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Thermodynamic study of sulphur hemi-oxide using mass spectrometry (1963); Etude thermodynamique de l'hemioxyde de soufre par spectrometry de masse (1963)

Abstract

The action of oxygen on sulphur, at low pressures, in a high frequency discharge has been studied by continuous mass-spectrometric analysis of the reaction products. The mass spectra of the gases produced by the discharge correspond to a mixture of SO{sub 2}, S{sub 2}O, S{sub 2} and O{sub 2}. We have measured up to 75 per cent of SO{sub 2} in the SO{sub 2} + S{sub 2}O mixture. We have concluded that the molecules S{sub 2}O{sub 2}, and SO are not present in the mixture. The ionisation potentials of the molecules and the potential required for the appearance of ion fragments in the gas discharge mixture have been studied by mass spectrometry. The heat of formation of S{sub 2}O has been estimated using the appearance potentials of the SO{sup +} ions coming from SO{sub 2}, and S{sub 2}O. ( 18.5 kcal/mole < {delta}H, (S{sub 2}O{sub g}) < 7 kcal/mole). We have measured the ionisation potentials of the molecules S{sub 2}, S{sub 4}, S{sub 6} and S{sub 8} which are respectively as follows: 9.7 {+-} 0.1 eV; 10.4 {+-} 0.5 eV; 8.5 {+-} 0.3 eV et 7.3 {+-} 0.3 eV. Finally we have studied the equilibrium for the formation of S{sub  More>>
Authors:
Hagemann, R [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Jan 15, 1964
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-2398
Resource Relation:
Other Information: TH: These es sciences physiques; 31 refs
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMBUSTION; FORMATION HEAT; HIGH-FREQUENCY DISCHARGES; IONIZATION POTENTIAL; MASS SPECTROSCOPY; OXYGEN; PRESSURE DEPENDENCE; SULFUR; SULFUR DIOXIDE; TEMPERATURE DEPENDENCE; THERMODYNAMICS
OSTI ID:
20818079
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: FR06R2398118208
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
66 pages
Announcement Date:
Dec 30, 2006

Citation Formats

Hagemann, R. Thermodynamic study of sulphur hemi-oxide using mass spectrometry (1963); Etude thermodynamique de l'hemioxyde de soufre par spectrometry de masse (1963). France: N. p., 1964. Web.
Hagemann, R. Thermodynamic study of sulphur hemi-oxide using mass spectrometry (1963); Etude thermodynamique de l'hemioxyde de soufre par spectrometry de masse (1963). France.
Hagemann, R. 1964. "Thermodynamic study of sulphur hemi-oxide using mass spectrometry (1963); Etude thermodynamique de l'hemioxyde de soufre par spectrometry de masse (1963)." France.
@misc{etde_20818079,
title = {Thermodynamic study of sulphur hemi-oxide using mass spectrometry (1963); Etude thermodynamique de l'hemioxyde de soufre par spectrometry de masse (1963)}
author = {Hagemann, R}
abstractNote = {The action of oxygen on sulphur, at low pressures, in a high frequency discharge has been studied by continuous mass-spectrometric analysis of the reaction products. The mass spectra of the gases produced by the discharge correspond to a mixture of SO{sub 2}, S{sub 2}O, S{sub 2} and O{sub 2}. We have measured up to 75 per cent of SO{sub 2} in the SO{sub 2} + S{sub 2}O mixture. We have concluded that the molecules S{sub 2}O{sub 2}, and SO are not present in the mixture. The ionisation potentials of the molecules and the potential required for the appearance of ion fragments in the gas discharge mixture have been studied by mass spectrometry. The heat of formation of S{sub 2}O has been estimated using the appearance potentials of the SO{sup +} ions coming from SO{sub 2}, and S{sub 2}O. ( 18.5 kcal/mole < {delta}H, (S{sub 2}O{sub g}) < 7 kcal/mole). We have measured the ionisation potentials of the molecules S{sub 2}, S{sub 4}, S{sub 6} and S{sub 8} which are respectively as follows: 9.7 {+-} 0.1 eV; 10.4 {+-} 0.5 eV; 8.5 {+-} 0.3 eV et 7.3 {+-} 0.3 eV. Finally we have studied the equilibrium for the formation of S{sub 2}O from sulphur and SO{sub 2} in a hot filament reactor. The measurement of the variation, between 1100 deg K and 1500 deg K, of the equilibrium constant for the reaction: SO{sub 2} + 3/2 S{sub 2} {r_reversible} 2 S{sub 2}O has made it possible to determine the enthalpy change of this reaction. ({delta}H = 5310 {+-} 370 cals) The sum of the states of the S{sub 2}O molecule, Z{sup 0}, has been calculated from the literature data. By applying to the S{sub 2}O formation equilibrium the equation: Log K{sub p} = {delta}Log Z{sup 0}/N - {delta}H{sup 0}{sub 0}/RT it has been possible to calculate the enthalpy of the reaction at absolute zero ({delta}H{sup 0}{sub 0} 4780 {+-} 60 cal/mole). Taking into account the specific heat integral between 0 deg K and 1300 deg K, the values obtained by this method and by using Van't Hoff's law are in good agreement. We have also examined the work concerning the heat of formation of SO to discover whether the formation of SO is possible between 1000 deg K and 1500 deg K starting from sulphur and SO{sub 2}. (author) [French] L'action de l'oxygene sur le soufre, a basse pression, dons une decharge haute frequence, a ete etudiee en analysant en continu, les produits de la reaction par spectrometrie de masse. Les spectres de masse du gaz issu de la decharge correspondent a un melange SO{sub 2}, S{sub 2}O, S{sub 2} et O{sub 2}. Nous avons mesure jusqu'a 75 pour rent de SO{sub 2} dans le melange SO{sub 2} + S{sub 2}O. Nous avons conclu a l'absence des molecules S{sub 2}O{sub 2}, et SO dans le melange. Les potentiels d'ionisation des molecules, et d'apparition des ions fragments du melange issu de la decharge, ont ete etudies par spectrometrie de masse. La chaleur de formation de S{sub 2}O a ete estimee a partir des mesures des potentiels d'apparition des ions SO{sup +} provenant de SO{sub 2}, et S{sub 2}O. (- 18.5 kcal/mole - < {delta}H, (S{sub 2}O{sub g}) < - 7 kcal/mole). Nous avons ete amenes a mesurer les potentiels d'ionisation des molecules S{sub 2}, S{sub 4}, S{sub 6} et S{sub 8} dont les valeurs sont respectivement: 9,7 {+-} 0,1 eV; 10,4 {+-} 0,5 eV; 8,5 {+-} 0,3 eV et 7,3 {+-} 0,3 eV. Nous avons enfin etudie l'equilibre de formation de StO a partir de soufre et de S{sub 2}O, dans un reacteur a filaments chauds. La mesure de la variation, entre 1100 deg K et 1500 deg K. de h constante d'equilibre de la reaction: SO{sub 2} + 3/2 S{sub 2} {r_reversible} 2 S{sub 2}O a permis de determiner la variation d'enthalpie de cette reaction ({delta}H = 5310 {+-} 370 calories) La somme d'etats de la molecule S{sub 2}O, Z{sup 0}, a ete calculee a partir des donnees bibliographiques. En appliquant a l'equilibre de formation de S{sub 2}O l'equation: Log K{sub p} = {delta}Log Z{sup 0}/N - {delta}H{sup 0}{sub 0}/RT nous avons calcule l'enthalpie de ia reaction au zero absolu ({delta}H{sup 0}{sub 0} = 4780 {+-} 60 cal/mole). Compte tenu de l'integrale des chaleurs specifiques entre 0 deg K et 1300 deg K. les valeurs obtenues par cette methode et par la loi de Van't Hoff concordent. Nous avons egalement examine les travaux concernant la chaleur de formation de SO, pour savoir si la formation de SO est possible entre 1000 deg K et 1500 deg K a partir de soufre et de SO{sub 2}. (auteur)}
place = {France}
year = {1964}
month = {Jan}
}