1.5% and 0.15% at irradiation in dry argon. It has been suggested that changes of radiation stability of lithium orthosilicate pebbles in air atmosphere comparing with irradiated pebbles in argon atmosphere is effect of chemical reaction of lithium orthosilicate surface with air containing - H2O and CO2 in irradiation process. As well as it has been suggested that silicon dioxide - lithium metasilicate admixtures do not affect formation mechanism of radiation defect and products of radiolysis in lithium orthosilicate pebbles.

Pulse radiolysis facilities and activities in Japan

International Nuclear Information System (INIS)

Ogasawara, M.

1995-01-01

Pulse radiolysis studies in Japan have been reviewed in special reference to the facilities and the people who have engaged in the experiments. Main achievement is summarized with the list of selected publications. (author)

Application of chemsimul for groundwater radiolysis

DEFF Research Database (Denmark)

Christensen, Hilbert; Bjergbakke, Erling

1986-01-01

The application of the radiation chemical computer program chemsimul, for the calculation of radiolysis in connection with the storage of high level waste has been studied. Methods have been developed for the diffusion of gases out of the irradiated system, for the continuous addition of Fe2...

Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

International Nuclear Information System (INIS)

Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

1982-01-01

By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

Radiation-induced chemical reaction of methane in the presence of X-and Y-type molecular sieves

International Nuclear Information System (INIS)

Shimizu, Y.; Nagai, S.

1990-01-01

The radiolysis of methane was investigated in the presence of X (13X) and Y (SK-40) type molecular sieves at 300 0 C. Product analysis showed that irradiation of methane over 13X and SK-40 produces hydrogen and hydrocarbons up to C 5 . The yields of hydrocarbons, except for ethylene, over 13X and SK-40 slightly increased with irradiation time. The yields of the main hydrocarbon products over SK-40 were larger than those in the absence of molecular sieve in contrast to those over 13X. It was found that no 13X shows catalytic activity for the radiolysis of methane; on the other hand, SK-40 shows it. The relations between the proportion of hydrocarbon yield of each carbon number to the hydrocarbon total yield over 13X and SK-40 and the carbon number were the same as those in the absence of molecular sieve. It was proved by comparison of these results with those over A-type molecular sieve (5A) that the order of the catalytic activities of the molecular sieves for the radiolysis of methane differs considerably from that found in thermal catalytic reactions. These results are discussed in terms of the concept of energy transfer and the relation between the pore size of the molecular sieves and the molecular diameters of the hydrocarbons produced. (author)

Radiolysis of actinides and technetium in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Delegard, C.H., Westinghouse Hanford

1996-07-10

The {gamma}-radiolysis of aerated alkaline aqueous solutions of Np(V), Np(VI), Pu(VI), Tc(IV), Tc(V), and TC(VII) was studied in the absence of additives and in the presence of CO{sub 3}{sup 2-}, NO{sub 3}{sup -}, NO{sub 2}{sup -}, EDTA, formate, and other organic compounds. The radiolytic reduction of Np(V), Np(VI), Pu(VI), and TC(VII) under different experimental conditions was examined in detail. The addition of EDTA, formate, and alcohols was found to considerably increase the radiation-chemical reduction yields. The formation of the Np(V) peroxo complex was observed in the {gamma}-radiolysis of alkaline aqueous solutions of Np (VI) in the presence of nitrate.

Highly magnetic Co nanoparticles fabricated by X-ray radiolysis

Science.gov (United States)

Clifford, Dustin M.; Castano, Carlos E.; Rojas, Jessika V.

2018-03-01

Advanced routes for the synthesis of nanomaterials, such as ferromagnetic nanoparticles, are being explored that are easy to perform using cost-effective and non-toxic precursors. Radiolytic syntheses based on the use of X-rays as ionizing radiation are promising towards this effort. X-rays were used to produce highly magnetic cobalt nanoparticles (NPs), stable in air up to 200 °C, from the radiolysis of water. Crystal structure analysis by XRD indicates a mixture of Cofcc, 63%, and Cohcp, 37%, phases. Magnetic analysis by VSM gave a saturation magnetization (Ms) 136 emu/g at 1 T and coercivity (Hc) = 325 Oe when the reaction solution was purged with N2 while an air-purged treatment resulted in Co NPs having 102 emu/g with a coercivity (Hc) 270 Oe. Overall, the reduction of Co2+ occurred in an aqueous reaction environment without addition of chemical reductants resulting in Co NPs with size distribution from 20 to 140 nm. This clean approach at ambient temperature produced highly magnetic Co NPs that may be used for switching devices (i.e. reed switches) or as additives for alloys that require high Curie points.

Resolved multisite OH-attack on aqueous aniline studied by pulse radiolysis

International Nuclear Information System (INIS)

Solar, S.; Solar, W.; Getoff, N.

1986-01-01

The individual formation and decay kinetics as well as the absorption characteristics of the simultaneously formed primary species by OH attack on aniline in aqueous solution (pH 8-9.6), saturated with N 2 O, have been determined by pulse radiolysis combined with a computer optimization procedure. Further the rate constant of e - sub(aq) with aniline was determined to (3.0+-0.1) x l0 7 dm 3 mol -1 cm -1 . Qualitative analysis of final products were also performed. (author)

Investigation into radiolysis of tbp labelled with 32P in the 30%tbp-diluent-HNO3 systems

International Nuclear Information System (INIS)

Novak, M.; Novak, Z.; Rokhon', A.

1975-01-01

Phosphorus-containing compounds, prepared by radiolysis of the TBP-diluent-HNO 3 system, are determined quantitatively. Effects of the HNO 3 concentration and the diluent type upon the degree of the TBP decomposition in the system under investigation were determined as well. To separate the TBP decomposition products the thin layer chromatography method was used, and for the quantitative determination TBP, labelled with 32 P was used. As a result of TBP radiolysis except dibutyl phosphate and monobutylphosphate other compounds are prepared, which contain phosphorus in a molecule, besides, their quantity depends on the nitric acid concentration and the diluent type (n-dodecan, carbon tetrachloride, mesitylen), together with which TBP was irradiated. The prepared compounds are grouped in the aqueous and organic phases

A fast-kinetic investigation of the redox chemistry of iridium chloride complexes using pulse radiolysis

International Nuclear Information System (INIS)

Crawford, C.L.; Gholami, M.R.; Roberts, S.L.; Hanrahan, R.J.

1992-01-01

Reactions initiated by OH radicals or e aq - in aqueous IrCl 6 3- solutions were studied by electron pulse radiolysis using a 600 keV Febetron electron accelerator. Solutions of IrCl 6 3- were made basic by adding Na 2 CO 3 ; using the carbonate competition method, we find the rate constant for the reaction of OH . with IrCl 6 3- to be 4.7 x 10 9 M -1 s -1 . The product IrCl 6 2- disappears rapidly in N 2 O-saturated basic solution or in neutral N 2 -saturated solution (N 2 O absent) but is nearly inert in neutral solution with N 2 O present. We find that IrCl 6 2- reacts rapidly with hydrogen peroxide in basic media, as confirmed on the benchtop and by stopped-flow kinetics. We therefore infer that reaction with HO 2 - may account for the loss of IrCl 6 2- under basic conditions. Since e aq - reduces Ir(III) chloride to the Ir(II) state with a rate constant of 6.1 x 10 9 M -1 s -1 , we suggest that loss of Ir(IV) in neutral deaerated solution without added N 2 O may involve electron transfer from Ir(II). Loss of Ir (IV) in aerated solution is attributed to reduction by the superoxide ion, O 2 - . Kinetic simulation of the system on the model described gives good agreement with our experimental results. (author)

Rate Constants for Reactions of Radiation-Produced Transients in Aqueous Solutions of Actinides

International Nuclear Information System (INIS)

Gordon, S.; Sullivan, J.C.; Ross, A.B.

1986-01-01

Rate constants have been critically compiled for reactions of ions of the actinides Am, Cf, Cm, Np, Pu, Th, and U, as well as the element Tc, in different oxidation states with various chemical species in aqueous solution. The reactants include products of the radiolysis of water (hydrated electrons, hydrogen atoms, hydroxyl radicals, hydrogen peroxide) and transient species derived from other solutes (e.g., carbonate radical). The data are useful in the estimation of migration properties of actinides, which are relevant to waste management studies

Formation and role of excited states in radiolysis - a foreword

International Nuclear Information System (INIS)

Singh, A.

1976-01-01

It is stated that the choice of contributions to the special issue of this Journal has been limited to those which bear on the details of the mechanisms of excited state formation and are likely to be useful to radiation chemists. Since more than half the energy deposited in radiolysis goes into excitation, studies on the fate of the excited species formed are very important. A brief reference is made to the subject matter of each of the fifteen contributions, and its significance to the development of the technique of radiolysis is outlined. (U.K.)

Matrix photoionization and radiolysis of the fluorobromomethanes. Infrared spectra and photochemistry of CFBr2+, CF2Br+, CF3+, and the parent cations

International Nuclear Information System (INIS)

Prochaska, F.T.; Andrews, L.

1978-01-01

The molecules CFBr 3 , CF 2 Br 2 , CF 3 Br, and C-13 enriched CF 3 Br have been subjected to matrix radiolysis and argon resonance photoionization during condensation with excess argon at 15 K. Infrared spectra showed stable and free radical products and new absorptions due to charged species. The molecular ion bands exhibited different behavior on filtered high-pressure mercury arc photolysis. Absorptions reduced by 220 to 1000-nm light are assigned to CFBr 2 + , CF 2 Br + , and CF 3 + ; other bands destroyed by photolysis are assigned to the parent cations. Li and Na atom reactions with the fluorobromomethane molecules confirmed the identification of the CFBr 2 and CF 2 Br free radicals. Other product bands destroyed by mercury arc light, some of which were generated upon photolysis of the sodium-fluorobromomethane samples, are assigned to molecular anions. 5 figures, 6 tables

Radiolysis of cyanocobalamin (vitamin B12)

International Nuclear Information System (INIS)

Juanchi, X.; Albarran, G.; Negron-Mendoza, A.

2000-01-01

Research on the radiolysis of vitamins is of considerable interest since these compounds are important nutritional constituents in foods and in dietetic supplements. In spite of these considerations there are few data and very often difficult to compare for the radiolytic behavior of vitamins. In this work we focused our attention on to the study of the radiolysis of cyanocobalamin (vitamin B 12 ) in solid state and in aqueous solutions. The procedure was followed by HPLC and UV-spectroscopy. The results obtained in aqueous solutions showed a dependence of the decomposition as a linear function of the dose. The G of decomposition for a 1x10 -5 M solution was 3.3. In the solid state the vitamin was very stable towards the irradiation in the conditions used in this study with a G=2.1x10 -3 . A study made with Serratia marcescens as a microbiological contaminant showed that at the sterilization dose there is a destruction of the vitamin in aqueous solution. In the solid state the degree of decomposition was 7%. (author)

The effects of γ-irradiation on the garlic oil contents in garlic bulbs and the radiolysis of allyl trisulfide

International Nuclear Information System (INIS)

Wei Genshuan, Wang Guanghui; Yang Ruipu; Wu Jilan

1995-01-01

The study of the effects of γ-irradiation on the garlic oil contents in the garlic bulbs and the radiolysis of allyl trisulfide and disulfide were carried out. The content of garlic oil in fresh garlic bulbs treated by gamma ray keeps nearly constant as stored for 10 months long. The main components of the garlic oil are allyl trisulfide (about 60%) and allyl disulfide (about 30%). The G values of radiolysis products of allyl disulfide and trisulfide in ethanol system were determined. The results show that allyl trisulfide is a very effective solvated electron scavenger and can oxidize CH 3 C HOH radical into acetaldehyde, which causes that the formation of 2,3-butanediol is extensively inhibited. (author)

The effects of γ-irradiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisulfide

International Nuclear Information System (INIS)

Wei Genshuan; Wang Guanghui; Yang Ruipu; Wu Jilan

1996-01-01

A study of the effects of γ-irradiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisufide and disulfide was carried out. The content of garlic oil in fresh garlic bulbs treated by gamma ray keeps nearly constant when stored for 10 months. The main components of garlic oil are allyl trisulfide (about 60%) and allyl disulfide (about 30%). The G values of radiolysis products of allyl disulfide and trisulfide in ethanol system were determined. The results show that allyl trisulfide is a very effective solvated electron scavenger and can oxidize CH 3 C . HOH radical into acetaldehyde, which means that the formation of 2,3-butanediol is extensively inhibited. (author)

A pulse radiolysis study of the reaction of the sulphate radical ion in aqueous solutions of styrene

International Nuclear Information System (INIS)

McAskill, N.A.; Sangster, D.F.

1979-01-01

The ultraviolet absorption spectra of the transient species formed during the pulse radiolysis of styrene and peroxydisulfate solutions showed that a benzyl-type radical was formed from styrene and the SO 4 - radical. The effect of adding Cl - was also studied. These results are in conflict with the claim that a phenylethyl radical was formed from SO 4 - via the styrene cation radical. That study was made on acetonitrile solutions of styrene, S 2 O 8 2- CUCl 2 and LiCl and the present results suggest that up to 70% of the SO 4 - radicals may have been converted into Cl 2 - radical which then reacted with styrene

Ion-molecule reactions: their role in radiation chemistry

International Nuclear Information System (INIS)

Lias, S.G.; Ausloos, P.

1975-01-01

A comprehensive review of ion--molecule reactions is presented, including information from mass spectrometric, organic chemistry, and NMR studies, from theoretical calculations, and from gas and liquid phase radiation chemistry. Special emphasis is placed on interpreting the role of ion--molecule reactions in systems under high energy irradiation. The discussion is presented under the following chapter headings: ion--molecule reactions and their role in radiation chemistry; unimolecular processes: the nature and structure of ionic intermediates in radiolysis; ion lifetimes and the fate of unreactive ions; kinetics and mechanisms of ion--molecule reactions; proton transfer reactions; negative atom and two-atom transfer reactions; condensation reactions; and, association or clustering reactions

Structure and dynamics of paramagnetic transients by pulsed EPR and NMR detection of nuclear resonance. [Pulse radiolysis of methanol in D/sub 2/O

Energy Technology Data Exchange (ETDEWEB)

Trifunac, A.D.

1981-01-01

Structure and dynamics of transient radicals in pulse radiolysis can be studied by time resolved EPR and NMR techniques. EPR study of kinetics and relaxation is illustrated. The NMR detection of nuclear resonance in transient radicals is a new method which allows the study of hyperfine coupling, population dynamics, radical kinetics, and reaction mechanism. 9 figures.

Radiolysis of DNA-protein complexes

Energy Technology Data Exchange (ETDEWEB)

Begusova, Marie [Department of Radiation Dosimetry, Nuclear Physics Institute, Na Truhlarce 39/64, CZ-18086, Prague 8 (Czech Republic)]. E-mail: begusova@ujf.cas.cz; Gillard, Nathalie [Centre de Biophysique Moleculaire, CNRS, rue Charles-Sadron, F-45071 Orleans Cedex 2 (France); Sy, Denise [Centre de Biophysique Moleculaire, CNRS, rue Charles-Sadron, F-45071 Orleans Cedex 2 (France); Castaing, Bertrand [Centre de Biophysique Moleculaire, CNRS, rue Charles-Sadron, F-45071 Orleans Cedex 2 (France); Charlier, Michel [Centre de Biophysique Moleculaire, CNRS, rue Charles-Sadron, F-45071 Orleans Cedex 2 (France); Spotheim-Maurizot, Melanie [Centre de Biophysique Moleculaire, CNRS, rue Charles-Sadron, F-45071 Orleans Cedex 2 (France)

2005-02-01

We discuss here modifications of DNA and protein radiolysis due to the interaction of these two partners in specific complexes. Experimental patterns of frank strand breaks (FSB) and alkali revealed breaks (ARB) obtained for DNA lac operator bound to the lac repressor and for a DNA containing an abasic site analog bound to the formamidopyrimidine-DNA glycosylase are reported. Experimental data are compared to predicted damage distribution obtained using the theoretical model RADACK.

Radiolysis of DNA-protein complexes

International Nuclear Information System (INIS)

Begusova, Marie; Gillard, Nathalie; Sy, Denise; Castaing, Bertrand; Charlier, Michel; Spotheim-Maurizot, Melanie

2005-01-01

We discuss here modifications of DNA and protein radiolysis due to the interaction of these two partners in specific complexes. Experimental patterns of frank strand breaks (FSB) and alkali revealed breaks (ARB) obtained for DNA lac operator bound to the lac repressor and for a DNA containing an abasic site analog bound to the formamidopyrimidine-DNA glycosylase are reported. Experimental data are compared to predicted damage distribution obtained using the theoretical model RADACK

Radiolabeling oligo nuclieotide with 90Y and its radiolysis

International Nuclear Information System (INIS)

Liu Changbin; Tian Jiahe; Zhang Jinming; Yin Dayi; Guo Zhe

2005-01-01

Objective: To evaluate labeling Morpholinos (MORF), a DNA analogue, with 90 Y using p-isothiocyanatobenzyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) as chelater and assess its stability and hybridization in vitro. Methods: A 25 mer MORF with a primary amine on the 3' equivalent end attached via a 10 member linker was conjugated with an isothiocyanate backbone derivative of DOTA. The conjugated product was labeled in various buffers over a different range of concentrations (0.5-2 mol/L) and pH(3-8.5). The labeled MORF was investigated for stability and hybridization in vitro. Results: By size exclusion high performance liquid chromatogram (HPLC) and instant thin layer chromatography (ITLC) analysis, the DOTA conjugated MORF was successfully radiolabeled, the labeling efficiency was (50 ± 12)%, the specific radioactivity was 5.05 x 10 6 MBq/mmol, radiochemistry purity >95%. The labeled MORF showed one sharp peak by HPLC that shifted completely to earlier retention times following addition of a polymer conjugated with the complementary MORF. In saline at room temperature and in serum at 37 degree C, the radioactivity profile of 90 Y showed a pronounced lower molecular weight peak which did not shifted and was shown due to 90 Y-DOTA resulting from radiolysis. Conclusion: MORF can be successfully labeled with 90 Y via DOTA as chelater, but care it must be taken to avoid the effect of radiolysis. (authors)

Pulse radiolysis study of NaNO/sub 2/ and NaNO/sub 3/ solutions. [Electrons

Energy Technology Data Exchange (ETDEWEB)

Broszkiewicz, R K [Institute of Nuclear Research, Warsaw (Poland)

1976-01-01

The pulse radiolysis of aqueous solutions of NaNO/sub 2/ and NaNO/sub 3/ has been done. In the nitrate solutions the transient species NO/sup 2 -//sub 2/ and NO/sub 2/ have been observed, the former reacting with water to produce NO, the latter dimerizing to N/sub 2/O/sub 4/. In the presence of O/sub 2/ and unidentified species with absorption maximum at 280 nm, probably a peroxy compound, is being formed. The radiolytic processes occurring in the nitrite solution do not depend on /NO/sub 02// and no effect of the direct energy absorption by NO/sup -//sub 2/ has been noticed. Transient species in the diluted nitrate solution are NO/sup 2 -//sub 3/ and the pernitrous ion; in concentrated solutions NO/sub 3/ is the main transient product. NO/sub 3/ is formed by the direct energy absorption by NO/sup -//sub 3/. Participation in tha effect of the cation should not be disregarded. There is evidence that the 340 nm peak in the transient spectrum is probably connected with N/sub 2/O/sub 4/ and not with NO/sub 3/. The tranient spectra, extinction coefficients of products and rate constants of relevant reactions are given.

Water Sorption and Gamma Radiolysis Studies for Uranium Oxides

Energy Technology Data Exchange (ETDEWEB)

Icenhour, A.S.

2002-02-27

During the development of a standard for the safe, long-term storage of {sup 233}U-containing materials, several areas were identified that needed additional experimental studies. These studies were related to the perceived potential for the radiolytic generation of large pressures or explosive concentrations of gases in storage containers. This report documents the results of studies on the sorption of water by various uranium oxides and on the gamma radiolysis of uranium oxides containing various amounts of sorbed moisture. In all of the experiments, {sup 238}U was used as a surrogate for the {sup 233}U. For the water sorption experiments, uranium oxide samples were prepared and exposed to known levels of humidity to establish the water uptake rate. Subsequently, the amount of water removed was studied by heating samples in a oven at fixed temperatures and by thermogravimetric analysis (TGA)/differential thermal analysis (DTA). It was demonstrated that heating at 650 C adequately removes all moisture from the samples. Uranium-238 oxides were irradiated in a {sup 60}Co source and in the high-gamma-radiation fields provided by spent nuclear fuel elements of the High Flux Isotope Reactor. For hydrated samples of UO{sub 3}, H{sub 2} was the primary gas produced; but the total gas pressure increase reached steady value of about 10 psi. This production appears to be a function of the dose and the amount of water present. Oxygen in the hydrated UO{sub 3} sample atmosphere was typically depleted, and no significant pressure rise was observed. Heat treatment of the UO{sub 3} {center_dot} xH{sub 2}O at 650 C would result in conversion to U{sub 3}O{sub 8} and eliminate the H{sub 2} production. For all of the U{sub 3}O{sub 8} samples loaded in air and irradiated with gamma radiation, a pressure decrease was seen and little, if any, H{sub 2} was produced--even for samples with up to 9 wt % moisture content. Hence, these results demonstrated that the efforts to remove trace

Nuclear magnetic resonance in pulse radiolysis. Chemically induced dynamic nuclear polarization

International Nuclear Information System (INIS)

Trifunac, A.D.; Johnson, K.W.; Lowers, R.H.

1976-01-01

Nuclear magnetic resonance and chemically induced dynamic nuclear polarization (CIDNP) were applied to the study of pulse radiolysis. Samples were irradiated with a 3-MeV electron beam from the Argonne Van de Graaff accelerator in an EPR magnet (approximately 4000 G) which had axial holes for beam access. A fast flow system transferred the irradiated solution to the rotating 5-mm NMR sample tube. The NMR spectra of mixtures of sodium acetate and methanol were presented to demonstrate the features of the CIDNP in pulse radiolysis

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

Energy Technology Data Exchange (ETDEWEB)

Wink, D A [National Cancer Inst., Frederick, MD (United States); Desrosiers, M F [National Inst. of Standards and Technology, Gaithersburg, MD (United States)

1991-01-01

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR{sub 2}{sup -}). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author).

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

International Nuclear Information System (INIS)

Wink, D.A.; Desrosiers, M.F.

1991-01-01

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR 2 - ). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author)

Radiolytic investigations of solutions of organophosphorus compounds in cyclohexane and benzene

International Nuclear Information System (INIS)

Otrebski, W.

1981-01-01

Organphosphorus compounds are used in various branches of the chemical industry, but in many cases the reaction mechanisms are not well elucidated and less is known about the intermediates of organophosphines. In order to learn more about these rather complicated processes several organophosphorus compounds were used as model substrates in cyclohexane or benzene solution. The systems have been investigated applying the pulse radiolysis technique and steady-state irradiation methods. As representative solutes were chosen diphenylphosphinous chloride, diphenylmethylphosphine, and triphenylphosphine. By means of the pulse radiolysis it was possible to obtain spectroscopic and kinetic data for characterization of the various transients. The final radiolytic products have been analyzed following steady-state and multipulse radiolysis. Since some of the rate constants were not directly accessible by the applied kinetic method, they have been determined by simulation computation. Thereby the experimental data obtained by pulse radiolysis were used. Based on the kinetic, spectroscopic and computed data as well as on the identification of final products, it was possible to elucidate the reaction mechanism of the diphenylphosphinous chloride/cyclohexane system. As a main primary specie was identified the diphenylphoshorus radical. Its spectral and kinetic data have been determined. The reactions of diphenylmethylphosphine involve the same radical, but only to a lesser extent. The reactions of the primary radiolysis products with triphenylphosphine yield mainly adducts. The results represent a contribution in the field of reaction kinetics of organophosphorus compounds. (author)

Recent results on solvation dynamics of electron and spur reactions of solvated electron in polar solvents studied by femtosecond laser spectroscopy and picosecond pulse radiolysis

International Nuclear Information System (INIS)

Mostafavi, M.

2006-01-01

Here, we report several studies done recently at ELYSE laboratory on the solvation dynamics of electron and on the kinetics of solvated electron in the spur reactions, performed by femtosecond laser spectroscopy and picosecond pulse radiolysis, respectively. Solvated electrons have been produced in polyol (1,2-Etanediol, 1,2-Propanediol and 1,3-Propanediol) by two-photon ionization of the solvent with 263 nm femtosecond laser pulses at room temperature. The two-photon absorption coefficient of these solvents at 263 nm has been determined. The dynamics of electron solvation in polyols has been studied by pump-probe transient absorption spectroscopy. So, time resolved absorption spectra ranging from 430 to 720 nm have been measured (Figure 1). A blue shift of the spectra is observed for the first tens of picoseconds. Using Bayesian data analysis method, the observed solvation dynamics are reconstructed with different models: stepwise mechanisms, continuous relaxation models or combinations of stepwise and continuous relaxation. That analysis clearly indicates that it is not obvious to select a unique model to describe the solvation dynamics of electron in diols. We showed that several models are able to reproduce correctly the data: a two-step model, a heterogeneous or bi-exponential continuous relaxation model and even a hybrid model with a stepwise transition and homogeneous continuous relaxation. Nevertheless, the best fits are given by the continuous spectral relaxation models. The fact that the time-evolution of the absorption spectrum of the solvated electron in diols can be accurately described by the temperature dependent absorption spectrum of the ground state solvated electron suggests that the spectral blue shift is mostly caused by the continuous relaxation of the electron trapped in a large distribution of solvent cages. Similar trends on electron solvation dynamics are observed in the cases of 1,2-ethanediol, 1,3-propanediol and 1,2 propanediol

Gamma radiolysis of Cu(II) complex of metronidazole

International Nuclear Information System (INIS)

Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

1990-01-01

Aqueous solutions of Cu(II)Metronidazole (Cu(II)M) at neutral pH were irradiated with 60 Co γ-rays under different conditions of radiolysis. The radiolytic formation of HNO 2 and Cu(I) was followed. The radiolytic yields of chromophore loss of Cu(II)M were also determined under different conditions. The OH radicals attack the metal complex to give the OH adducts of the ligand at C 2 , C 4 , and C 5 either directly or through the formation of Cu(III) species. The C 5 -OH adduct, however, undergoes oxidative denitration and as a result the metal complex is decomposed. The OH adducts also undergo electron transfer to Cu(II) ion to give reduced complex. No denitration was observed due to the reaction of e eq - with the metal complex. On the other hand, the nitro group of the ligand in the complex undergoes successive 4-electron reduction to give hydroxylamino derivative. From the competition kinetics using t-butyl alcohol as the scavenger of OH in N 2 O saturated solution of the metal complex, the rate constant for the reaction of OH with complex was evaluated to be ca. 2.1x10 9 dm 3 mol -1 s -1 which is of the same order as that observed in the case of free metronidazole. (author)

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

Energy Technology Data Exchange (ETDEWEB)

Lee, Ju-Woon [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Oh, Sang-Hee [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Kim, Jae-Hun [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Byun, Eui-Hong [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Ree Kim, Mee [Department of Food and Nutrition, Chungnam National University, Gung-Dong 220, Yuseong, Daejeon 305-764 (Korea, Republic of); Baek, Min [Atomic Energy Policy Division, Ministry of Science and Technology, Government Complex-Gwacheon, Kyunggi 427-715 (Korea, Republic of); Byun, Myung-Woo [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of)]. E-mail: mwbyun@kaeri.re.kr

2007-05-15

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring.

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

International Nuclear Information System (INIS)

Lee, Ju-Woon; Oh, Sang-Hee; Kim, Jae-Hun; Byun, Eui-Hong; Ree Kim, Mee; Baek, Min; Byun, Myung-Woo

2007-01-01

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring

Investigation of OH dynamics in the argon sensitized pulse radiolysis of water vapor

International Nuclear Information System (INIS)

Bera, R.K.; Hanrahan, R.J.

1986-01-01

Reactions of OH radical were studied in systems containing 650 torr Ar and from 0.5 to 9 torr H 2 O using the method of pulse radiolysis-absorption spectroscopy. It was found that initial concentrations of OH radical increased as a function of water vapor pressure. Although loss of OH with time followed approximate second order kinetics, the raw data were fitted arbitrarily to a first order rate expression, because a second order fit requires knowledge of absolute initial OH concentrations. These can be computed from measured initial OH absorption if the extinction coefficient is known, but an accurate value was not available initially. The half-life for OH loss decreased at higher water pressures. Dependence of OH half-life on OH concentration occurs because homogeneous OH loss processes are second order in reaction intermediates, whose concentration increases with added H 2 O. A contribution by water in chaperoning OH/OH and OH/H combination is also important

Accumulation of radiation defects and products of radiolysis in lithium orthosilicate pebbles with silicon dioxide additions under action of high absorbed doses and high temperature in air and inert atmosphere

Energy Technology Data Exchange (ETDEWEB)

Zarins, A.; Supe, A. [Laboratory of Radiation Chemistry of Solids, Institute of Chemical Physics, University of Latvia, Kronvalda Bulvaris 4, LV-1010 Riga (Latvia); Kizane, G., E-mail: gunta.kizane@lu.lv [Laboratory of Radiation Chemistry of Solids, Institute of Chemical Physics, University of Latvia, Kronvalda Bulvaris 4, LV-1010 Riga (Latvia); Knitter, R. [Karlsruhe Institute of Technology, Institute for Applied Materials (IAM-WPT), POB 3640, 76021 Karlsruhe (Germany); Baumane, L. [Laboratory of Radiation Chemistry of Solids, Institute of Chemical Physics, University of Latvia, Kronvalda Bulvaris 4, LV-1010 Riga (Latvia)

2012-10-15

One of the technological problems of a fusion reactor is the change in composition and structure of ceramic breeders (Li{sub 4}SiO{sub 4} or Li{sub 2}TiO{sub 3} pebbles) during long-term operation. In this study changes in the composition and microstructure of Li{sub 4}SiO{sub 4} pebbles with 2.5 wt% silicon dioxide additions, fabricated by a melt-spraying process, were investigated after fast electron irradiation (E = 5 MeV, dose rate up to 88 MGy h{sup -1}) with high absorbed dose from 1.3 to 10.6 GGy at high temperature (543-573 K) in air and argon atmosphere. Three types of pebbles with different diameters and grain sizes were investigated. Products of radiolysis were studied by means of FTIR and XRD. TSL and ESR spectroscopy were used to detect radiation defects. SEM was used to investigate structure of pebbles. Experiments showed that Li{sub 4}SiO{sub 4} pebbles with a diameter of 500 {mu}m had similar radiation stability as pebbles with diameter <50 {mu}m which were annealed at 1173 K for 128 h in argon and air atmosphere. As well as determined that lithium orthosilicate pebbles with size 500 (1243 K 168 h) and <50 {mu}m (1173 K 128 h) have a higher radiation stability in air and argon atmosphere than pebbles with size <50 {mu}m (1073 K 1 h). Degree of decomposition {alpha}{sub 10.56} of the lithium orthosilicate pebbles at an absorbed dose of 10.56 GGy in air atmosphere is 1.5% and 0.15% at irradiation in dry argon. It has been suggested that changes of radiation stability of lithium orthosilicate pebbles in air atmosphere comparing with irradiated pebbles in argon atmosphere is effect of chemical reaction of lithium orthosilicate surface with air containing - H{sub 2}O and CO{sub 2} in irradiation process. As well as it has been suggested that silicon dioxide - lithium metasilicate admixtures do not affect formation mechanism of radiation defect and products of radiolysis in lithium orthosilicate pebbles.

Reactions of metal-substituted myoglobins with excess electrons studied by pulse radiolysis and low-temperature gamma-radiolysis

International Nuclear Information System (INIS)

Miki, Hideho; Nakajima, Atushi; Ogasawara, Masaaki; Tamura, Mamoru

1990-01-01

Reactions of metal-substituted myoglobins with excess electrons in electron-pulse-irradiated aqueous solutions at room temperature and γ-irradiated aqueous matrices at 77 K were studied for the purpose of probing the functional role of heme iron. The rate constants for the reactions of various myoglobins with hydrated electrons were not much different from each other, and were close to those of diffusion-controlled reactions. In contrast, the reduction rates of myoglobins with dithionite depended markedly on the kind of central metals in the myoglobins. The difference was interpreted in terms of Marcus' theory for electron-transfer reactions. Effects of the 6-coordinate structure of the cobalt(III) species on the reaction with dithionite was also discussed. The steady-state optical-absorption measurements of γ-irradiated matrices containing cobaltimyoglobin at 77 K demonstrated the reduction of cobalt(III) species by excess electrons produced by the action of ionizing radiation. It was shown, by electron-spin resonance spectroscopy, that a 6-coordinated cobalt(II) species produced at 77 K transformed to a 5-coordinate one at higher temperatures, as reported previously. However, structural relaxation was not observed by optical spectroscopy either in the solutions or in the low-temperature matrices. It was concluded, therefore, that the intermediate 6-coordinate cobalt(II) species gave an optical absorption spectrum which was indistinguishable from that of the relaxed 5-coordinate cobalt(II) species. (author)

Redox reaction in photochemical and ionizing irradiation systems

International Nuclear Information System (INIS)

Slama-Schwok, A.

1985-09-01

This work presents a basic study of electron transfer reactions which could be involved in appropriate systems for photochemical conversion and storage of solar energy. The aim was to extend the knowledge to new photosensitizers and quenchers and to compare them with the most popular photosensitizers-quenchers system, i.e. a rubidium complex. The photosensitizer studied here is an irridium complex. We studied in this work the air oxidation of bromide to Br 3 - and H 2 O 2 using the irridium complex as the sensitizer. The reducing properties of the reduced irridium complex photosensitizer were studied, using the pulse radiolysis techniques. In conclusion, the oxidation reduction properties of the irridium and its lowest excited state correspond to most of the photosensitizer for electron transfer reactions. The energy temporary present in the charge separation products can be stored using appropriate environment such as polyelectrolytes

Study of the radiolysis of succinic acid - applications in the dosimetry of high doses

International Nuclear Information System (INIS)

Andrade e Silva, L.G.

1978-01-01

A study is made of the effect of the gama radiation dose and of particle size of succinic acid (fine powder of large crystals) in relation with the formation of CO 2 and CO + H 2 , which are the main gaseous products of radiolysis. A different yield of CO + H 2 is found when the succinic acid is used as powder compared to the material in the form of large crystals. The reason for this difference is searched, studying the influence of heating and sublimation of the succinic acid prior to irradiation. The influence, in the mentioned yield, of the surface area of succinic acid particles, of the presence of oxygen (air) and of the rapid recrystallization of the acid are also studied. The formation of intermediate species in the radiolysis of succinic acid is examined. The system used in ethanol-succinic acid at 77K. Analysis are made using an electronic paramagnetic resonance spectrometer. The possibility of using succinic acid as a dosimeter for high level gama radiation doses is discussed [pt

Radiolysis of solutions in anthraquinone derivatives

International Nuclear Information System (INIS)

Kriminskaya, Z.K.

1996-01-01

Stationary radiolysis of anthraquinones in solutions of ethanol, propanol-2 and water by gamma-radiation (dose rate of 1.6 Gy/s) is studied. It is shown that anthraquinones are reduced in the above solutions up to anthrahydroquinones, whereby all reduction particles participate in the reduction process. The reverse process of the post-radiation oxidation of anthrahydroquinones up to anthraquinones is a radical process

Irradiation of fish fillets: Relation of vapor phase reactions to storage quality

Science.gov (United States)

Spinelli, J.; Dollar, A.M.; Wedemeyer, G.A.; Gallagher, E.C.

1969-01-01

Fish fillets irradiated under air, nitrogen, oxygen, or carbon dioxide atmospheres developed rancidlike flavors when they were stored at refrigerated temperatures. Packing and irradiating under vacuum or helium prevented development of off-flavors during storage.Significant quantities of nitrate and oxidizing substances were formed when oxygen, nitrogen, or air were present in the vapor or liquid phases contained in a Pyrex glass model system exposed to ionizing radiation supplied by a 60Co source. It was demonstrated that the delayed flavor changes that occur in stored fish fillets result from the reaction of vapor phase radiolysis products and the fish tissue substrates.

Oxidation of ortho- and para-aminobenzoic acid. A pulse radiolysis- and gamma radiolysis study

International Nuclear Information System (INIS)

Solar, Sonja; Getoff, Nikola; Zona, Robert; Solar, Wolfgang

2011-01-01

The oxidation of anthranilic acid (ortho-aminobenzoic acid, ANA) and para-aminobenzoic acid (PABA) by · OH, N 3 · and O ·- in basic solution was studied by pulse radiolysis. The kinetic and spectroscopic characteristics of the intermediate transients were determined. For ANA the site attack of the OH radicals was established to be ∼50% on the -NH 2 moiety and ∼50% on the aromatic ring with an overall rate constant k( · OH+ANA)=(5.5x10 9 ) dm 3 mol -1 s -1 . The rate constant of PABA was k( · OH+PABA)=8x10 9 dm 3 mol -1 s -1 . The OH-adducts of both compounds showed a first order decay of 0.8x10 5 and 1.2x10 5 s -1 , respectively, whereby the corresponding anilino-radicals were formed. The rate constant of ANA with solvated electrons was k(e - aq +ANA)=2.9x10 9 dm 3 mol -1 s -1 . The radiation induced decomposition of both substrates was studied by gamma radiolysis as a function of the absorbed dose. They exhibited a distinct radiation resistance, the initial degradation yields were ∼0.16 μmol J -1 , i.e. only 28% of the · OH radicals contributed to their decomposition. The hydroxylation process was of minor importance, the yield of hydroxylated aminobenzoic acids was≤0.01 μmol J -1 .

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

Science.gov (United States)

Wink, David A.; Desrosiers, Marc F.

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.

Gamma-ray radiolysis of methyl iodide in air, in presence of water vapor

International Nuclear Information System (INIS)

Aubert, F.

2002-03-01

This work aims at modelling the processes involved in gamma-radiolysis of methyl iodide diluted in air in presence of steam. It is to determine quantitative and qualitative information, to quantify the importance of the organic iodides destruction in case of a nuclear reactor accident. The main data for radiochemistry and iodine compounds (I x O y and INO x ) formation were reviewed and analysed. Literature data about air products radiolysis reactivity towards I 2 and CH 3 I were used to develop a mechanistic model for methyl iodide destruction in the gas phase under gamma irradiation. An ab initio study was realised for a better understanding of atomic nitrogen ( 4 S and 2 D) reactivity towards CH 3 I. The model was tested on the available experimental data and constitute a way to investigate the main processus involved in methyl iodide destruction. For the low CH 3 I concentrations, about 10 -7 - 10 -8 mol.dm -3 , N and e - are mainly responsible for the destruction. I 2 O 4 (highest iodine oxide in the model) and IONO 2 are the main resulting iodinated' compounds. (author)

Pulse radiolysis of butyl acrylate in aqueous solution

International Nuclear Information System (INIS)

Kujawa, P.; Ulanski, P.; Rosiak, J.M.; Mohid, N.; Zaman, K.; Manshol, W.

1998-01-01

The pulse radiolysis of n-butyl acrylate (nBA) in aqueous solution was studied. The rate constant of the reaction of nBA with hydroxyl radicals was calculated as 1.5x10 10 dm 3 mol -1 s -1 . The absorption spectrum of the OH · -nBA adduct appeared to have a broad maximum at 300 nm. This spectrum was attributed to the α-carbon centred radicals. It decayed with the first-order rate constant k=1.5x10 4 s -1 (pH 10.8). The rate constant of the nBA reaction with hydrated electrons was determined as k=1.6x10 10 dm 3 mol -1 s -1 . The spectrum of H · -nBA adduct was similar to that recorded for OH · adduct. It decayed with first-order kinetics at k=1.0x10 4 s -1 . Spectra of the electron adduct were characterised by the band with a maximum at 285 nm (pH 10.0) or at 280 nm (pH 4.0) with ε=10500 dm 3 mol -1 cm -1 . In acidic solution, radical anion formed upon addition of hydrated electrons to the nBA molecule, undergoes fast, reversible protonation. The decay of the reversibly protonated electron adduct was a second-order process at k=2.5x10 9 dm 3 mol -1 s -1 . This reaction took place at the carbonyl oxygen. Slow, irreversible protonation of the electron adduct at high pH takes place at the β-carbon atom at k=2.9x10 4 s -1

Coloring Jupiter's clouds: Radiolysis of ammonium hydrosulfide (NH4SH)

Science.gov (United States)

Loeffler, Mark J.; Hudson, Reggie L.

2018-03-01

Here we present our recent studies on the color and spectral reflectance changes induced by ∼0.9 MeV proton irradiation of ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. Ultraviolet-visible spectroscopy was used to observe and identify reaction products in the ice sample and digital photography was used to document the corresponding color changes at 10-160 K. Our experiments clearly show that the resulting color of the sample depends not only on the irradiation dose but also the irradiation temperature. Furthermore, unlike in our most recent studies of irradiation of NH4SH at 120 K, which showed that higher irradiation doses caused the sample to appear green, the lower temperature studies now show that the sample becomes red after irradiation. However, comparison of these lower temperature spectra over the entire spectral range observed by HST shows that even though the color and spectrum resemble the color and spectrum of the GRS, there is still enough difference to suggest that another component may be needed to adequately fit spectra of the GRS and other red regions of Jupiter's clouds. Regardless, the presence of NH4SH in the atmosphere of Jupiter and other gas giants, combined with this compound's clear alteration via radiolysis, suggests that its contribution to the ultraviolet-visible spectra of any of these object's clouds is significant.

Radiolysis of cyanocobalamin (vitamin B{sub 12})

Energy Technology Data Exchange (ETDEWEB)

Juanchi, X.; Albarran, G.; Negron-Mendoza, A

2000-03-01

Research on the radiolysis of vitamins is of considerable interest since these compounds are important nutritional constituents in foods and in dietetic supplements. In spite of these considerations there are few data and very often difficult to compare for the radiolytic behavior of vitamins. In this work we focused our attention on to the study of the radiolysis of cyanocobalamin (vitamin B{sub 12}) in solid state and in aqueous solutions. The procedure was followed by HPLC and UV-spectroscopy. The results obtained in aqueous solutions showed a dependence of the decomposition as a linear function of the dose. The G of decomposition for a 1x10{sup -5} M solution was 3.3. In the solid state the vitamin was very stable towards the irradiation in the conditions used in this study with a G=2.1x10{sup -3}. A study made with Serratia marcescens as a microbiological contaminant showed that at the sterilization dose there is a destruction of the vitamin in aqueous solution. In the solid state the degree of decomposition was 7%. (author)

Radiolytic gas production from concrete containing Savannah River Plant waste

International Nuclear Information System (INIS)

Bibler, N.E.

1978-01-01

To determine the extent of gas production from radiolysis of concrete containing radioactive Savannah River Plant waste, samples of concrete and simulated waste were irradiated by 60 Co gamma rays and 244 Cm alpha particles. Gamma radiolysis simulated radiolysis by beta particles from fission products in the waste. Alpha radiolysis indicated the effect of alpha particles from transuranic isotopes in the waste. With gamma radiolysis, hydrogen was the only significant product; hydrogen reached a steady-state pressure that increased with increasing radiation intensity. Hydrogen was produced faster, and a higher steady-state pressure resulted when an organic set retarder was present. Oxygen that was sealed with the wastes was depleted. Gamma radiolysis also produced nitrous oxide gas when nitrate or nitrite was present in the concrete. With alpha radiolysis, hydrogen and oxygen were produced. Hydrogen did not reach a steady-state pressure at 137 Cs and 90 Sr), hydrogen will reach a steady-state pressure of 8 to 28 psi, and oxygen will be partially consumed. These predictions were confirmed by measurement of gas produced over a short time in a container of concrete and actual SRP waste. The tests with simulated waste also indicated that nitrous oxide may form, but because of the low nitrate or nitrite content of the waste, the maximum pressure of nitrous oxide after 300 years will be 238 Pu and 239 Pu will predominate; the hydrogen and oxygen pressures will increase to >200 psi

Pulse radiolysis study on aqueous solution of nicotine

International Nuclear Information System (INIS)

Wang Shilong; Mei Wang; Ni Yaming; Yao Side; Wang Wenfeng

2004-01-01

Nicotine has been studied for the first time by pulse radiolysis techniques. It has been found that hydrated electrons, hydrogen radicals and hydroxyl radicals can react with nicotine to produce anion radicals and neutral radicals, respectively, and the related rate constants have been determined. (authors)

Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

International Nuclear Information System (INIS)

Shkrob, I.A.; Trifunac, A.D.

1995-01-01

Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

Flash photolysis and pulse radiolysis of the Co(sep)3+-X- (sep = sepulchrate; X = I, Br) systems in aqueous solution

International Nuclear Information System (INIS)

Pina, F.; Maestri, M.; Ballardini, R.; Mulazzani, Q.G.; D'Angelantonio, M.; Balzani, V.

1986-01-01

The Co(sep) 3+ complex (sep = sepulchrate = 1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]eicosane) in aqueous solution forms ion pairs with the I - and Br - anions, which exhibit a relatively intense charge-transfer absorption. In deoxygenated aqueous solution no net reaction is obtained upon continuous light excitation in the ion-pair charge-transfer bands, but formation of transient species is observed in flash photolysis experiments. For the Co(sep) 3+ -I - system, I 2 - ions are formed that decay in the 50-μs time scale to give I 3 - . The latter species disappears in a time scale of seconds, leading the system back to the preexcitation conditions. For the Co(sep) 3+ -Br - system, only formation of the Br 2 - transient is observed, followed by regeneration of the preexcitation conditions in the 20-μs time scale. In order to elucidate the kinetic aspects of the transient formation and disappearance, pulse radiolysis experiments on the Co(sep) 3+ -I - and Co(sep) 3+ -Br - systems have been carried out. The rate constants of the reactions of Co(sep) 2+ with I 2 - , I 3 - , and Br 2 - have been measured, and a complete picture of the redox processes that follow flash photolysis and pulse radiolysis excitations has been obtained. 5 figures

Pulse radiolysis of malachite green leucocyanide in alcoholic solvents, the influence of oxygen

International Nuclear Information System (INIS)

Grodkowski, J.; Stuglik, Z.; Wieczorek, G.

1992-01-01

The solutions of malachite green leucocyanide (MGCN) in methanol, n-propanol and 2-propanol were investigated using pulse radiolysis. In the presence of oxygen, MG + -carbonium ions were radiolytically formed in two different time steps. The yield of MG + in the slower process was dependent on oxygen concentration and was proportional to the yield of intermediate MG radicals. The yield of MG was about ten times higher in 2-propanol than in methanol and n-propanol solutions. The reactants responsible for MG oxidation to MG + were RO 2 , hydroxyalkylperoxyl radicals derived from alcohols. The rate constant for MG reaction with RO 2 were estimated as (6.5±1) x 10 8 M -1 s -1 . The molar extinction coefficient of MG was calculated. (author)

Air effect on polycarbonate radiolysis

International Nuclear Information System (INIS)

Terence, Mauro C.; Araujo, Elmo S.; Guedes, Selma M.L.

1995-01-01

The formation and decay of radicals in the radiolysis of new type of polycarbonate (G scission = 0,73) was investigated by electron spin resonance spectroscopy in the presence and absence of air at room temperature. The air does not interfere in the formation of radicals because they are formed as consequence of direct interaction of radiation. But the air interferes in their decays. During the irradiation the air reacts with all isopropyl radicals and with 2/3 of phenoxy + phenyl radicals. (author). 5 refs., 3 figs

Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

International Nuclear Information System (INIS)

Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

1981-01-01

By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

Magnetic resonance methods used to study the mobility of lithium ions and the formation of gamma radiolysis products in lithium silicates

International Nuclear Information System (INIS)

Pronin, I.S.; Nikiforov, A.S.; Vashman, A.A.

1986-01-01

The authors present the results of research on the mobility of lithium ions and the formation of radiation induced paramagnetic centers in the gamma radiolysis of lithium ortho- and metasilicates; nuclear magnetic resonance of Li-7 and electroparamagnetic resonance were used in the studies

Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

International Nuclear Information System (INIS)

Stout, R B

2001-01-01

A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

Characterisation and activation of catalysts for recombination of radiolysis gas; Charakterisierung und Aktivierung von Katalysatoren zur Rekombination von Radiolysegas

Energy Technology Data Exchange (ETDEWEB)

Bolz, Michael; Koehler, Jan; Schorle, Rolf; Helf, Achim [EnBW Kernkraft GmbH, Philippsburg (Germany). Kernkraftwerk Philippsburg, Teilbereich Chemie

2011-07-01

Radiolysis gas is produced by radiolysis of cooling water during the operation of boiling water reactors. Small amounts of radiolysis gas can accumulate at dead ends of pipes in the water-steam circuit. Under certain conditions, it can accumulate even to higher concentrations. To avoid these accumulations, small catalysts are built in. As part of a diploma thesis, the catalysts were analysed and characterised. (orig.)

Development of subpicosecond pulse radiolysis system

International Nuclear Information System (INIS)

Kozawa, T.; Saeki, A.; Okamoto, K.; Numata, Y.; Kaseda, K.; Yamamoto, T.; Suemine, S.; Yoshida, Y.; Tagawa, S.

2000-01-01

Subpicosecond pulse radiolysis system was developed to elucidate the primary processes of radiation chemistry in the time region of femtosecond. The system consists of a femtosecond electron linac as an irradiation source, a femtosecond laser as an analyzing light and a jitter compensation system which was designed to reduce the effect of jitter between an electron pulse and a laser pulse on the time resolution. The time resolution of 800 fs was achieved. (author)

Intermediate products of radiolytic conversions of 6-aminophenalenone in ethanol

International Nuclear Information System (INIS)

Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

1992-01-01

Intermediate products of the conversions of 6-aminophenalenone in ethanol were investigated by pulse radiolysis. In alkaline medium the main product is the 6-aminophenalenone radical cation, the optical absorption spectrum of which contains two bands with maxima at 355 and 400 nm. The precursors of this particle are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium, radical cations are protonated in reactions with alcohol and hydrogen ions. The H-adduct of 6-aminophenalenone that arises has optical absorption maxima at 350 and 390 nm. The presence of two maxima is due to two different structures of the product. The molar extinction coefficients of the radical anions and H-adducts of 6-aminophenalenone and the rate constants of the reactions involving them were estimated. 6 refs., 4 figs., 2 tabs

Construction of ion beam pulse radiolysis system

Energy Technology Data Exchange (ETDEWEB)

Chitose, Norihisa; Katsumura, Yosuke; Domae, Masafumi; Ishigure, Kenkichi; Murakami, Takeshi [Tokyo Univ. (Japan)

1996-10-01

An ion beam pulse radiolysis system has been constructed at HIMAC facility. Ion beam of 24 MeV He{sup 2+} with the duration longer than 1 {mu}s is available for irradiation. Three kinds of aqueous solutions, (C{sub 6}H{sub 5}){sub 2}CO, NaHCO{sub 3} and KSCN, were irradiated and the absorption signals were observed. (author)

Gamma-radiolysis of the 2-methyl-2-propanol-water system: yields of methane and ethane

International Nuclear Information System (INIS)

Silaev, M.M.; Afanas'ev, A.M.; Kalyazin, E.P.

1991-01-01

The dependence of methane and ethane yields on the concentration and corresponding electron part of alcohol during γ-radiolysis of 2-methyl-2-propanol-water system has been investigated. Irradiation was realized at room temperature, dose rate of 7.7 Gy/s up to absorbed doses of 0.4-14 kGy. The observed deviations of radiation-chemical yields of products from additivity rule, positive in case of methane and negative in case of ethane, are explained

Study of polysilane mainchain electronic structure by picosecond pulse radiolysis

International Nuclear Information System (INIS)

Habara, H.; Saeki, A.; Kunimi, Y.; Seki, S.; Kozawa, T.; Yoshida, Y.; Tagawa, S.

2000-01-01

The electronic structure of a charged polysilane molecle is studied. The transient absorption spectroscopy was carried out for charged radicals of poly (methylphenylsilane): PMPS by pico-second and nanosecond pulse radiolysis technique. It was observed that the peak of the transient absorption spectra shifted to longer wavelength region within a few nsec, and an increase was observed in the optical density at 370 nm, which had been already assigned to the radical anions of PMPS. It is ascribed to inter-segment electron transfer (intra-molecular transfer) through polymer chain. The nanosecond pulse radiolysis experiments gave similar kinetic traces in near-UV and IR region. This suggests the presence of an interband level, that is, a polaron level occupied by an excess electron or a hole. (author)

Radiolysis of fluoro ethylene-propylene copolymer

International Nuclear Information System (INIS)

Hill, D.J.T.; Mohajerani, S.; Pomery, P.J.; Whittaker, A.K.

1998-01-01

Full text: Poly(tetrafluoroethylene-co-perfluoropropylene) (FEP), is used for medical and sophisticated aerospace applications. where a specialty polymer with high radiation-stability is required. Hence, an understanding of the radiation chemical processes is important and will lead to the design and development of the appropriate material for different applications. FEP like other fluoropolymers exhibits unique characteristics such as resistance to chemical attack by solvents, chemical inertness, thermal stability, excellent weathering resistance and outstanding electrical properties. Combination of theses properties together with a radiation stable polymer provides an excellent profile for a polymer appropriate for applications mentioned previously. The behavior of FEP upon irradiation depends on the environment and the temperature of the radiolysis. The mechanical and physical changes for un-irradiated as well as irradiated FEP have been studied using NMR, DMA, TGA and the mechanism of the crosslinking and degradation was studied using ESR. FEP has been known to degrade when irradiated at room temperature. However, there is evidence that irradiation of FEP in vacuum at temperatures above its glass transition temperature will result in crosslinking reactions predominating over chain scission or degradation. The FEP under study is a linear, semi-crystalline fluoroplastic with the glass transition temperature of 84-86 deg C. This fluoropolymer is commercially produced by copolymerisation of tetrafluoroethylene and perfluoropropylene

Some reactions of oxidizing radicals with enzymes in aqueous solution

International Nuclear Information System (INIS)

Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

1979-01-01

A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

Low Energy Nuclear Reaction Products at Surfaces

Science.gov (United States)

Nagel, David J.

2008-03-01

This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

Gamma radiolysis effects on basalt groundwater

International Nuclear Information System (INIS)

Gray, W.J.

1983-10-01

Gamma radiolysis of basalt groundwater containing 700 ppM methane produces a milky liquid that is a suspension of fine particles of a high molecular weight hydrocarbon somewhat like polyethylene. The ability of these polymers to chelate with, or otherwise sorb, metal ions from aqueous solution was measured using Cu +2 as a representative cation. Values in the range 0.3 to 0.8 millimoles of Cu per liter of solution were found. 5 references, 2 figures, 2 tables

Pulse radiolysis of malachite green leucocyanide in alcoholic solvents, the influence of oxygen

Energy Technology Data Exchange (ETDEWEB)

Grodkowski, J; Stuglik, Z; Wieczorek, G [Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

1992-04-01

The solutions of malachite green leucocyanide (MGCN) in methanol, n-propanol and 2-propanol were investigated using pulse radiolysis. In the presence of oxygen, MG{sup +}-carbonium ions were radiolytically formed in two different time steps. The yield of MG{sup +} in the slower process was dependent on oxygen concentration and was proportional to the yield of intermediate MG radicals. The yield of MG was about ten times higher in 2-propanol than in methanol and n-propanol solutions. The reactants responsible for MG oxidation to MG{sup +} were RO{sub 2}, hydroxyalkylperoxyl radicals derived from alcohols. The rate constant for MG reaction with RO{sub 2} were estimated as (6.5{+-}1) x 10{sup 8}M{sup -1}s{sup -1}. The molar extinction coefficient of MG was calculated. (author).

Precursor of fragment radicals in the radiolysis of normal alkanes. [Gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Isildar, M; Schuler, R H [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry

1978-01-01

It is found that the yields of fragment radicals produced in the radiolysis of n-hexane are not significantly affected by the changes in the ion recombination processes that occur when HI is added to the system. From this observation it is concluded that in the radiolysis of normal alkanes, carbon-carbon bond rupture results predominantly either from high energy processes that do not directly involve ionic precursors or, more likely, from the dissociation of the initial ions at very early times (< 10/sup -11/s) before a substantial fraction of the geminate ions undergo neutralization.

Principal processes in the radiolysis of gases with fission recoils and gamma rays. Annual progress report, October 16, 1975--October 15, 1976

International Nuclear Information System (INIS)

Meisels, G.G.

1976-12-01

The methods for assessing track temperature in gases were examined and that based on differences in activation energies of abstraction reactions was developed using two techniques. The first is based on total product analysis of species which have iso- or n-propyl radicals as precursors. The other is concerned with the same radicals, but employs 14 C 2 H 4 as a scavenger and the radical-sampling technique for quantitation of the two intermediates. In the gamma radiolysis of propane, the relative yields of the two radicals are independent of pressure between 0.005 and 0.02 g/cm 3 . The analysis of lifetimes of ion-molecule reaction intermediates using a simple combination of RRKM and Langevin theory with retention of angular momentum in the complex was continued. It suggests that the third order rate constant derived from collisional deactivation experiments of CO 3 - should depend approximately on the T/sup -1.5/ suggesting caution in the use of temperature dependencies to derive information on transition states. Methodology of rate constant determinations by time resolved measurements was analyzed, and a new approach based on predicted arrival time distributions was developed. The rate constant for the dimer ion (CO 2 ) 2 + with methane to give the displacement product CO 2 CH 4 + was evaluated as 1.6 x 10 -9 cc/sec -1

Spin trapping of cyanoalkyl radicals in the liquid phase γ radiolysis of nitriles

International Nuclear Information System (INIS)

Mao, S.W.; Kevan, L.

1976-01-01

The following radicals have been identified in the liquid phase γ radiolysis of several nitriles by spin trapping with phenyl tert-butyl nitrone: CH 2 CN in acetonitrile, H and CH 3 CHCN(question) in propionitrile, CH(CN) 2 in malononitrile, and H, CN, and CH 2 CH 2 CN in succinonitrile. γ proton splittings are observed for the CH 2 CN and CH(CH) 2 spin adducts. The results are discussed in comparison with solid phase radiolysis data and with alkyl radical spin adduct splittings

Effect of electrostatic interactions on electron-transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

Fast reactions of electron transfer are studied by pulsed radiolysis. By this technique radicals and ionic radicals with high redox potentials are created homogeneously in the solution in about 10 -8 second. For solvated electron effect of electrostatic interaction on kinetics of reactions limited by diffusion is obtained with a good approximation by the Debye equation when ion mobility is known. Deviation from the theory occurs in ion pair formation, which is evidenced experimentally in reactions between anions when cations are complexed by a cryptate. Slow reactions k 8 M -1 s -1 are more sensitive to electrostatic interactions than reactions limited by diffusion. When there is no ion pair formation the velocity constant depends upon dielectric constant of the solvent and reaction distance. 17 refs

State of knowledge on the water radiolysis in cemented wasteforms and its approach by simulation

International Nuclear Information System (INIS)

Bouniol, P.

2004-01-01

The decomposition of water under radiation within the cementitious matrix is at the origin of a potential source of harmful effects in the wasteform and their environment (pressurization and emanation of di-hydrogen) which can have an impact on the safety. In the aim of a better evaluation of the 'H 2 ' risk induced by such a complex and heterogeneous system, this document is an analysis of the elements necessary for a global understanding of the radiolysis in the cemented wasteform to be achieved: - summary of the basic knowledge on water radiolysis with transposition to the cementitious medium, - critical review of the various phenomenologies at work in a wasteform (radioactive source-term, gas transport, mineral equilibria); description of their mutual couplings and of their feedback on radiolytic chemistry; identification of the determining parameters, - presentation of a selection of experimental facts putting in light some theoretical points, - presentation of an outline of operational model deriving from the global vision; presentation of an adapted tool for simulation (CHEMSIMUL) and study of the influence of the principal parameters, starting from a reference case. The main result of this work is that it is shown, in the case of a βγ source term, that the control of the pore fluid composition by calcium octo-hydrate peroxide constitutes an efficient regulating mechanism for the radiolysis and H 2 production. Not likely possible in the case of an α source term, this suggests a separate management of the wasteform according to their radiological contents. The gaps and limits of the model which are also evoked are promising of a lot of research prospects, primarily of a fundamental nature (impact of the porous medium). (author)

Effects of radiolysis on yttrium-90-labeled Lym-1 antibody preparations.

Science.gov (United States)

Salako, Q A; O'Donnell, R T; DeNardo, S J

1998-04-01

The physical half-life of 2.6 days and 2.2 MeV beta emissions of 90Y provide excellent properties for radioimmunotherapy applications. However, the clinically useful beta particles may be a source of radiation-induced damage of 90Y-labeled immunoconjugate radiopharmaceuticals during preparation or short-term storage. The stability of 90Y-labeled Lym-1 antibody was studied in standard radiopharmacy conditions to establish a formulation at which radiolysis is not a problem. Lym-1-21T-BAD immunoconjugate intermediate was prepared according to our standard procedure, then labeled with 90Y at 1, 2, 4 and 9.4 mCi/mg Lym-1 using 0.5 M tetramethylammonium acetate, pH 7, labeling buffer. Each mixture was challenged in diethylenetriaminepentaacetic acid to remove nonspecifically bound 90Y. The 90Y-21T-BAD-Lym-1 products were purified by centrifuged molecular sieving column chromatography. The radiochemical purity and immunoreactivity of each preparation was monitored daily by high-performance liquid chromatography (HPLC) and solid-phase radioimmunoassay, respectively, for 3 days. The preparation at 2 mCi/mg was also formulated in 4% (wt/vol) human serum albumin (HSA) overall and at 9.4 mCi/mg in five-fold water, 4 and 10% (wt/vol) HSA overall; all were monitored as above. The monomeric quality and purity profile of products at 1 and 2 mCi/mg were retained (> or = 80%) as was their immunoreactivity (> or = 75%) over 3 days. The radiochemical purity and immunoreactivity of the product at 4 mCi/mg declined to 65% and 28%, respectively, by 3 days after preparation and in just 48 hr, the product at 9.4 mCi/mg had degraded to 21% in radiochemical purity with only 3% immunoreactivity. The current HPLC data and earlier published chromatographic evidence did not support a compromised radiochemical integrity of 90Y-DOTA complexes by loss of 90Y from the DOTA chelate. Radiolysis of 90Y-labeled antibody preparations did not appear to be a problem at 90Y-21T-BAD-Lym-1 products < or = 2 m

E-beam radiolysis for oil spill clean up

International Nuclear Information System (INIS)

Patterson, E.L.; Jackson, N.B.; Thornberg, S.M.; Samlin, G.E.

1992-12-01

This paper describes preliminary experiments to investigate electron-beam radiolysis of model compounds appropriate for crude oil spills on water or soil. Since no previous work in this area is known to exist, the rate of destruction of such concentrated organic materials in aqueous media is not known. The experiments conducted here were designed to provide preliminary estimates of the destruction rate and the estimated costs. Samples of model compounds were irradiated to dose levels up to 700 Mrad (H 2 0) and the change in chemical composition was determined by mass spectrometry/gas chromatography and Fourier transform infrared spectroscopy. It was found that a dose of 700 Mrads reduced the liquid volume of the model compound by 60% and that the major effect of irradiation was the formation of long chain alkanes and dimethyl and ethyl benzenes. Under certain conditions a solid polymer was found to form. When alcohol was present in the model compound, additional products included small quantities of ethane diodic acid, butanol, butanediol, and various other alcohols. Further research is recommended to obtain a better analysis of the products, better values for the destruction rates, and better understanding of dose rate effects

γ-radiolysis of aqueous and aqueous-ethanol solutions of cobalt(3) cyanide complexes

International Nuclear Information System (INIS)

Kutsaev, V.G.; Potapov, I.A.; Rozenkevich, M.B.; Sakharovskij, Yu.A.; Bulgakova, G.P.; Zagorets, P.A.

1984-01-01

The method of stationary γ-radiolysis has been used to investigate Na 3 [Co 3 (CN) 6 ] and K 2 [Co 3 (CN) 5 H 2 O] reduction in aqueous solutions in the presence of NaCN, KCN, KCl and C 2 H 5 OH additions. [Co 2 (CN) 5 ] 3- ion is shown to be the product of reduction. Radiation-chemical yield increases in the presence of alkali metal cyanides and large quantities (10-20 vol.%) of C 2 H 5 OH. Energy consumption for radiation-chemical reduction of Co 3 cyanide complexes is 50 times lower than for photochemical one

Solid state radiolysis of sulphur-containing amino acids. Cysteine, cystine and methionine

International Nuclear Information System (INIS)

Franco Cataldo; Pietro Ragni; Susana Iglesias-Groth; Arturo Manchado

2011-01-01

The sulphur-containing proteinaceous amino acids l-cysteine, l-cystine and l-methionine were irradiated in the solid state to a dose of 3.2 MGy. This dose corresponds to that delivered by radionuclide decay in a timescale of 1.05 x 10 9 years to the organic matter buried at a depth >20 m in comets and asteroids. The purity of the sulphur-containing amino acids was studied by differential scanning calorimetry (DSC) before and after the solid state radiolysis and the preservation of the chirality after the radiolysis was studied by chirooptical methods (optical rotatory dispersion, ORD) and by FT-IR spectroscopy. Although the high radiation dose of 3.2 MGy delivered, all the amino acids studied show a high radiation resistance. The best radiation resistance was offered by l-cysteine. The radiolysis of l-cysteine leads to the formation of l-cystine. The radiation resistance of l-methionine is not at the level of l-cysteine but also l-methionine is able to survive the dose of 3.2 MGy. Furthermore in all cases examined the preservation of chirality after radiolysis was clearly observed by the ORD spectroscopy although a certain level of radioracemization was measured in all cases. The radioracemization is minimal in the case of l-cysteine and is more pronounced in the case of l-methionine. In conclusion, the study shows that the sulphur-containing amino acids can survive for 1.05 x 10 9 years and, after extrapolation of the data, even to the age of the Solar System i.e. to 4.6 x 10 9 years. (author)

Positive ion scavenging by olefins in trans-decalin: TRMC and product analysis studies

International Nuclear Information System (INIS)

Warman, J.M.; Leng, H.C. de; Haas, M.P. de; Anisimov, O.A.

1990-01-01

The rate constants for scavenging of the mobile positive ion in trans-decalin have been measured using the time-resolved microwave conductivity (TRMC) pulse radiolysis technique for a series of olefins and cyclopropane. For the olefins the values vary from ≤2 x 10 8 dm 3 /mol/s for ethylene to 1.6 x 10 11 dm 3 /mol/s for cyclohexene. Steady-state (γ) radiolysis of solutions of isobutene in trans-decalin results in the formation of isobutane and C 8 and C 14 products which display different dependences on solute concentration. The results are explained in terms of the formation of a complex between the solvent radical cation and isobutene which can dissociate, within a timescale of approx. 1 ns, to give isobutane or on neutralisation leads to the formation of C 14 condensation products. The C 8 products which are formed above 5 x 10 -2 mol/dm 3 are attributed to reaction of the complex with isobutene to form the olefin dimer cation. Cyclopropane is unreactive, i.e. k 8 dm 3 /mol/s, towards the mobile positive ion in trans-decalin (author)

Study of the effect of water radiolysis on zirconolite dissolution; Etude de l'effet de la radiolyse de l'eau sur la livixation de la zirconolite

Energy Technology Data Exchange (ETDEWEB)

Tribet, M

2007-09-15

surface state (crystalline or amorphous) and the experimental conditions (solid irradiation or not). The behaviour of Ti and Zr is enhanced (about 100 times) in presence of complexing species such as fluoride ions. Nevertheless, the alteration remains very weak, even in presence of complexing species and is sorely observable on the solid surface. Elementary releases are first kinetically controlled: if we base on Nd releases, the dissolution under radiolytic conditions is about 5 orders of magnitude higher than out of radiolysis. However, this kinetic step is shorter, a couple of hours, compared to a couple of days out of radiolysis. When there is only water radiolysis, a thermodynamic step is then observed as soon as the leachate is saturated in respect to the Zr and Ti hydroxides phases: elemental releases then become constant. When the solid is also irradiated, colloids are observed, although the leachate is not saturated in respect with hydroxides phases. The formation of these colloids could arise from chemical equilibriums modification induced by ionizations occurring in the solid during its irradiation. The radiolytic production of H{sub 2}O{sub 2} is lower than predicted by the calculated primary yield, because of the consumption of H{sub 2}O{sub 2} or its precursors by chemical reactions involving others radiolytic species such as H2 or the aqueous electron. (author)

An Advantage of the Equivalent Velocity Spectroscopy for Femtsecond Pulse Radiolysis

CERN Document Server

Kondoh, Takafumi; Tagawa, Seiichi; Tomosada, Hiroshi; Yang Jin Feng; Yoshida, Yoichi

2005-01-01

For studies of electron beam induced ultra-fast reaction process, femtosecond(fs) pulse radiolysis is under construction. To realize fs time resolution, fs electron and analyzing light pulses and their jitter compensation system are needed. About a 100fs electron pulse was generated by a photocathode RF gun linac and a magnetic pulse compressor. Synchronized Ti: Sapphire laser have a puleswidth about 160fs. And, it is significant to avoid degradation of time resolution caused by velocity difference between electron and analyzing light in a sample. In the 'Equivalent velocity spectroscopy' method, incident analyzing light is slant toward electron beam with an angle associated with refractive index of sample. Then, to overlap light wave front and electron pulse shape, electron pulse shape is slanted toward the direction of travel. As a result of the equivalent velocity spectroscopy for hydrated electrons, using slanted electron pulse shape, optical absorption rise time was about 1.4ps faster than normal electro...

Proton-transfer reactions in ionized gases

International Nuclear Information System (INIS)

Stiller, W.; Schmidt, R.; Schuster, R.

1985-01-01

Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

Radiolysis of Fricke solution: initial experiments with the pelletron facility

International Nuclear Information System (INIS)

Sharma, S.B.; Rao, B.S.M.

1994-01-01

Experimental details of heavy ion irradiation of aqueous solutions using the Nuclear Science Centre (NSC) pelletron facility and the initial results from the radiolysis of Fricke solution using oxygen-16 ions are reported. (author). 4 refs., 1 fig

High energy gamma-ray production in nuclear reactions

International Nuclear Information System (INIS)

Pinston, J.A.; Nifenecker, H.; Nifenecker, H.

1989-01-01

Experimental techniques used to study high energy gamma-ray production in nuclear reactions are reviewed. High energy photon production in nucleus-nucleus collisions is discussed. Semi-classical descriptions of the nucleus-nucleus gamma reactions are introduced. Nucleon-nucleon gamma cross sections are considered, including theoretical aspects and experimental data. High energy gamma ray production in proton-nucleus reactions is explained. Theoretical explanations of photon emission in nucleus-nucleus collisions are treated. The contribution of charged pion currents to photon production is mentioned

Retention of sulfur and nitrogen oxides from the exhaust gases by radiolysis, a modern method of environmental protection

International Nuclear Information System (INIS)

Macarie, Rodica; Zissulescu, Ecaterina; Martin, Diana; Radoiu, Marilena

2000-01-01

Industry, especially the power industry, is a great generator of gaseous pollutants (SO x , NO x , CO 2 , CO). The oxides are responsible for the 'acid rains' which have a great negative impact on the environment, human beings and animals, while CO 2 emissions contribute to the increase of the greenhouse effect. Retention of the sulfur and nitrogen oxides from the exhaust gases can be carried out either by conventional methods (using chemical adsorbents) or by non-conventional ones (radiolysis). Recently, non-conventional methods have bee given priority, including exhaust gas irradiation with an accelerated electron beam as a more efficient alternative to the gas desulfurization. In order to increase the efficiency of the accelerated electron beam injected into the exhaust gas, the effect of microwave utilization has been investigated. The company S.C. ICPET S.A.-Bucuresti, in cooperation with INFLPR-Bucuresti, investigated the retention by radiolysis of the sulfur and nitrogen oxides from a synthetic mixture of exhaust gases in an installation developed in the laboratory by means of accelerated electron beams, microwaves and by the accelerated electron beams and microwave combined. The paper presents the results obtained in the laboratory experiments and the advantages of radiolysis in comparison with the chemical conventional methods, namely: simultaneous removal of SO 2 and NO x , solid by-products that can be used as fertilizers in agriculture, simple technologies that do not imply catalysts or adsorbents, no waste waters. (authors)

A pulse radiolysis investigation of the interactions of drugs and dyes with macromolecules and ribosomes

International Nuclear Information System (INIS)

Phillips, G.O.; Power, D.M.; Davies, J.V.

1975-01-01

The reactions of hydrated electrons produced during pulse radiolysis have been utilized to investigate the binding of eleven penicillins and four cephalosporins to bovine serum albumin. A primary binding site exists in the serum albumin molecule, which results indicate to be a hydrophobic cleft in the surface of the molecule separated by a distance > 0.5 mm from a cationic amino acid residue, probably lysine. Interaction of drugs with this binding site leads to a conformational change in the protein resulting in a decrease in reactivity towards hydrated electrons. Interaction of cephalosporin C and 6-amino penicillanic acid with serum albumin involves another site which consists of a cationic amino acid residue separted from anionic residue by a distance >0.7nm. Drug binding at this site induces a conformational change in serum albumin leading to greatly increased reactivity towards hydrated electrons. This increase is associated with an increased availability of disulphide bridges. Cephalosporin C also binds hydrophobically to serum a;lbumin resulting in a decrease in reactivity towards esub(aq)sup(-); such binding can be prevented by palmitic acid. Recent data clearly indicate that the pulse radiolysis technique can be further extended to investigate the nature of the interactions of bacterial ribosome suspensions with amino-acridines. Ion binding between benzoflavine and ribosomes has been examined over a wide temperature range and the thermodynamic parameters governing the interaction have been evaluated. (author)

Pulse radiolysis studies concerning oxidative degradation processes in linear polymers

International Nuclear Information System (INIS)

Schnabel, Wolfram

1986-01-01

On the basis of pulse radiolysis experiments carried out with various polymers in dilute solution three modes of action of molecular oxygen, 0 2 , can be discriminated with respect to main-chain scission: (a) 0 2 acts as a promoter, (b) 0 2 acts as an inhibitor, and (c) 0 2 acts as a fixing agent for main-chain breaks. The promoting mode of action (a) is due to the inhibition of simultaneously occurring intermolecular crosslinking (DNA, polymethylvinylketone) and/or to the combination of peroxyl radicals with the subsequent formation of readily decomposing oxyl radicals (polyethylene oxide, polyacrylamide, polyvinylpyrrolidone, polyribouridylic acid, polyriboadenylic acid, polyribocytidylic acid). The inhibiting mode of action (b) pertains to the reaction of 0 2 with macroradicals that otherwise undergo main-chain rupture (amylose polymethylmethacrylate). Fixing of main-chain ruptures (mode c) becomes important, if macroradicals generated by a very fast rupture of bonds in the main-chain, are prone to recombine quickly. This mode of action was evidenced in the case of polybutenesulfone where main-chain scission involves the extrusion of small segments of the chain. (author)

One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its transition metal complexes in aqueous-isopropanol-acetone mixed solvent: a steady state-state and pulse radiolysis study

International Nuclear Information System (INIS)

Das, Saurabh; Mandal, Parikshit C.; Rath, Madhab C.; Mukherjee, Tulsi

1998-01-01

One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its Cu(II) and Ni(II) and Fe(III) complexes have been studied in aqueous-isopropanol-acetone solvent. Results indicate that the reducing ketyl radical generated reacts with the ligand forming semiquinones which undergoes a disproportionation reaction. Formation and decay rates of semiquinones was calculated using pulse radiolysis. (author)

Free radical reactions of daunorubicin

International Nuclear Information System (INIS)

Houee-Levin, C.

1991-01-01

Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

Development of hydrogen oxidizing bacteria using hydrogen from radiolysis or metal corrosion; Developpement de populations microbiennes oxydant l'hydrogene produit par radiolyse ou par corrosion des metaux

Energy Technology Data Exchange (ETDEWEB)

Libert, M F; Sellier, R; Marty, V; Camaro, S [CEA Cadarache, Dept. d' Entreposage et de Stockage des Dechets (DCC/DESD/SEP), 13 - Saint-Paul-lez-Durance (France)

2000-07-01

The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H{sub 2} production in a bituminized nuclear waste environment were simulated in the present study: - H{sub 2} production by iron corrosion under anaerobic conditions was simulated by adding 10% of H{sub 2} in the atmosphere; - H{sub 2} production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H{sub 2} in water allows the growth of hydrogen oxidizing bacteria leading to: - CO{sub 2} and N{sub 2} production; - H{sub 2} consumption; - lower NO{sub 3}{sup -} concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO{sub 3}{sup -} release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H{sub 2} instead of hydrocarbons. (authors)

The enhancement of positronium yields by the hydroxide ion in the radiolysis of water

International Nuclear Information System (INIS)

Beling, C.D.; Smith, F.A.

1984-01-01

Measurements of o-Ps yield and quenching rate have been made at 21 deg C in aqueous solutions of sodium hydroxide up to 8 M. The observed enhancement is considered within the spur model and attributed to the scavenging of H 2 + O by the OH - ion with an estimated scavenging constant K = 0.354 M -1 . By making use of the measured yields of H 2 , OH radical and e - sub(aq) from long time-scale experiments we can estimate the ratio of the reaction rates of an epithermal electron state. The Ps enhancement coefficient may then be related to these reaction rates and the scavenging constant of H 2 + O. The decrease in equivalent conductance with increasing NaOH concentration up to approx. 12 M suggests the importance of associated and dissociated OH - species. When the total NaOH concentrations are re-expressed as concentrations of dissociated OH - ions a linear increase in o-Ps intensity is found. The fitted enhancement coefficient bears excellent agreement with that estimated from the foregoing consideration of reaction rates. Our analysis shows that the relative yields of both Ps and e - sub(aq) should be in agreement. Within experimental error the data from pulse radiolysis shows that this is in fact the case. (author)

Radiolytic oxidation of propane: Computer modeling of the reaction scheme

Science.gov (United States)

Gupta, Avinash K.; Hanrahan, Robert J.

The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

Solid state radiolysis of non-proteinaceous amino acids in vacuum. Astrochemical implications

International Nuclear Information System (INIS)

Franco Cataldo; Giancarlo Angelini; Yaser Hafez; Susana Iglesias-Groth

2013-01-01

The analysis of the amino acids present in Murchison meteorite and in other carbonaceous chondrites has revealed the presence of 66 different amino acids. Only eight of these 66 amino acids are proteinaceous amino acids used by the present terrestrial biochemistry in protein synthesis, the other 58 amino acids are somewhat 'rare' or unusual or even 'unknown' for the current terrestrial biochemistry. For this reason in the present work a series of 'uncommon' non-proteinaceous amino acids, namely, l-2-aminobutyric acid, R(-)-2-aminobutyric acid, 2-aminoisobutyric acid (or α-aminoisobutyric acid), l-norleucine, l-norvaline, l-β-leucine, l-β-homoalanine, l-β-homoglutamic acid, S(-)-α-methylvaline and dl-3-aminoisobutyric acid were radiolyzed in vacuum at 3.2 MGy a dose equivalent to that emitted in 1.05 x 10 9 years from the radionuclide decay in the bulk of asteroids or comets. The residual amount of each amino acid under study remained after radiolysis was determined by differential scanning calorimetry in comparison to pristine samples. For optically active amino acids, the residual amount of each amino acid remained after radiolysis was also determined by optical rotatory dispersion spectroscopy and by polarimetry. With these analytical techniques it was possible to measure also the degree of radioracemization undergone by each amino acid after radiolysis. It was found that the non-proteinaceous amino acids in general do not show a higher radiation and radioracemization resistance in comparison to the common 20 proteinaceous amino acids studied previously. The unique exception is represented by ?-aminoisobutyric acid which shows an extraordinary resistance to radiolysis since 96.6 % is recovered unchanged after 3.2 MGy. Curiously α-aminoisobutyric acid is the most abundant amino acid found in carbonaceous chondrites. In Murchison meteorite α-aminoisobutyric acid represents more than 20 % of the total 66 amino acids found in this meteorite. (author)

A pulse-radiolysis study of the manganese-containing superoxide dismutase from Bacillus stearothermophilus

International Nuclear Information System (INIS)

McAdam, M.E.; Fox, R.A.; Lavelle, F.; Fielden, E.M.

1977-01-01

The enzymic reaction mechanism of a manganese-containing superoxide dismutase from Bacillus stearothermophilus was studied by using pulse radiolysis. During catalysis (pH 8.9; 25 0 C), changes occurring in the kinetics of substrate disappearance and in the visible absorption of the enzyme at 480 nm established that the simple two-step mechanism found for copper- and iron-containing superoxide dismutases was not involved. At a low ratio ( 2 sup(-.) was close to exponential, whereas at much higher ratios (> 100) the observed decay was predominantly zero-order. The simplest interpretation of the results invokes a rapid one-electron oxidation-reduction cycle ('the fast cycle') and, concurrently, a slower reaction giving a form of the enzyme that is essentially unreactive towards O 2 sup(-.) but which undergoes a first-order decay to yield fully active native enzyme ('the slow cycle'). The fast cycle involved the native enzyme Esub(A) and a form of the enzyme Esub(B) which could be obtained also be treating the form Esub(A) with H 2 O 2 . Computer calculations made with such a simple model predicted behaviour in excellent agreement with the observed results. (author)

Radiolysis compounds in bacon and chicken. Final report 18 Sep 81-20 Sep 82

International Nuclear Information System (INIS)

Merritt, C. Jr.

1984-01-01

The results of this study are in agreement with the precepts established in studies published previously on beef, chicken, ham, and pork. The radiolysis compounds from bacon, chicken, ham, and pork are comparable in identity and amounts to those found in irradiated beef for comparable compositions and irradiation parameters (temperature, dose, etc.). The results of this study support the conclusions drawn in the CORC report of 'commonality in chemistry, predictability of products, and extrapolation of results.' Consequently, the same conclusions can be drawn concerning the wholesomeness of irradiated bacon, chicken, ham, and pork as for other irradiated meat products of similar composition and irradiation parameters as reported in the FASEB report and its supplements (I and II) on irradiated beef

Cationic polymerization of styrene by means of pulse radiolysis

International Nuclear Information System (INIS)

Egusa, S.; Arai, S.; Kira, A.; Imamura, M.; Tabata, Y.

1977-01-01

The radiation-induced cationic polymerization of styrene has been studied by microsecond pulse radiolysis. It was possible to observe absorption bands of a monomer cation radical (St. + ) at 630 nm and at 350 nm in a mixture of isopentane and n-butyl chloride at - 165 0 C. Three absorption bands, around 1600 nm, at 600 nm and at 450 nm, grew in parallel with the decay of St. + after pulse. The 1600-nm and 600-nm bands were assigned to an associated dimer cation radical (St 2 . + ), and the 450-nm band to a bonded dimer cation radical (St-St. + ) by comparison of absorption spectra of α-methylstyrene, 1,2-dihydronaphthalene and trans-β-methylstyrene. The kinetic behaviour of these species suggests that St-St. + and a part of St 2 . + are formed by the reaction of St. + with a styrene monomer, and the rest of St 2 . + may be formed by positive charge transfer from a solvent cation radical to an auto-associated neutral dimer of styrene. A long-lived absorption band at 340 nm grew with the decay of St-St. + . This band is considered due to a growing polymer carbonium ion. (author)

Dynamic molecular oxygen production in cometary comae

Science.gov (United States)

Yao, Yunxi; Giapis, Konstantinos P.

2017-05-01

Abundant molecular oxygen was discovered in the coma of comet 67P/Churyumov-Gerasimenko. Its origin was ascribed to primordial gaseous O2 incorporated into the nucleus during the comet's formation. This thesis was put forward after discounting several O2 production mechanisms in comets, including photolysis and radiolysis of water, solar wind-surface interactions and gas-phase collisions. Here we report an original Eley-Rideal reaction mechanism, which permits direct O2 formation in single collisions of energetic water ions with oxidized cometary surface analogues. The reaction proceeds by H2O+ abstracting a surface O-atom, then forming an excited precursor state, which dissociates to produce O2-. Subsequent photo-detachment leads to molecular O2, whose presence in the coma may thus be linked directly to water molecules and their interaction with the solar wind. This abiotic O2 production mechanism is consistent with reported trends in the 67P coma and raises awareness of the role of energetic negative ions in comets.

A pulse radiolysis based singlet oxygen luminescence facility

International Nuclear Information System (INIS)

Gorman, A.A.; Hamblett, I.; Land, E.J.

1989-01-01

In this paper the authors report the first successful time-resolved detection of singlet oxygen, O 2 ( 1 Δ g ), luminescence using the pulse radiolysis technique. The use of this technique (a) to produce high concentrations of solute (S) triplet states in aerated benzene (B) via a combination of channels 1-4 and (b) to subsequently form O 2 ( 1 Δ g ) via channel 5 has already been described. The method complements direct pulsed laser excitation of S in that formation of 3 S*, and therefore of O 2 ( 1 Δ g ), is still efficient in those instances where intersystem crossing (channel 4) is unimportant. In the latter situation a laser-based experiment would require an additional light-absorbing sensitizer which could subsequently transfer triplet energy to high concentrations of S. Such experiments, certainly of a quantitative nature, are usually doomed to failure because of competitive light absorption problems. No such problems exist with pulse radiolysis, and the high available triplet energy of 3 B* (84 kcal mol -1 ) ensures that virtually any solute of interest, in the O 2 ( 1 Δ g ) context, will be efficiently promoted to its triplet state

Radiation-chemical decomposition of heavy metal azides - II. Silver azide radiolysis scheme

International Nuclear Information System (INIS)

Ryabykh, S.M.

1987-01-01

As a result of complex studies on the nature and properties of final products and intermediate particles using a wide number of experimental topography and radiolysis kinetics methods, we offer the AgN 3 radiolysis scheme including the following stages: homogeneous excitation of electron subsystem with 'hot' electrons and holes formed; 'hot' electron and hole thermalization with possible formation of N 4 - radical in volume on the point defects; electron localization on the immobile structural defects whose neighbourhood is rich in the mobile positively charged point defects; metal particle formation due to electrostatic attraction of the nearby mobile defect to the localized electron, with no thermal excitation; metal particle growth, according to both the diffusional mechanism of delivering the volume of corresponding positively charged point defect with consequent electron capture, and by decomposing anions on the interphase with the consequent border layer cation addition to the growing metal particle, interior space formation in the volume by disintegrating 'hot' excitons into ion defect pairs; nitrogen formation on the exterior and interior surfaces, as well as those formed by radiation, either by trapping the hole by surface cation vacancy or by removing the surface cation of the hole with the consequent addition of the second hole to the Vsub(F)-center, and by disintegrating the activated complex into three nitrogen molecules. For the above stages the characteristic parameters are determined by means of direct measurement and calculation. The kinetics and energy conditions of the process are also found. (author)

Pulse radiolysis of pyridine and methylpyridines in aqueous solutions

DEFF Research Database (Denmark)

Solar, S.; Getoff, N.; Sehested, K.

1993-01-01

The radicals formed from pyridine, 3-methylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine and 2,4,6-trimethylpyridine by attack of H, e(aq)-, OH and O.- in aqueous solutions were investigated by pulse radiolysis in the pH-range 1-13.8. The UV-vis. absorption spectra as well as the formation...

η production in proton-nucleus reactions

International Nuclear Information System (INIS)

Cassing, W.; Batko, G.; Vetter, T.; Wolf, G.

1991-01-01

The production of η-mesons in proton-nucleus reactions is analysed with respect to primary nucleon-nucleon (NN→NN η ) and secondary pion-nucleon (πN→ηN) production processes on the basis of Hartree-Fock groundstate momentum distributions and free on-shell production processes. The folding model adopted compares well for meson production with more involved simulations based on VUU transport equations. Similar to K + production in proton-nucleus reactions the η-mesons are primarily produced by the πN→ηN channel. However, η-mesons are absorbed in nuclei via excitation of the N * (1535) resonance which leads to strong distortions of the primordial spectra. On the other hand, the experimental mass dependence of the differential cross sections might yield information about the in-medium properties of this resonance. (orig.)

Kinetics of polymer degradation in solution. 6. Laser flash photolysis and pulse radiolysis studies of polymethylvinylketone in solution using the light scattering detection method

Energy Technology Data Exchange (ETDEWEB)

Lindenau, D; Beavan, S W; Beck, G; Schnabel, W [Hahn-Meitner-Institut fuer Kernforschung Berlin G.m.b.H. (Germany, F.R.)

1977-01-01

Polymethylvinylketone (PMVK) was irradiated in solution with 2 ..mu..s pulses of 15 MeV electrons or with 15 ns flashes of 262 nm light. The change of the intensity of the light scattered by the solution (LSI) after the irradiation was measured. For the radiolysis experiments, a main chain scission process tausub(1/2) (decr) approximately 20 ..mu..s) and a subsequent crosslinking process (tausub(1/2) (incr) approximately 0.4 sec) could be discriminated. The LSI change pertaining to the main chain degradation was found to be due to disentanglement diffusion, whereas the LSI change pertaining to the crosslinking process could be correlated to a chemical reaction. The rate constant for combination of lateral macroradicals in acetone solution was estimated as 2 k/sub 2/ - (4.5 +- 1.5)10/sup 6/ M/sup -1/ sec/sup -1/. Stationary irradiation with /sup 60/Co-..gamma..-rays showed that PMVK is predominantly crosslinked to form a macrogel when irradiated in the solid state or in solution at concentrations greater than 100 g/l. At lower concentrations, microgel formation occurred. Photolysis of PMVK in solution yielded only main chain degradation. The LSI change was found to be due to disentanglement diffusion as during radiolysis. It was concluded that the same mechanism for main chain rupture is operative as in radiolysis. Stationary irradiations with uv light (lambda > 260 nm ) resulted in main chain degradation; no indication of crosslinking was obtained.

PARIS project: Radiolytic oxidation of molecular iodine in containment during a nuclear reactor severe accident

Energy Technology Data Exchange (ETDEWEB)

Bosland, L. [Institut de Radioprotection et de Surete Nucleaire, DPAM, SEMIC, LETR - CEN Cadarache, BP 3, 13115 Saint Paul Lez Durance (France)], E-mail: loic.bosland@irsn.fr; Funke, F. [AREVA NP GmbH, Technical Center, P.O. Box 1109, D-91001 Erlangen (Germany); Girault, N. [Institut de Radioprotection et de Surete Nucleaire, DPAM, SEMIC, LETR - CEN Cadarache, BP 3, 13115 Saint Paul Lez Durance (France); Langrock, G. [AREVA NP GmbH, Technical Center, P.O. Box 1109, D-91001 Erlangen (Germany)

2008-12-15

In case of a hypothetical severe accident in a nuclear LWR (light water reactor), the high radiation fields reached in the reactor containment building due to the release of fission products from the reactor core could induce air radiolysis. The air radiolysis products could, in turn, oxidise gaseous molecular iodine into aerosol-borne iodine-oxygen-nitrogen compounds. Thereby, this reaction involves a change of iodine speciation and a decrease of iodine volatility in the reactor containment atmosphere. Kinetic data were produced within the PARIS project on the air radiolysis products formation and destruction, and on their reaction with molecular iodine, with the objective of developing and validating existing kinetic models. The current paper includes the non-iodine tests of the PARIS project whose objective was to determine the rates of formation and destruction of air radiolysis products in the presence of both structural containment surfaces (decontamination coating ('paint') and stainless steel), aerosol particles such as silver rich particles (issued from the control rods) in boundary conditions representative for LWR or PHEBUS facility containments. It is found that the air radiolysis products concentration increases with dose and tend to approach saturation levels at doses higher than about 1 kGy. This behaviour is more evident in oxygen/steam atmospheres, producing ozone, than in air/30% (v/v) steam atmospheres, the latter favouring the model-predicted on-going production of nitrogen dioxide even at very high doses. No significant effect of temperature, dose rate and hydrogen addition (4%, v/v) was observed. Furthermore, the inserted surfaces do not exhibit significant effects on the air radiolysis concentrations. However, these 'non-noticeable influence' could be due to a masking of small effects by the appreciable scattering of the experimental air radiolysis product concentrations. The PARIS results are then analysed using two

PARIS project: Radiolytic oxidation of molecular iodine in containment during a nuclear reactor severe accident

International Nuclear Information System (INIS)

Bosland, L.; Funke, F.; Girault, N.; Langrock, G.

2008-01-01

In case of a hypothetical severe accident in a nuclear LWR (light water reactor), the high radiation fields reached in the reactor containment building due to the release of fission products from the reactor core could induce air radiolysis. The air radiolysis products could, in turn, oxidise gaseous molecular iodine into aerosol-borne iodine-oxygen-nitrogen compounds. Thereby, this reaction involves a change of iodine speciation and a decrease of iodine volatility in the reactor containment atmosphere. Kinetic data were produced within the PARIS project on the air radiolysis products formation and destruction, and on their reaction with molecular iodine, with the objective of developing and validating existing kinetic models. The current paper includes the non-iodine tests of the PARIS project whose objective was to determine the rates of formation and destruction of air radiolysis products in the presence of both structural containment surfaces (decontamination coating ('paint') and stainless steel), aerosol particles such as silver rich particles (issued from the control rods) in boundary conditions representative for LWR or PHEBUS facility containments. It is found that the air radiolysis products concentration increases with dose and tend to approach saturation levels at doses higher than about 1 kGy. This behaviour is more evident in oxygen/steam atmospheres, producing ozone, than in air/30% (v/v) steam atmospheres, the latter favouring the model-predicted on-going production of nitrogen dioxide even at very high doses. No significant effect of temperature, dose rate and hydrogen addition (4%, v/v) was observed. Furthermore, the inserted surfaces do not exhibit significant effects on the air radiolysis concentrations. However, these 'non-noticeable influence' could be due to a masking of small effects by the appreciable scattering of the experimental air radiolysis product concentrations. The PARIS results are then analysed using two different kinetic models

Hole transfer in DNA studied by pulse radiolysis

International Nuclear Information System (INIS)

Majima, T.; Kawai, K.; Takada, T.

2003-01-01

Attention has been paid to charge transfer in DNA with respect to oxidation damage of DNA and nano bio-devices such as DNA molecular wire. We report hole transfer in DNA during pulse radiolysis of molecule-conjugated DNA (M-DNA). Direct measurement of the charge transfer in DNA has never been reported due to the low extinction coefficient of nucleobase radical ions and to difficult definition of nucleobases. We have used M-DNA in which M radical cation has enough extinction coefficient and distinct absorption. Radical cation was generated in M-DNA during pulse radiolysis in water, and hole transfer through DNA was monitored by time-resolved transient absorption spectra of the radical cations. Hole was generated in Py-DNA by pulse radiolysis in water. Hole transfer to Py through DNA was monitored by transient absorption of Py'+ at 465 nm. The hole hopping rate (k) from G-region to Py was determined to be 104 s-1 which decreased with intervening A-T base-pairs between Py and G-region. We suppose that G(-H+)-radical and C(+H+) basepair can alive in DNA more than 100 us and that this long lifetime is responsible to the long-distance hole transfer. The dependence of k against the distance between the G-region and Py led to the slope of 0.3 Angstroms-1 which is due to multi-step k with the smaller distance dependence. On the other hand, beta = 0.6 Angstroms-1 was found for the single-step k in DNA. On the basis of pulse radiolytic studied on various molecule-conjugated DNA, we found that hole transfer between two chromophores (A and B)-conjugated DNA increased with decreasing the distance between A and B and was accelerated slightly with increasing the number of Gs of the bridge between A and B, and that k was modulated by the bridged base sequences. We also found that weak distance dependent hole transfer in DNA by adenine hopping mechanism

Atmospheric chemistry of HFC-134a. Kinetic and mechanistic study of the CF3CFHO2 + NO2 reaction

DEFF Research Database (Denmark)

Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.

1994-01-01

A pulse radiolysis system was used to study the kinetics of the reaction of CF3CFHO2 with NO2. By monitoring the rate of the decay of NO2 using its absorption at 400 nm the reaction rate constant was determined to be k = (5.0 +/- 0.5) x 10(-12) cm3 molecule-1 s-1. A long path length Fourier......-transform infrared technique was used to investigate the thermal decomposition of the product CF3CFHO2NO2. At 296 K in the presence of 700 Torr of air, decomposition of CF3CFHO2NO2 was rapid (greater than 90% decomposition within 3 min). The results are discussed in the context of atmospheric chemistry of CF3CFH2...

γ Radiolysis of C60 fullerene in water and water/ammonia mixtures: relevance of fullerene fate in ices of interstellar medium

International Nuclear Information System (INIS)

Iglesias-Groth, S.; Angelini, G.; Cataldo, F.

2013-01-01

The γ radiolysis of fullerene C 60 dispersed in H 2 O, H 2 O/NH 3 , H 2 O/methanol and H 2 O/NH 3 /methanol was studied at 250 and 500 kGy. It was found that C 60 originally insoluble in the above mentioned hosting matrix became soluble as a consequence of multiple hydroxylation and oxidation reaction produced by the free radicals generated by the radiolysis of the hosting matrix. The changes undergone by C 60 were studied by infrared spectroscopy (FT-IR) and by electronic absorption spectroscopy. The astrochemical consequences of the present study are that C 60 ejected in the interstellar medium for instance from protoplanetary and planetary nebulae can condense together with water and other ices in dense molecular clouds. Under the action of high energy radiation C 60 reacts with the free radicals generated from the matrix where it is embedded it is solubilized and consequently its carbon content becomes available for further abiotic processes of synthesis of molecules of astrobiological interest. The behavior of C 60 appears comparable to that of common PAHs which are also hydroxylated and oxidized under similar conditions. (author)

Pulse radiolysis experiments: synthesis and analysis of composite spectra

Energy Technology Data Exchange (ETDEWEB)

Schuler, R H; Buzzard, G K [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry

1976-01-01

Methods are outlined for compiling optical spectra obtained in pulse radiolysis experiments in a form suitable for detailed synthesis and analysis of composite spectra. The experimental data are processed with a programmable calculator having a cassette recorder for the storage of the output data files and a peripheral plotter. The spectra are first smoothed by fitting them parabolically segment by segment. The overall spectrum is then assembled in digital form by interpolating the fitted data on a 1 nm grid and the results are stored on cassette files for further processing. Composite spectra can be readily calculated and plotted from the data on these files or known components can be subtracted from observed spectra to examine underlying contributions. The use of the fairly simple data processing methods described here permits an interactive mode of operation by the investigator which can maximize insight into details of the various contributions to an observed spectrum. Several examples of the use of these methods in conjunction with data obtained with a computer controlled pulse radiolysis data acquisition system are given.

Chemical effects produced by the ionizing radiation in the mercury beating heart reaction

International Nuclear Information System (INIS)

Castillo-Rojas, S.; Burillo, G.; Gonzalez-Chavez, J.L.; Vicente, L.

2002-01-01

Complete text of publication follows. In a recent paper we have shown the existence of complex modes of oscillation in the study of the extinction dynamics of the mercury beating heart reaction. It was proposed that one of the species responsible for the oscillatory movements of this reaction is the mercury(I), in anyone in their forms, either free or molecular. the formation of Hg 2 2+ from γ irradiation of 60 Co to the system Hg 0 /H 2 SO 4 (6M) allowed to elucidate the probable mechanism of reaction. The objective of this work is to study how the ionizing radiation affects the dynamics of extinction of this reaction, which is related with the existence of certain chemical species. The study was carried out in 2 ways: a) Method I: H 2 SO 4 (6M) was first irradiated and to the irradiated solution the Hg 0 was added and b) Method II: the system Hg 0 /H 2 SO 4 (6M) was irradiated. The different irradiated systems were put into reaction with Fe 0 to investigate if there were differences between the two irradiated systems and how the complex modes of oscillation of the reaction were affected. The quantity of Hg 2 2+ produced by method I is bigger than in method II. This is explained because the majority species produced by radiolysis of H 2 SO 4 are sulfate radical and H 2 O 2 that act as oxidizer agents and their potential values allow to suppose that these substances react with Hg 0 to produce Hg 2 2+ . On the other hand, by method II mercury clusters (Hg 4 3+ ) are formed as was reported by Sukhov and Ershov in pulse radiolysis of aqueous Hg 2 2+ solutions. We assume that the formation of these mercury clusters has to be observed with the decrease of the Hg 2 2+ concentration when one makes the radiolysis by method II. In general, the preliminary studies allow establishing that the ionizing radiation does not affect the extinction dynamics but it increases the half-life of this reaction

Electron transfer reactions in structural units of copper proteins

International Nuclear Information System (INIS)

Faraggi, M.

1975-01-01

In previous pulse radiolysis studies it was suggested that the reduction of the Cu(II) ions in copper proteins by the hydrated electron is a multi-step electron migration process. The technique has been extended to investigate the reduction of some structural units of these proteins. These studies include: the reaction of the hydrated electron with peptides, the reaction of the disulphide bridge with formate radical ion and radicals produced by the reduction of peptides, and the reaction of Cu(II)-peptide complex with esub(aq)sup(-) and CO 2 - . Using these results the reduction mechanism of copper and other proteins will be discussed. (author)

Formation of by-products at radiation - chemical treatment of water solutions of chloroform

International Nuclear Information System (INIS)

Ahmedov, S.A.; Abdullayev, E.T.; Gurbanov, M.A.; Gurbanov, A.H.; Ibadov, N.A.

2006-01-01

Full text: Radiation-chemical treatment is considered as a perspective method of water purification from chloroform. It provides the high level of purification (98 percent) of water solutions from chloroform and other chlorine-containing compounds. Meanwhile, other chlorine-containing products can be formed during the process of chloroform degradation and as a result of it the quality of water can change. This work studies the formation of by-products of γ-radiolysis of water solutions at various initial contents of chloroform. Dichlormethane and tetrachlorethane are identified as by-products. It is shown that at high contents of chloroform after certain adsorbed dose the forming products are reducing till their full disappearing. At small contents of chloroform in the studied interval of doses di-chlor-methane is forming. Differences of dose dependences of by-products at various contents of chloroform can be connected with the transition from radical mechanism to chain reaction at high concentrations of chloroform in solutions saturated by oxygen. pH-solutions also reduces during the radiation till pH=1, although this reduction also depends on initial concentration of chloroform. Essential change of pH occurs only at the radiolysis of water solutions containing chloroform ≥0,2 percent. And at radiating of 0,03 percent solution pH reduces only till 4 - 4,5

Combinations of Aromatic and Aliphatic Radiolysis.

Science.gov (United States)

LaVerne, Jay A; Dowling-Medley, Jennifer

2015-10-08

The production of H(2) in the radiolysis of benzene, methylbenzene (toluene), ethylbenzene, butylbenzene, and hexylbenzene with γ-rays, 2-10 MeV protons, 5-20 MeV helium ions, and 10-30 MeV carbon ions is used as a probe of the overall radiation sensitivity and to determine the relative contributions of aromatic and aliphatic entities in mixed hydrocarbons. The addition of an aliphatic side chain with progressively from one to six carbon lengths to benzene increases the H(2) yield with γ-rays, but the yield seems to reach a plateau far below that found from a simple aliphatic such as cyclohexane. There is a large increase in H(2) with LET (linear energy transfer) for all of the substituted benzenes, which indicates that the main process for H(2) formation is a second-order process and dominated by the aromatic entity. The addition of a small amount of benzene to cyclohexane can lower the H(2) yield from the value expected from a simple mixture law. A 50:50% volume mixture of benzene-cyclohexane has essentially the same H(2) yield as cyclohexylbenzene at a wide variation in LET, suggesting that intermolecular energy transfer is as efficient as intramolecular energy transfer.

UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298-K

DEFF Research Database (Denmark)

Nielsen, O.J.; Ellermann, T.; Bartkiewicz, E.

1992-01-01

The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm....... The measured cross section near the absorption maximum was sigma(CHF2O2)(240 nm) = (2.66 +/- 0.46) x 10(-18) cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 --> products, defined as d[R]/dt = 2k(1obs)[CHF2O2]2, k(1......obs) = (5.0 +/- 0.7) x 10(-12) cm3 molecule-1 s-1 (+/- 2-sigma). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals....

Energy conservation and maximal entropy production in enzyme reactions.

Science.gov (United States)

Dobovišek, Andrej; Vitas, Marko; Brumen, Milan; Fajmut, Aleš

2017-08-01

A procedure for maximization of the density of entropy production in a single stationary two-step enzyme reaction is developed. Under the constraints of mass conservation, fixed equilibrium constant of a reaction and fixed products of forward and backward enzyme rate constants the existence of maximum in the density of entropy production is demonstrated. In the state with maximal density of entropy production the optimal enzyme rate constants, the stationary concentrations of the substrate and the product, the stationary product yield as well as the stationary reaction flux are calculated. The test, whether these calculated values of the reaction parameters are consistent with their corresponding measured values, is performed for the enzyme Glucose Isomerase. It is found that calculated and measured rate constants agree within an order of magnitude, whereas the calculated reaction flux and the product yield differ from their corresponding measured values for less than 20 % and 5 %, respectively. This indicates that the enzyme Glucose Isomerase, considered in a non-equilibrium stationary state, as found in experiments using the continuous stirred tank reactors, possibly operates close to the state with the maximum in the density of entropy production. Copyright © 2017 Elsevier B.V. All rights reserved.