Isotope effects in the gas phase radiolysis of H2S and D2S

1976 ◽  
Vol 54 (17) ◽  
pp. 2767-2772
Author(s):  
Robert D. McAlpine ◽  
O. A. Miller ◽  
A. W. Boyd

Gas phase radiolysis studies have been carried out on mixtures of H2S and D2S using as irradiation sources, either a Gammacell or a Febetron 705 pulsed electron accelerator. Separation factors (α = (H/D)prod ÷ (H/D)react) were obtained for various values of xD (the mole fraction of D2S), dose rate and temperature, as well as with the addition of SF6. All of the observed α values, for 0.2 ≤ xD ≤ 0.8, fall on the following empirical straight line.[Formula: see text]The addition of neon to a D2S/H2S mixture gives a value of α which decreases as the partial pressure of neon increases. For a 70% D2S/30% H2S mixture, &([a-z]+); = 1.9 ± 0.1 for the pure mixture and 1.28 ± 0.08 when 90 kPa of neon has been added to 10 kPa of the mixture. The &([a-z]+); values described by eq. 1 are interpreted as arising from kinetic isotope effects in the reactions of (translationally) hot H or D atoms with H2S, HDS, or D2S to form H2, HD or D2.Hydrogen yields from the gas phase radiolysis of pure H2S and pure D2S have been determined for dose rates from 4 × 1016 to 2 × 1028 eV g−1 s−1. Using dose rates of up to 2 × 1027 eV g−1 s−1, ΔG = G(H2) − G(D2) = 0.5. For the highest dose rate used (2 × 1028 eV g−1 s−1), ΔG = 1.5. The larger value of ΔG at very high dose rates is thought to arise from the dissociative neutralization processes. A possible mechanism is discussed.

1970 ◽  
Vol 48 (19) ◽  
pp. 3029-3033 ◽  
Author(s):  
C. Willis ◽  
O. A. Miller

Carbon monoxide has been irradiated with single intense pulses from an electron accelerator at a dose rate of ~ 2 × 1027 eV g−1 s−1. The yield of carbon dioxide obtained was G(CO2) = 0.7 ± 0.1 with a very small yield of carbon suboxide, G(C3O2) ≤ 0.02.Addition of propene reduces the carbon dioxide yield to almost zero while addition of propane has no effect. This suggests that propene is acting as an oxygen atom scavenger rather than as a quencher of an excited state of carbon monoxide. However, rate constant data do not support this suggestion and it is concluded that the residual yield of carbon dioxide observed at high dose rates arises from reaction 9[Formula: see text]where CO+ is in an A2Π or B2Σ+ state.


1974 ◽  
Vol 5 (22) ◽  
Author(s):  
YOSHIHIKO HATANO ◽  
SATOSHI TAKAO ◽  
HIDEKI NAMBA ◽  
TAKUMI UENO ◽  
SHOJI SHIDA

1974 ◽  
Vol 47 (3) ◽  
pp. 741-742 ◽  
Author(s):  
Yoshihiko Hatano ◽  
Satoshi Takao ◽  
Hideki Namba ◽  
Takumi Ueno ◽  
Shoji Shida

1990 ◽  
Vol 201 ◽  
Author(s):  
E. Cortesi ◽  
F. Namavar ◽  
R. F. Pinizzotto ◽  
H. Yang

AbstractWe have studied Separation by IMplantation of OXygen (SIMOX) processes using very high dose rates (40–60 μA/cm2). For a dose of 4 × 1017 O+/cm2 at 160 keV, the structure formed by implantation at 50 μA/cm2 is very similar to that associated with lower dose rates. The same dose implanted at a dose rate of 60 μA/cm2, however, results in the formation of pits in the silicon surface as well as a somewhat different oxide structure. Implantation through a surface oxide layer appears to result in a structure similar to that associated with lower dose rate implantation. These and higher dose samples suggest that the threshold for pit formation is related to both dose rate and dose.


1973 ◽  
Vol 51 (24) ◽  
pp. 4056-4061 ◽  
Author(s):  
A. W. Boyd ◽  
C. Willis ◽  
O. A. Miller

The isotope effect in the formation of hydrogen has been measured for H2O–D2O mixtures (10–90% H2O, 0.5–1.0 mg ml−1, 412–138 °C) with and without 1 mol% SF6 at 2 × 1027 eV g−1 s−1. The values of α ((H/D) radiolytic hydrogen/(H/D) H2O–D2O) for the reactions of hydrogen atoms are in the range 3–6 varying with H/D ratio of the substrate. Consideration of possible mechanisms for these large α values leads to the conclusions that reaction of the hydrogen atoms to form hydrogen involves the substrate and that the species H3O may be formed as an intermediate.


1970 ◽  
Vol 48 (22) ◽  
pp. 3463-3472 ◽  
Author(s):  
Clive Willis ◽  
P. E. Bindner

Ozone yields have been measured in CO2–O2 mixtures irradiated with single pulses from a Febetron 705 at a dose rate of 1026 eV g−1 s−1. Low concentrations of carbon dioxide in oxygen rapidly reduce the yield from G(O3) = 12.8 to G(O3) ≈ 9. At 300 Torr total pressure, as the oxygen concentration is reduced, the ozone yield decreases from this yield of G(O3) ≈ 9 to an extrapolated yield, at zero oxygen, of close to G(O3) = 7.8. Changes of yields with composition are explained in terms of ionic reactions, the main neutralization process being[Formula: see text]At 700–1500 Torr total pressure, the ozone yields are lower than that at 300 Torr. It is proposed that clustering of the ionic species affects the products of the neutralization reaction.Sulfur hexafluoride suppresses the dissociative neutralization reaction and ozone yields from mixtures containing 1.5–2% SF6 are those predicted from direct neutral dissociation processes in the pure gases.Computer calculations are used to compare the experimental results to the proposed mechanism and, in general, a good fit is obtained.


1972 ◽  
Vol 50 (1) ◽  
pp. 83-92 ◽  
Author(s):  
A. W. Boyd ◽  
C. Willis ◽  
G. C. Lalor

Total hydrogen yields and their isotopic ratios have been measured in the single pulse, high dose rate radiolysis of H2O–D2O mixtures and acidic, basic, and nitrous oxide solutions. The yield from D2O is ~11% lower than in H2O at 7 × 1027 eV g−1s−1. In acid solutions the yields from H2O and D2O are the same within 5%. This yield, G(H2) = 1.15 ± 0.05 has been used to derive a value of kH+OH = 2.5 ± 0.3 × 1010 M−1 s−1.Using the literature values for primary yield data and for the reaction rate constants, values of α have been determined for the various hydrogen forming processes by computer calculation. We obtain values for hydrogen formation of αspur = 2.1 ± 0.1, αe+e = 6.0 ± 0.1, αH+H (effective) = 3.2 ± 0.1, and αe+H (effective) = 1.3 ± 0.2. Detailed consideration of the mechanisms involved suggest that there are little or no isotopic preferences in H + H and e + H reactions.


1963 ◽  
Vol 41 (6) ◽  
pp. 1463-1468 ◽  
Author(s):  
T. W. Woodward ◽  
R. A. Back

The effect of electric fields on the γ-radiolysis of ethane, propane, and the butanes has been investigated briefly at 800 mm pressure, with dose rates between 2 × 1010 and 400 × 1010 ev/cc sec. Yields of hydrogen were reduced when a saturation field was applied, except with ethane at low dose rate, where a slight increase in hydrogen yield was observed. With propane and n-butane, the yield of hydrogen in the presence of a saturation field was independent of dose rate, while with ethane, it decreased with decreasing dose rate. At the same time, a dose rate dependence was discovered in the simple radiolysis, in the absence of any field, of ethane, propane, and n-butane, a decrease in the yield of hydrogen at low dose rates being observed. An explanation of these observations is suggested in terms of a competition between neutralization of ions in the gas phase and diffusion of ions to the wall. High dose rates should favor the former process, and low dose rates the latter. At sufficiently high dose rates, all ions should be neutralized in the gas phase. At sufficiently low dose rates, all ions should diffuse to the wall before neutralization, and it is suggested that the radiolysis under these conditions should closely resemble that in the presence of a saturation field at higher dose rates.


Cancers ◽  
2021 ◽  
Vol 13 (19) ◽  
pp. 4942
Author(s):  
Maria Grazia Ronga ◽  
Marco Cavallone ◽  
Annalisa Patriarca ◽  
Amelia Maia Leite ◽  
Pierre Loap ◽  
...  

The development of innovative approaches that would reduce the sensitivity of healthy tissues to irradiation while maintaining the efficacy of the treatment on the tumor is of crucial importance for the progress of the efficacy of radiotherapy. Recent methodological developments and innovations, such as scanned beams, ultra-high dose rates, and very high-energy electrons, which may be simultaneously available on new accelerators, would allow for possible radiobiological advantages of very short pulses of ultra-high dose rate (FLASH) therapy for radiation therapy to be considered. In particular, very high-energy electron (VHEE) radiotherapy, in the energy range of 100 to 250 MeV, first proposed in the 2000s, would be particularly interesting both from a ballistic and biological point of view for the establishment of this new type of irradiation technique. In this review, we examine and summarize the current knowledge on VHEE radiotherapy and provide a synthesis of the studies that have been published on various experimental and simulation works. We will also consider the potential for VHEE therapy to be translated into clinical contexts.


The electron beam generated by a 15 MeV linear accelerator has been employed to induce reactions in aerated aqueous solutions of 1 to 25 mM ferrous sulphate, and of 0⋅1 to 1 mM ceric sulphate. The radiation was delivered in pulses of 1⋅3 μ s duration and over a range of dose rates from 0⋅5 to 20000 rads/pulse. Radiation yields at constant dose rate were compared with the aid of a chemical dose monitor. A system of two thin, widely spaced, irradiation vessels was employed to determine the variation of yield of any one system over successive known ranges of dose rate. The yield of ferric sulphate in the iron system was found to decrease with increasing dose rate in the range 0⋅01 to 10 krads/pulse by an overall factor of 0⋅85, and was appreciably dependent on the initial concentrations of dissolved oxygen and of ferrous sulphate at high dose rates. Yields of hydrogen and of hydrogen peroxide were practically independent of dose rate. The observations have been interpreted on the basis of inter-radical reactions which occur when the reaction zones of neighbouring clusters overlap. The following reactions can account for all the data: OH + Fe 2+ → Fe 3+ + OH ¯ , (1) H + O 2 → HO 2 , (2) H + OH → H 2 O. (7) The values k 1 / k 7 = 0⋅0062, and k 2 / k 7 = 0⋅22 are reasonably consistent with the observations. In the ceric sulphate system the yield of cerous sulphate increases progressively over the range 0⋅01 to 10 krads/pulse by an overall factor of 1⋅4. The data accord with the view that at high dose rates OH radicals react with them selves ultimately to form hydrogen peroxide, in competition with their normal reaction with cerous sulphate.


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