Radical and Molecular Yields in the γ-Radiolysis of D<sub>2</sub>O and H<sub>2</sub>O Vapor

Baxendale, J. H.; Gilbert, G. P.

doi:10.1021/ja01057a048

Cited by 13 publications

(6 citation statements)

References 1 publication

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“…This yield is reduced by --3 G units by the addition of an electron scavenger such as SF6 or N 2 0 (2, 3). The hydrogen yield from a mixture of water vapor (D20) and benzene is G(D2) x 0.5 (4). These results are consistent with the following reactions [ H + C6H6 + no Hz [9] e + SF, (or NzO) + H3O' + no H or Hz…”

Section: Introductionsupporting

confidence: 83%

Radiolysis of water vapor with fission fragments

Boyd¹,

Miller²

1968

Can. J. Chem.

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Water vapor, and mixtures of water vapor with radical and electron scavengers, have been irradiated with fission fragments a t temperatures from 170 to 365 "C and densities from 1-50 n~g / n~l .The unimolecular hydrogen yield is the same as in y-ray irradiations. In D20-C6HIz mixtures the HD yield and HD/H2 ratio are lower than in y-ray irradiations and N 2 0 and SF6 have little effect. The HD yield reaches a limiting value (G(HD) -4) with increasing linear energy transfer suggesting that a fraction of the D atoms formed are hot.

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Section: Introductionsupporting

confidence: 83%

Radiolysis of water vapor with fission fragments

Boyd¹,

Miller²

1968

Can. J. Chem.

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“…5 is close to the values which Baxendale 4 reports in the presence of added organic scavengers, and although measured with a radiation seems unreasonably high. Taking '' molecular " g(H2)-0.5 129 13 and assuming that the additional H2 is formed by radical-radical reactions, Hofmann's data indicate a total g(-H2O) = 22.6, which is in conflict with other published data.…”

Section: Discussion P U R E Water V a P O U Rmentioning

confidence: 68%

The ?-radiolysis of water vapour in the presence of NH3 and O2

Anderson¹,

Knight²,

Winter³

1966

Trans. Faraday Soc.

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Measurements of H2 production from pure water vapour as a function of dose indicate that, like liquid water, it is essentially stable to y radiation. The net yield of H2 is very low leading to a mean integral value of G(H+0007 but the amount of H2 obtained depends critically on the care taken in cleaning the cells and admitting the water, and it is concluded that previously-published yields are all integral values obtained under a variety of conditions. Measurement of the primary yields in the presence of N H 3 and of NH3fO2 gives g(0H) = 6.650.2, g(H) = 5-7f0.2, g(H2) = 047f0.01, but no distinction can be made between yields of electrons and H atoms in this work.Primary processes of ionization and charge recombination are considered in view of earlier postulates, together with physical evidence which demonstrates the stability of ion clusters in water vapour even at low pressures. It is suggested that, under certain conditions in the vapour phase, charge neutralization of the H3Of ion leads to the same yield of radicals as in liquid water.Published data on the radiolysis of water vapour are sparse and contradictory, both in the absence and presence of added scavengers. Values for G(H2) from the radiolysis of pure water vapour vary from 0.014 to 5.9,1-5 while the value for the radical pair yield g(H)* = 11.7, obtained by Firestone 3 in studies of the Dz/H20 exchange reaction, has been challenged by Baxendale and Gilbert,4 who report g(HJ = 8 k0.7 from measurements in the presence of organic scavengers. These values are of prime importance in understanding the radiolysis of water vapour, and we have extended the previous work by measurements both in pure water vapour and on the addition of NH3 and 0 2 . EXPERIMENTAL PREPARATIONSamples were irradiated in Pyrex cells ; the cell volumes varied from 100 to 1000 ml. The cells carried a B10 glass joint with a fragile tip for reopening under vacuum. Water samples were prepared in separate tubes containing a septum break seal, which were joined to the cell by fusion. Water was admitted to the main irradiation cell by breaking the septum with a glass rod before irradiation. These water tubes were filled on an all-glass mercury-free vacuum line in which the water vapour was not allowed to come into contact with any greased stopcocks during addition or transfer. An all-glass valve was designed for use with this system. The amount of water distilled into each water tube was monitored by measuring the difference in height of water in a precision-bore capillary after filling and sealing each tube. The metering tube was filled with water, which was first boiled to remove most of the dissolved gases, and then subjected to several cycles of freezing at -78"C, pumping to 10-6 mm Hg and thawing. Water tubes were evacuated to 10-6 mm Hg before distilling water into them and again before they were sealed. This technique of admitting water separately was developed because of difficulty experienced in adding 0 2 * Primary yields are written as g(x) and experimental yields as G(x).

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“…An additional piece of thermodynamic information, the standard volume change for the hydrogen-bonding process, can be obtained from Mm which can be written as14 Mm = (pv*rC0r/10'JtTXAV°-ß °/ (8) where p is the density of the solution, R is the gas constant, ß is the coefficient of thermal expansion of the solvent, cp is the constant pressure specific heat of the solvent, and for the mechanism under consideration is given by14 = (l/8tfaCo)i[(l + 4tfaC")/(l + 8tfaC0)I/!] -1} (9) where K& is the association constant for the reaction as given in eq 1. The term ßAH°/pcp is assumed to be negligible relative to AV°in the 1 wt % water-dioxane system.…”

Section: Results and Treatment Of Datamentioning

confidence: 99%

A Kinetic Study of the Hydrogen-Bond Dimerization of 2-Pyridone¹

Gg¹,

Ho²

1966

J. Am. Chem. Soc.

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Radical and Molecular Yields in the γ-Radiolysis of D₂O and H₂O Vapor

Cited by 13 publications

References 1 publication

Radiolysis of water vapor with fission fragments

Radiolysis of water vapor with fission fragments

The ?-radiolysis of water vapour in the presence of NH3 and O2

A Kinetic Study of the Hydrogen-Bond Dimerization of 2-Pyridone¹

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Radical and Molecular Yields in the γ-Radiolysis of D2O and H2O Vapor

Cited by 13 publications

References 1 publication

Radiolysis of water vapor with fission fragments

Radiolysis of water vapor with fission fragments

The ?-radiolysis of water vapour in the presence of NH3 and O2

A Kinetic Study of the Hydrogen-Bond Dimerization of 2-Pyridone1

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Radical and Molecular Yields in the γ-Radiolysis of D₂O and H₂O Vapor

A Kinetic Study of the Hydrogen-Bond Dimerization of 2-Pyridone¹