Studies on hydrogen–oxygen systems in the electrical discharge. III. Surface effects

Brunet, Paul; Deglise, X.; Giguère, Paul A.

doi:10.1139/v70-340

Cited by 10 publications

(5 citation statements)

References 9 publications

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“…With the latter the two bands at 820 and 760 cm-I. as well as all the peroxide bands, were somewhat weaker, in agreement with recent observations made in this laboratory (29).…”

Section: The New Bandssupporting

confidence: 92%

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄

Giguère¹,

Herman²

1970

Can. J. Chem.

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The infrared absorption of the products from electrically dissociated H 2 0 or D 2 0 vapor and other hydrogen-oxygen systems trapped at liquid nitrogen temperature was measured between 4000 and 300 cm-'. Four new absorption bands were found in the deuterated systems at 857, 820,760, and about 440 cm-'. By isotopic substitution of 180 the frequencies are shifted to 806, 775, 717, and -420 cm-' as expected for 0-0 vibrations. In the hydrogen systems this region is obscured by the strong libration bands of H 2 0 and H 2 0 2 molecules. Temperature and composition effects show that more than one new species is involved. Accordingly the new spectra are assigned to the often postulated polyoxides, H 2 0 3 and H 2 0 4 , stabilized in the water-peroxide matrix. The more abundant, and also more stable, H 2 0 3 has a half-life of some 5 h at -65 "C.The observed frequencies are consistent with zigzag chain structures linked by single covalent bonds as in hydrogen polysulfides. Relative concentrations of the polyoxides are estimated at 5 to 10 mole% depending on the composition of the starting material. Possible mechanisms of formation and decomposition are discussed.

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“…With the latter the two bands at 820 and 760 cm-I. as well as all the peroxide bands, were somewhat weaker, in agreement with recent observations made in this laboratory (29).…”

Section: The New Bandssupporting

confidence: 92%

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄

Giguère¹,

Herman²

1970

Can. J. Chem.

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“…However, we cannot deduce whether O 2 was formed on the Al surface or in the radical source. Brunet et al 35 proposed that O 2 is formed on the inner wall of the radical source when H 2 O is dissociated in microwave-induced plasma. Nevertheless, we believe that O 2 was partly formed by the following surface reactions:…”

Section: Deposition Of H 2 O Fragmentsmentioning

confidence: 99%

Experimental studies of surface reactions among OH radicals that yield H2O and CO2 at 40–60 K

Oba

Watanabe

Kouchi

et al. 2011

Phys. Chem. Chem. Phys.

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We investigated the OH-related formation routes of two astrophysically important molecules, H(2)O and CO(2), under relatively warm astrophysical conditions. OH radicals, together with other neutral species such as H, O, H(2), and O(2), were produced in H(2)O microwave-discharge plasma and cooled to 100 K before being deposited on an Al substrate at 40-60 K. H(2)O formed at 40 and 50 K, but not at 60 K. Taking the experimental conditions into account, a possible route of H(2)O formation is via reactions involving OH + OH, which yield H(2)O(2) as the main reaction product. The present study is the first to show experimentally that surface reactions of two OH radicals can yield H(2)O at low temperatures. The products' branching ratio was 0.2 and 0.8 for H(2)O and H(2)O(2), respectively. When CO was co-deposited with neutral species that formed in the H(2)O plasma, CO(2) was formed at 40-60 K. H(2)CO(3) formed at 40 and 50 K. The present results may suggest that chemical reactions related to OH radicals are effective at yielding various molecules in relatively warm astrophysical environments, such as protostars.

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“…The discharge-flow system was essentially the same as before (5), except for a larger capacity vacuum system featuring a three-stage mercury diffusion pump (Leybold) with 45 1 s-' maximum capacity around 0.1 Torr (6). A large, spherical-shape, liquid nitrogen trap prevented back-streaming of mercury vapor.…”

Section: Methodsmentioning

confidence: 99%

“…Previous studies of these systems (1,5,7,19) For personal use only. and hydrogen peroxide yields on the "time of flight" of the vapor through the discharge zone.…”

Section: Distance Efectmentioning

confidence: 99%

Studies on Hydrogen–Oxygen Systems in the Electrical Discharge. VII. Deuterium Isotope Effects in the Chemistry of the Hydrogen Polyoxides

Arnau¹,

Giguère²

1975

Can. J. Chem.

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Can. J. Chem. 53,2490(1975. The kinetics of oxygen evolution on warming the trapped products (at -196 "C) from water or hydrogen peroxide vapor dissociated in a glow discharge were studied by the manometric method. Under closely controlled conditions it was possible to distinguish clearly the decomposition of the two intermediates, H 2 0 3 and H204. The latter begins to decompose measurably following crystallization of the glassy solid at about -115"; the trioxide decomposes readily between -50 and -35". Typically, the yields of H 2 0 3 from dissociated water vapor were of the order of 3 to 5 molz; those of H204, only about one-tenth as much. Varying the distance between the microwave discharge and the cold trap was found to affect differently the yields of the various products. Those of water and peroxide showed a simple, direct correlation; the minor constituents H2O3 and Hz04 followed entirely different patterns. Only a small fraction of the peroxide is formed via the H 2 0 4 intermediate inqhese systems. Less water, and more of the higher oxides, were obtained from dissociated hydrogen peroxide than from water vapor.The deuterated systems showed some unusual isotope effects. The yields of D 2 0 3 were always higher (up to twice and even more) than those of H z 0 3 under similar conditions. The other products showed little or no such effect, except for occluded oxygen and ozone which decreased by about half. Finally: the deuterium polyoxides decompose at slightly higher temperatures (10 to 15") than their hydrogen analogs. Mechanisms are proposed for the formation and decomposition of the polyoxides. Les systtmes deutCriCs presentent des effets isotopiques remarquables. Ainsi les rendements en D203 sont toujours plus forts (jusqu'a deux fois et mCme davantage) que ceux en Hz03 dans les mtmes conditions. Les autres produits ne montrent pas ou peu d'effet semblable, sauf I'oxygene et I'ozone occlus qui sont ?I moitiC moins abondants. Les polyoxydes de deuterium se dCcomposent a des tempkratures un peu plus 6levCes (de 10 a 15 "C) que ceux d'hydrogtne. On propose des mecanismes pour la formation et la dCcomposition des polyoxydes.

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Studies on hydrogen–oxygen systems in the electrical discharge. III. Surface effects

Cited by 10 publications

References 9 publications

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄

Experimental studies of surface reactions among OH radicals that yield H2O and CO2 at 40–60 K

Studies on Hydrogen–Oxygen Systems in the Electrical Discharge. VII. Deuterium Isotope Effects in the Chemistry of the Hydrogen Polyoxides

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Studies on hydrogen–oxygen systems in the electrical discharge. III. Surface effects

Cited by 10 publications

References 9 publications

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H2O3 and H2O4

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H2O3 and H2O4

Experimental studies of surface reactions among OH radicals that yield H2O and CO2 at 40–60 K

Studies on Hydrogen–Oxygen Systems in the Electrical Discharge. VII. Deuterium Isotope Effects in the Chemistry of the Hydrogen Polyoxides

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Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄

Studies on hydrogen–oxygen systems in the electrical discharge. IV. Spectroscopic identification of the matrix-stabilized intermediates, H₂O₃ and H₂O₄