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)

Subpicosecond pulse radiolysis in liquid methyl-substituted benzene derivatives

International Nuclear Information System (INIS)

Okamoto, Kazumasa; Kozawa, Takahiro; Saeki, Akinori; Yoshida, Yoichi; Tagawa, Seiichi

2007-01-01

The early processes of radiation chemistry in the picosecond time region in methyl-substituted benzene derivatives have been investigated using subpicosecond pulse radiolysis. In o-xylene, a fairly slow geminate ion recombination was observed within 50 ps after the electron beam irradiation; this is due to the smaller electron mobility. The kinetic traces were analyzed using the Smoluchowski equation with exponential and modified-Gaussian (YGP) functions as the distribution of thermalized electrons. Only exponential functions well reproduced the experimental data within 50 ps after the electron pulse

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)

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 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 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.

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)

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

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

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

Pulse radiolysis based on a femtosecond electron beam and a femtosecond laser light with double-pulse injection technique

International Nuclear Information System (INIS)

Yang Jinfeng; Kondoh, Takafumi; Kozawa, Takahiro; Yoshida, Youichi; Tagawa, Seiichi

2006-01-01

A new pulse radiolysis system based on a femtosecond electron beam and a femtosecond laser light with oblique double-pulse injection was developed for studying ultrafast chemical kinetics and primary processes of radiation chemistry. The time resolution of 5.2 ps was obtained by measuring transient absorption kinetics of hydrated electrons in water. The optical density of hydrated electrons was measured as a function of the electron charge. The data indicate that the double-laser-pulse injection technique was a powerful tool for observing the transient absorptions with a good signal to noise ratio in pulse radiolysis

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 liquid water using picosecond electron pulses produced by a table-top terawatt laser system

International Nuclear Information System (INIS)

Saleh, Ned; Flippo, Kirk; Nemoto, Koshichi; Umstadter, Donald; Crowell, Robert A.; Jonah, Charles D.; Trifunac, Alexander D.

2000-01-01

A laser based electron generator is shown, for the first time, to produce sufficient charge to conduct time resolved investigations of radiation induced chemical events. Electron pulses generated by focussing terawatt laser pulses into a supersonic helium gas jet are used to ionize liquid water. The decay of the hydrated electrons produced by the ionizing electron pulses is monitored with 0.3 μs time resolution. Hydrated electron concentrations as high as 22 μM were generated. The results show that terawatt lasers offer both an alternative to linear accelerators and a means to achieve subpicosecond time resolution for pulse radiolysis studies. (c) 2000 American Institute of Physics

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

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)

Pulse radiolysis apparatus for monitoring at 2000 Å

DEFF Research Database (Denmark)

Christensen, H.C.; Nilsson, G.; Pagsberg, Palle Bjørn

1969-01-01

A pulse radiolysis apparatus with photometric monitoring has been built around an 11 MeV, 250 mA peak current, linac that delivers single 0.25 to 4 μsec pulses. The novel features of the apparatus include (1) a 450 W xenon lamp as the analyzing light source which in pulsed operation had a 25 times...... increased luminance; (2) a fast electronic switch that cut out the signal due to the Cerenkov radiation; (3) a secondary emission chamber that allowed the simultaneous measurement of the current and the direction of the pulsed electron beam; and (4) a system for remote controlled change of liquid samples...

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

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)

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

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)

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...

Set-up for pulse radiolysis of agressive substances

International Nuclear Information System (INIS)

Kozlowska-Milner, E.; Broszkiewicz, R.; Stanikowski, J.

1975-01-01

A set-up for the pulse radiolysis of aggressive substances with a relatively low consumption of the liquid, tested for anhydrous HNO 3 , has been described. The samples have been irradiated with single pulses of 10 MeV electrons at the linear accelerator type LAE 13-9. The absorption spectra of the irradiated samples (within a range of 300-800 nm) were provided by a xenon lamp. The variations of the voltage from the photomultiplier, coupled with an oscilloscope, were registered with the aid of a Polaroid camera. (T.G.)

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

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

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)

Radiation chemistry and advanced polymer materials studied by picosecond pulse radiolysis combined with femtosecond laser

International Nuclear Information System (INIS)

Tagawa, S.; Yoshida, Y.; Miki, M.; Yamamoto, T.; Ushida, K.; Izumi, Y.

1996-01-01

We have synchronized a single picosecond MeV electron pulse from L-band linear accelerator (linac) of The Institute of Scientific and Industrial Research of Osaka University to a single femtosecond laser pulse of Ti:Sapphire laser. It is an essential technique for the future femtosecond pulse radiolysis and is also applied to many kinds of combined application of more than two different beams from accelerators in very short time range. Radiation chemistry and new type of polymers have been studied by LL (laser-linac) twin picosecond pulse radiolysis. Especially the early events in radiation chemistry such as geminate recombination processes of electrons and radical cations are have been studied in both liquids and solids. (author)

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)

Radiolysis of spray solutions

International Nuclear Information System (INIS)

Habersbergerova, A.; Janovsky, I.

1985-01-01

The factors were studied affecting thiosulfate radiolysis in the so-called spray solution for nuclear power plant containments. The reaction mechanism of primary radiolytic reactions leading to thiosulfate decomposition was studied using pulse radiolysis. Also measured was hydrazine loss in the irradiation of the bubbling solution intended for the capture of volatile chemical forms of radioiodine. Pulse radiolysis was used to study the kinetics of hydrazine reaction with elemental iodine. (author)

Pulse radiolysis of LiBr-KBr melts. Optical transient absorption spectra

International Nuclear Information System (INIS)

Sawamura, S.; Gebicki, J.L.; Mayer, J.; Kroh, J.

1990-01-01

Absorption spectra of the irradiated melts of LiBr and LiBr-KBr mixtures were investigated in the temperature range 673-873 K by nanosecond pulse radiolysis. The visible band ascribed to e s - shows the apparent shift towards longer wavelengths with increasing temperature and increasing content of KBr in the mixture. The UV transient absorption was attributed to superimposed Br 2 - and Br 3 - bands. The relation between the transition energy of visible band and the inverse mean ion distance is given for alkali bromide and chloride systems. (author)

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...

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

Ion beam pulse radiolysis system at HIMAC

Energy Technology Data Exchange (ETDEWEB)

Chitose, N; Katsumura, Y; Domae, M; Ishigure, K [Tokyo Univ. (Japan); Murakami, T

1997-03-01

An ion beam pulse radiolysis system has been constructed at HIMAC facility. Ion beam of 24MeV 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 corresponding to (C{sub 6}H{sub 5}){sub 2}CO{sup -}, CO{sub 3}{sup -}, and (SCN){sub 2}{sup -} respectively were observed. Ghost signals which interfere with the measurement are also discussed. (author)

A pulse radiolysis study of hyperoside isolated from Hypericum mysorense

International Nuclear Information System (INIS)

Hariharapura, Raghu C.; Mahal, H.S.; Srinivasan, R.; Jagani, Hitesh; Vijayan, P.

2015-01-01

Background: The recent growth in knowledge of free radicals in biology is producing a medical revolution that promises a new age in health and disease management. In the last two decades there has been an explosive interest in the role of oxygen free radicals, more generally known as “reactive oxygen species” and of “reactive nitrogen species” in experimental and clinical medicine. Methods: The flowering top extract of Hypericum mysorense possessing potent anti-oxidant activity was subjected to bio-active guided isolation. Pulse radiolysis technique was used to determine the transient spectrum and rate constant for the one-electron oxidation of hyperoside by · OH, N 3 · , NO 2 · , NO · , CCl 3 OO · radicals in aqueous solution. Results: Three compounds were isolated and characterized as rutin, quercetin-3-O-galactoside (hyperoside) and quercetin from spectral analysis. The hyperoside radical showed pK a1 and pK a2 at 5.4 and 9.2. Both, Cu(II) and iron(II) ions form chelate with hyperoside. The Cu–hyperoside chelate was able to scavenge O 2 ·− , k=7.0(±0.3)×10 6 dm 3 mol −1 s −1 at pH 9. The repair rates for tryptophan and guanosine radicals by hyperoside were also determined. Conclusion: The reduction potential of hyperoside radical was determined by cyclic voltammetric and pulse radiolysis methods. - Highlights: • Hyperoside, rutin and quercetin were isolated from extract of Hypericum mysorense. • Rate constant of hyperoside was determined by Pulse radiolysis technique. • The hyperoside radical showed pK a1 and pK a2 at 5.4 and 9.2. • Cu(II) and iron(II)ions form chelate with hyperoside. • Hyperoside can repair the damage to guanosine, tryptophan radicals

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 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

Gas phase collision dynamics by means of pulse-radiolysis methods

International Nuclear Information System (INIS)

Hatano, Yoshihiko

1989-01-01

After a brief survey of recent advances in gas-phase collision dynamics studies using pulse radiolysis methods, the following two topics in our research programs are presented with emphasis on the superior advantages of the pulse radiolysis methods over the various methods of gas-phase collision dynamics, such as beam methods, swarm methods and flow methods. One of the topics is electron attachment to van der Waals molecules. The attachment rates of thermal electrons to O 2 and other molecules in dense gases have been measured in wide ranges of both gas temperatures and pressures, from which experimental evidence has been obtained for electron attachment to van der Waals molecules. The results have been compared with theories and discussed in terms of the effect of van der Waals interaction on the electron attachment resonance. The obtained conclusions have been related with investigations of electron attachment, solvation and localization in the condensed phase. The other is Penning ionization and its related processes. The rate constants for the de-excitation of He(2 1 P), He(2 3 S), Ne( 3 P 0 ), Ne( 3 P 1 ), Ne( 3 P 2 ), Ar( 1 P 1 ), Ar( 3 P 1 ), by atoms and molecules have been measured in the temperature range from 100 to 300 K, thus obtaining the collisional energy dependence of the de-excitation cross sections. The results are compared in detail with theories classified according to the excited rare gas atoms in the metastable and resonance states. (author)

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)

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

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.

7-MeV electron LINAC based pulse radiolysis facility at RPCD, BARC

International Nuclear Information System (INIS)

Naik, C.B.; Nadkarni, S.A.; Toley, M.A.; Shinde, S.J.; Naik, P.D.

2017-01-01

7-MeV electron LINAC based pulse radiolysis facility is operational in Chemistry Group of BARC since 1986. The Accelerator is housed in B-132 room in basement of Modular Labs. BARC Accelerator was procured from Radiation Dynamics Inc. UK and its detection system was indigenously developed

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)

Pulse radiolysis of alkanes in the gas-phase, ion-molecule reactions and neutralization mechanisms of hydrocarbon ions

International Nuclear Information System (INIS)

Ausloos, P.

1975-01-01

A discussion is presented of the fate of unreactive hydrocarbon ions in various selected gaseous systems. It is shown that experiments performed with the high radiation dose rates obtained in pulse radiolysis experiments have several advantages over conventional low dose rate experiments for the elucidation of the mechanism of homogeneous neutralization of unreactive hydrocarbon ions. This is so because the charged species has a much shorter lifetime with respect to neutralization under high dose rate (pulse radiolysis) conditions, so that the reaction of the ions with minor impurities or accumulated products is much less probable than in low dose rate experiments. It is further shown through a few examples, that quantitative information about the rate contants of neutralization events and ion-molecule reactions can be obtained when the dose rate is high enough for neutralization and chemical reaction to be in competition. Once reliable rate constants for neutralization and ion-molecule reactions are derived, one can obtain a quantitative evaluation of the products which will by formed in the pulse radiolysis of a hydrocarbon gas mixture from a computer calculation. (author)

Measurement of far-infrared subpicosecond coherent radiation for pulse radiolysis

Energy Technology Data Exchange (ETDEWEB)

Kozawa, T. E-mail: kozawa@sanken.osaka-u.ac.jp; Mizutani, Y.; Yokoyama, K.; Okuda, S.; Yoshida, Y.; Tagawa, S

1999-06-01

Using a magnetic bunch compression method, a 26.5 MeV subpicosecond electron single bunch was generated with the L-band linac of Osaka University. The coherent transition radiation emitted from the subpicosecond single bunch was observed at wavelengths from 100 to 700 {mu}m. The intensity was 7.9x10{sup 9} times higher than that of the incoherent transition radiation obtained by calculation. The length of the compressed electron bunch was evaluated to be roughly 50 fs (rms) from the analysis of the spectra of the transition radiation. The coherent transition radiation has high enough intensity to be applied to pulse radiolysis as a pulsed light source.

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)

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)

Absorbed Dose Distribution in a Pulse Radiolysis Optical Cell

DEFF Research Database (Denmark)

Miller, Arne; McLaughlin, W. L.

1975-01-01

When a liquid solution in an optical cell is irradiated by an intense pulsed electron beam, it may be important in the chemical analysis of the solution to know the distribution of energy deposited throughout the cell. For the present work, absorbed dose distributions were measured by thin...... radiochromic dye film dosimeters placed at various depths in a quartz glass pulse radiolysis cell. The cell was irradiated with 30 ns pulses from a field-emission electron accelerator having a broad spectrum with a maximum energy of ≈MeV. The measured three-dimensional dose distributions showed sharp gradients...... in dose at the largest penetration depths in the cell and at the extreme lateral edges of the cell interior near the optical windows. This method of measurement was convenient because of the high spatial resolution capability of the detector and the linearity and absence of dose-rate dependence of its...

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

Picosecond pulse radiolysis study of primary reactions in solutions

International Nuclear Information System (INIS)

El-Omar, Abdel Karim

2013-01-01

Following the discovery of ionizing radiations and their chemical effects, it was important to study and comprehend the formation mechanisms of short lived free radicals and molecular products. In order to perform such studies, researchers and research groups worked on developing tools allowing both formation and detection of those species at short time scales. Nowadays, pulse radiolysis imposed itself as a fundamental and efficient tool allowing scientists to probe chemical effects as well as reaction mechanisms in studied media. The Laboratoire de Chimie Physique d'Orsay 'LCP' is an interdisciplinary laboratory hosting the platform of fast kinetics known as 'ELYSE'. Due to its femtosecond laser and its picosecond electron accelerator, we have the possibility to study chemical effects of ionizing radiations interaction with media at ultrashort times up to ∼5 ps.Knowing that we are interested in primary reactions induced in aqueous media by ionizing radiations, ELYSE represents the essential tool in performing our studies. The obtained results concern:- First direct determination of hydroxyl radical 'HO*' radiolytic yield as function of time at picosecond time scale;- Direct effect of ionizing radiation in highly concentrated aqueous solutions as well as investigation of the ultrafast electron transfer reaction between solute molecules and positive holes 'H 2 O*+' formed upon water radiolysis;- Study at room temperature of electron transfer reaction between solvated electron (electron donor) and organic solutes (electron acceptors) en viscous medium;- Study at room temperature of electron's solvation dynamics in ethylene glycol and 2-propanol. (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...

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

Electron energy device for LINAC based Pulse Radiolysis Facility of RPCD

International Nuclear Information System (INIS)

Toley, M.A.; Shinde, S.J.; Chaudhari, B.B.; Sarkar, S.K.

2015-07-01

The pulse radiolysis facility is the experimental centerpiece of the radiation chemistry activities of the Radiation and Photochemistry Division (RPCD) of Bhabha Atomic Research Centre. This facility was created in 1986 which is based on a 7 MeV Linear Electron Accelerator (LINAC) procured from M/s Radiation Dynamics Ltd., UK. The electron energy is one of the principal parameters that influence the dose distribution within the sample irradiated with a beam of energetic electrons. An easy-to-use and robust device has been developed that can reliably detect day-today small variations in the beam energy. It consists of two identical aluminum plates except for their thickness, which are electrically insulated from each other. The thickness of each plate is carefully selected depending on the electron beam energy. The charge (or current) collected by each plate, under irradiation is measured. The ratio of the charge (or current) signal from the front plate to the sum of the signals from the front and rear plates is very sensitive to the beam energy. The high sensitivity and robustness make this device quite suitable for Electron energy measurement for Pulse radiolysis Facility at RPCD. (author)

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

Nanosecond time-resolved EPR in pulse radiolysis via the spin echo method

International Nuclear Information System (INIS)

Trifunac, A.D.; Norris, J.R.; Lawler, R.G.

1979-01-01

The design and operation of a time-resolved electron spin echo spectrometer suitable for detecting transient radicals produced by 3 MeV electron radiolysis is described. Two modes of operation are available: Field swept mode which generates a normal EPR spectrum and kinetic mode in which the time dependence of a single EPR line is monitored. Techniques which may be used to minimize the effects of nonideal microwave pulses and overlapping sample tube signals are described. The principal advantages of the spin echo method over other time-resolved EPR methods are: (1) Improved time resolution (presently approx.30--50 nsec) allows monitoring of fast changes in EPR signals of transient radicals, (2) Lower susceptibility to interference between the EPR signal and the electron beam pulse at short times, and (3) Lack of dependence of transient signals on microwave field amplitude or static field inhomogeneity at short times. The performance of the instrument is illustrated using CIDEP from acetate radical formed in pulsed radiolysis of aqueous solutions of potassium acetate. The relaxation time and CIDEP enhancement factor obtained for this radical using the spin echo method compare favorably with previous determinations using direct detection EPR. Radical decay rates yield estimates of initial radical concentrations of 10 -4 10 -3 M per electron pulse. The Bloch equations are solved to give an expression for the echo signal for samples exhibiting CIDEP using arbitrary microwave pulse widths and distributions of Larmor frequencies. Conditions are discussed under which the time-dependent signal would be distorted by deviations from an ideal nonselective 90 0 --tau--180 0 pulse sequence

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...

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.

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)

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

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)

Energy transfer from an alkene triplet state during pulse radiolysis

International Nuclear Information System (INIS)

Barwise, A.J.G.; Gorman, A.A.; Rodgers, M.A.J.

1976-01-01

Pulse radiolysis of a benzene solution of norbornene containing low concentrations of anthracene results in delayed formation of anthracene triplet: this is the result of diffusion-controlled energy transfer from the alkene triplet state which has a natural lifetime in benzene of 250 ns. The use of various hydrocarbon acceptors has indicated that Esub(T)=20 000+-500 cm -1 for the relaxed T 1 state of the alkene, at least 5000 cm -1 below that of the spectroscopic state. (Auth.)

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....

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)

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

Programming for controlling of pulse radiolysis setup. Program RADIO96

International Nuclear Information System (INIS)

Mirkowski, J.; Grodkowski, J.

1998-01-01

Program RADIO96 was written in Pascal using DELPHI 1.0 (Borland) programming platform. It can operate on IBM PC compatible computers in WINDOWS 3x or WINDOWS'95 environment. The program is dedicated to the pulse radiolysis setup based on the linear electron accelerator LAE 13/9 of the Department of Radiation Chemistry and Technology of the INCT. This work was based on apparatus and results described before and also on programming manuals of used equipment and technical data of programming platform. (author)

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

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

Materials of 4. international meeting on pulse investigations in physics, chemistry and biology. PULS'94

International Nuclear Information System (INIS)

1994-01-01

4. International Meeting on Pulse Investigations in Physics, Chemistry and Biology, PULS'94 has been organized in honor of Professor Jerzy Kroh, the precursor of radiation chemistry in Poland. The meeting has been divided into three sessions: the historical session (H) with four review lectures, lecture session (L) collected 23 papers and poster session (P) with 39 posters. The fundamental studies on early stages of radiolysis have been presented for different systems being irradiated. The pulse radiolysis and flash photolysis methods has been predominantly used in reported experimental works. The reaction of intermediate products of radiolysis and photolysis such a trapped and solvated electrons, ions and radicals has been extensively studied. The reaction mechanisms and kinetics have been also discussed

Programming for time resolved spectrum in pulse radiolysis experiments

International Nuclear Information System (INIS)

Betty, C.A.; Panajkar, M.S.; Shirke, N.D.

1993-01-01

A user friendly program in Pascal has been developed for data acquisition and subsequent processing of time resolved spectra of transient species produced in pulse radiolysis experiments. The salient features of the program are (i) thiocyanate dosimetry and (ii) spectrum acquisition. The thiocyanate dosimetry is carried out to normalize experimental conditions to a standard value as determined by computing absorbance of the transient signal CNS -2 that is produced from thiocyanate solution by a 7 MeV electron pulse. Spectrum acquisition allows the acquisition of the time resolved data at 20 different times points and subsequent display of the plots of absorbance vs. wavelength for the desired time points during the experiment. It is also possible to plot single time point spectrum as well as superimposed spectra for different time points. Printing, editing and merging facilities are also provided. (author). 2 refs., 7 figs

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

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 .

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)

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)

Measurement system for pulse radiolysis at linear electron accelerator LAE 13/9

International Nuclear Information System (INIS)

Mirkowski, J.; Grodkowski, J.

1999-01-01

A new control and measurement system for a pulse radiolysis setup based on the linear electron accelerator LAE 13/9 is described. It consists of CAMAC apparatus, two oscilloscopes: Tektronix TDS620 and Iwatsu TS8123, and PC computer as a control unit for programming and controlling of the experiments and for results processing. The program is written using DELPHI 1.0 (Borland) programming platform and it can operate in WINDOWS 3.x or WINDOWS 95 environment. (author)

8. International Conference on Pulse Investigations in Chemistry, Biology and Physics - PULS'2008. Abstracts

International Nuclear Information System (INIS)

2008-01-01

The Report comprises abstracts of 68 communications (oral and posters) presented during the 8. International Conference on Pulse Investigations in Chemistry, Biology and Physics - PULS'2008, held on September 6 - 12, 2008 in Cracow. Presentations cover a variety of research fields representing different fields of pulse radiolysis in chemistry, biology and physics

8. International Conference on Pulse Investigations in Chemistry, Biology and Physics - PULS'2008. Abstracts

Energy Technology Data Exchange (ETDEWEB)

NONE

2008-07-01

The Report comprises abstracts of 68 communications (oral and posters) presented during the 8. International Conference on Pulse Investigations in Chemistry, Biology and Physics - PULS'2008, held on September 6 - 12, 2008 in Cracow. Presentations cover a variety of research fields representing different fields of pulse radiolysis in chemistry, biology and physics.

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)

Pulse radiolysis with (sub) nanosecond time resolution using a 3 MV electron accelerator

International Nuclear Information System (INIS)

Luthjens, L.H.

1986-01-01

In this thesis the development of equipment for pulse radiolysis is described and the application of the technique to time-resolved measurements of the fluorescence emission of excited states formed after irradiation of some alkanes is dealt with. A review is given of the development of the pulsed 3MV Van de Graaf electron accelerator for the generation of subnanosecond electron beam pulses and of the development of the equipment for optical detection as accomplished by the author. The initial stage of a further development for shorter pulses and higher time resolution is briefly discussed. A collection of papers on the development of apparatus and a collection of papers dealing with the results obtained from measurements of the fluorescence of excited states, formed by the recombination of electrons and ions in irradiated alkanes such as cyclohexane and the decalines, are included. (Auth.)

Fiber-optic control system for LAE 10 accelerator and pulse radiolysis experimental set

International Nuclear Information System (INIS)

Dzwigalski, Z.; Zimek, Z.

2006-01-01

The LAE 10 accelerator is used in nanosecond pulse radiolysis experiments as a source of 10 ns pulses of high energy electrons. The accelerator system was elaborated in the years 1991-1993. Inseparable connections of the optical fiber marrow with E/O and O/E converters (executed in welding technique) ensured a high stability of the optical parameters at a very long time. The preparation of connections needed adoption of expensive instrumentation from an optoelectronic laboratory in Warsaw. In presented paper authors describe their own action to improve operation of the LAE 10 accelerator existing in the Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

One-electron reduction of anthraquinone sulphonates: a pulse radiolysis study

International Nuclear Information System (INIS)

Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

1991-01-01

Semiquinone free radicals, derived from 2-sulphonate, 1,5-disulphonate and 2,6-disulphonate derivatives of 9,10-anthraquinone, have been studied using pulse radiolysis and kinetic absorption spectrophotometry techniques. Spectroscopic characteristics of both neutral and anionic species have been ascertained. Kinetics of formation and decay, reactivity with oxygen and one-electron reduction potential values have been estimated. The semiquinone radicals have been shown to be very stable under suitable pH conditions where the equilibrium (2 semiquinone ↔ quinone + hydroquinone) lies predominantly to the left. From a measurement of the equilibrium constants at different pH, values of E 2 and E m have been calculated. (author)

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)

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

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

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).

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

Pulse radiolysis studies in model lipid systems

International Nuclear Information System (INIS)

Patterson, L.K.; Hasegawa, K.

1978-01-01

The kinetic and spectral behavior of radicals formed by hydroxyl radical attack on linoleate anions has been studied by pulse radiolysis. Reactivity of OH toward this surfactant is an order of magnitude greater in monomeric form (kOH + linoleate = 8.0 x 10 9 M -1 sec -1 ) than in mecellar form (kOH + lin(micelle) = 1.0 x 10 9 M -1 sec -1 ). Abstraction of a hydrogen atom from the doubly allylic position gives rise to an intense absorption in the UV region (lambda max = 282-286 nm, epsilon approximately 3 x 10 4 M -1 cm -1 ) which may be used as a probe of radical activity at that site. This abstraction may occur, to a small extent, directly via OH attack. However, greater than 90% of initial attack occurs at other sites. Subsequent secondary abstraction of doubly allylic H atoms appears to occur predominantly by: (1) intramolecular processes in monomers, (2) intermolecular processes in micelles. Disappearance of radicals by secondary processes is slower in the micellar pseudo phase than in monomeric solution. (orig.) 891 HK 892 KR [de

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

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)

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)

CO2·- radical induced cleavage of disulfide bonds in proteins. A gamma-ray and pulse radiolysis mechanistic investigation

International Nuclear Information System (INIS)

Favaudon, V.; Tourbez, H.; Lhoste, J-M.; Houee-Levin, C.

1990-01-01

Disulfide bond reduction by the CO 2 ·- radical was investigated in aponeocarzinostatin, aporiboflavin-binding protein, and bovine immunoglobulin. Protein-bound cysteine free thiols were formed under γ-ray irradiation in the course of a pH-dependent and protein concentration dependent chain reaction. The chain efficiency increased upon acidification of the medium, with an apparent pK a around 5, and decreased abruptly below pH 3.6. It decreased also at neutral pH as cysteine accumulated. From pulse radiolysis analysis, CO 2 ·- proved able to induce rapid one-electron oxidation of thiols and of tyrosine phenolic groups in addition to one-electron donation to exposed disulfide bonds. The bulk rate constant of CO 2 ·- uptake by the native proteins was 5- to 10-fold faster at pH 3 than at pH 8, and the protonated form of the disulfide radical anion, appeared to be the major protein radical species formed under acidic conditions. Formation of the disulfide radical cation, phenoxyl radical Tyr-O · disproportionation, and phenoxyl radical induced oxidation of preformed thiol groups should also be taken into consideration to explain the fate of the oxygen-centered phenoxyl radical

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

Studies of some elementary processes involving electrons in the gas phase by pulse-radiolysis microwave-cavity technique

International Nuclear Information System (INIS)

Sunagawa, Takeyoshi; Makita, Takeshi; Musasa, Hirofumi; Tatsumi, Yoshitsugu; Shimamori, Hiroshi

1995-01-01

The pulse radiolysis-microwave cavity technique has been employed for detection of free electrons in the gas phase. Presented are results of the observation of electron disappearance by attachment to molecules, the electron thermalization (energy loss) processes in the presence of an electron-attaching compound, and the formation of electrons by Penning ionization. (author)

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)

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

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.

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.

Improvements in detection system for pulse radiolysis facility

CERN Document Server

Rao, V N; Manimaran, P; Mishra, R K; Mohan, H; Mukherjee, T; Nadkarni, S A; Sapre, A V; Shinde, S J; Toley, M

2002-01-01

This report describes the improvements made in the detection system of the pulse radiolysis facility based on a 7 MeV Linear Electron Accelerator (LINAC) located in the Radiation Chemistry and Chemical Dynamics Division of Bhabha Atomic Research Centre. The facility was created in 1986 for kinetic studies of transient species whose absorption lies between 200 and 700 nm. The newly developed detection circuits consist of a silicon (Si) photodiode (PD) detector for the wavelength range 450-1100 nm and a germanium (Ge) photodiode detector for the wavelength range 900-1600 nm. With these photodiode-based detection set-up, kinetic experiments are now routinely carried out in the wavelength range 450-1600 nm. The performance of these circuits has been tested using standard chemical systems. The rise time has been found to be 150 ns. The photo-multiplier tube (PMT) bleeder circuit has been modified. A new DC back-off circuit has been built and installed in order to avoid droop at longer time scales. A steady baselin...

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 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)

Programming a microcomputer for online data acquisition and processing in pulse radiolysis experiments. Part 2: Spectrum acquisition and processing

International Nuclear Information System (INIS)

Panajkar, M.S.; Moorthy, P.N.; Shirke, N.D.

1989-01-01

In pulse radiolysis experiments one of the informations sought is the absorption spectrum of the transient species generated in the system. As the transient species decay over a period of time, it is necessary to acquire the spectrum at fixed times after the pulse. The present report describes the necessary methodology for on-line acquisition and processing of such time resolved spectra from transient signals captured in a digital storage scope interfaced to an IBM compatible personal computer. (author). 11 figs

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

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.)

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)

Structural and dynamical properties of solvated electrons; a study of kinetic spectroscopy using pulse radiolysis

International Nuclear Information System (INIS)

Huis, C. van

1977-01-01

In this thesis the pulse radiolysis experiments of hexamethyl-phosphortriamide (HMPA), propanol-1, 3-methylpentane and mixtures of propanol-1 and 3-methylpentane are reported. In the pulse radiolysis of HMPA, carried out at room temperature, the high yield of esub(s) - (G=2) and the very high wavelength of the maximum absorption (max= 2200 nm) in the esub(s) - absorption spectrum are explained by considering the aprotic nature and the molecular structure of this compound. In the experiment with propanol-1 (temperature range 93deg-123degK) a temporal shift to lower wavelengths in the time range of 10 s-10 ms is observed. In further experiments biphenyl was used as electron scavenger. It was concluded that after the electron pulse the following sequence of events takes place: 1) electron redistribution in times shorter than 1 s; 2) dipole reorientation during 10 s-10 ms; 3) recombination of a part of the solvated electrons; 4) a reaction of the solvated electrons with the neighbouring propanol-1 molecules. In the experiments with 3-methylpentane at 103deg-113degK an esub(s) - absorption band with third order decay kinetics was observed. This is attributed to geminate recombination. The activation energy of the recombination process was 0.4 eV. The experiments with mixtures of propanol-1 and 3-methylpentane were carried out at 103degK. At low propanol-1 concentrations the build-up at 500 nm obeys first order kinetics, whereas at high concentrations this build-up can be split up into three first order components, as was measured in pure propanol-1. The half-lives of the three components were in the ratio of 1:10:100. In the last chapter theoretical models for the electron redistribution and the matric relaxation are discussed and compared with the experiments

Effects of energy, distance and orientation on electron transfer rates studied by pulse radiolysis in organic media

International Nuclear Information System (INIS)

Miller, J.R.

1987-01-01

In the past few years the methods of radiation chemistry in organic media have made an enormous change in how we view electron transfer processes, as these media have proved the most useful for studying long distance electron transfer between molecules. This paper briefly summarizes a few of the aspects of this area and discusses some of the attributes and limitations of radiation tehniques, particularly pulse radiolysis, in organic solvents. 14 refs., 2 figs

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)

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

Investigation of reactivity of inorganic free radicals relative to ferrocyanide- and octacyanomolybdate-ions in aqueous solutions by the method of pulse radiolysis

International Nuclear Information System (INIS)

Gogolev, A.V.; Fedoseev, A.M.; Makarov, I.F.; Pikaev, A.K.

1989-01-01

In aqueous solutions by the method of pulse radiolysis (dose per impulse-7.96-47.8 Gy, electron energy-5 MeV) the reactivity of Cl 2 - , Br 2 - , I 2 - , (SCN) 2 - , CO 3 - , SeO 3 - , SO 4 - radicals towards ferrocyanide ions and of Br 2 - , CO 3 - , SO 4 - radicals tawards octacyanomolybdate ions is studied. Linear dependence of rate constant logarithm of Cl 2 - , Br 2 - , I 2 - reactions with cyanide complexes on the difference of redox potentials of reacting particles ΔE 0 is obtained. Radicals containing oxygen react with cyanide complexes more rapidly than can be expected on the basis of ΔE 0 values. The effect of solution ionic strength, charge of reacting particles and radical nature on the reaction rate is discussed

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)

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)

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.

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

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...

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)

Oxidation of cinnamic acid derivatives: A pulse radiolysis and theoretical study

International Nuclear Information System (INIS)

Yadav, Pooja; Mohan, Hari; Maity, Dilip Kumar; Suresh, Cherumuttathu H.; Rao, B.S. Madhav

2008-01-01

Second order rate constants in the range of (k = 1.6-4.5) x 10 9 dm 3 mol -1 s -1 were obtained for the · OH induced oxidation of nitro- and methoxycinnamic acid derivatives in neutral solutions using pulse radiolysis. The transient absorption spectra exhibited a broad peak around 360-410 nm in o-methoxy, o- and p-nitrocinnamates or two peaks around 310-330 and 370-410 nm in other isomers. Quantum chemical calculations revealed that addition of · OH to olefinic moiety yielded considerably more stable structures than ring addition products and the para system among the latter is the most stable. Spin density analysis suggested that olefinic adducts retained the aromaticity in contrast to its loss in ring · OH adducts. An excellent linear correlation between the relative stabilities of the · OH adducts (after accounting for the aromatic stabilization in olefinic adducts) and the maximum S d values is also obtained

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

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 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)

The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

DEFF Research Database (Denmark)

Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

1976-01-01

Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...

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)

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 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)

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...

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

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 nucleic acids and their base constituents: bibliographies on radiation chemistry: Pt. 11

Energy Technology Data Exchange (ETDEWEB)

Sonntag, C von; Ross, A B

1987-01-01

For this compilation the data stored by the Radiation Chemistry Data Center bibliographic database through 1986 were processed using the SELECT keywords: purines, pyrimidines, nucleotides, nucleosides, nucleic acids and pulse radiolysis. The number of citations found was reduced by about one-third by eliminating privately published symposia papers, theses and papers not strictly relevant to this topic, e.g. on flavins, NADH, one-electron reduction of nitrouracil or the redox potential of isobarbituric acid. On the other hand, a few more papers known to us but not revealed by the keywords were added. The bibliography is arranged in approximately chronological order, references grouped by year of publication. Reviews are collected at the end of the bibliography in a separate section.

Pulse radiolysis of nucleic acids and their base constituents: bibliographies on radiation chemistry: Pt. 11

International Nuclear Information System (INIS)

Sonntag, C. von; Ross, A.B.; Notre Dame Univ., IN

1987-01-01

For this compilation the data stored by the Radiation Chemistry Data Center bibliographic database through 1986 were processed using the SELECT keywords: purines, pyrimidines, nucleotides, nucleosides, nucleic acids and pulse radiolysis. The number of citations found was reduced by about one-third by eliminating privately published symposia papers, theses and papers not strictly relevant to this topic, e.g. on flavins, NADH, one-electron reduction of nitrouracil or the redox potential of isobarbituric acid. On the other hand, a few more papers known to us but not revealed by the keywords were added. The bibliography is arranged in approximately chronological order, references grouped by year of publication. Reviews are collected at the end of the bibliography in a separate section. (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

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)

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

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

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.

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.

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

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.

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

International Nuclear Information System (INIS)

Garrison, W.M.

1985-01-01

The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

Energy Technology Data Exchange (ETDEWEB)

Garrison, W.M.

1985-01-01

The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs.

Ion pairing of radical ions of aromatic alkenes and alkynes studied by pulse radiolysis

International Nuclear Information System (INIS)

Yamamoto, Satoshi; Yamamoto, Yukio; Hayashi, Koichiro

1991-01-01

Pulse radiolysis of 1,2-dichloroethane solutions of trans,trans-1,4-bis(2-phenylethenyl)benzene and 1,4-bis(2-phenylethynyl)benzene was undertaken in the presence of Bu 4 NPF 6 (Bu=butyl) to investigate the effect of ion pairing of the solute radical cations with PF 6 - . It was also undertaken for the tetrahydrofuran solutions of the above compounds in the presence of Bu 4 NPF 6 and NaBPh 4 , where the solute radical anions are generated and form ion pairs with Bu 4 N + and Na + . The decay of the radical ions, which is due to neutralization, is retarded by the ion pairing. The rate constants for the neutralization reactions in the free-ion and ion-paired states were determined. Also presented are the data for the radical ions of trans-stilbene, diphenylacetylene, trans,trans-1,4-diphenyl-1,3-butadiene, and diphenylbutadiene. The radical ions of the aromatic alkynes are less stabilized by the ion pairing than those of the aromatic alkenes having the same carbon skeletons probably because of more extensive charge delocalization of the former radical ions. Spectral shifts to shorter wavelengths caused by the ion pairing are appreciable for the radical anions. Dependence of the spectral shifts on the size of the radical anions is described. (author)

Oxidative degradation processes in synthetic and biological polymers as studied by pulse radiolysis experiments

International Nuclear Information System (INIS)

Schnabel, W.

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, O 2 can be discriminated with respect to main-chain scission: (a) O 2 acts as a promoter, (b) O 2 acts as an inhibitor, and (c) O 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 and/or to the combination of peroxyl radicals with the subsequent formation of readily decomposing oxyl radicals. The inhibiting mode of action (b) pertains to the reaction of O 2 with macroradicals that otherwise undergo main-chain rupture. 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)

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.

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)

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.

A pulse-radiolysis study of the manganese-containing superoxide dismutase from Bacillus stearothermophilus

International Nuclear Information System (INIS)

McAdam, M.E.; Lavelle, F.; Fox, R.A.; Fielden, E.M.

1977-01-01

The mechanism of catalysis of the manganese-containing superoxide dismutase from Bacillus stearothermophilus has been shown to involve a 'fast cycle' and a 'slow cycle' (McAdam, M.E., Fox, R.A., Lavelle, F., and Fielden, E.M., Biochem. J.; 165:71 (1977)). Further properties of the enzyme are now considered. Pulse-radiolysis studies, under conditions of low substrate concentration to enzyme concentration (i.e. when the fast cycle predominates), showed that enzyme activity decreases as pH increases (6.5 to 10.2). Activity was unaffected by the addition of H 2 O 2 or NaN 3 but slightly decreased by KCN. Both H 2 O 2 and the reducing radical anion CO 2 sup(-.) caused a decrease in A 480 of the native enzyme. The rate of the fast catalytic cycle was independent of temperature (5 to 55 0 C), and as temperature increased the slow catalytic cycle became relatively more important. Arrhenius parameters of the rate constants were estimated. The possible identity of the various forms of the enzyme is considered. (author)

Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

Science.gov (United States)

Revina, A. A.; Amiragova, M. I.; Volod'ko, V. V.; Vannikov, A. V.

Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O ⨪2 decay was monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O ⨪2. A red shift of O ⨪2 absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions.

Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

International Nuclear Information System (INIS)

Revina, A.A.; Volod'ko, V.V.; Vannikov, A.V.

1989-01-01

Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O 2 .-bar decay as monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O 2 .-bar . A red shift of 0 2 .-bar absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2 s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions. (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

Ultra-fast pulse radiolysis: A review of the recent system progress and its application to study on initial yields and solvation processes of solvated electrons in various kinds of alcohols

International Nuclear Information System (INIS)

Muroya, Yusa; Lin Mingzhang; Han Zhenhui; Kumagai, Yuta; Sakumi, Akira; Ueda, Toru; Katsumura, Yosuke

2008-01-01

In order to study radiation-induced fast phenomena, a new pulse radiolysis system with higher time resolution based on pulse-and-probe method was developed and utilized for practical work. A few picosecond electron beam generated from a linear accelerator, in which a laser photocathode RF-gun is introduced, was synchronized with a femtosecond laser pulse which is employed as the analyzing light. The synchronization precision between them was suppressed within 1.6 ps (rms). Converting the fundamental laser into white light continuum or optical parametric amplification allows to measure in the wide wavelength from visible to infrared region

Factors affecting the equilibrium constant of homolysis of complexes with metal-carbon σ bonds in aqueous solutions. Pulse radiolysis studies

International Nuclear Information System (INIS)

Meyerstein, D.; Ben-Gurion Univ. of the Negev, Beersheba

1989-01-01

Pulse-Radiolysis is a powerful technique for the determination of the equilibrium constants of the homolytic cleavage of metal-carbon σ bonds in aqueous solutions. In most systems studied the observed reaction is: L m-1 M (n+1) -R + L ↔ ML m. n + ·R. Therefore the results do not enable a direct determination of the metal-carbon bond dissociation energies. The results obtained indicate that these equilibrium constants are not directly related to the redox potential of either L .m M (n) or of ·R, or to the activation energies for the homolytic cleavage of a family of similarly substituted ethanes. (author)

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....

Interfacial radiolysis effects in tank waste speciation. 1997 annual progress report

International Nuclear Information System (INIS)

Orlando, T.M.

1997-01-01

'The purpose of this program is to deliver pertinent, fundamental information that can be used to make technically defensible decisions on safety issues and processing strategies associated with mixed chemical and radioactive waste cleanup. In particular, an understanding of radiolysis in mixed-phase systems typical of U. Department of Energy (DOE) heterogeneous, radioactive/chemical wastes will be established. This is an important scientific concern with respect to understanding tank waste chemistry issues; it has received relatively little attention. The importance of understanding solid-state radiolysis, secondary electron interactions, charge-transfer dynamics, and the general effect of heterogeneous solids (interface and particulate surface chemistry) on tank waste radiation processes will be demonstrated. In particular, the author will investigate (i) the role of solid-state and interfacial radiolysis in the generation of gases, (ii) the mechanisms of organic compound degradation, (iii) scientific issues underlying safe interim storage, and (iv) the effects of colloid surface-chemical properties on waste chemistry. Controlled radiolysis studies of NaNO 3 solids and SiO 2 particles were carried out using pulsed, low- (5--150 eV) and high- (3 MeV) energy electron-beams at Pacific Northwest National Laboratory (PNNL) and at Argonne National Laboratory (ANL), respectively. The pulsed, low-energy electron beams probe the inelastic scattering and secondary cascading effects produced by high-energy beta and gamma particles. Pulsed radiolysis allows time-resolved measurements of the high-energy processes induced by these particles. Using low-energy (10--75 eV) electron-beam irradiation of nominally dry NaNO 3 solution-grown and melt-grown single crystals, they observed H + , Na + , O + , NO + , NO, NO 2 , O 2 , and O( 3 P) desorption signals. The threshold measurements and yields indicate that the degradation proceeds mainly via destruction of the nitrate moiety. The

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)

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)

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

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

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)

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)

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.

Triplet state and semiquinone free radical of 5-methoxyquinizarin : a laser flash photolysis and pulse radiolysis study

International Nuclear Information System (INIS)

Pal, H.; Patil, D.K.; Mukherjee, T.; Mittal, J.P.

1992-01-01

The triplet(T) state properties like T-T absorption spectra, quantum yield, energy level and decay kinetics of 5-methoxyquinizarin (5-methoxy-1, 4-dihydroxy-9, 10-anthraquinone; MQZ) have been investigated in cyclohexane, acetonitrile and isopropyl alcohol using nanosecond laser flash photolysis technique. In isopropylalcohol, a neutral semiquinone radical is also formed which has been characterised by comparing the long lived transient spectra with the MQZ-semiquinone spectra obtained by pulse radiolysis of MQZ in the same solvent. A relatively small amount of a long lived transient formed in cyclohexane and acetonitrile, along with the triplet state of MQZ, could not be characterised unambiguously, but has been attributed to the semiquinone radical of MQZ, produced by the reaction of the excited states of the quinone with the solvent. The quantum yield of the semiquinone radical in isopropyl alcohol is considerably higher than the triplet quantum yield, showing that both the excited singlet and the triplet states of the quinone probably react with the solvent molecules to form the semiquinone radical. The photophysical properties of the triplet and the semiquinone radical of MQZ have been compared with those of simple 1,4-disubstituted anthraquinones. (author). 23 refs., 5 figs., 1 tab

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

Photosynthetic pigments and model compounds studied by pulse radiolysis

International Nuclear Information System (INIS)

Jensen, N.-H.

1980-05-01

The photosynthetic pigments chlorophyll a and alltrans-β-carotene as well as the quinone model compound duroquinone have been studied in solution by pulse radiolysis combined with time-resolved absorption and resonance Raman spectroscopy. In benzene solution the excited triplet states of the subtrates were produced either directly in the case of duroquinone or by triplet energy transfer from triplet naphthalene in the case of chlorophyll a and β-carotene. All relevant rate constants involved in the reactions of the excited states in benzene were determined, including i) the rate constants for energy transfer from triplet naphthalene to chlorophyll a with k = (3.6+-0.6).10 9 M -1 s -1 and β-carotene with k = (10.7+-1.2).10 9 M -1 s -1 ii) the rate constants of triplet annihilation of chlorophyll a: (1.4+-0.3).10 9 M -1 s -1 , β-carotene: (3.6+-0.4).10 9 M -1 s -1 , duroquinone: (3.0+-0.6).10 9 M -1 s -1 . For β-carotene it is suggested that triplet-triplet annihilation produces the optically forbidden excited 1 Asub(g) state. The first-order components of the triplet decays were strongly dependent upon irradiation dose in the case of naphthalene and duroquinone but apparently only slightly dependent on or independent or irradiation dose in the case of chlorophyll a and β-carotene. Apparent bimolecular rate constants for triplet quenching by radiolytically produced free radicals are determined. The triplet state of duroquinone is quenched by ground state duroquinone with a rate constant of (1.2+-0.3).10 6 M -1 s -1 . The excited triplet state of all-trans-β-carotene has been investigated by time-resolved resonance Raman spectroscopy. Six transient Raman bands at 965 cm -1 , 1009 cm -1 , 1125 cm -1 , 1188 cm -1 , 1236 cm -1 and 1496 cm -1 were observed. The spectra suggest that the C = C band order is decreased and that the molecule may be substantially twisted, presumably at the 15,15 1 band, in the triplet state. The radical anion of chlorophyll a with

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)

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.

Study of radicals or radical ions formed by radiolysis of n-methylacetamide and of its mixtures with water and some organic solvents. Problem of solvation of electrons in structured media

International Nuclear Information System (INIS)

Tran-Thi, Thu-Hoa

1978-01-01

Based on two hypotheses (effect of structure, and electron affinity), and on the use of two complementary techniques (pulsed radiolysis and gamma radiolysis), this research thesis reports the study of the fate of primary species formed during the radiolysis of N-methylacetamide, either pure or mixed with other solvents. The author first presents experimental conditions, the experimental techniques and their results for both types of radiolysis, and then discusses these results

Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 7. Trp -> TyrO radical transformation in hen egg-white lysozyme. Effects of pH, temperature, Trp62 oxidation and inhibitor binding

DEFF Research Database (Denmark)

Bobrowski, K.; Holcman, J.; Poznanski, J.

1997-01-01

Intramolecular long-range electron transfer (LRET) in hen egg-white lysozyme (HEWL) accompanying Trp --> TyrO radical transformation was investigated in aqueous solution by pulse radiolysis as a function of pH (5.2-7.4) and temperature (283-328K). The reaction was induced by highly selective...... below its denaturation temperature. Selective oxidation by ozone of the Trp62 indole side-chain in HEWL to N'-formylkynurenine (NFKyn62-HEWL) caused a large drop in the initial yield of Trp(.) radicals, G(Trp(.))(i). This was accompanied by a relatively small decrease in k(5) but selective oxidation...

Valence isomerization of hexamethyl(dewar benzene) radical cation. Pulse radiolytic investigation

International Nuclear Information System (INIS)

Gebicki, J.; Marcinek, A.; Mayer, J.

1989-01-01

Organic radical ions are important intermediates in a wide variety of electron-transfer reactions. Both the steady-state and time-resolved techniques have been extensively applied to probe various aspects of their chemistry. We have recently established that low-temperature pulse radiolysis can be successfully applied to the kinetic study of radical ion transformations with very low activation barriers. The target of the present investigation is the hexamethyl(Dewar benzene) (HMDB)-hexamethylbenzene (HMDB) system. Studies by the CIDNP technique indicated the presence of two distinguishable radical cations in the system HMDB-HMB. This view has not been supported by a nanosecond spectroscopic observation which failed to reveal any evidence for a radical cation other than HMB sm-bullet+ . The aim of this work is to present spectroscopic evidence for two different radical cations HMDB sm-bullet+ -HMB sm-bullet+ and the activation barrier for their interconversion

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

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

. Therefore, it was suggested that the supercritical primary alcohols, for example methanol, as the simplest alcohol and an analogue of water, might become a promising substitute of water in a radiolysis study. As our knowledge, the yield of solvated electron in methanol at high temperatures and pressures, especially at supercritical condition, is still unknown now. In this work, the yield of solvated electron in methanol has been investigated at different temperatures from room temperature to supercritical condition by a method of nanosecond pulse radiolysis. By using 4,4'-bipyridyl as a scavenger, the temperature-, pressure- and density-dependent yields of solvated electron, i.e., G-values, have been measured for the first time, which revealing a special density effect on the yield in supercritical methanol. With increasing temperature under 9 MPa, the yield just changes slightly below 230 deg. C, and increases dramatically to peak at around 250 deg. C, after that decreases again. The pressure and density dependence of the yields at elevated temperatures are also measured and discussed. The results imply that, in supercritical region, especially near to critical point, the density effect becomes predominant influence on the yield of radiolysis products. (authors)

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)

Ozone decomposition in water studied by pulse radiolysis. 2. OH and HO4 as chain intermediates

International Nuclear Information System (INIS)

Staehelin, J.; Buehler, R.E.; Hoigne, J.

1984-01-01

Ozone decomposition in pure water involves a chain mechanism, initiated by the reaction OH - +O 3 and propogated by O 2 - and OH. In the present studies this chain is initiated by pulse radiolysis of aqueous solutions of ozone. The chain propogation steps were studied in two parts. By computer simulation of the rate curves, it is shown that from OH + O 3 and intermediate HO 4 must be formed, most likely a charge-transfer complex (HO.O 3 ), which eventually decays into HO 2 . The derived rate constants for the formation of the various species are included. The spectrum of HO 4 is derived. It is similar to the one of ozone, but the absorption coefficients are about 50% larger. In the presence of high ozone concentration, the dominant chain termination reactions are HO 4 + HO 4 and HO 4 + HO 3 . The effect on chain length, dose, overall rate, and pH and of added scavengers is described. The implications for the natural ozone decay mechanism are discussed

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)

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...

Solvation of the electron in alcohols studied using the Argonne picosecond pulse radiolysis system

International Nuclear Information System (INIS)

Jonah, C.D.; Kenney-Wallace, G.A.

1979-01-01

With a stroboscopic pulse radiolysis system, it is possible to measure the reactions of solvated electrons and dry electrons and the solvation time of electrons in alcohols from 20 psec to 350 psec. The solvation in alcohol and alcohol-alkane solutions is a complex process which depends on the microscopic structure of the fluid, so that the studies of solvation in alcohols as a function of temperature or as a function of the concentration of the alcohols must take into account the structure of the fluid being studied. The relaxation processes may not be dominant at low temperature. However, in room temperature alcohols, pre-existing traps are the dominant means of electron trapping. The extrapolation to water may be reasonable since water and alcohols both give similar final species. To obtain such idea of the solvation process in alcohols, the change of the absorption of electrons at 500 nm was measured. At very low concentration of alcohols in alkanes, electrons form a complex with a cluster of alcohol molecules, and the most probable size of this cluster is two alcohols (C 4 , C 10 ). The species formed is not solvated electrons, since the characteristic spectrum of solvated electrons is absent, and the conductivity of the species is far above that of solvated electrons. (Yamashita, S.)

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

Role of radiolytically generated species in radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution: Steady state and pulse radiolysis study

International Nuclear Information System (INIS)

Bhardwaj, Y.K.; Mohan, H.; Sabharwal, S.; Majali, A.B.

2000-01-01

Radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution has been investigated by steady state and pulse radiolysis techniques. Effect of dose, dose rate, monomer concentration, pH and ambient conditions on polymerization was investigated. The reactions of primary radicals of water radiolysis such as OH radical, e - aq , H atom, O· - and some oxidizing radicals like N· 3 , Cl· - 2 ,Br· - 2 , and reducing specie like CO· - 2 with SSS have also been investigated. SSS reacts with OH radical with a rate constant of 5.9x10 9 dm 3 mol -1 s -1 at pH 6.3. The results indicate that ∼83% of OH radicals undergo electron transfer reaction resulting in a cation radical species while remaining ∼17% react via addition reaction. The hydrated electron reacts with SSS with a rate constant 1.3x10 10 dm 3 mol -1 s -1 to form an anion that undergoes fast protonation to form H-adduct at pH 6.3. At high pH (>10) the anion is able to transfer electron to methyl vilogen and p-nitro aceto phenone (p-NAP) where as H-adduct is unable to transfer electron. At pH ∼1 H atom reaction with SSS is diffusion controlled with a rate constant of 5x10 9 dm 3 mol -1 s -1 and results in formation of H adduct. It was seen that anion reacts with solute an order faster than cation generated radiolytically indicating anionic initiation of polymerization of SSS. Molecular weight of the polymer formed by radiation polymerization, determined by viscosity measurement, are of the order of 10 7 and higher molecular weight polymers are obtained at lower dose rates. In presence of a crosslinking agent gelation of polymer is much faster than the monomer and a polymer concentration ∼20% is most efficiently crosslinked. (author)

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...

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

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)

Pulsed EPR studies of small reactive radicals produced by ionizing radiation

International Nuclear Information System (INIS)

Lawler, R.G.

1985-01-01

For several years we have participated in a collaborative research effort to apply the pulsed EPR-pulse radiolysis technique to several problems associated with the dynamics of small reactive radicals formed during radiolysis of aqueous solutions using 3 MeV electrons from a Van de Graaff accelerator. We will discuss experimental techniques and applications arising from this work, with particular emphasis on problems requiring high initial radical concentrations and EPR time resolution of one microsecond or better. 2 figs., 2 tabs

Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

International Nuclear Information System (INIS)

Torche, Faycal

2012-01-01

This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

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

Combined radiolysis/GLC as a tool for the investigation of stabilizing mechanisms

International Nuclear Information System (INIS)

Koch, J.; Eckert, W.R.

1977-01-01

Combined radiolysis/GLC was used to prove the chemical incorporation of lauric acid from cadmium laurate into polyvinyl chloride. The samples were exposed for 10 days to x-rays at a dose rate of 0.345 Mrad/hr

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.)

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.

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

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)

Structural analysis of radiolysis products of sennoside

International Nuclear Information System (INIS)

Song, Hyun Pa; Kim, Dong Ho

2011-01-01

The purpose of the present investigation was to analyze the structural changes of gamma irradiated sennoside B (prodrug) and to provide the possibility for application of irradiation to induce structural changes of the prodrugs for enhanced bioavailability. Sennoside B (200 ppm) in 70% methanol solution with or without the use of hydrogen peroxide or nitrous oxide gas was irradiated with 1, 3, 5, 10 and 20 kGy by gamma ray. The radiolysis products of gamma irradiated sennoside B solution were identified and determined by TLC, HPLC and LC-MS/MS. The sennoside B quantity decreased when irradiation dose increased and completely degraded at 10 kGy of irradiation. There was a linear relationship between the production of the radiolysis compounds and the absorbed dose of the gamma ray irradiated sennoside B. Radiolysis products yields increased on the addition of nitrous oxide gas into the sennoside B solution. No anthraquinone compounds were formed after irradiation of sennosie B. Scission of the O-glycoside bond and consequently formation of aglycone of sennoside B was observed

Structural analysis of radiolysis products of sennoside

Energy Technology Data Exchange (ETDEWEB)

Song, Hyun Pa; Kim, Dong Ho [KAERI, Daejeon (Korea, Republic of)

2011-01-15

The purpose of the present investigation was to analyze the structural changes of gamma irradiated sennoside B (prodrug) and to provide the possibility for application of irradiation to induce structural changes of the prodrugs for enhanced bioavailability. Sennoside B (200 ppm) in 70% methanol solution with or without the use of hydrogen peroxide or nitrous oxide gas was irradiated with 1, 3, 5, 10 and 20 kGy by gamma ray. The radiolysis products of gamma irradiated sennoside B solution were identified and determined by TLC, HPLC and LC-MS/MS. The sennoside B quantity decreased when irradiation dose increased and completely degraded at 10 kGy of irradiation. There was a linear relationship between the production of the radiolysis compounds and the absorbed dose of the gamma ray irradiated sennoside B. Radiolysis products yields increased on the addition of nitrous oxide gas into the sennoside B solution. No anthraquinone compounds were formed after irradiation of sennosie B. Scission of the O-glycoside bond and consequently formation of aglycone of sennoside B was observed

Identification and evaluation of radiolysis products of irradiated chloramphenicol by HPLC-MS and HPLC-DAD

Energy Technology Data Exchange (ETDEWEB)

Hong, L; Altorfer, H R [Institute of Pharmaceutical Science, Swiss Federal Institute of Technology (ETH), Zurich (Switzerland); Horni, A; Hesse, M [Institute of Organic Chemistry, University of Zurich, Zurich (Switzerland)

2005-07-01

The radiolysis products of chloramphenicol under {gamma}-radiation sterilization were investigated systematically in the present study. Eight main radiolysis products were identified and quantified by HPLC-MS and HPLC-DAD, including two compounds that have never been reported. The minor radiolysis products were quantified, which shows that they are at the concentration levels below the threshold for identification. Carbon-carbon rupture reaction and oxidation reaction were proposed as the main radiolysis reactions of chloramphenicol powder. The applicability of {gamma}-sterilization for chloramphenicol products was quantitatively evaluated with qualitative and quantitative data and the data were compared to the threshold requirements of international regulations for identification. It was concluded that toxicities of the radiolysis products of chloramphenicol produced by {gamma}-radiation sterilization can be neglected, the radiolysis products are safe for human health from chemical view. (author)

Identification and evaluation of radiolysis products of irradiated chloramphenicol by HPLC-MS and HPLC-DAD

International Nuclear Information System (INIS)

Hong, L.; Altorfer, H.R.; Horni, A.; Hesse, M.

2005-01-01

The radiolysis products of chloramphenicol under γ-radiation sterilization were investigated systematically in the present study. Eight main radiolysis products were identified and quantified by HPLC-MS and HPLC-DAD, including two compounds that have never been reported. The minor radiolysis products were quantified, which shows that they are at the concentration levels below the threshold for identification. Carbon-carbon rupture reaction and oxidation reaction were proposed as the main radiolysis reactions of chloramphenicol powder. The applicability of γ-sterilization for chloramphenicol products was quantitatively evaluated with qualitative and quantitative data and the data were compared to the threshold requirements of international regulations for identification. It was concluded that toxicities of the radiolysis products of chloramphenicol produced by γ-radiation sterilization can be neglected, the radiolysis products are safe for human health from chemical view. (author)

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)

One-electron transfer equilibria and redox potentials of radicals studied by pulse radiolysis

International Nuclear Information System (INIS)

Meisel, D.; Czapski, G.

1975-01-01

The pulse radiolysis technique is utilized for measurements of the equilibrium constants for electron transfer between the durosemiquinone radical anion and oxygen, menadione, and indigodisulfonate. These equilibrium constants are in turn used for calculations of one-electron redox potentials for these systems. Each of these equilibrium constants was determined experimentally and independently and found to be self-consistent. Only for the reactions of the semiquinone radical ions with oxygen could the electron transfer reaction be followed directly. For the reactions between the various quinone-semiquinone systems substantial indirect evidence is presented that these equilibria are achieved rapidly. In those cases equilibrium constants were determined from studies of the effect of quinone concentrations on the relative yields of the semiquinones. A method for distinguishing between kinetic competition and equilibrium is outlined and its usefulness is emphasized. The DQ parallel DQ - (DQ = duroquinone) and IDS parallel IDS - (IDS = indigodisulfonate) systems were employed as reference couples as the redox potentials for those systems are either available in the literature (IDS parallel IDS - ) or may be calculated from available data (DQ parallel DQ - ). Taking E 7 1 , the redox potential for the first one-electron reduction step at pH 7, of DQ parallel DQ - as -0.235 V or of IDS parallelIDS - as -0.247 V both yield E 7 1 = -0.325 V for the O 2 parallel O 2 - system (1 atm of O 2 ) and E 2 1 = -0.20 V for the menadione system. (U.S.)

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)

Pulse radiolytic investigation of the hypoxanthine-xanthine-uric acid system: evidence for transient species

International Nuclear Information System (INIS)

Santamaria, J.; Pasquier, C.; Ferradini, C.; Pucheault, J.

1984-01-01

The oxidation in aqueous solutions of hypoxanthine into xanthine and xanthine into uric acid by OH radicals has been investigated using pulse radiolysis and fast kinetic absorption spectrophotometry. After hypoxanthine irradiations the spectrum of transient R 1 has been characterized. This radical is formed with a rate constant k/sub (Hyx+OH) = 6.5 x 10 9 M -1 sec -1 and disappears by disproportionation leading to xanthine and hypoxanthine with a rate constant 2K/sub (R 1 + r 1 / = 1.3 x 10 8 M -1 sec - 1 . After xanthine irradiations a radical intermediate R 2 is formed with a rate constant k/sub(X+ OH)/= 5.2 x 10 8 M -1 sec -1 and disappears through a second-order reaction 2K/sub (R 2 + R 2 )/ = 2.0 x 10 8 M -1 sec -1 . Finally, after aeration only uric acid and xanthine are measured

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)

Pulse radiolytic reduction of amino and hydroxy disubstituted anthraquinones (Preprint no. RC-15)

International Nuclear Information System (INIS)

Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

1991-01-01

One-electron reduction of 1-amino-4-hydroxy-9, 10-anthraquinone (AHAQ) and 1,4-diamino-9, 10-anthraquinone (DAAQ) in various matrices has been investigated by electron pulse radiolysis. Spectroscopic and kinetic parameters, acid dissociation constants (pK a ) of the reduced semiquinone radicals and one-electron reduction potential for AHAQ have been measured. (author). 2 tabs

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)

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)

Pulse radiolytic and electrochemical investigations of intramolecular electron transfer in carotenoporphyrins and carotenoporphyrin-quinone triads

International Nuclear Information System (INIS)

Land, E.J.; Lexa, D.; Bensasson, R.V.; Gust, D.; Moore, T.A.; Moore, A.L.; Liddell, P.A.; Nemeth, G.A.

1987-01-01

Thermodynamic and kinetic aspects of intramolecular electron-transfer reactions in carotenoporphyrin dyads and carotenoid-porphyrin-quinone triads have been studied by using pulse radiolysis and cyclic voltammetry. Rapid (<1 μs) electron transfer from carotenoid radical anions to attached porphyrins has been inferred. Carotenoid cations, on the other hand, do not readily accept electrons from attached porphyrins or pyropheophorbides. Electrochemical studies provide the thermodynamic basis for these observations and also allow estimation of the energetics of photoinitiated two-step electron transfer and two-step charge recombination in triad models for photosynthetic charge separation

Study of unstable valences of cadmium and samarium by pulse radiolysis. Influence of complexation by some synthetical ionophores

International Nuclear Information System (INIS)

Lerat-Parizot, O.

1992-01-01

Instable valences of cations in solution are evidenced by pulse radiolysis, in spite of a lifetime often lower than a milli-second they participate to electron transfer reactions, owing to their redox potential. In this work are studied Cd + and Sm 2+ obtained respectively by reduction of Cd 2+ and Sm 3+ by a solvated electron. The reactivity of Cd + in a cryptand and in a coronand is studied; it is a powerful reducing agent (redox potential -2V) going back to the stable valence by electron transfer to an acceptor. Transfer kinetics is studied by reduction of organic molecules, effect of solvents and ligands is also examined. For samarium the reduction kinetics by hydrated electrons is increased when the ion is in a cryptand in agreement with electrochemical observations, showing that the valence 2+ is stabilized in respect to the valence 3+ for lanthanides. The difference of behaviour between Cd + and Sm 2+ is probably due to the fact that for Cd the transferred electron comes from the external layer and for Sm it is a f electron protected by the 5s and 5p orbitals

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.

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

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

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

One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone and some of its transition metal complexes in aqueous solution and in aqueous isopropanol-acetone-mixed solvent: a steady-state and pulse radiolysis study

International Nuclear Information System (INIS)

Das, S.; Bhattacharya, A.; Mandal, P.C.; Rath, M.C.; Mukherjee, T.

2002-01-01

One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone (DHA) and its complexes with Cu(II), Ni(II) and Fe(III), by acetone ketyl radical, (CH 3 ) 2 C·OH, was carried out in aqueous solution and in aqueous isopropanol acetone mixed solvent using both steady-state gamma radiolysis and pulse radiolysis techniques. The rate constants for the reduction of DHA at different pH values by the ketyl radical are in the order of ∼10 9 dm 3 mol -1 s -1 , whereas those for the metal complexes are comparatively less. These rate constants are, however, in conformity with the one-electron reduction potentials of the ligand in free DHA and in its metal complexes. Decay kinetics of the one-electron reduced semiquinones of the free ligand and its metal complexes suggest disproportionation of the semiquinone in the case of the free ligand and intermolecular electron transfer from the co-ordinated semiquinone radical to the metal centre in the case of the metal complexes

Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one). 2: A comparative study on edaravone derivatives

International Nuclear Information System (INIS)

Hata, Kuniki; Katsumura, Yosuke; Lin, M.; Yamashita, Shinichi; Muroya, Yusa; Fu Haiying; Nakagawa, Hidehiko

2011-01-01

A comparative study using the pulse radiolysis technique was carried out to investigate transient absorption spectra and rate constants for the reactions of OH radical and N 3 radical with edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) and its four analogue compounds, 1,3-dimethyl-2-pyrazolin-5-one, 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one, 1-phenyl-3-trifluoromethyl-2-pyrazolin-5-one and 1-(4-chlorophenyl)-3-methyl-2-pyrazolin-5-one. The results showed that, unlike reaction mechanisms previously proposed, the phenyl group of edaravone played an important role in the reaction with OH radical and OH adducts to the phenyl group were formed. Quantum chemical calculations also strongly supported this attribution and suggested that the most favorable site for attacks by OH radical is the ortho position of the phenyl group. Moreover, the rate constants for the reactions of edaravone and its analogues towards OH radical and N 3 radical were about 8.0 x 10 9 , and 4.0 x 10 9 dm 3 mol -1 s -1 , respectively. Edaravone displayed higher reactivity compared to the others, in contrast to a previous report in which 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one showed the highest reactivity towards Hydroxyl radical OH. (author)

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.

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.

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

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

One-electron reduction of 9,10-anthraquinone, 1-amino-9,10-anthraquinone and 1-hydroxy-9,10-anthraquinone in aqueous-isopropanol-acetone mixed solvent: a pulse radiolysis study

International Nuclear Information System (INIS)

Pal, H.; Mukherjee, T.; Mittal, J.P.

1994-01-01

The semiquinone radicals produced by one-electron reduction of 9,10-anthraquinone, 1-amino- 9,10-anthraquinone and 1-hydroxy-9,10-anthraquinone have been characterized in aqueous-organic mixed solvent comprising of 30.2 mol dm -3 water, 5 mol dm -3 isopropanol and 1 mol dm -3 acetone, using the pulse radiolysis technique. Spectroscopic characteristics, the kinetic parameters of formation and decay and one acid dissociation constants of the semiquinones and one-electron reduction potentials of the quinones have been estimated. The characteristics of the present semiquinone systems have been compared with those of other similar systems. The observed differences in characteristics of the semiquinones due to different substitutions have been analysed. (Author)

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 ...

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)

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

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

High Doses Gamma Radiolysis of PVC: Mechanisms of Degradation

International Nuclear Information System (INIS)

Colombani, J.

2006-01-01

PVC radiolysis leads to the formation of various degradation products: radicals, gas, oxidized products or polyenes. In order to predict the formation of the degradation products with regard to irradiation and ageing parameters, it is important to improve the understanding of the radiolysis mechanisms of PVC. Thus, we used several analytical techniques (Electron Spin Resonance, Fourier Transform Infrared spectroscopy, Nuclear Magnetic Resonance, Size Exclusion Chromatography) to get information on PVC samples irradiated at high doses (up to 4MGy) under different conditions. Gamma irradiation induces the formation of various radicals into PVC. Older studies were generally focused on the effect of low dose and/or low temperature irradiations on PVC. We present here ESR signals of PVC irradiated at high doses and at room temperature. We show that peroxyl radicals are producted by radiolysis under aerobe conditions and that polyenyl radicals are formed under anaerobe conditions. PVC radiolysis induces gas production and especially hydrogen chloride. Production of hydrogen chloride is well known until 1 MGy. We have studied by FTIR, the evolution of the quantity of HCl produced until 4 MGy. We show that higher irradiation dose leads to the lower radiolytic yield of HCl (G(HCl)). Moreover, G(HCl) obtained in aerobe conditions is about fourfold as great as G(HCl) observed in anaerobe radiolysis. Propagation and termination reactions induce degradation products: polyene sequences and crosslinking reactions are observed under anaerobe conditions; oxidized products with addition of chain scissions are formed under aerobe conditions. Although the literature about PVC radiolysis is rich, the main reacting pathways are not well established. Moreover the high doses studies are almost non-existent. We show by FTIR that aerobe radiolysis induces formation of ketons and acids. NMR experiments confirme these results but also focuse on small acids formed (with 2, 3 or 4 carbons). The

Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one). 2: A comparative study on edaravone derivatives

Energy Technology Data Exchange (ETDEWEB)

Hata, Kuniki; Katsumura, Yosuke [Tokyo Univ., School of Engineering, Tokyo (Japan); Lin, M; Yamashita, Shinichi [Japan Atomic Energy Agency, Advanced Science Research Center, Tokai, Ibaraki (Japan); Muroya, Yusa [Tokyo Univ., Nuclear Professional School, Tokai, Ibaraki (Japan); Haiying, Fu [Chinese Academy of Sciences, Shanghai (China); Nakagawa, Hidehiko [Nagoya City Univ., Graduate School of Pharmaceutical Sciences, Nagoya, Aichi (Japan)

2011-01-15

A comparative study using the pulse radiolysis technique was carried out to investigate transient absorption spectra and rate constants for the reactions of OH radical and N{sub 3} radical with edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) and its four analogue compounds, 1,3-dimethyl-2-pyrazolin-5-one, 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one, 1-phenyl-3-trifluoromethyl-2-pyrazolin-5-one and 1-(4-chlorophenyl)-3-methyl-2-pyrazolin-5-one. The results showed that, unlike reaction mechanisms previously proposed, the phenyl group of edaravone played an important role in the reaction with OH radical and OH adducts to the phenyl group were formed. Quantum chemical calculations also strongly supported this attribution and suggested that the most favorable site for attacks by OH radical is the ortho position of the phenyl group. Moreover, the rate constants for the reactions of edaravone and its analogues towards OH radical and N{sub 3} radical were about 8.0 x 10{sup 9}, and 4.0 x 10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, respectively. Edaravone displayed higher reactivity compared to the others, in contrast to a previous report in which 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one showed the highest reactivity towards Hydroxyl radical OH. (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

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)

Pulse radiolysis studies on the formation and transformation of the one-electron reduced intermediate of Kalafungin and an analogue solution

International Nuclear Information System (INIS)

Anderson, R.F.; Packer, J.E.; Brimble, A.; Nairn, M.R.

1996-01-01

Kalafungin 1 is a member of the pyranonaphthoquinone family of antibiotics which are produced various species of Streptomyces and have in common the benzoisochromanquinone skeleton. Apart from their already documented activity against Gram-positive bacteria, fungi, and mycoplasmas, it has been suggested that in vivo reduction causes a transformation to an active hydroquinone form which functions as a bis-alkylating agent. 2 Moore 2 , 3 has suggested that these pyranonaphthoquinones may exhibit antitumour activity since the proposed mechanism of action resembles that of the anticancer agent mitomycin C 3. 2 . Rapid one-electron reduction of kalafungin 1 and a closely related analogue 2 has been carried out using The University of Auckland's pulse radiolysis facility. Pulsed electrons (4 Gy in 200 ns from a 4 MeV linear accelerator) were delivered to de-aerated aqueous solutions (10 mmol.L -1 phosphate, pH 7.0) containing 0.1 mol.L -1 sodium formate and 50 - 200 μmol.L -1 kalafungin 1 or lactol 2. Radical formation and transformations were followed by time-resolved uv/visible spectrophotometry. The transformations observed are independent of both the concentration of the parent compound and radiation doses (i.e. semiquinone concentration). The accompanying changes in absorption are consistent with the radical centre of the semiquinone species undergoing intramolecular rearrangement onto the fused non-aromatic ring structure of the compound. Possible ring opening mechanisms and the position of radical relocalisation will be discussed, as well as the involvement of radical transformation and redox chemistry in the biological activity of kalafungin1

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.

Pulse radiolysis study of aqueous cyanamide solutions

International Nuclear Information System (INIS)

Draganic, I.G.; Draganic, Z.D.; Sehested, K.

1978-01-01

The radiolysis of oxygen-free, aqueous solutions of cyanamide was studied by fast kinetic spectrophotometry. Computer simulation of the reaction mechanisms was used to evaluate the experimental data. Four different species are identified: (1) the radical anion (NH 2 CN) - absorbing light in the UV with lambda/sub max/ 240 = 1500 M -1 cm -1 ; the disappearance is a second-order process with 2k = 1.3 x 10 9 M -1 s -1 ; (2) the hydrogen adduct, NH 2 C(H) double bond N (or NH 2 C double bond NH), with lambda/sub max/ 300 nm and epsilon 300 = 150 M -1 cm -1 decaying by second-order kinetics with 2k = 3.1 x 10 9 M -1 s -1 ; (3) the hydroxyl radical preferentially adds to the cyano group, NH 2 C(OH) double bond N (or NH 2 C double bond NOH). This species rearranges in the submicrosecond scale to NH 2 C ( double bond O) NH (lambda/sub max/ 325 nm and epsilon/sub 325 = 1900 M -1 cm -1 ) and disappears by a second-order process with 2k = 6.3 x 10 9 M -1 s -1 . (4) It is estimated that about 10% of OH radicals attack the substituent group and by H abstraction produce the NHCN radical (lambda/sub max/ 370 nm and epsilon 370 = 1800 M -1 cm -1 ); it disappears by a pseudo-first-order process attributed to a hydrolysis reaction. At increasing acidities, protonation of this radical takes place, NHCN + H + → + NH 2 CN; the protonated form decays faster and absorbs more strongly. In a cyanamide solution containing S 2 O 8 2- , the SO - 4 . radicals react with cyanamide, k = 1 x 10 8 M -1 s -1 , producing + NH 2 CN radicals. The dependence of the optical density at 325 nm on the dose rate and solute concentration are quantitatively consistent with the assumption that the OH radicals react with the NH 2 C(=O)NH species with k = 4 x 10 9 M -1 s -1

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)

4-Amino-3H-pyrimidin-2-one ('isocytosine') is a short-lived non-radical intermediate formed in the pulse radiolysis of cytosine in aqueous solution

International Nuclear Information System (INIS)

Nien Schuchmann, Man; Naumov, Sergej; Schuchmann, Heinz-Peter; Sonntag, Justus von; Sonntag, Clemens von

2005-01-01

In the pulse radiolysis of 2'-deoxycytidine (dCyd) in N 2 O-saturated solutions containing 0.5M tertiary butanol to completely scavenge the water radicals, a short-lived intermediate (λmax=287nm) is observed by UV spectroscopy which is attributed to dCydH + , generated in the reaction of dCyd with H + formed during the pulse. By reacting with OH - , which is formed in the pulse in amounts matching that of H + , this intermediate disappears in the μs time range without a change of the spectrum. Similarly, cytosine (Cyt) gives rise to CytH + which, in contrast, in part transforms into another species (λmax=286nm) which can be assigned to isocytosine 1, 4-amino-3H-pyrimidin-2-one, a tautomer of Cyt which is formed by two routes (i) deprotonation of CytH + at N(1) by OH - and (ii) deprotonation of Cyt and reprotonation of the Cyt anion by water at N(3). Compared to Cyt, 1 is richer in Gibbs' free enthalpy by 14kJmol -1 . Its presence in low equilibrium concentrations has also been observed by conventional UV spectroscopy, making use of the increase of its equilibrium concentration with increasing temperature. From these data, an absorption coefficient of 3.3x10 4 dm 3 mol -1 cm -1 at 286nm has been calculated. Supporting quantum chemical calculations are also reported

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.

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)

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 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

Radical production in the radiolysis of benzene

International Nuclear Information System (INIS)

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

1998-01-01

Complete text of publication follows. Benzene is the prototypical aromatic compound and yet the radiation chemistry of the radicals formed in its radiolysis is not well understood. Temporal information on the yield of phenyl radical, the major radical produced in the radiolysis, is important for understanding the radiation chemistry of many other types of aromatic compounds including some polymers. The effects of track structure on the production of phenyl radicals have been examined using iodine-scavenging techniques. The variation of the yields of iodobenzene and the other major molecular products such as biphenyl as a function of iodine concentration gives a good indication of the competition kinetics occurring in particle tracks. Experimental results of the scavenger experiments will be shown and their implications in the radiolysis of condensed hydrocarbons will be discussed

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

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

Pulse radiolytic and spectrophotometric investigation of the binding of bilirubin to bovine serum albumin

International Nuclear Information System (INIS)

Adhikari, S.; Guha, S.N.; Gopinathan, C.

1994-01-01

Bilirubin (BR) exhibits marked change in its absorption properties in the presence of bovine serum albumin (BSA). The λ max of BR observed at 440 nm is red shifted by about 20 nm with 8% increase in band intensity when BSA is present in the matrix. Medium polarity and salt effects were also studied in this system and it was inferred that BR is bound to BSA to form a complex, which becomes unstable at high salt concentration or in a medium of low dielectric constant such as water-alcohol mixture. Pulse radiolysis study of this system employing CO 2 .- radical revealed that BR blocks the sites of CO 2 .- attack in the BSA molecule. (author). 3 refs., 2 figs

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.

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)

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

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

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

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).

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)

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.

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.)

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

Analysis of water radiolysis in relation to stress corrosion cracking of stainless steel at high temperatures - Effect of water radiolysis on limiting current densities of anodic and cathodic reactions under irradiation

International Nuclear Information System (INIS)

Ishigure, Kenkichi; Nukii, Takashi; Ono, Shoichi

2006-01-01

Electrochemical corrosion potential (ECP) is an important measure for environmental factor in relation to stress corrosion cracking (SCC) of metal materials. In the case of SCC for in-core materials in nuclear reactors, radiolysis of coolant water decisively controls ECP of metal materials under irradiation. In the previous models for ECP evaluation of stainless steel, radiolysis of reactor water in bulk was considered to calculate the bulk concentrations of the radiolysis products. In this work, the radiolysis not only in bulk but also in the diffusion layer at the interface between stainless steel and bulk water was taken into account in the evaluation of ECP. The calculation results shows that the radiolysis in the diffusion layer give significant effects on the limiting current densities of the redox reactions of the radiolysis products, H 2 O 2 and H 2 , depending on dose rate, flow rate and water chemistry, and leads to the significant increase in the ECP values in some cases, especially in hydrogen water chemistry conditions

Pulse-radiolytic investigation of the reduction of titanium(III) ions in aqueous solutions

International Nuclear Information System (INIS)

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

1979-01-01

The absorption spectrum and decay kinetics of intermediates formed by the reaction of titanium(III) ions with H atoms, hydrated electrons, and carboxyl radicals have been studied in aqueous solution using the pulse-radiolysis technique. The product of the reaction with H atoms in acid solution is a Ti 3+ -H hydride intermediate which decomposes by a first-order process with a half-life of ca. 3 s. Titanium(II) is formed by reaction with hydrated electrons and CO 2 H radicals. The absorption spectrum of titanium(II) and the kinetics of its reactions are reported and discussed. The formation of molecular hydrogen by reaction of Ti 2+ with water is suppressed by the other solutes in the solutions. Titanium(III) reacts with CO 2 H, CH 2 CO 2 H, and CH(CO 2 H) 2 radicals to give titanium-radical complexes. (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

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

Investigation of molecular mechanisms in photodynamic action and radiobiology with nanosecond flash photolysis and pulse radiolysis. Progress report, July 1, 1974--June 30, 1975

International Nuclear Information System (INIS)

Grossweiner, L.I.

1975-01-01

Initial mechanisms in the UV photooxidation of aromatic amino acids are being investigated with laser flash photolysis at 265 nm in connection with enzyme inactivation. Aqueous tryptophan (Trp) is photoionized by an efficient monophotonic process, followed by a hitherto unreported pseudo-first order recombination competing with bimolecular e - /sub aq/ decay and electron scavengers. Measurements of the photoionization quantum efficiency, the aromatic radical extinction coefficients, and the electron decay kinetics are reported. The flash photolysis of N-formylkynurenine (FK) has been studied in connection with its role in ''internal'' photodynamic action in bovine carbonic anhydrase (BCA). The triplet state of FK oxidizes Trp to the radical formed also by UV photolysis, leading to the FK semiquinone which reacts with oxygen to produce O 2 - . The same FK semiquinone species is formed by radiolytic reduction by e - /sub aq/ and CO 2 - . A parallel radiolysis study on BCA using radical anions as probes of specific residues has shown that the zinc atom protects against the inactivating attack of e - /sub aq/ and CO 2 - . Evidence for sensitive aromatic residues in BCA has been found with this technique. Photodynamic damage to biological membranes is being studied with spin label ESR methods. New work is reported on damage to unsaturated lipids sensitized by Eosin based on changes in the temperature-dependence of the spin label rotational correlation time. Preliminary results with diploid yeast membranes (Saccharomyces cerevisiae) show a loosening of the structure accompanying photodynamic inactivation. (U.S.)

Gel chromatographic investigations for the radiolysis of cattle serum albumin and desoxyribonucleic acid

International Nuclear Information System (INIS)

Leithner, L.H.

1983-01-01

Aqueous solutions of RSa, DNA and solutions which contained both substances were irradiated under N 2 , O 2 and N 2 O. The products of radiolysis were examined by gel chromatography, where after treatment with sodium dodecyl sulphate and mercapto-ethanol, the proportion of non-covalent combinations and of disulphide groups was determined. If one irradiates RSA solutions under N 2 and N 2 O, the yield of aggregate and the molecular size of the particles in the aggregate rise with the dose of radiation, until at the maximum dose of 1714 Gy, all RSA molecules are aggregated by covalent combination. Dimers are first formed under N 2 , and dimers and trimers are formed under N 2 O. The radiolysis of RSA under O 2 leads to the formation of protein fractions. When DNA solutions are irradiated with a dose of 857 Gy, then regardless of the existing gas condition, only DNA fractions are formed. The irradiation of sample solutions, which contain both RSA and DNA, shows that combinations of protein and nucleic acid only occur under N 2 and N 2 O, but not under O 2 . The decomposition of DNA under N 2 is largely prevented in the presence of protein, while under N 2 O DNA is decomposed. Although the cross linkages between the DNA and the RSA were missing, irradiation under O 2 in the presence of protein only led to partial decomposition of DNA, as the primary radicals of the water were collected by the protein. (orig.) [de

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)

Radiolysis of the polyethylene/water system: Studies on the role of hydroxyl radical

Energy Technology Data Exchange (ETDEWEB)

Billamboz, Nicolas [Laboratoire de Chimie Physique et Rayonnement Alain Chambaudet, UMR CEA E4, Universite de Franche-Comte, 16 route de Gray, 25030 Besancon Cedex (France); Grivet, Manuel, E-mail: manuel.grivet@univ-fcomte.f [Laboratoire de Chimie Physique et Rayonnement Alain Chambaudet, UMR CEA E4, Universite de Franche-Comte, 16 route de Gray, 25030 Besancon Cedex (France); Foley, Sarah [Laboratoire de Chimie Physique et Rayonnement Alain Chambaudet, UMR CEA E4, Universite de Franche-Comte, 16 route de Gray, 25030 Besancon Cedex (France); Baldacchino, Gerard [CEA, IRAMIS, SIS2M, Laboratoire de Radiolyse, Bat. 546, F-91191 Gif-sur-Yvette (France); CNRS, Laboratoire Claude Frejacques, F-91191 Gif-sur-Yvette (France); Hubinois, Jean-Charles [CEA, DAM, Valduc, F-21120 Is-sur-Tille (France)

2010-01-15

The role of hydroxyl radical on polyethylene degradation under aqueous conditions has been studied. The reactivity of HO{sup .} towards PE is highlighted by pulse radiolysis experiments on a PE powder suspension in water using the thiocyanate competition technique. Infrared analysis of PE films irradiated in the presence of water is performed. Solutions have been either degassed with Ar, in order to remove O{sub 2} which would react with the PE, or N{sub 2}O which enhances the production of HO{sup .} radicals. Oxygenated groups and double bond groups created at the surface of PE are characterized using IR analysis, and the results for both saturated solution systems are compared.

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)

Prediction of spur overlap time, radical yield profiles, and decomposition of trichloroethylene induced by various pulse types of electron beam

International Nuclear Information System (INIS)

Kim, D.-W.; Han, K.-C.; Lee, W.-K.; Ihm, S.-K.

1996-01-01

A kinetic model was suggested to compute the yield profiles of primary radicals generated from water radiolysis. For various cases including pulse radiolysis and steady irradiation time of spur overlap was computed in order to ensure homogeneity over the entire system. As a result, consistency to roughly first order kinetics was resulted for decomposition of 1 ppm trichloroethylene (TCE) and slight deviation from the linear model was predicted for 10 ppm TCE. (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)

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

γ-Irradiation-induced radiolysis of inulin in aqueous solutions

International Nuclear Information System (INIS)

Tsyba, I.A.; Revina, A.A.; Shostenko, A.G.

1997-01-01

Radiochemical transformations of inulin in aqueous solutions, in air, in the presence of inert gases, helium, nitrogen and in nitrous oxide exposed to various doses of 60 Co γ-irradiation were investigated. It was shown that interactions in inulin with OH radicals are principally responsible for radiolytic decomposition of inulin. The data on radiolysis of more simple model systems were used to make available decomposition spectra of γ-irradiated aerated aqueous solution of inulin. 9 refs., 6 figs

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 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

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)

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)

Decomposition of PCBs in oils using gamma radiolysis

International Nuclear Information System (INIS)

Mincher, B.J.; Arbon, R.E.; Schwendiman, G.L.

1996-01-01

This paper investigates the radiolysis of the polychlorinated biphenyls (PCBs) in several oil matrices. The results of mechanism and kinetic studies in isooctane are presented. The decomposition of PCBs in isooctane is shown to occur by reductive dechlorination due to electron capture and to proceed with pseudo-first-order kinetics. The rate is dependent on the initial PCB concentration. Electron capture detection gas chromatograms confirm that dechlorination also occurs with commercial Aroclor PCBs in irradiated transformer and hydraulic oils. The results of a demonstration experiment involving PCB contaminated waste hydraulic oils are presented

Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

International Nuclear Information System (INIS)

Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

2006-01-01

Room-temperature ionic liquids, which are nonvolatile and nonflammable, have been proposed as 'green solvents' for new applications in chemical synthesis, separation chemistry, electrochemistry and other areas. In the separation chemistry, the hydrophobic ionic liquids have been practically expected to be alternative to traditional organic solvents for solvent extraction of 4f and 5f elements from the viewpoints of the immiscibility in water, especially in the spent nuclear fuel reprocessing. However, the chemical reaction or kinetics studies are important to apply the ionic liquids for various processes. To understand the effects of ionic liquids on chemical reactions, pulse radiolysis studies of ionic liquid have been carried out on nanosecond scale by using a 27 MeV electron beam and an analyzing light source of xenon lamp. In the experiment, a hydrophobic ionic liquid of diethylmethyl(2-methoxy)ammonium-bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI) salt was used. The ionic liquid of DEMMA-TFSI was prepared by reacting equimolar amounts of diethylmethyl(2-methoxy)ammonium chloride (C 10 H 20 F 6 N 2 O 5 S 2 Cl, >98%, Nisshinbo) with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , SynQuest Labs., Inc.) in aqueous solutions at room temperature. The ionic liquid was separated from the aqueous phase, purified by repeated extractions with water to LiCl and excess reagent, and finally dried at 110 degree C under vacuum. The transient absorptions of the ionic liquid were measured at wavelengths from 350 to 1400 nm, in which two photodiodes of silicon ( 1000 nm) were used. The spectrum of solvated electrons in the ionic liquid of DEMMA-TFSI was obtained with an absorption peak of 1060 nm and a wide bandwidth of about 600 nm (FWHM). The decay constant of the solvated electrons in the ionic liquid was 1.54 x 10 7 s -1 , which is independent on the wavelength. The absorption peak of the spectrum was blue-shifted from 1060 to 780 nm with increasing water

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)

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)

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)

Investigating Pulsed Discharge Polarity Employing Solid-State Pulsed Power Electronics

DEFF Research Database (Denmark)

Davari, Pooya; Zare, Firuz; Blaabjerg, Frede

2015-01-01

condition plays an important role in maintaining the desired performance. Investigating the system parameters contributed to the generated pulses is an effective way in improving the system performance further ahead. One of these parameters is discharge polarity which has received less attention....... In this paper, effects of applied voltage polarity on plasma discharge have been investigated in different mediums at atmospheric pressure. The experiments have been conducted based on high voltage DC power supply and high voltage pulse generator for point-to-point and point-to-plane geometries. Furthermore......, the influence of electric field distribution is analyzed using Finite Element simulations for the employed geometries and mediums. The experimental and simulation results have verified the important role of the applied voltage polarity, employed geometry and medium of the system on plasma generation....

One electron transfer equilibria and redox potentials of radicals studies by pulse radiolysis. Progress report, September 1, 1975--July 1, 1976

International Nuclear Information System (INIS)

Meisel, D.; Czapski, G.

1976-01-01

The pulse radiolysis technique is utilized for measurements of the equilibrium constants for electron transfer between the durosemiquinone radical anion and oxygen, menadione and indigo disulfonate. These equilibrium constants are in turn used for calculations of one-electron redox potentials for these systems. Each of these equilibrium constants was determined experimentally and independently and found to be self consistent. Only for the reactions of the semiquinones with oxygen could the electron transfer reaction be followed directly. For the reactions between the various quinone/semiquinone systems substantial indirect evidence is presented that these equilibria are achieved rapidly. In those cases equilibrium constants were determined from studies of the effect of quinone concentrations on the relative yields of the semiquinones. A method for distinguishing between kinetic competition and equilibrium is outlined and its usefulness is emphasized. The DQ/DQ - (DQ = duroquinone) and IDS/IDS - (IDS = indigo disulfonate) systems were employed as reference couples as the redox potentials for those systems are either available in the literature (IDS/IDS - ) or may be calculated from available data (DQ/DQ - ). Taking E 7 1 , the redox potential for the first one-electron reduction step at pH 7, of DQ/DQ - as -0.235 volts or of IDS/IDS - as -0.125 volts, both yield E 7 1 = -0.325 V for the O 2 /O 2 - system (1 atm O 2 ) and E 7 1 = -0.20 for the menadione system

Investigations Of A Pulsed Cathodic Vacuum Arc

Science.gov (United States)

Oates, T. W. H.; Pigott, J.; Denniss, P.; Mckenzie, D. R.; Bilek, M. M. M.

2003-06-01

Cathodic vacuum arcs are well established as a method for producing thin films for coatings and as a source of metal ions. Research into DC vacuum arcs has been going on for over ten years in the School of Physics at the University of Sydney. Recently a project was undertaken in the school to design and build a pulsed CVA for use in the investigation of plasma sheaths and plasma immersion ion implantation. Pulsed cathodic vacuum arcs generally have a higher current and plasma density and also provide a more stable and reproducible plasma density than their DC counterparts. Additionally it has been shown that if a high repetition frequency can be established the deposition rate of pulsed arcs is equal to or greater than that of DC arcs with a concomitant reduction in the rate of macro-particle formation. We present here results of our investigations into the building of a center-triggered pulsed cathodic vacuum arc. The design of the power supply and trigger mechanism and the geometry of the anode and cathode are examined. Observations of type I and II arc spots using a CCD camera, and cathode spot velocity dependence on arc current will be presented. The role of retrograde motion in a high current pulsed arc is discussed.

Investigations Of A Pulsed Cathodic Vacuum Arc

International Nuclear Information System (INIS)

Oates, T.W.H.; Pigott, J.; Denniss, P.; Mckenzie, D.R.; Bilek, M.M.M.

2003-01-01

Cathodic vacuum arcs are well established as a method for producing thin films for coatings and as a source of metal ions. Research into DC vacuum arcs has been going on for over ten years in the School of Physics at the University of Sydney. Recently a project was undertaken in the school to design and build a pulsed CVA for use in the investigation of plasma sheaths and plasma immersion ion implantation. Pulsed cathodic vacuum arcs generally have a higher current and plasma density and also provide a more stable and reproducible plasma density than their DC counterparts. Additionally it has been shown that if a high repetition frequency can be established the deposition rate of pulsed arcs is equal to or greater than that of DC arcs with a concomitant reduction in the rate of macro-particle formation. We present here results of our investigations into the building of a center-triggered pulsed cathodic vacuum arc. The design of the power supply and trigger mechanism and the geometry of the anode and cathode are examined. Observations of type I and II arc spots using a CCD camera, and cathode spot velocity dependence on arc current will be presented. The role of retrograde motion in a high current pulsed arc is discussed

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

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)

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.

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

The analysis of radiolysis impurities in 18F-FDG and methods of repurification

International Nuclear Information System (INIS)

Jinming Zhang; Yungang Li; Jian Liu; Xiaojun Zhang; Jiahe Tian

2010-01-01

To investigate the radio impurity in the radiolysis of 18 F-FDG at high radiodose and radioconcentrated solutions and develop methods of repurification. The radiolysis of 18 F-FDG was analyzed by TLC. The radio-impurity was confirmed by biodistribution and small animal PET/CT studies. 18 F-FDG was unstable at high radioconcentration over 37 GBq/mL or under basic condition. TLC, biodistribution and PET/CT all indicated that the main autoradiolysis byproduct was free fluoride ion. The radiolyzed 18 F-FDG was repurified by solid-phase extraction (SPE) column. The repurified 18 F-FDG had a radiochemical purity (RCP) of over 99% and significantly lower bone uptake than that was before repurification (P = 0.0003). There was a positive correlation between the recovery yield and the purity of 18 F-FDG (R 2 = 0.66). (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...

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 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.

Formation of peroxynitrite from the oxidation of hydrogen peroxide by nitrosonium ion (NO+): A pulse radiolysis study

International Nuclear Information System (INIS)

Goldstein, S.; Czapski, G.

1996-01-01

The rate constant of the reaction of sm-bullet N 3 with sm-bullet NO has been determined to be (4.4 ± 0.5) x 10 9 M -1 s -1 using the pulse radiolysis technique at pH 7.6-8.3 and 21 degrees C. The reaction of sm-bullet 3 with sm-bullet NO takes place through an innersphere electron-transfer mechanism yielding N 3 NO as an intermediate, which subsequently decays to N 2 O and N 2 . Peroxynitrite was formed when H 2 O 2 was added to the sm-bullet N 3 / sm-bullet NO system at pH 5.8-8.3. The maximum yield of peroxynitrite, which was obtained at [H 2 O 2 ] > 0.2 M, was ∼34% of the initially produced sm-bullet N 3 , indicating that N 3 NO does not react directly with H 2 O 2 . The authors conclude that, in the presence of high concentrations of H 2 O 2 , ∼64% of the N 3 NO decomposes into N 2 O and N 2 , whereas the remaining 34% yields NO + or H 2 NO 2 + , which subsequently reacts with H 2 O 2 to form peroxynitrite. The comparison of kinetic results with those obtained previously in the H + /HNO 2 /H 2 O 2 system shows that the nitrosating species in both systems differ. As H 2 NO 2 + is the precursor of NO + in the H + /HNO 2 /H 2 O 2 system, the authors conclude that the reactive intermediate in this system is most probably NO + . From the dependence of the yield of peroxynitrite on [H 2 O 2 ], the ratio between the rate constants of the reactions of NO + with H 2 O 2 and H 2 O was determined to be 65 M -1 . These rate constants were estimated to be k 7 > 3 x 10 8 and k -4 [H 2 O] > 4.6 x 10 6 s -1 , respectively

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.)

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

Pulse-radiolytic one-electron reduction of anthraquinone and chloro-anthraquinones in aqueous-isopropanol-acetone mixed solvent

International Nuclear Information System (INIS)

Rath, M.C.; Pal, H.; Mukherjee, T.

1996-01-01

One-electron reduction of 9,10-anthraquinone and some chloro-anthraquinones and the characteristics of the semiquinones thus formed have been investigated in aqueous-isipropanol-acetone mixed solvent using electron pulse radiolysis technique. Spectroscopic characteristics, kinetic parameters of formation and decay, and the acid/base behaviour of the semiquinones have been investigated. The one-electron reduction potential of the quinones have been measured following electron transfer equilibria with a reference redox system (methyl viologen) and the values thus obtained have been compared with those of some other anthrasemiquinone systems. An analysis of the characteristics of the semiquinones shows that α-chloro substituents adjacent to the C=O group act as electron withdrawing groups. (author)

Quatenary structure of methemoglobin II. Pulse radiolysis study of the binding of oxygen to the valence-hybrid. Progress report, December 1, 1978-November 30, 1979

International Nuclear Information System (INIS)

Chevion, M.; Ilan, Y.A.; Samuni, A.; Navok, T.; Czapski, G.

1979-01-01

The pulse-radiolysis of solutions of adult human methemoglobin was used in order to reduce a single heme-iron within the protein tetramers. The valence-hybrids thus formed were reacted with oxygen. Kinetics of the reactions were studied. The effects of pH and inositol-hexaphosphate were examined. The kinetics of the ligation of oxygen to stripped valence-hybrids showed a single-phase behavior at the pH range 6.5 to 9. As the pH was lowered below 6.5 a second, slower phase became apparent. In the presence of IHP, above pH 8, the kinetics of oxygem binding was of a single phase. As the pH was lowered a transition to a second, slower phase was noticed. Below pH 7 the slower phase was the only detectable one. The analysis of the relative contribution of the faster phase to the total reaction as a function of the pH showed a typical transition curve characterized by a pK = 7.5 and a Hill parameter n =2.9. On the basis it is concluded that human adult stripped methemoglobin resides in an R quarternary structure while the presence of IHP stabilizes the T structure at pH below 7.5

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.)

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)

Method for pulse to pulse dose reproducibility applied to electron linear accelerators

International Nuclear Information System (INIS)

Ighigeanu, D.; Martin, D.; Oproiu, C.; Cirstea, E.; Craciun, G.

2002-01-01

An original method for obtaining programmed beam single shots and pulse trains with programmed pulse number, pulse repetition frequency, pulse duration and pulse dose is presented. It is particularly useful for automatic control of absorbed dose rate level, irradiation process control as well as in pulse radiolysis studies, single pulse dose measurement or for research experiments where pulse-to-pulse dose reproducibility is required. This method is applied to the electron linear accelerators, ALIN-10 of 6.23 MeV and 82 W and ALID-7, of 5.5 MeV and 670 W, built in NILPRP. In order to implement this method, the accelerator triggering system (ATS) consists of two branches: the gun branch and the magnetron branch. ATS, which synchronizes all the system units, delivers trigger pulses at a programmed repetition rate (up to 250 pulses/s) to the gun (80 kV, 10 A and 4 ms) and magnetron (45 kV, 100 A, and 4 ms).The accelerated electron beam existence is determined by the electron gun and magnetron pulses overlapping. The method consists in controlling the overlapping of pulses in order to deliver the beam in the desired sequence. This control is implemented by a discrete pulse position modulation of gun and/or magnetron pulses. The instabilities of the gun and magnetron transient regimes are avoided by operating the accelerator with no accelerated beam for a certain time. At the operator 'beam start' command, the ATS controls electron gun and magnetron pulses overlapping and the linac beam is generated. The pulse-to-pulse absorbed dose variation is thus considerably reduced. Programmed absorbed dose, irradiation time, beam pulse number or other external events may interrupt the coincidence between the gun and magnetron pulses. Slow absorbed dose variation is compensated by the control of the pulse duration and repetition frequency. Two methods are reported in the electron linear accelerators' development for obtaining the pulse to pulse dose reproducibility: the method

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)

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.).

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)

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

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

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

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.)

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)

Structure and dynamics of paramagnetic transients by pulsed EPR and NMR detection of nuclear resonance

International Nuclear Information System (INIS)

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

Unimolecular H2 elimination during the liquid phase radiolysis and photolysis of alkane - alkane mixtures

International Nuclear Information System (INIS)

Wojnarovits, L.; Foeldiak, G.

1980-01-01

Unimolecular H 2 elimination from alkanes was investigated in cyclopentane-cyclohexane, n-hexane-cyclohexane and cyclohexane-cyclooctane mixtures during fluradiolysis and 7.6 eV photolysis. During the radiolysis of all systems, and when the fluorescence shift law allowed it, during the photolysis as well, inhibited H 2 detachment was observed from the first component and sensitized hydrogen molecule elimination from the second. It has been concluded that the same excited state (the lowest singlet, S 1 ) is responsible for the H 2 elimination during radiolysis and photolysis and this is that one that gives rise to fluorescence in the experiments of other authors. The H 2 and H elimination from alkanes generally have different excited precursors. The direct population of S 1 by γ-irradiation is of limited importance and this intermediate is mainly produced in ''charge neutralization'' processes. (author)

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.

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)

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.

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

Investigation of laser plasma instabilities using picosecond laser pulses

International Nuclear Information System (INIS)

Kline, J L; Montgomery, D S; Yin, L; Flippo, K A; Shimada, T; Johnson, R P; Rose, H A; Albright, B J; Hardin, R A

2008-01-01

A new short-pulse version of the single-hot-spot configuration has been implemented to enhance the performance of experiments to understand Stimulated Raman Scattering. The laser pulse length was reduced from ∼200 to ∼3 ps. The reduced pulse length improves the experiment by minimizing effects such as plasma hydrodynamic evolution and ponderomotive filamentation of the interaction beam. In addition, the shortened laser pulses allow full length 2D particle-in-cell simulations of the experiments. Using the improved single-hot-spot configuration, a series of experiments to investigate kλ D scaling of SRS has been performed. Details of the experimental setup and initial results will be presented

Gamma radiolysis and vinyl esters

International Nuclear Information System (INIS)

De Bruyn, H.; Balic, R.; Gilbert, R.G.

1998-01-01

The principle behind γ relaxation of free-radical polymerizations is that the source of initiating radicals can be switched off 'instantaneously'. In the absence of initiating radicals the only kinetic events remaining are propagation, transfer and termination. For monomers whose propagation rate coefficients have been determined, relaxation behaviour can be interpreted to determine radical-loss rate coefficients and test models of loss mechanisms. This technique has been employed successfully on styrene and MMA emulsion polymerizations. In the present study, vinyl acetate and vinyl neo-decanoate (a ten-carbon-branched homologue of vinyl acetate) were studied, with the propagation rate coefficients for both monomers being established by pulsed-laser polymerization. Both were found to exhibit rapid γ relaxation rates in emulsion polymerization. This is a surprising result because mechanisms for rapid relaxation in emulsion polymerizations require that chain transfer to monomer (which is rapid for both monomers) is followed by exit from the particle into the aqueous phase with subsequent re-entry into a radical-containing particle leading to bimolecular termination. It is not unreasonable to suppose that this may be possible for vinyl acetate which is fairly water soluble (∼0.3 M). However, vinyl neo-decanoate is virtually insoluble (∼0.00004 M) and hence desorption is extremely unlikely. The most likely explanation for the observed rapid relaxations is that some of the radicals produced by γ radiolysis are slow to initiate vinyl esters and hence act as radical traps. As vinyl esters are known to be particularly unreactive monomers. it is feasible that this experimental artifact affects them to a much greater extent than some of the monomers studied successfully with this technique in the past

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)

Guanosine radical reactivity explored by pulse radiolysis coupled with transient electrochemistry.

Science.gov (United States)

Latus, A; Alam, M S; Mostafavi, M; Marignier, J-L; Maisonhaute, E

2015-06-04

We follow the reactivity of a guanosine radical created by a radiolytic electron pulse both by spectroscopic and electrochemical methods. This original approach allows us to demonstrate that there is a competition between oxidation and reduction of these intermediates, an important result to further analyse the degradation or repair pathways of DNA bases.

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

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)

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.

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)

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)

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

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.)

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.

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)

Theoretical investigations of quantum correlations in NMR multiple-pulse spin-locking experiments

Science.gov (United States)

Gerasev, S. A.; Fedorova, A. V.; Fel'dman, E. B.; Kuznetsova, E. I.

2018-04-01

Quantum correlations are investigated theoretically in a two-spin system with the dipole-dipole interactions in the NMR multiple-pulse spin-locking experiments. We consider two schemes of the multiple-pulse spin-locking. The first scheme consists of π /2-pulses only and the delays between the pulses can differ. The second scheme contains φ-pulses (0Quantum discord is obtained for the first scheme of the multiple-pulse spin-locking experiment at different temperatures.

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

Air effect on polycarbonate radiolysis; Efeito do ar na radiolise do policarbonato

Energy Technology Data Exchange (ETDEWEB)

Terence, Mauro C.; Araujo, Elmo S.; Guedes, Selma M.L. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

1995-12-31

The formation and decay of radicals in the radiolysis of new type of polycarbonate (G{sub 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.

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

Experimental investigation of electron beam wave interactions utilising short pulses

International Nuclear Information System (INIS)

Wiggins, Samuel Mark

2000-01-01

Experiments have investigated the production of ultra-short electromagnetic pulses and their interaction with electrons in various resonant structures. Diagnostic systems used in the measurements included large bandwidth detection systems for capturing the short pulses. Deconvolution techniques have been applied to account for bandwidth limitation of the detection systems and to extract the actual pulse amplitudes and durations from the data. A Martin-Puplett interferometer has been constructed for use as a Fourier transform spectrometer. The growth of superradiant electromagnetic spikes from short duration (0.5-1.0 ns), high current (0.6-2.0 kA) electron pulses has been investigated in a Ka-band Cherenkov maser and Ka- and W-band backward wave oscillators (BWO). In the Cherenkov maser, radiation spikes were produced with a peak power ≤ 3 MW, a duration ≥ 70 ps and a bandwidth ≤ 19 %. It is shown that coherent spontaneous emission from the leading edge of the electron pulse drives these interactions, giving rise to self-amplified coherent spontaneous emission (SACSE). BWO spikes were produced with a peak power ≤ 63 MW and a pulse duration ∼ 250 ps in the Ka-band and ≤ 12 MW and ∼ 170 ps in the W-band. Evidence of superradiant evolution has been observed in the measurements of scaling laws such as power scaling with the current squared and duration scaling inversely with the fourth root of the power. An X-band free-electron maser amplifier, in which a short (1.0ns) injected radiation pulse interacts with a long (∼ 140 ns) electron beam, has been investigated. The interaction is shown to evolve in the linear regime. The peak output power was 320 kW, which corresponded to a gain, approximately constant across the band, of 42 dB. Changes to the spectrum, that occur when the input radiation pulse is injected into electrons with an energy gradient, have been analysed. (author)

International seminar on structural investigations on pulsed neutron sources. Proceedings

International Nuclear Information System (INIS)

Aksenov, V.L.; Balagurov, A.M.; Taran, Yu.V.

1993-01-01

The proceedings of the International seminar on structural investigations using pulsed neutron sources are presented. The seminar is dedicated to the memory of Dr. Yu.M. Ostanevich, a world acknowledged physicist. The problems of structural analysis using pulsed neutron source at the IBR-2 reactor are discussed

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

Radiolysis of carbohydrates and of carbohydrate-containing foodstuffs

International Nuclear Information System (INIS)

Diehl, J.F.; Adam, S.; Delincee, H.; Jakubick, V.

1978-01-01

Toxicological evaluation of irradiated foodstuffs requires knowledge of radiation-induced chemical changes. A review of the literature reveals much information on the radiation chemistry of pure substances, e.g., dilute solutions of individual carbohydrates. Much less is known about the interactions of food constituents during irradiation. In an effort to remedy this situation, radiation effects on various compounds have been studied in systems of increasing complexity. In one approach, gas chromatography was used to investigate the radiolysis of tehalose in pure solution and in the presence of amino acids or proteins. In another approach, radiation-induced aggregation of proteins and of [ 14 C]tryptophan with proteins was studied in the absence and presence of carbohydrates (trehalose, starch), emulsified sunfower oil, and a mixture of carbohydrates and emulsified sunflower oil

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

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.

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

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

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

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.

Pulse radiolytic one-electron reduction of 1,4-amino and hydroxy disubstituted 9,10-anthraquinones

International Nuclear Information System (INIS)

Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

1992-01-01

The semiquinone radicals produced by one-electron reduction of 1-amino-4-hydroxy-9,10-anthraquinone and 1,4-diamino-9,10-anthraquinone have been studied in aqueous-organic mixed solvent using pulse radiolysis technique. Spectroscopic characteristics, kinetic characteristics of formation and decay, acid/base behaviour and redox characteristics of the semiquinones have been investigated and compared with those of some similar systems studied earlier. It has been shown that the variation of the disproportionation equilibria involving the reduced semiquinone radicals, the parent quinone and the fully reduced hydroquinone with pH of the solutions follow a similar trend as observed in the case of other dihydroxy quinones. Stability of the semiquinones over a broad pH range and their thermodynamic properties have been correlated. (Author)

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)

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)

An investigation of pulsed high density plasmas

International Nuclear Information System (INIS)

Timmermans, C.J.

1984-01-01

In this thesis a wall-stabilized argon cascade arc is studied at values of pulsed pressure up to 14 bar and a pulsed current range up to 2200 A with a time duration of about 2 ms. The basic plasma is a CW cascade arc with a 5 mm diameter plasma column and a length of 90 mm, which operates at a 60 A DC current and at one atmosphere filling pressure. The author starts with an extensive summary of the CW arc investigations. After a brief introduction of the basic transport equations the mass equations of the constituent particles are treated using the extended collisional radiative model. The energy balance equations and the momentum balance are discussed. The electron density is determined from measurements of the continuum radiation. The final chapter contains the experimental results on the electron temperatures and electron densities in the pressure and current pulsed plasma. Attention is given to the deviations from local thermodynamic equilibrium values of the ground level densities of the different argon systems. (Auth.)

Inactivation of catalase by free radicals derived from oxygen via gamma radiolysis

International Nuclear Information System (INIS)

Malhaire, J.P.; Gardes-Albert, M.; Ferradini, C.; Sabourault, D.; Ribiere, C.

1991-01-01

The inactivation of catalase (10 -5 mol/l) by OH· or OH·/O 2 - · free radicals, at pH 7.4, has been investigated using γ radiolysis with doses up to 9000 Gy. Maxima initial G-values of catalase inactivation have been determined. These values are inferior to those of the free radicals OH· and O 2 - · produced by water radiolysis. Nevertheless, the presence of O 2 /O 2 - · enhances the inactivation due to OH· radicals. The general shape of the inactivation curves as a function of the radiation dose is biphasic: an initial rapid phase (from 0 to ∼ 500 Gy) followed by a slow phase (from ∼ 500 to 9000 Gy). The addition of H 2 O 2 at the beginning of irradiation decreases the inactivation yield by OH· radicals. This phenomenon could be due to the formation of compound-I (catalase-H 2 O 2 ) which would be less sensitive towards OH· radicals than catalase. In the presence of 0.1 mol/l ethanol, catalase (5 x 10 -6 mol/l) is not inactived by O 2 - · and RO 2 · (from ethanol) radicals for an irradiation dose of 2000 Gy, implying a complete protecting effect by ethanol [fr

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.)

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)

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.

Investigation of the pulsed electrochemical deposition of ZnO

International Nuclear Information System (INIS)

Dunkel, Christian; Lüttich, Franziska; Graaf, Harald; Oekermann, Torsten; Wark, Michael

2012-01-01

The influence of pulse parameters on the morphology of ZnO prepared by pulsed cathodic electrodeposition from oxygen-saturated aqueous ZnCl 2 solution on ITO (indium tin oxide)/glass substrates was investigated. It was found that the ratio between the pulse and the pause duration has a crucial influence on the crystal growth, reaching the highest density of the films with pause/pulse-ratios between 0.25 and 1. Longer pauses cause an Ostwald-like ripening of the ZnO crystals and therewith a strong change in the crystal morphology from roundly shaped to hexagonal. Also the hydrophilicity of the substrate resulting from pre-treatment has a crucial influence on the deposited films, leading to films only consisting of few large and separately grown ZnO crystals for highly hydrophilic substrates and an increasing fraction of small densely grown ZnO crystals with increasing hydrophobicity.

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.

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

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

The pulse radiolysis of aqueous solutions of simple RCN compounds

International Nuclear Information System (INIS)

Draganic, I.G.; Draganic, Z.D.; Markovic, V.M.

1976-01-01

Fast kinetic spectrophotometry was used to study the absorption spectra of short-living intermediates produced by reactions of RCN molecules with H, esub(aq) - and OH. The spectra were obtained on the microsecond time scale after an electron pulse from a Febetron 707 accelerator in aqueous solutions of the following compounds: hydrocyanic acid, acetonitrile, propionitrile, malononitrile and succinonitrile. It has been found that all intermediates absorb in the U.V. range (lamba 9 dm 3 mol -1 s -1 . In the presence of an efficient scavenger for hydroxyl radicals, the same transient spectra were registered in acid and neutral solutions suggesting that the protonations of esub(aq) - adducts of these RCN molecules were complete within a submicrosecond time interval. (author)

Role of groundwater oxidation potential and radiolysis on waste glass performance in crystalline repository environments

International Nuclear Information System (INIS)

Jantzen, C.M.; Bibler, N.E.

1986-01-01

Laboratory experiments have shown that groundwater conditions in a granite repository will be as reducing as those in a basalt repository. Chemical analysis of the reduced groundwaters confirmed that the Fe 2+ /Fe 3+ couple controls the oxidation potential (Eh). The reducing groundwater conditions were found to decrease the time-dependent release of soluble elements (Li and B) from the waste glass. However, due to the lower solubility of multivalent elements released from the glass when the groundwaters are reducing, these elements have significantly lower concentrations in the leachates. Gamma radiolysis reduced the oxidation potential of both granitic and basaltic groundwater in the absence of both waste glass and oxygen. This occurred in tests at atmospheric pressure where H 2 could have escaped from the solution. The mechanism for this decrease in Eh is under investigation but appears related to the reactive amorphous precipitate in both groundwaters. The results of these tests suggest that radiolysis may not cause the groundwaters to become oxidizing in a crystalline repository when abundant Fe 2+ species are present

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.)

Study of the effect of water radiolysis on zirconolite dissolution

International Nuclear Information System (INIS)

Tribet, M.

2007-09-01

Zirconolite is one of the matrices foreseen for the confinement of minor actinides in case of deep geological disposal. Indeed, zirconolite (general formula: CaZr x Ti 3-x O 7 (0.8 ≤ x ≤ 1.37)) is able to incorporate rare earth elements and actinides by substitution in calcium and zirconium sites and, moreover, its chemical durability into water is well known. However, in case of deep geological disposal, after a long period, water can reach the confinement matrix and can be radiolysed at the moment of the radionuclide alpha decays. In this work we have thus studied the effects of water radiolysis induced by charged particles (alphas or protons) on the dissolution of a synthetic sintered zirconolite. The formula of this zirconolite is Ca 0,8 Nd 0,2 ZrTi 1,8 Al 0,2 O 7 where Nd simulates the presence of trivalent and tetravalent actinides. We performed the irradiations with external ion beams in two distinct geometries where the fluences ranged from 10 15 to 10 16 ions.cm -2 . In the first geometry the beam stops into water before the surface/water interface. In the second one the beam gets through the sample before stopping at the surface/water interface. The use of these different configurations allows to study the respective influence of parameters such as sample irradiation, Linear Energy Transfer at the surface/water interface or total deposited energy. The irradiations were performed on both crystalline and amorphous zirconolites in pure water or with complexing species such as F - . The sample dissolution has been monitored through the release of cations. The radiolytic production of H 2 O 2 has also been measured. Our results show that the water radiolysis has an effect on the preferential release of Zr, Ti and Nd: for these elements, releases are one or two order of magnitude higher than releases out of radiolysis. Such preferential releases occur whatever the temperature (20 or 50 C), the surface state (crystalline or amorphous) and the experimental

Pulse radiolysis investigations on oxidation reactions of bilirubin in aqueous solutions (Preprint No. RC-3)

International Nuclear Information System (INIS)

Mohan, Hari; Gopinathan, C.

1988-02-01

The oxidation of bilirubin in aqueous solutions have been investigated by different oxidizing species such as CH 3 I.OH, Br 2 - and CO 3 - . The rate constant for the oxidation of bilirubin has been determined from the formation kinetics of bilirubin cations. (author). 3 refs

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

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)

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

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)

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)

Interfacial electron-transfer equilibria and flat-band potentials of α-Fe2O3 and TiO2 colloids studied by pulse radiolysis

International Nuclear Information System (INIS)

Dimitrijevic, N.M.; Savic, D.; Micic, O.I.; Nozik, A.J.

1984-01-01

The kinetics and equilibria of electron transfer between methylviologen cation radicals and α-Fe 2 O 3 or TiO 2 colloidal particles were studied with the pulse-radiolysis technique. The rates of electron transfer to both colloids are lower than those predicted for a diffusion-controlled reaction. For higher pHs (TiO 2 , pH > 2; α-Fe 2 O 3 , pH > 9) the established equilibrium MV + in equilibrium MV 2+ + (e - )/sub coll/ is strongly influenced by the MV 2+ concentration and pH. The MV + equilibrium concentration can be exploited to derive the flat-band potential of the semiconductor colloids. The method for determining the flat-band potential of the particles is independent of whether the injected electrons are free or trapped, and whether the electrons raise the bulk Fermi level toward the conduction band or just produce a space charge. The flat-band potentials for both colloids appear to be somewhat more negative (-0.1 to -0.2 V) than the corresponding single-crystal electrodes. Also, the flat-band potentials become slightly more negative with increasing radiation dose (initial MV + concentration). The effect of absorbed radiation dose is explained by the corresponding changes in the ratio of oxidized to reduced forms of the redox couple, which in turn changes the adsorbed ionic charge on the semiconductor surface. For colloidal particles of TiO 2 stabilized by poly(vinyl alcohol) (PVA), the flat-band potentials were almost the same as those for PVA-free TiO 2 sols. The decrease of particle diameter from 800 to 70 A does not affect the value of the flat-band potentials for TiO 2 and α-Fe 2 O 3 colloids. 28 references, 9 figures

Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

International Nuclear Information System (INIS)

Bors, W.; Saran, M.; Michel, C.

1982-01-01

The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

Radical Ions of 3-Styryl-quinoxalin-2-one Derivatives Studied by Pulse Radiolysis in Organic Solvents.

Science.gov (United States)

Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Álvaro; Berrios, Eduardo; Bobrowski, Krzysztof

2018-04-12

The absorption-spectral and kinetic behaviors of radical ions and neutral hydrogenated radicals of seven 3-styryl-quinoxalin-2(1 H)-one (3-SQ) derivatives, one without substituents in the styryl moiety, four others with electron-donating (R = -CH 3 , -OCH 3 , and -N(CH 3 ) 2 ) or electron-withdrawing (R = -OCF 3 ) substituents in the para position in their benzene ring, and remaining two with double methoxy substituents (-OCH 3 ), however, at different positions (meta/para and ortho/meta) have been studied by UV-vis spectrophotometric pulse radiolysis in neat acetonitrile saturated with argon (Ar) and oxygen (O 2 ) and in 2-propanol saturated with Ar, at room temperature. In acetonitrile solutions, the radical anions (4R-SQ •- ) are characterized by two absorption maxima located at λ max = 470-490 nm and λ max = 510-540 nm, with the respective molar absorption coefficients ε 470-490 = 8500-13 100 M -1 cm -1 and ε 510-540 = 6100-10 300 M -1 cm -1 , depending on the substituent (R). All 4R-SQ •- decay in acetonitrile via first-order kinetics, with the rate constants in the range (1.2-1.5) × 10 6 s -1 . In 2-propanol solutions, they decay predominantly through protonation by the solvent, forming neutral hydrogenated radicals (4R-SQH • ), which are characterized by weak absorption bands with λ max = 480-490 nm. Being oxygen-insensitive, the radical cations (4R-SQ •+ ) are characterized by a strong absorption with λ max = 450-630 nm, depending on the substituent (R). They are formed in a charge-transfer reaction between a radical cation derived from acetonitrile (ACN •+ ) and substituted 3-styryl-quinoxalin-2-one derivatives (4R-SQ) with a pseudo-first-order rate constant k = (2.7-4.7) × 10 5 s -1 measured in solutions containing 0.1 mM 4R-3-SQ. The Hammett equation plot gave a very small negative slope (ρ = -0.08), indicating a very weak influence of the substituents in the benzene ring on the rate of charge-transfer reaction. The decay of 4R

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.

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

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.

Kinetics of radiolysis of irradiated ligno celluloses into soluble products in water and rumen liquid

International Nuclear Information System (INIS)

Tukenmez, I.; Bakioglu, A.T.; Ersen, M.S.

1997-01-01

In order to increase the low bio hydrolysis of ligno celluloses in biotechnological and biological processes where these materials are used as raw materials and ruminant feed, the substrates were pretreated with irradiation to induce radiolytic depolymerisation and then kinetics of their radiolysis into soluble products in water and rumen liquid were analyzed. Wheat straw used as a representative lignocellulose substrate was irradiated at 0-2.5 MGy doses at 20''o''C with an optimum equilibrium humidity of 6.6% in Cs-137 gamma irradiator with a dose rate of 1.8 kGy/h, and soluablefractions in water and in situ rumen liquid were determined gravimetrically. Based on these data, a reaction mechanism was proposed for the radiolysis of ligno celluloses into soluble fractions. From the corresponding reaction rate equations with this mechanism a dose dependent kinetics was derived for the radiolysis of ligno celluloses into water/rumen liquid-soluble products. Defined by this kinetics, the threshold doses for the radiolysis of the substrate into water/rumen liquid-soluble products were respectively found 80.6 kGy and 186.0 kGy, and fractional radiolytic decomposition yields 0.193 MGy''-1''.It was emphasized that developed kinetic models may be used for the process design of irradiation pretreatments to improve the bio hydrolysis of ligno celluloses.(2figs. and 17 refs.)

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)

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

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)

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 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

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

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

Experimental investigation of 1 GW repeatable ultra-wide band pulse radiating source

International Nuclear Information System (INIS)

Meng Fanbao; Ma Hongge; Zhou Chuanming; Yang Zhoubing; Lu Wei; Ju Bingquan; Yu Huilong

2001-01-01

The single cycle pulse of 1.6 GW peak power with 20 Hz repetition-rate was generated. It radiated a peak power of more than 500 MW with a coaxial biconical antenna. The technological problems of the insulation and energy loss during generating and radiating high peak power ultra-wide band (UWB) pulse have been resolved. The experiments show that the material insulation and dispersion in sub-nanosecond pulse should be investigated deeply

Experimental investigation of 1 GW repeatable ultra-wide band pulse radiating source

Energy Technology Data Exchange (ETDEWEB)

Fanbao, Meng; Hongge, Ma; Chuanming, Zhou; Zhoubing, Yang; Wei, Lu; Bingquan, Ju; Huilong, Yu [China Academy of Engineering Physics, Chengdu (China)

2000-11-01

The single cycle pulse of 1.6 GW peak power with 20 Hz repetition-rate was generated. It radiated a peak power of more than 500 MW with a coaxial biconical antenna. The technological problems of the insulation and energy loss during generating and radiating high peak power ultra-wide band (UWB) pulse have been resolved. The experiments show that the material insulation and dispersion in subnanosecond pulse should be investigated deeply.

Adjacent effect on positive charge transfer from radical cation of n-dodecane to scavenger studied by supbicosecond pulse radiolysis, statistical and Monte Carlo approach

International Nuclear Information System (INIS)

Saeki, A.; Tagawa, S.; Kozawa, T.; Yoshida, Y.

2003-01-01

Time-dependent behaviors of radical cation in n-dodecane in the presence of high-concentrated cation scavenger triethylamine were measured by subpicosecond pulse radiolysis system. The significant reduction of the initial yield in the optical density was observed. This reduction were not able to be explained by the first order rate constant. Therefore, we assumed that this phenomena occur due to the adjacent effect of the solute molecules. We approached this effect by the statistical model and configurational-bias Monte Carlo method. In both methods, we supposed a condition that the cation site in the radical cation is delocalized and will be scavenged rapidly within the time resolution if the solute molecules is adjacent to any sites of the solvent. In addition to the adjacent effect, the fact that a large part of the solvent molecules is excluded by the solute molecules especially at high concentration was taken into consideration. First, we formulated this effect by a statistical model. In addition to the above assumption, this model is based on the following assumption; the effects of molecule's shape, conformation and interaction among molecules were ignored and the aggregation of the solute molecules were treated randomly. As a result, the formula indicated good agreement with the experimental data. Second, as another approach, we adopted the configurational-bias Monte Carlo simulation to reproduce the liquid system. The OLPS model was used to describe the intermolecular and intramolecular potentials. The adjacent effect estimated by this method corresponded to the experimental data with a threshold of 0.5 nm. This value are close to a typical reaction radius. The average number of adjacent solvent molecules and the distribution of aggregated solute's number were also collected from the position data

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)

Pulse radiolysis study of monomer and dimer cations of styrene, 1-methylstyrene and 1,1'-diphenylethylene

International Nuclear Information System (INIS)

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

1977-01-01

In pulse-irradiated solutions of styrene, 1-methylstyrene and 1,1'-diphenylethylene, the decay kinetics of the olefin monomer cations and the formation kinetics of the corresponding dimer cations have been studied at room temperature. The solutions were irradiated with 15-nsec 15-ampere pulses of 1-MeV electrons from an Elit-type accelerator. The total dose per pulse was approximately 10 krad. The monomer cations were generated with rate constants of about 10 11 M -1 sec -1 . From the time decay of the monomer light absorption and the growth in time of the dimer absorption rate constants for the dimer formation between 0.8x10 10 and 1.2x10 10 M -1 sec -1 have been determined. (T.I.)

Corrosive gas generation potential from chloride salt radiolysis in plutonium environments

International Nuclear Information System (INIS)

Tandon, L.; Allen, T.H.; Mason, R.E.; Penneman, R.A.

1999-01-01

The specific goal of this project was to evaluate the magnitude and practical significance of radiation effects involving mixtures of chloride salts and plutonium dioxide (PuO 2 ) sealed in stainless steel containers and stored for up to 50 yr, after stabilization at 950 C and packaging according to US Department of Energy (DOE) standards. The potential for generating chemically aggressive molecular chlorine (and hydrogen chloride by interaction with adsorbed water or hydrogen gas) by radiolysis of chloride ions was studied. To evaluate the risks, an annotated bibliography on chloride salt radiolysis was created with emphasis on effects of plutonium alpha radiation. The authors present data from the material identification and surveillance (MIS) project obtained from examination and analysis of representative PuO 2 items from various DOE sites, including the headspace gas analysis data of sealed mixtures of PuO 2 and chloride salts following long-term storage

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

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

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.

Radiolysis of kaempferol in water/methanol mixtures. Evaluation of antioxidant activity of kaempferol and products formed.

Science.gov (United States)

Marfak, Abdelghafour; Trouillas, Patrick; Allais, Daovy-Paulette; Champavier, Yves; Calliste, Claude-Alain; Duroux, Jean-Luc

2003-02-26

Oxidative reaction between hydroxymethyl radical ((*)CH(2)OH) and kaempferol, in methanol and methanol/water mixtures, was studied by gamma-radiolysis using a (60)Co source. Radiolysis was performed with concentrations and doses ranging from 5 x 10(-)(5) M to 5 x 10(-)(3) M and from 0.5 kGy to 14 kGy, respectively. Kaempferol degradation was followed by HPLC. Results showed that (*)CH(2)OH reacts with kaempferol at the 3-OH group and produces two depsides (K1 and K2) and other products including K3. K1, K2, and K3 were identified by NMR, LC-MS, and HRMS. The kaempferol degradation pathway leading to the K1, K2, and K3 formation is proposed. It was observed that the more water concentration in the irradiation medium increases, the more K2 concentration increases. Comprehension of food preservation is not clear because many phenomena occurring during irradiation are not established. Radiolysis of kaempferol in water/methanol mixtures helps to elucidate the phenomenon and it is possible that during the treatment of nutriments by gamma-irradiation, a series of products such as depside K2 could be formed. Antioxidant properties of kaempferol radiolysis products were evaluated according to their capacity to decrease the EPR DPPH (1,1-diphenyl-2-picrylhydrazil) signal and to inhibit superoxide radicals formed by the enzyme reaction "xanthine + xanthine oxidase".

Determination of one-electron reduction potentials of some radiosensitive compounds by pulse radiolysis

International Nuclear Information System (INIS)

Zuo Zhihua; Yao Side; Li Hucheng; Lin Nianyun; Jin Yizun

1994-01-01

One-electron reduction potential (E 7 1 ) is one of the important parameters of radiosensitive compound with high electron affinity. In this work one-electron reduction potentials of some radiosensitizers, such as Miso, 911, CMNa, SMU-1, SMU-2, SMD, SNN, S 3 and BSO, were determined pulse radiolytically by using anthraquinone-2-sulfate (AQS), duroquinone (DQ) and methyl viologen (MV 2+ ) as references

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.

Radiation chemistry of hydrocarbon and alkyl halide systems. Progress report, August 1, 1977--August 1, 1978

International Nuclear Information System (INIS)

Hanrahan, R.J.

1978-01-01

Progress of experimental work is reported on pulse radiolysis of simple alkyl halides in the gas phase, gas phase radiolysis of CHF 3 -CH 3 I mixtures, gamma radiolysis of the system CO/H 2 , and improvements in equipment and facilities

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

Pulse radiolysis studies on liquid alkanes and related polymers

International Nuclear Information System (INIS)

Tagawa, S.; Hayashi, N.; Yoshida, Y.; Washio, M.; Tabata, Y.

1989-01-01

Absorption spectra of alkane radical cations, alkane excited states, and alkyl radicals and electrons in irradiated neat liquid alkanes at room temperature were assigned on subnanosecond and nanosecond time scale after an electron pulse. Two broad visible and near-infrared absorption bands of alkane excited states and radical cations, and UV absorption band of alkyl radicals was observed in neat n-alkanes. In neat cyclohezane and trans-decalin, very broad visible absorption band mainly due to alkane excited states and UV absorption band of alkyl radicals were observed. In neat neopentane and isooctane, visible absorption bands were not observed, although UV absorption bands of alkyl radicals were observed. The wavelengths of absorptive peaks of alkane radical cations and excited states become longer with increasing the number of carbon atoms of n-alkanes. The lifetimes of alkane radical cations become shorter with decreasing the number of carbon atoms of n-alkanes and are shorter than those of electrons in neat alkanes. The main processes of the alkyl radical formation finish within the time resolution of our system (about 20 ps). The alkyl radicals are produced mainly from excited radicals cations and partly from higher excited states, the lowest excited states, radical cations, and thermal hydrogen atoms, In irradiated ethylene-propylene copolymers, broad absorption bands of excited states and tail parts of absorption bands of radical cations and electrons were observed in visible and near-infrared region, although UV absorption of alkyl radicals was not confirmed lack of transparency of polymer films. (author)

Performance investigation of the pulse and Campbelling modes of a fission chamber using a Poisson pulse train simulation code

Energy Technology Data Exchange (ETDEWEB)

Elter, Zs. [CEA, DEN, DER, Instrumentation, Sensors and Dosimetry Laboratory, Cadarache, F-13108 Saint-Paul-lez-Durance (France); Chalmers University of Technology, Department of Applied Physics, Division of Nuclear Engineering, SE-412 96 Göteborg (Sweden); Jammes, C., E-mail: christian.jammes@cea.fr [CEA, DEN, DER, Instrumentation, Sensors and Dosimetry Laboratory, Cadarache, F-13108 Saint-Paul-lez-Durance (France); Pázsit, I. [Chalmers University of Technology, Department of Applied Physics, Division of Nuclear Engineering, SE-412 96 Göteborg (Sweden); Pál, L. [Centre for Energy Research, Hungarian Academy of Sciences, H-1525 Budapest 114, POB 49 (Hungary); Filliatre, P. [CEA, DEN, DER, Instrumentation, Sensors and Dosimetry Laboratory, Cadarache, F-13108 Saint-Paul-lez-Durance (France)

2015-02-21

The detectors of the neutron flux monitoring system of the foreseen French GEN-IV sodium-cooled fast reactor (SFR) will be high temperature fission chambers placed in the reactor vessel in the vicinity of the core. The operation of a fission chamber over a wide-range neutron flux will be feasible provided that the overlap of the applicability of its pulse and Campbelling operational modes is ensured. This paper addresses the question of the linearity of these two modes and it also presents our recent efforts to develop a specific code for the simulation of fission chamber pulse trains. Our developed simulation code is described and its overall verification is shown. An extensive quantitative investigation was performed to explore the applicability limits of these two standard modes. It was found that for short pulses the overlap between the pulse and Campbelling modes can be guaranteed if the standard deviation of the background noise is not higher than 5% of the pulse amplitude. It was also shown that the Campbelling mode is sensitive to parasitic noise, while the performance of the pulse mode is affected by the stochastic amplitude distributions.

Electron migration in hydrated biopolymers following pulsed irradiation at low temperatures

International Nuclear Information System (INIS)

Lith, D. van.

1987-01-01

Charge migration in biopolymer-water mixtures and the effect of water concentration on the charge migration is investigated by measuring the electrical conductivity and the light emission with the pulse radiolysis technique. A preliminary account of the microwave conductivity observed in hydrated DNA and collagen at low temperature after pulsed irradiation is given. The results show that when hydrated DNA or collagen are irradiated at low temperatures, conductivity transients with microsecond lifetime are observed. It is tentatively concluded that these transients are due to the highly mobile dry electron. The effect of water concentration on mobility, lifetime and migration distance of the electron is discussed. The effect of additives to the hydrated systems on the behaviour of the electron is described. It is shown that the observed effects of the additives confirm the earlier conclusions that the dry electron is the species responsible for the radiation induced conductivity. The water concentration in the DNA- and collagen-systems could be varied only between zero and approximately fifty percent, due to inhomogeneities which occur at higher water concentrations. Experiments on gelatin, a biopolymer which forms homogeneous samples with levels of hydration varying from almost zero to 100% water (ice) are described. Both the radiation induced and the dark microwave conductivity have been studied as a function of water content. Preliminary results of a study of the light emission from pulse irradiated DNA-water mixtures are reported in an attempt to establish a relation between the observed electron migration and the formation of excited states via charge neutralization. (Auth.)

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)

Pulsed radiation studies of carotenoid radicals and excited states

International Nuclear Information System (INIS)

Burke, M.

2001-04-01

The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of β-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar (∼1 x 10 7 M -1 s -1 ) for β-carotene and zeaxanthin and somewhat lower (∼0.5 x 10 7 M -1 s -1 ) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for β-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number of conjugated double bonds, the longer chain systems having

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)

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

Radiolysis of D(+)-carnitine by 60Co-γ-radiation and formation of L(+)-β-methylcholine

International Nuclear Information System (INIS)

Loester, Heinz; Strack, Erich; Seim, Hermann

1986-01-01

The radiolysis of D(+)-carnitine by 60 Co-γ-radiation was examined to obtain optically active β-methylcholine. It was found that the radiolysis leads to a number of trimethylammonium bases but to no other betaines. (+)-β-Methylcholine and acetonyltrimethylammonium could be identified by means of common analytical methods. The amounts of methylamines formed by irradiation were very small. Racemization of the D(+)-carnitine did not occur during irradiation, L(-)-carnitine was not found when an enzymatical determination method was used. The fact that (+)-β-methylcholine was formed from D(+)-carnitine is pharmacologically important, because acetyl-L(+)-β-methylcholine has a strong interaction with muscarinic receptors. (author)

An experimental investigation of pulsed laser-assisted machining of AISI 52100 steel

Science.gov (United States)

Panjehpour, Afshin; Soleymani Yazdi, Mohammad R.; Shoja-Razavi, Reza

2014-11-01

Grinding and hard turning are widely used for machining of hardened bearing steel parts. Laser-assisted machining (LAM) has emerged as an efficient alternative to grinding and hard turning for hardened steel parts. In most cases, continuous-wave lasers were used as a heat source to cause localized heating prior to material removal by a cutting tool. In this study, an experimental investigation of pulsed laser-assisted machining of AISI 52100 bearing steel was conducted. The effects of process parameters (i.e., laser mean power, pulse frequency, pulse energy, cutting speed and feed rate) on state variables (i.e., material removal temperature, specific cutting energy, surface roughness, microstructure, tool wear and chip formation) were investigated. At laser mean power of 425 W with frequency of 120 Hz and cutting speed of 70 m/min, the benefit of LAM was shown by 25% decrease in specific cutting energy and 18% improvement in surface roughness, as compared to those of the conventional machining. It was shown that at constant laser power, the increase of laser pulse energy causes the rapid increase in tool wear rate. Pulsed laser allowed efficient control of surface temperature and heat penetration in material removal region. Examination of the machined subsurface microstructure and microhardness profiles showed no change under LAM and conventional machining. Continuous chips with more uniform plastic deformation were produced in LAM.

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).

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)

Modern trends in theoretical radiation chemistry development

International Nuclear Information System (INIS)

Kaplan, I.G.

1983-01-01

Most important trends in the development of radiation chemitry theory are considered. Wide use of electronic computers for modeling different stages of radiolysis in conjUnction with advanced precision experimental methods (picosecond pulse radiolysis, acceptor additions method, magnetic method of detecting interstitial active particles) is noted. Information obtained in photochemistry and molecular spectroscopy, including laser photolysis, is in common use in developing the theory. It is noted that data on the processes occurring within less than 10 -12 s time can be obtained now only on the base of theoretical representations about the mechanism of ionizing irradiation interaction with molecular medium. Therefore, special attention in the review is paid to investigation of primary radiolysis processes. Besides investigation of primary medium excitation processes theoretical investigations into the ways of energy degradation, knocked out electrons and their further state are continued. It is noted that a considerable number of papers deal with the nature and behaviour of radiation-induced excess electrons in non-polar solutions and solid matrices. Works on application of diffusion kinetics in radiolysis have been developed in recent years

Investigation of pulsed barrier discharge in water-air gap

International Nuclear Information System (INIS)

Taran, V.S.; Krasnyj, V.V.; Lozina, A.S.; Shvets, O.M.

2013-01-01

This article presents the results of the use of a pulsed dielectric barrier discharge with water electrode and diaphragm. The spectroscopic and electrical investigations of such discharge were conducted. The ozone concentration in an aqueous solution comprised 0.7 mg/l with high-voltage pulsed power at 120 W. The discharge reviewed emission spectrum lines of molecular nitrogen and hydroxyl radicals in the range of 200...800 nm in the water-air gap. The intensity changing of luminescence lines of OH and N 2 singles depending on the applied voltage and discharge gap has been determined. Aqueous solution of indigo was used in order to determine the impact level on the organic material. Experiments on inactivation of test E. coli cultures have been carried out.

A pulse radiolysis study

Indian Academy of Sciences (India)

Unknown

The rate constant in the reaction of N3. • with the ortho isomer is lower by an order of magnitude (k = 4⋅9 ± 0⋅4 × 108 dm3 mol–1s–1). The rates of the reaction of. − aq e with ortho and meta isomers were found to be diffusion controlled. The transient absorption spectrum measured in the. •. OH with o- hydroxycinnamic acid ...

Water radiolysis in a crack tip under gamma ray irradiation

International Nuclear Information System (INIS)

Satoh, Tomonori; Uchida, Shunsuke; Satoh, Yoshiyuki

2002-01-01

Under a non-irradiation condition, oxidant, e.g., O 2 and H 2 O 2 , in a crack tip is supplied from the bulk water. But under irradiation conditions, even if the diffusion of radiolytic species is not sufficient, direct radiolysis in the crack tip causes high concentrations of radiolytic species. As a result of measurements and Monte Carlo calculation of gamma ray energy deposition, it has been confirmed that the energy deposition rate in the gap water is larger than that in the bulk water. The energy absorption rate increases as the gap width decreases and reaches 1.3 times that in the bulk water. In order to evaluate crack propagation rate for irradiation assisted stress corrosion cracking (IASCC) of stainless steel, a water radiolysis model in a crevice is proposed. A larger energy deposition rate in the crevice water produces many more radiolytic species, which causes high oxidant concentrations in spite of enhanced recombination of the species at the crevice inner surface. So, for IASCC evaluation, crevice water chemistry plays an important role to determine the crack propagation rate under irradiation. (authors)

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

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

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

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...

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

Study of the radiolysis of some simple alcohols

International Nuclear Information System (INIS)

Roux, Jean-Claude

1974-01-01

In the first part of this research thesis, the author recalls optical properties of electrons solvated in alcohols, and the various hypotheses of description of the mechanism of electron solvation in these polar environments. In the next parts, the author reports the study of reduced and oxidized species, presents a new model to explain the formation of aldehydes during the radiolysis of primary alcohols. He notices that this mode of formation does not comply with diffusion models. The FORTRAN software used for diffusion kinetic calculations, and experimental techniques are presented in appendix [fr

Radiolysis: an efficient method of studying radicalar antioxidant mechanisms

International Nuclear Information System (INIS)

Gardes-Albert, M.; Jore, D.

1998-01-01

The use of the radiolysis method for studying radicalar antioxidant mechanisms offers the different following possibilities: 1- quantitative evaluation of antioxidant activity of molecules soluble in aqueous or non aqueous media (oxidation yields, molecular mechanisms, rate constants), 2- evaluation of the yield of prevention towards polyunsaturated fatty acids peroxidation, 3- evaluation of antioxidant activity towards biological systems such as liposomes or low density lipoproteins (LDL), 4- simple comparison in different model systems of drags effect versus natural antioxidants. (authors)

Radiation chemistry of aqueous solutions of hydrazine at elevated temperatures: Pt. 2. Solutions containing oxygen

International Nuclear Information System (INIS)

Buxton, G.V.; Stuart, C.R.

1997-01-01

Here, we investigate the effects of oxygen on the radiation chemistry of hydrazine at elevated temperatures. The chemistry of this system is important to reactor coolant chemistry, particularly under start-up conditions when hydrazine is added to suppress corrosion which would otherwise be caused by the ingress of oxygen. The radiation chemistry of aqueous solutions of hydrazine has been investigated previously in the presence of oxygen by Ershov et al., but only at room temperature. In those experiments, both steady-state γ-radiolysis and pulse radiolysis were used to deduce the mechanism of decomposition of hydrazine in the presence of oxygen. (author)

Pulsed Q-switched ruby laser annealing of Bi implanted Si crystals investigated by channeling

International Nuclear Information System (INIS)

Deutch, B.I.; Shih-Chang, T.; Shang-Hwai, L.; Zu-Yao, Z.; Jia-Zeng, H.; Ren-Zhi, D.; Te-Chang, C.; De-Xin, C.

1979-01-01

Channeling was used to investigate pulsed, Q switched ruby-laser annealed and thermally annealed Si single crystals implanted with 40-keV Bi ions to a dose of 10 15 atoms/cm 2 . After thermal annealing, residual damage decreased with increasing annealing temperature to a minimum value of 30% at 900 0 C. The Bi atoms in substitutional sites reached a maximum value (50%) after annealing at 750 0 C but decreased with increasing annealing temperature. Out diffusion of Bi atoms occurred at temperatures higher than 625 0 C. For comparison, the residual damage disappeared almost completely after pulsed-laser annealing (30 ns pulse width, Energy, E = 3J/cm 2 ). The concentration of Bi in Si exceeded its solid solubility by an order of magnitude; 95% of Bi atoms were annealed to substitutional sites. Laser pulses of different energies were used to investigate the efficiency of annealing. (author)

Radiolysis ob benzene, toluene and phenol aqueous solutions utilizing high energy electron beam; Radiolisis de benceno, tolueno y fenol en solucion acuosa utilizando haces de electrones

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Vanderhaghen, D E

1999-12-31

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 {mu}A). 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

Radiolysis ob benzene, toluene and phenol aqueous solutions utilizing high energy electron beam; Radiolisis de benceno, tolueno y fenol en solucion acuosa utilizando haces de electrones

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Vanderhaghen, D.E

1998-12-31

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 {mu}A). 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

Investigations on the pulse operation of YAYOI

International Nuclear Information System (INIS)

1977-04-01

This report is composed of ten independent documents concerning the pulse operation of YAYOI, which were prepared in the period between July, 1976, and March, 1977. The titles of the documents included in this report are: (1) the operational sequence of the linac neutron generating facility, (2) safety systems of linac pulse operation and the treatment and preservation of neutron generating targets, (3) nuclear calculation concerning linac pulse operation, (4) simulated natural uranium core, (5) linac neutron target system, (6) computer processing accompanying linac pulse operation, (7) fundamental concept of electron beam generation within the reactor room, (8) reactor room shielding requirements for the linac neutron source, (9) TOF measuring room, and (10) utilization of low energy neutrons from P-YAYOI operation. (Aoki, K.)

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�

Experimental investigation of plasma dynamics in dc and short-pulse magnetron discharges

International Nuclear Information System (INIS)

Seo, Sang-Hun; In, Jung-Hwan; Chang, Hong-Young

2006-01-01

The spatiotemporal evolution of the electron energy distribution function (EEDF) and of plasma parameters such as the electron density, the electron temperature and the plasma and floating potentials has been investigated using spatially and temporally resolved single Langmuir probe measurements in dc and mid-frequency, short-pulse magnetron discharges with a repetition frequency of 10 kHz and a duty cycle of 10%. In the pulsed discharge of the short duty cycle, a peak electron temperature higher than 10 eV was observed near the cathode fall region during the early phase of the pulse-on, which is about three times higher than the steady-state value of the electron temperature in the dc discharge. The temporal evolution of the measured EEDFs showed the initial efficient electron heating during the early phase of the pulse-on and the subsequent relaxation of electron energy by the inelastic collisions and the diffusive loss. The high-energy electrons generated during the pulse-on phase diffused the downstream region toward the grounded substrate, resulting in a bi-Maxwellian EEDF consisting of the background low-energy electrons and the high-energy electrons. The results of the spatially and temporally resolved probe measurements will be presented and the enhanced efficiency of the electron heating in the short-pulse discharge will be explained on the basis of the global model of a pulsed discharge

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.)

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)

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

Pulse radiolytic one-electron reduction of 2-hydroxy- and 2,6-dihydroxy-9,10-anthraquinones

International Nuclear Information System (INIS)

Pal, Haridas; Mukherjee, Tulsi; Mittal, J.P.

1994-01-01

The semiquinone free radicals produced by one-electron reduction of 2-hydroxy-9-10-anthraquinone (2HAQ) and 2,6-dihydroxy-9,10-anthraquinone (26DHAQ) in aqueous formate solution, water-isopropyl alcohol-acetone mixed solvent and isopropyl alcohol have been studied using the pulse radiolysis technique. The absorption characteristics, kinetic parameters of formation and decay, acid-base behaviour and redox characteristics of the semiquinones have been investigated and compared with the corresponding characteristics of a few intramolecularly hydro-bonded anthrasemiquinone derivatives. The non-hydrogen-bonded semiquinones show two pKsub(a) values (4.7 and 10.7 for 2HAQ and 5.4 and 8.7 for 26DHAQ, respectively) within the pH range 1-14, whereas other intramolecularly hydrogen-bonded semiquinones show only one pKsub(a). The one-electron reduction potential (E' 7 ) values for 2HAQ (-440 mV) and 26DHAQ (- 400 mV) are more negative than those of the intramolecularly hydrogen-bonded systems. (Author)

Gamma radiolysis of 3-methylpentane. Effect of added olefins on the formation of C12-olefins

International Nuclear Information System (INIS)

Laet, M. de; Tilquin, B.

1991-01-01

Contributions of congruent (parent derived) olefins to the formation of unsaturated heavy products (C 12 H 24 ) are investigated. Effects of dose or of olefinic additives on the G yield values are studied by capillary gas chromatography. The dose dependence is explained by transfer of positive charge to congruent olefins (C 6 H 12 ) even though their concentrations build up linearly with dose. γ Irradiation of 3-methylpentane containing pentenes or butenes (0.2-2 mol %) provides good examples of transfer of energy, however the results are unexpected. C-H scission in the radiolysis of solid 3-methylpentane is also reviewed. (author)

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

Spin trapping study on the nature of radicals generated by X radiolysis and peroxidation of linolenic acid

International Nuclear Information System (INIS)

Azizova, O.A.; Osipov, A.N.; Zubarev, V.E.; Yakhyaev, A.V.; Vladimirov, Yu.A.; Savov, V.M.; Kagan, V.E.

1983-01-01

The radicals of linolenic acid and their spin adducts (SA) with PBN formed during X radiolysis of linolenic acid and in lipid peroxidation with ferrous ions were investigated and identified. It was found that in the absence of oxygen in pure linolenic acid at 77 K X irradiation produces alkyl and carboxyl radicals. In the presence of the spin trap alkyl radical spin adducts were formed. Irradiation of linolenic acid in the presence of oxygen at 77 K also resulted in the formation of alkyl radicals. These radicals were transformed into peroxy radicals in the interaction of alkyl radical with oxygen upon heating to 117 K. In the presence of spin trap X irradiation of linolenic acid and heating of the sample up to 300 K gave rise to EPR spectra of SA alkyl and unidentified radicals. Lipid peroxidation of linolenic acid induced by ferrous ions in the presence of spin trap also formed radicals and SA of linolenic acid. The spectral parameters of SA generated with ferrous ions in lipid peroxidation and of those generated during X radiolysis do not differ. The similarity of spectral parameters of SA in these two cases suggests a similarity in the structure of linolenic acid radicals. (author)

Isotope effect in gamma-radiolysis of absorbed ammonia

Energy Technology Data Exchange (ETDEWEB)

Lyapina, T G; Kotov, A G [Nauchno-Issledovatel' skij Fiziko-Khimicheskij Inst., Moscow (USSR)

1975-07-01

The radiolysis of NH/sub 3/ of various isotopic compounds adsorbed on silica gel or zeolite at 77degK was studied. Experimental data were treated using the kinetic equation dR/dt=GI-kIR where R=radical concentration, G=radical yield, k=radical termination constant and I=radiation dose rate. Both the values of G and R for NH/sub 3/ adsorbed on silica gel are affected by the isotopic effect of /sup 15/N, but not on zeolite. The isotopic effect is explained by the influence of protonated acidity of the silica gel surface.

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)

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)

Modification of DNA radiolysis by DNA-binding proteins: Structural aspects

Czech Academy of Sciences Publication Activity Database

Davídková, Marie; Štísová, Viktorie; Goffinont, S.; Gillard, N.; Castaing, B.; Maurizot, M. S.

2007-01-01

Roč. 122, 1-4 (2007), s. 100-105 ISSN 0144-8420. [Symposium on Microdosimetry /14./. Venezia, 13.11.2005-18.11.2005] R&D Projects: GA MŠk 1P05OC085 Grant - others:GA MŠk(CS1) Barrande 2005-6-018-1 Institutional research plan: CEZ:AV0Z10480505 Keywords : specific DNA-protein complexes * radiolysis * ionizing radiation Subject RIV: BO - Biophysics Impact factor: 0.528, year: 2007

Radiation-induced reactions of Cl-, CO32-, and Br- in seawater, - Model calculation of gamma radiolysis of seawater

International Nuclear Information System (INIS)

Hata, Kuniki; Hanawa, Satoshi; Kasahara, Shigeki; Muroya, Yusa; Katsumura, Yosuke

2012-09-01

Gamma-radiolysis of seawater has been simulated to estimate the concentrations of radiolysis products. Although gas products such as H 2 , O 2 and H 2 O 2 in irradiated pure water quickly attain the steady state with very low concentrations, the products in seawater monotonically increase with dose. It was found that H 2 is produced almost linearly with dose, and corresponding G-value was 4.4 x 10 -8 mol J -1 . As similar result was obtained from the calculation of 8 x 10 -4 mol dm -3 NaBr solution, the origin of the linear increase in seawater was attributable to be the reactions of Br - . According to the sensitivity analysis, three reactions, 1: Br - + ·OH → BrOH· - , 2: BrOH· - → Br - + ·OH, and 3: BrOH· - → Br· + OH - , determined the concentrations of the products. The presence of Cl - and HCO 3 - in seawater hardly affected the concentrations of the radiolysis products. Oxyanions derived from Cl - and Br - were not obtained at observable concentration. (authors)

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.

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

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)

Investigation of the Pulsed Annular Gas Jet for Chemical Reactor Cleaning

Directory of Open Access Journals (Sweden)

Zvegintsev Valery Ivanovich

2012-01-01

Full Text Available The most economical technology for production of titanium dioxide pigment is plasma-chemical syntheses with the heating of the oxygen. The highlight of the given reaction is formation of a solid phase as a result of interactions between two gases, thus brings the formation of particle deposits on the reactor walls, and to disturbing the normal operation of the technological process. For the solving of the task of reactor internal walls cleaning the pulsed gaseous system was suggested and investigated, which throws circular oxygen jet along surfaces through regular intervals. Study of aerodynamic efficiency of the impulse system was carried by numerical modeling and experimentally with the help of a specially created experimental facility. The distribution of the pulsed flow velocity at the exit of cylindrical reactor was measured. The experimental results have shown that used impulse device creates a pulsed jet with high value of the specified flow rate. It allows to get high velocities that are sufficient for the particle deposits destruction and their removal away. Designed pulsed peelings system has shown high efficiency and reliability in functioning that allows us to recommend it for wide spreading in chemical industry.

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.

Antioxidant activity of hydrated carboxylated nanodiamonds and its influence on water γ-radiolysis

Science.gov (United States)

Santacruz-Gomez, Karla; Sarabia-Sainz, A.; Acosta-Elias, M.; Sarabia-Sainz, M.; Janetanakit, Woraphong; Khosla, Nathan; Melendrez, R.; Pedroza Montero, Martin; Lal, Ratnesh

2018-03-01

Water radiolysis involves chemical decomposition of the water molecule into free radicals after exposure to ionizing radiation. These free radicals have deleterious effects on normal cell physiology. Carboxylated nanodiamonds (cNDs) appear to modulate the deleterious effects of γ-irradiation on the pathophysiology of red blood cells (RBCs). In the present work, the antioxidant activity of hydrated cNDs (h-cNDs) on limiting oxidative damage (the water radiolysis effect) by γ-irradiation was confirmed. Our results show that h-cNDs have remarkable free radical scavenging ability and preserve the enzymatic activity of catalase after γ-irradiation. The underlying mechanism through which nanodiamonds exhibit antioxidant activity appears to depend on their colloidal stability. This property of detonation synthesized nanodiamonds is improved after carboxylation, which in turn influences changes in the hydrogen bond strength in water. The observed stability of h-cNDs in water and their antioxidant activity correlates with their protective effect on RBCs against γ-irradiation.

Enhanced safety margins during wet transport of irradiated fuel by catalytic recombination of radiolysis hydrogen and oxygen

International Nuclear Information System (INIS)

Spencer, J.T.; Bankhead, M.; Hodge, N.A.

2004-01-01

BNFL has developed and tested a new method for use in wet transport of irradiated fuel. The method uses a catalyst to recombine the hydrogen and oxygen produced from radiolysis. The catalyst is installed in the nitrogen ullage gas region. It has twin benefits as it eliminates a gas mixture that could, in principle, exceed the safe target levels set to ensure safety during Transport, and it also reduces overall gas pressure. Pure water radiolysis predictions, from experiment and theory, indicate very low levels of hydrogen and oxygen generation. BNFL's historic experience is that in some transport packages it is possible to produce higher levels of hydrogen and oxygen. This drives the need to improve on our existing ullage gas remediation technology. Our studies of the radiolysis science and our flask data suggest it is the interaction of the liquors and material surfaces that is giving rise to the enhanced levels of hydrogen and/or oxygen. This technical paper demonstrates the performance of the recombiner catalyst under normal and extreme conditions of transport. The paper will present experimental data that shows the recombiner catalyst working to manage the hydrogen and oxygen levels

Optically isolated electronic trigger system for experiments on a subnanosecond time scale with a pulsed Van de Graaff electron accelerator

International Nuclear Information System (INIS)

Luthjens, L.H.; Vermeulen, M.J.W.; Hom, M.L.

1980-01-01

An optically isolated electronic trigger system for a pulsed Van de Graaff electron accelerator, producing an external pretrigger pulse 75 ns before arrival of the electron pulse at the target, is described. The total time jitter between trigger signal and electron pulse is 50 ps. The measurement of optical and electrical transients on a subnanosecond time scale with a sequential sampling oscilloscope is demonstrated. The contribution of various parts of the equipment to the total jitter is discussed. Those contributions to the jitter due to the electron transit time fluctuations in the accelerator assuming a constant acceleration voltage gradient and to the shot noise in the photomultiplier detector of the trigger system are calculated to be 5 ps and 12 to 21 ps respectively. Comparison with the experimental results leads to the conclusion that a considerable part of the total jitter may be attributed to acceleration voltage gradient fluctuations, to accelerator vibrations and possibly to density fluctuations in the insulation gas. Possible improvements of the trigger system are discussed. The apparatus is used for pulse radiolysis experiments with subnanosecond time resolution down to 100 ps in combination with subnanosecond time duration electron pulses

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.

Radiation 2006. In association with the Polymer Division, Royal Australian Chemical Institute. Incorporating the 21st AINSE Radiation Chemistry Conference and the 18th Radiation Biology Conference, conference handbook

International Nuclear Information System (INIS)

Anderson, R. F.

2006-01-01

Full text: The pulse radiolysis technique is used at the University of Auckland to study fast reactions in solution in a number of biomedical research projects. In this overview of free radical strategies to attack treatment-resistant hypoxic tumour cells, the role played by pulse radiolysis in the development of bioreductive drugs and in the protection of normal tissues will be discussed

Pulse radiolysis of pyridinecarboxylic acids in aqueous solution

DEFF Research Database (Denmark)

Solar, S.; Getoff, N.; Sehested, K.

1991-01-01

The reactivity of OH, e(aq)- and H radicals towards aqueous carboxypyridines: picolinic acid (2-pyridinecarboxylic acid), PA; isonicotinic acid (4-pyridinecarboxylic acid), i-NA; 2,6-pyridinedicarboxylic acid, 2,6-PDCA; and 3,5-pyridinedicarboxylic acid, 3,5-PDCA was investigated in the pH-range 1...... radical are: 20% for PA, 75% for i-NA, 60% for 2,6-PDCA and 25% for 3,5-PDCA (a yield of 50% has been found earlier for nicotinic acid, NA)....

Pulsed radiation studies of carotenoid radicals and excited states

Energy Technology Data Exchange (ETDEWEB)

Burke, M

2001-04-01

The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of {beta}-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar ({approx}1 x 10{sup 7} M{sup -1}s{sup -1}) for {beta}-carotene and zeaxanthin and somewhat lower ({approx}0.5 x 10{sup 7} M{sup -1}s{sup -1}) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for {beta}-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number

Investigations on Surface Milling of Hardened AISI 4140 Steel with Pulse Jet MQL Applicator

Science.gov (United States)

Bashir, Mahmood Al; Mia, Mozammel; Dhar, Nikhil Ranjan

2018-06-01

In this article, an experimental investigation was performed in milling hardened AISI 4140 steel of hardness 40 HRC. The machining was performed in both dry and minimal quantity lubricant (MQL) conditions, as part of neat machining, to make a strong comparison of the undertaken machining environments. The MQL was impinged int the form of pulse jet, by using the specially developed pulse-jet-attachment, to ensure that the cutting fluid can be applied in different timed pulses and quantities at critical zones. The tool wear, cutting force and surface roughness were taken as the quality responses while cutting speed, table feed rate and flow rate of the pulse were considered as influential factors. The depth of cut was kept constant at 1.50 mm because of its less significant effects and the straight oil was adopted as cutting fluid in pulse-jet-MQL. The effects of different factors, on the quality responses, are analyzed using ANOVA. It is observed that MQL applicator system exhibits overall better performance when compared to dry milling by reducing surface roughness, cutting force and prolonging tool life but a flow rate of 150 ml/h has tremendous effects on the responses. This investigation and afterward results are expected to aid the industrial practitioner and researcher to adopt the pulse-MQL in high speed milling to prolong tool life, reduce tool wear, diminish cutting force generation and promote better surface finish.

Analysis of final products from the liquid alkanes radiolysis at low dose, low temperature and high dose rate

International Nuclear Information System (INIS)

Tilquin, B.; Doncker, J. de.

1991-01-01

Yields of final products (dimers) from the radiolysis of n-hexane and 2,3-dimethylbutane are studied by capillary chromatographic techniques for trace analysis. Reaction of intermediates with the products, the alkane molecules or impurities, is reduced by using low dose (1 kGy), low temperature (195 K) and high dose rate (LINAC). Temperature is the most important experiment variable; by reducing the temperature, reactions with significant activation energies do not compete with radical-radical termination reactions. Products from LINAC radiolysis provide information about active species (reactive fragment, allylic radical...) which deserve a more detailed examination by direct methods [fr

Role of groundwater oxidation potential and radiolysis on waste glass performance in crystalline repository environments

International Nuclear Information System (INIS)

Jantzen, C.M.; Bibler, N.E.

1985-01-01

Laboratory experiments have shown that groundwater conditions in a Stripa granite repository will be as reducing as those in a basalt repository. The final oxidation potential (Eh) at 70 0 C for Stripa groundwater deaerated and equilibrated with crystalline granite was -0.45V. In contrast, the oxidation potential at 60 0 C for Grande Ronde groundwater equilibrated with basalt was -0.40V. The reducing groundwater conditions were found to slightly decrease the time-dependent release of soluble components from the waste glass. Spectrophotometric analysis of the equilibrated groundwaters indicated the presence of Fe 2+ confirming that the Fe 2+ /Fe 3+ couple is controlling the oxidation potential. It was also shown that in the alkaline pH regime of these groundwaters the iron species are primarily associated with x-ray amorphous precipitates in the groundwater. Gamma radiolysis in the absence of waste glass and in the absence of oxygen further reduces the oxidation potential of both granitic and basaltic groundwaters. The effect is more pronounced in the basaltic groundwater. The mechanism for this decrease is under investigation but appears related to the reactive amorphous precipitate. The results of these tests suggest that H 2 may not escape from the repository system as postulated and that radiolysis may not cause the groundwaters to become oxidizing in a crystalline repository when abundant Fe 2+ species are present. 23 refs., 3 figs., 3 tabs

Characterisation and activation of catalysts for recombination of radiolysis gases; Charakterisierung und Aktivierung von Katalysatoren zur Rekombination von Radiolysegas

Energy Technology Data Exchange (ETDEWEB)

Koehler, J.; Schorle, R.; Helf, A.; Bolz, M. [EnBW Kernkraft GmbH, Philippsburg Rheinschanzinsel (Germany). Kernkraftwerk Philippsburg

2010-07-01

Stoichiometric amounts of hydrogen and oxygen are produced by the radiolysis of a coolant during the operation of a boiling water reactor. However small amounts of radiolysis gas are collected at the blind end of a line such as in front of shut-off valves and accumulate to higher concentrations. In order to counteract this enrichment, small catalysts are incorporated into the lines. In the scope of a diploma work the performance of these small catalysts was further studied and characterized. The contribution under consideration summarizes the results obtained.

Synthesis of silver nanoparticles by radiolysis, photolysis and chemical reduction of AgNO3 in Hibiscus sabdariffa infusion (karkade)

International Nuclear Information System (INIS)

Cataldo, Franco; Ursini, Ornella; Angelini, Giancarlo

2016-01-01

Silver nanoparticles of different average diameters were synthesized by γ-radiolysis, UV-photolysis and chemical reduction of AgNO 3 solutions in Hibiscus sabdariffa infusion commonly known as 'karkade'. The UV-photolysis was performed either by using a conventional Hg low pressure lamp emitting at 254 nm and also by using a new compact UV-LED source emitting at 360 nm. The kinetics rate constant of silver nanoparticles synthesis produced by γ-radiolysis and UV photolysis were determined and the average diameter of the resulting nanoparticles was estimated. (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

Experimental investigations of pulse shape control in passively mode-locked fiber lasers with net-normal dispersion

International Nuclear Information System (INIS)

Wang, L R; Han, D D

2013-01-01

Pulse shape control in passively mode-locked fiber lasers with net-normal dispersion is investigated experimentally. Three kinds of pulses with different spectral and temporal shapes are observed, and their pulse-shaping mechanisms are discussed. After a polarization-resolved system external to the cavity, the maximum intensity differences of the two polarization components for the rectangular-spectrum (RS), Gaussian-spectrum (GS), and super-broadband (SB) pulses are measured as ∼20 dB, ∼15 dB, and ∼1 dB, respectively. It is suggested that the equivalent saturable absorption effect plays an increasingly important role from the RS to GS and then to SB pulses in the pulse-shaping processes, while the spectral filtering effect declines. This work could help in systematically understanding pulse formation and proposing guidelines for the realization of pulses with better performance in fiber lasers. (paper)

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.

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)

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

Reaction of hydrogen atoms produced by radiolysis and photolysis in solid phase at 4 and 77 K

International Nuclear Information System (INIS)

Miyazaki, Tetsuo

1991-01-01

The behavior of H atoms in the solid phase has been reviewed with special attention to comparison of H atoms produced by radiolysis with those produced by photolysis. The paper consists of three parts. I -Production of H atoms: (1) the experimental results which indicate H-atom formation in the radiolysis of solid alkane are summarized; (2) ESR saturation behavior of trapped H atoms depends upon the method of H-atom-production, i.e. photolysis or radiolysis, and upon the initial energy of H atoms in the photolysis. II - Diffusion of H atoms: (1) activation energies for thermally-activated diffusion of H atoms are shown; (2) quantum diffusion of H atoms in solid H 2 is explained in terms of repetition of tunneling reaction H 2 + H → H + H 2 . III -Reaction of H atoms: (1) reactions and trapping processes of hot H atoms have been shown in solid methane and argon by use of hot H atoms with specified initial energy; (2) when H atoms are produced by the radiolysis of solvent alkane or by the photolysis of HI in the alkane mixtures at 77 K, the H atoms react very selectively with solute alkane at low concentration. The selective reaction of the H atom has been found in eight matrices; (3) activation energy for a hydrogen-atom-abstraction reaction by thermal H atoms at low temperatures is less than than several kJ mol -1 because of quantum tunneling. The absolute rate constants for H 2 (D 2 , HD) + H(D) tunneling reactions have been determined experimentally in solid hydrogen at 4.2K; (4) theoretical studies for tunneling reactions H 2 (D 2 ,HD) + H(D) at ultralow temperatures were reviewed. The calculated rate constants were compared with the rate constants obtained experimentally. (author)

Formation of novel reactive intermediate by electron-laser dual beam irradiation

International Nuclear Information System (INIS)

Ishida, Akito; Takamuku, Setsuo

1992-01-01

The pulse radiolysis system of the Institute of Scientific and Industrial Research, Osaka University, (ISIR) has been progressed to observe a highly reactive species, which is produced by successive irradiation of electron and laser or of CW-UV-light and electron. The dual beam irradiation system, which consists of the beam synchronization system, the optical alignment, and the measurement system, is described in detail. Dual beam irradiation studies on 2-methylbenzophenone and some compounds with a C=N bond have been carried out by use of this system. Pulse radiolysis of 2-methylbenzophenone in benzene induced formation of an unstable photoenol via the triplet state, which was irradiated by a visible laser pulse to give dihydroanthrone. Pulse radiolysis of syn-benzalaniline and a nitrileylide in 2-methyltetrahydrofuran, which were produced by steady state photoirradiation at low temperature, enabled us to observe their very unstable radical anions. (author)

Investigation of the Pulse Height Distribution of Boron Trifluoride Proportional Counters

Energy Technology Data Exchange (ETDEWEB)

Andersson, I Oe; Malmskog, S

1962-08-15

The report describes a theoretical and experimental investigation of the factors that determine the pulse height distribution of BF{sub 3}, proportional counters irradiated by thermal neutrons. The branching ratio of the {sup 10}B (n,{alpha}) {sup 7}Li reaction for thermal neutrons has been measured.

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)

The direct effect in the gamma radiolysis of frozen aqueous solutions of nitrates

International Nuclear Information System (INIS)

Kalecinski, J.

1974-01-01

The gamma radiolysis of frozen at 77 and 195 K solutions of lithium, sodium, potassium, magnesium, strontium and silver nitrates was examined. The yields of the direct effect G(NO 2 - ) were shown to depend on the type of the nitrate and to correlate with the free volumes of the solutions. (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.

Radiolysis effects on fuel corrosion within a failed nuclear waste container

International Nuclear Information System (INIS)

Sunder, S.; Shoeshmith, D.W.; Christensen, H.C.

2003-01-01

The concept of geological disposal of used nuclear fuel in corrosion resistant containers is being investigated in several countries. In the Canadian Nuclear Fuel Waste Management Program (CNFWMP), it is assumed that the used fuel will be disposed of in copper containers. Since the predicted lifetimes of these containers are very long (>106 years), only those containers emplaced with an undetected defect will fail within the period for which radionuclide release from the fuel must be considered. Early failure could lead to the entry of water into the container and subsequent release of radionuclides. The release rate of radionuclides from the used fuel will depend upon its dissolution rate. The primary mechanism for release will be the corrosion of the fuel driven by radiolytically-produced oxidants. The studies carried out to determine the effects of water radiolysis on fuel corrosion are reviewed, and some of the procedures used to predict corrosion rates of used fuel in failed nuclear waste containers described. (author)

FT-IR investigation of proton transfer in irradiated ice at 90 K in the absence of mobile bjerrum defects

International Nuclear Information System (INIS)

Devlin, J.P.; Richardson, H.H.

1984-01-01

Samples of cubic and amorphous ice containing isolated D 2 O molecules have been prepared using established methods. Radiolysis with 1.7 MeV electrons at 90 K has been observed to convert the D 2 O in H 2 O cubic ice to primarily coupled HOD pairs (HOD) 2 rather than isolated HOD. Based on the assumption that radiolysis produces an abundance of mobile protons but relatively few mobile orientational defects this result was predictable, i.e., the motion of protons through D 2 O sites converts the D 2 O to coupled (HOD) 2 , while extensive conversion of (HOD) 2 units to isolated HOD requires the passage of orientational defects. Thus, the vanishingly small amount of isolated HOD formed during irradiation has been interpreted as evidence that no significant number of mobile orientational defects are produced by radiolysis. The ability to observe (HOD) 2 as a dominant spectroscopic species has added to the credibility of an earlier thermal study of the kinetics of proton motion in ice that was dependent on the quantitative determination of the (HOD) 2 concentration as a function of reaction time. Furthermore, the observation that protons produced radiolytically fall rapidly into shallow traps, from which they are released by modest warming (to approx.130 K), supports a suggestion by Warman that, for a brief period following a radiolysis pulse, mobile protons are in pseudoequilibrium with protons immobilized by association with L defects. The D 2 O isolated in amorphous ice was similarly converted to HOD by mobile protons produced during radiolysis. However, the broader infrared bands of the amorphous samples have prevented assigning the HOD to a particular form [(HOD) 2 or isolated HOD]. The interesting result was the indication that the proton mobility in amorphous ice is comparable to that for cubic ice

Further investigations into pulsed optically stimulated luminescence from feldspars using blue and green light

DEFF Research Database (Denmark)

Ankjærgaard, Christina; Jain, Mayank; Kalchgruber, R.

2009-01-01

The purpose of this paper is to investigate characteristics of luminescence signals resulting from pulsed optical stimulation of feldspars and thereby to understand the underlying processes giving rise to the signal. Fourteen different feldspar specimens were investigated using time-resolved opti......The purpose of this paper is to investigate characteristics of luminescence signals resulting from pulsed optical stimulation of feldspars and thereby to understand the underlying processes giving rise to the signal. Fourteen different feldspar specimens were investigated using time...... suggests that the TR-OSL signal decay is governed by the recombination process and not by the excited state lifetime. Furthermore data from the TR-OSL signal dependence on stimulation time and preheat temperature suggest that the recombination process may not be a sum of exponentials, although the model...... cannot be rejected definitively....

Effect of temperature on the radiolysis of N/sub 2/O/sub 4/ in fast reactors

Energy Technology Data Exchange (ETDEWEB)

Nesterenko, V B; Nichipor, G V; Ukraintseva, L V

1974-01-01

The effects of temperature on radiolysis of gaseous nitrogen tetraoxide in fast reactors on assumption of radical mechanism have been studied. Energy transfer is assumed negligible. Data are obtained with ECM Minsk-22.

DNA radiolysis in DNA-protein complex: a stochastic simulation of attack by hydroxyl radicals

Czech Academy of Sciences Publication Activity Database

Běgusová, Marie; Giliberto, S.; Gras, J.; Sy, D.; Charlier, M.; Spotheim Maurizot, M.

2003-01-01

Roč. 79, č. 6 (2003), s. 385-391 ISSN 0955-3002 R&D Projects: GA AV ČR IAA1048103 Institutional research plan: CEZ:AV0Z1048901 Keywords : radiolysis * DNA-protein complexes * hydroxyl radicals Subject RIV: BO - Biophysics Impact factor: 2.165, year: 2003

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

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

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

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

Experimental investigation of powerful pulse current generators based on capacitive storage and explosive magnetic generators

Science.gov (United States)

Shurupov, A. V.; Zavalova, V. E.; Kozlov, A. V.; Shurupov, M. A.; Povareshkin, M. N.; Kozlov, A. A.; Shurupova, N. P.

2018-01-01

Experimental models of microsecond duration powerful generators of current pulses on the basis of explosive magnetic generators and voltage impulse generator have been developed for the electromagnetic pulse effects on energy facilities to verify their stability. Exacerbation of voltage pulse carried out through the use of electro explosive current interrupter made of copper wires with diameters of 80 and 120 μm. Experimental results of these models investigation are represented. Voltage fronts about 100 ns and the electric field strength of 800 kV/m are registered.

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)

Triplet State Resonance Raman Spectroscopy

DEFF Research Database (Denmark)

Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn

1978-01-01

Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied......Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied...

AFR report for 1974

International Nuclear Information System (INIS)

Westermark, T.

1975-01-01

The research of the radiation chemistry group at the Department of Nuclear Chemistry concerns the development of detection systems for pulse radiolysis and the radiation induced chemistry of hydrocarbons, sulphur and phosphorus compounds. The pulse radiolysis instrument consists of a 7 MeV microtron-accelerator equipped with optical and ac/dc conductivity detection systems. A mini computer PDP 11/40 is coupled on line to the detection systems. (Auth.)

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

Investigating Tribological Characteristics of HVOF Sprayed AISI 316 Stainless Steel Coating by Pulsed Plasma Nitriding

Science.gov (United States)

Mindivan, H.

2018-01-01

In this study, surface modification of aluminum alloy using High-Velocity Oxygen Fuel (HVOF) thermal spray and pulsed plasma nitriding processes was investigated. AISI 316 stainless steel coating on 1050 aluminum alloy substrate by HVOF process was pulsed plasma nitrided at 793 K under 0.00025 MPa pressure for 43200 s in a gas mixture of 75 % N2 and 25 % H2. The results showed that the pulse plasma nitriding process produced a surface layer with CrN, iron nitrides (Fe3N, Fe4N) and expanded austenite (γN). The pulsed plasma nitrided HVOF-sprayed coating showed higher surface hardness, lower wear rate and coefficient of friction than the untreated HVOF-sprayed one.

Dosimetry of steady-state gamma rays or pulsed X rays using liquid-core optical waveguides

International Nuclear Information System (INIS)

Radak, B.B.; McLaughlin, W.L.; Simic, M.G.; Warasawas, W.

1987-01-01

A liquid-core optical waveguide (OWG) sensor of ionizing radiation can be used for dosimetry over broad absorbed-dose ranges, by means of a relatively simple experimental arrangement. The analyzing visible light from one of several narrow wavelength-band sources at the proximal end of the OWG is propagated efficiently through a tightly coiled waveguide containing a radiochromic solution. This solution constitutes the sensor and attenuates the measuring light according to the simple Beer-Lambert relationship, where increases in the optical absorbance, measured photometrically at the distal end of the OWG, are proportional to the concentrations of the radiation-induced absorbing species (dye molecules), which in turn are proportional to the absorbed dose in the sensor. When the analyzing light is of broad spectral distribution, the absorbance vs dose relationship becomes sublinear. The apparatus may be adapted either to the spectrophotometric measurement of absorbed dose rate or integrated absorbed dose during gamma radiolysis or to dosimetry in the pulse radiolysis or flash photolysis of radiation-stimulated chromophores. The OWG principle works with any transparent liquid or gel sensor held as the core material of a flexible plastic tubing, whose refractive index is less than that of the light-propagating core. (author)

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)

γ-Ray radiolysis and theoretical study on radical ions of star-shaped oligofluorenes having a truxene or isotruxene as a core

International Nuclear Information System (INIS)

Fujitsuka, Mamoru; Tojo, Sachiko; Yang, Jye-Shane; Majima, Tetsuro

2013-01-01

Highlights: ► Radiolysis provides absorption spectra of radical ions of star-shaped oligofluorenes. ► Absorption spectroscopic properties depend on oligomer size extensively. ► TDDFT provides reasonable assignments to the visible and near-IR absorption bands. ► Extensive charge delocalization was indicated by planarization of oligomers. - Abstract: Poly- and oligofluorenes have been intensively studied for years, because of their excellent properties as photo- and electro-functional materials. Especially, star-shaped oligofluorenes as two-dimensional oligomers are interesting materials for wide researchers. To understand their electronic properties in charged states, absorption spectra of radical cation and radical anion of star-shaped oligomers with varied size were investigated by means of γ-ray radiolysis. The absorption spectra of their radical ions ranged from the visible to near-IR regions were successfully obtained. By using the theoretical calculation, the observed peaks were assigned. It is indicated that the transition between HOMO and LUMO of the original neutral state plays a significant role in the visible region. Furthermore, it is indicated that the star-shaped oligofluorenes tend to take a planar structure upon oxidation and reduction

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

Titles and works - Accreditation to Supervise Research

International Nuclear Information System (INIS)

Baldacchino, Gerard

2004-01-01

After a presentation of his academic curriculum and activities, the author proposes an overview of his research works. He identifies and discusses his scientific objectives and motivations which notably addressed the radiolysis of heavy ions, and more particularly the effect of high linear energy transfers (LET). He proposes an overview of his research thesis which addressed the geometry relaxation of molecules after their light excitation in an excited electronic status, and of his works on water radiolysis at high LET (effect of LET on radiolysis efficiencies, pulsed radiolysis with particles possession a high LET, Monte Carlo simulation of radiolysis with heavy ions), on application of radiolysis to molecules of biological interest, and on the influence of solvent confinement and on problems of local dosimetry. Then, the author presents his current research projects: radiolysis of supercritical water, effects of LET in radiolysis

The application of high-speed photography and spectrography for investigations of erosive pulsed plasma streams

International Nuclear Information System (INIS)

Kiselevskiy, L.I.; Minko, L.Ja.

The extensive information of pulsed plasma dynamic processes related to formation and interaction of plasma streams with a surrounding medium and obstacles is obtained with the help of high-speed photo and spectrography. The wave structure of pulsed supersonic under-expanded erosive plasma jets is studied. Some physical processes which are due to interactions of laser radiation with the laser-produced erosive plasma and of this plasma with a surrounding medium are investigated. The wide possibilities of frame photography of spectra quantitative spectroscopic investigations of fast-proceeding plasma processes are shown on the basis of joint use of high-speed photographic apparatus (type SFR) and standard spectrographs. The radial distribution of charged-particle concentrations at separate moments of time is obtained from the broadening of spectral lines at the brightness of the continuous spectrum of an erosive plasma jet from a pulsed accelerator

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.

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