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Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963)

Abstract

The rates of formation of the decomposition products of biphenyl; hydrogen, methane, ethane, ethylene, as well as triphenyl have been measured in the vapour and liquid phases at 460 deg. C. The study of the decomposition products of biphenyl at different temperatures between 400 and 460 deg. C has provided values of the activation energies of the reactions yielding the main products of pyrolysis in the vapour phase. Product and Activation energy: Hydrogen 73 {+-} 2 kCal/Mole; Benzene 76 {+-} 2 kCal/Mole; Meta-triphenyl 53 {+-} 2 kCal/Mole; Biphenyl decomposition 64 {+-} 2 kCal/Mole; The rate of disappearance of biphenyl is only very approximately first order. These results show the major role played at the start of the decomposition by organic impurities which are not detectable by conventional physico-chemical analysis methods and the presence of which accelerates noticeably the decomposition rate. It was possible to eliminate these impurities by zone-melting carried out until the initial gradient of the formation curves for the products became constant. The composition of the high-molecular weight products (over 250) was deduced from the mean molecular weight and the dosage of the aromatic C - H bonds by infrared spectrophotometry. As a result the existence in tars  More>>
Authors:
Clerc, M [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Jun 15, 1962
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-2386
Resource Relation:
Other Information: TH: These sciences; 51 refs
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ACTIVATION ENERGY; BIPHENYL; CHEMICAL REACTION KINETICS; IMPURITIES; PYROLYSIS; PYROLYSIS PRODUCTS; TAR; TEMPERATURE RANGE 0400-1000 K
OSTI ID:
20818067
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France); Faculte des Sciences de l'Universite de Paris, 75 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR06R2386118196
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
74 pages
Announcement Date:
Dec 30, 2006

Citation Formats

Clerc, M. Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963). France: N. p., 1962. Web.
Clerc, M. Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963). France.
Clerc, M. 1962. "Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963)." France.
@misc{etde_20818067,
title = {Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963)}
author = {Clerc, M}
abstractNote = {The rates of formation of the decomposition products of biphenyl; hydrogen, methane, ethane, ethylene, as well as triphenyl have been measured in the vapour and liquid phases at 460 deg. C. The study of the decomposition products of biphenyl at different temperatures between 400 and 460 deg. C has provided values of the activation energies of the reactions yielding the main products of pyrolysis in the vapour phase. Product and Activation energy: Hydrogen 73 {+-} 2 kCal/Mole; Benzene 76 {+-} 2 kCal/Mole; Meta-triphenyl 53 {+-} 2 kCal/Mole; Biphenyl decomposition 64 {+-} 2 kCal/Mole; The rate of disappearance of biphenyl is only very approximately first order. These results show the major role played at the start of the decomposition by organic impurities which are not detectable by conventional physico-chemical analysis methods and the presence of which accelerates noticeably the decomposition rate. It was possible to eliminate these impurities by zone-melting carried out until the initial gradient of the formation curves for the products became constant. The composition of the high-molecular weight products (over 250) was deduced from the mean molecular weight and the dosage of the aromatic C - H bonds by infrared spectrophotometry. As a result the existence in tars of hydrogenated tetra, penta and hexaphenyl has been demonstrated. (author) [French] Les vitesses de formation des produits de decomposition du biphenyle: hydrogene, methane, ethane, ethylene, ainsi que des triphenyles, ont ete mesurees en phase vapeur et en phase liquide a 460 deg. C. L'etude des produits de decomposition du biphenyle a differentes temperatures comprises entre 400 et 460 deg. C, a fourni les valeurs des energies d'activation des reactions conduisant aux principaux produits de la pyrolyse en phase vapeur. Produit et Energie d'activation: Hydrogene 73 {+-} 2 kcal/Mole; Benzene 76 {+-} 2 kcal/Mole; Metatriphenyle, 53 {+-} 2 kcal/Mole; Decomposition du biphenyle 64 {+-} 2 kcal/Mole; La vitesse de disparition du biphenyle n'est que tres approximativement du premier ordre. Ces resultats ont montre le role majeur dans les debuts de decomposition par des impuretes organiques non detectables par l'analyse physico-chimique classique et dont la presence accelere notablement la vitesse de decomposition. Ces impuretes ont pu etre eliminees par fusion de zone poursuivie jusqu'a constance de la pente initiale des courbes de formation des produits. La composition des produits de masse moleculaire elevee (superieure a 250) a ete deduite de la masse moleculaire moyenne et du dosage par spectrophotometry infrarouge des liaisons C - H aromatiques. Ainsi on a ete amene a admettre l'existence dans les goudrons de tetra, penta et hexaphenyles hydrogenes. (auteur)}
place = {France}
year = {1962}
month = {Jun}
}