The Radiation—Induced Decomposition of the Alkali and Alkaline Earth Perchlorates. I. Product Yields and Stoichiometry<sup>1a</sup>

Prince, Loïc; Johnson, Everett R.

doi:10.1021/j100886a002

Cited by 24 publications

(14 citation statements)

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“…Furthermore, partial escape of chlorine dioxide (ClO 2 ) from the sample between irradiation and ex situ detection methods cannot be ruled out completely. The other methods used in this study (i.e., X-ray diffraction and FTIR spectroscopy) could not evidently identify the structures of the decomposition products (Prince & Johnson 1965).…”

Section: Tpd Profiles Of Magnesium Perchlorate Hexahydrate Samplesmentioning

confidence: 77%

“…Here, by probing the radiolysis products of magnesium perchlorate hexahydrate (Mg(ClO 4 ) 2 •6H 2 O) via soft photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS, Kaiser et al 2010;Zhang et al 2011;Golan et al 2013;Jones & Kaiser 2013;Abplanalp et al 2016), we demonstrate the very first in situ detection of thechlorine dioxide radical (ClO 2 ). Although there have been earlier works investigating the radiolytic decomposition of perchlorates ( -ClO 4 ), these studies exploited only offline and ex situ detection methods (Cole 1960;Prince & Johnson 1965;Quinn et al 2013). This may allow the sample to be chemically altered between irradiation and measurement by oxidation of the chlorine oxide radicals initially formed.…”

Section: Introductionmentioning

confidence: 99%

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IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

Góbi

Bergantini

Kaiser

2016

ApJ

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Magnesium perchlorate hexahydrate (Mg(ClO 4) 2 •6H 2 O) samples were exposed to energetic electrons to investigate the products of the decomposition of perchlorates in the Martian soil and to infer their role in the degradation of organics on Mars. The samples were monitored online and in situ via infrared spectroscopy as well as electron impact (EI-QMS) and reflectron time-of-flight mass spectrometry coupled with single photon ionization (PI-ReTOF-MS). Our study reveals that besides chlorates (-ClO 3) and molecular oxygen (O 2), the chlorine dioxide radical (ClO 2) was observed online and in situ for the first time as a radiolysis product of solid perchlorates. Chlorine dioxide, which is used on Earth as a strong oxidizing agent in water disinfection and bleaching, represents a proficient oxidizer-potentially more powerful than molecular oxygen-to explain the lack of abundant organics in the Martian soil.

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Section: Tpd Profiles Of Magnesium Perchlorate Hexahydrate Samplesmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

Góbi

Bergantini

Kaiser

2016

ApJ

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“…In addition to chlorine dioxide and hypochlorite formation, radiolysis of alkali and alkaline Earth perchlorates [e.g., (MgClO 4 ) 2 ] can also result in the formation of chlorate and chlorite (Prince and Johnson, 1965). The presence of perchlorate radiolysis products in martian soils presents a number of important ramifications for Mars exploration, the habitability of martian soil, and the search for organic compounds.…”

Section: Discussionmentioning

confidence: 99%

Perchlorate Radiolysis on Mars and the Origin of Martian Soil Reactivity

et al. 2013

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Results from the Viking biology experiments indicate the presence of reactive oxidants in martian soils that have previously been attributed to peroxide and superoxide. Instruments on the Mars Phoenix Lander and the Mars Science Laboratory detected perchlorate in martian soil, which is nonreactive under the conditions of the Viking biology experiments. We show that calcium perchlorate exposed to gamma rays decomposes in a CO 2 atmosphere to form hypochlorite (ClO -), trapped oxygen (O 2 ), and chlorine dioxide (ClO 2 ). Our results show that the release of trapped O 2 (g) from radiation-damaged perchlorate salts and the reaction of ClO -with amino acids that were added to the martian soils can explain the results of the Viking biology experiments. We conclude that neither hydrogen peroxide nor superoxide is required to explain the results of the Viking biology experiments.

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“…The following radiation damage mechanisms can be proposed for the formation and decay of (310, from Cloy a t 300 K : [16] have shown that the C10, is the most dominant radiation damage product. However, these studies suggested only low concentrations of Cloy, CIO-, and C1-radicals.…”

Section: Dissociation Mechanismsmentioning

confidence: 99%

ESR and Optical Absorption Studies of ClO₃ in Ba(ClO₄)₂ · 3H₂O Single Crystals

Sastry

Rao

1982

Physica Status Solidi (b)

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The CIO, radical observed in y-irradiated Ba(CIO,), . 3 H,O is studied by ESR and optical absorption techniques. The radical orientation and stability with increased irradiation and thermal and UV light bleaching are discussed. A temperature variation study by ESR reveals that there is an increase of 13.8% and a decrease of 4% in the chlorine p-orbital and s-orbital spin densities, respectively, when the temperature is lowered from 300 to 77 K. A comparison of the results obtained for CIO, with the other iso-electronic trioxide radicals shows that the maximum fractional change in the spin densities occurs in the case of CIO, and that these changes depend on the electronegativity of the central atom. IntrodactionThe presence of the C10, radical in X-or y-irradiated perchlorates and chlorates [l to 61 has been well established in earlier studies. Though the host lattice dependence of the stabilities of paramagnetic radicals is well known, the stability of C10, was studied only in a few lattices [3,5, 61. Besides, there is no report on the study of the temperature variation of the magnetic parameters of this radical, though such studies were reported for C10, [7]. These studies give an understanding of the structural changes of the radical as well as the effects of molecular and lattice vibrations.Recently we reported the proton spin-flip satellite lines associated with the C10, radical in Ba(C10,), . 3 H,O [S]. I n the present paper we discuss the orientation, the effect of increased y-irradiation, thermal and UV light induced reactions, and the temperature dependence of the hyperfine coupling constants of this radical. These investigations may help in understanding the effect of the present lattice on the stability and behaviour of the C10, radical besides the effect of structural changes or niolecular and lattice vibrations on its spin Hamiltonian. Crystal StructureThe crystal structure of Ba(C10,), -3 H,O is hexagonal biniolecular with unit cell dimensions a = 0.72944 nm and c = 0.96744 nm. The X-ray crystallographic study l) Madras 600036, India.') On sabbatical leave till June 1982 a t the Physikalische Chemie 111,

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The Radiation—Induced Decomposition of the Alkali and Alkaline Earth Perchlorates. I. Product Yields and Stoichiometry^1a

Cited by 24 publications

References 2 publications

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

Perchlorate Radiolysis on Mars and the Origin of Martian Soil Reactivity

ESR and Optical Absorption Studies of ClO₃ in Ba(ClO₄)₂ · 3H₂O Single Crystals

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The Radiation—Induced Decomposition of the Alkali and Alkaline Earth Perchlorates. I. Product Yields and Stoichiometry1a

Cited by 24 publications

References 2 publications

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO2) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO2) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

Perchlorate Radiolysis on Mars and the Origin of Martian Soil Reactivity

ESR and Optical Absorption Studies of ClO3 in Ba(ClO4)2 · 3H2O Single Crystals

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The Radiation—Induced Decomposition of the Alkali and Alkaline Earth Perchlorates. I. Product Yields and Stoichiometry^1a

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO₂) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

ESR and Optical Absorption Studies of ClO₃ in Ba(ClO₄)₂ · 3H₂O Single Crystals