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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; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux

Abstract

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 {alpha} position of the NO{sub 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  More>>
Authors:
Rosilio, C [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
May 01, 1968
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-3637
Resource Relation:
Other Information: TH: These docteur ingenieur; 67 refs; PBD: May 1968
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; ALKANES; CHEMICAL ANALYSIS; ELECTRON SPIN RESONANCE; IRRADIATION; NITROGEN; PHOTOLYSIS; RADICALS; RADIOLYSIS
OSTI ID:
20523419
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR04R3637091474
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
[127] pages
Announcement Date:
May 29, 2005

Citation Formats

Rosilio, C. 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; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux. France: N. p., 1968. Web.
Rosilio, C. 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; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux. France.
Rosilio, C. 1968. "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; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux." France.
@misc{etde_20523419,
title = {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; Etude par resonance paramagnetique electronique des radicaux formes par radiolyse a 77 K des nitroalcanes et de leurs solutions dans les verres organiques analyse par chromatographie des produits de la radiolyse du nitromethane en solution dans l'ethanol en milieux vitreux}
author = {Rosilio, C}
abstractNote = {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 {alpha} position of the NO{sub 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) [French] Dans le but d'expliquer la formation des produits finals formes au cours de la photolyse et la radiolyse des nitroalcanes, nous nous sommes proposes d'identifier les especes paramagnetiques se formant intermediairement au cours de la radiolyse. Notre etude porte sur la structure et la reactivite des radicaux formes par irradiation 7 des derives nitres a 77 K, et sur le mecanisme de formation et de disparition de ces radicaux dans les differentes matrices utilisees. Les radicaux resultant de l'arrachement d'un hydrogene en {alpha} du groupe NO{sub 2}, et les radicaux resultant de reactions d'addition sur le groupe nitre caracterises par un electron non apparie sur l'azote ont ete identifies, soit dans la radiolyse des nitroalcanes purs, soit dans la radiolyse a 77 K des nitroalcanes en solution dans les verres organiques. La conformation et les mouvements des radicaux dans les matrices, le mecanisme de formation des radicaux observes resultant generalement de la capture par les nitroalcanes des especes primaires de la radiolyse ont ete etudies. Les nitroalcanes en solution dans l'ethanol se manifestent a la fois comme capteurs d'electrons et de radicaux libres. L'etude de la radiolyse des nitroalcanes en solution dans un verre polaire d'ethanol a ete completee par des analyses chimiques des produits finals de la radiolyse; elle nous a permis de deduire l'efficacite de capture des electrons pieges et des radicaux libres par les nitroalcanes dans l'ethanol. Pour cela nous avons dose, pour le systeme nitro-methane - ethanol les rendements radiochimiques de-l'hydrogene, de l'acetaldehyde et du glycol en fonction de la concentration en capteur. Un mecanisme de disparition des radicaux observes a ete propose. (auteur)}
place = {France}
year = {1968}
month = {May}
}