The Ultraviolet Absorption Spectra of Simple Hydrocarbons III. In Vapor Phase in the Schumann Region

Absorption spectra measurements between λ = 2300A and 1500A were made for fourteen ethylenic hydrocarbons, which included four butenes, five pentenes, one hexene, two heptenes and two octenes. A comparative study of these results together with those from the earlier papers in the series has shown th...

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Veröffentlicht in:The Journal of chemical physics 1936-12, Vol.4 (12), p.760-768
Hauptverfasser: Carr, Emma P., Stücklen, Hildegard
Format: Artikel
Sprache:eng
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Zusammenfassung:Absorption spectra measurements between λ = 2300A and 1500A were made for fourteen ethylenic hydrocarbons, which included four butenes, five pentenes, one hexene, two heptenes and two octenes. A comparative study of these results together with those from the earlier papers in the series has shown the existence of certain general relationships between the absorption spectra of all ethylenic derivatives. The number of alkyl groups bound to the carbon atoms of the C=C bond determines the wave number of the first absorption band; there is a progressive shift toward the visible with increasing number of alkyl groups but the nature of the alkyl group has almost no influence on the position of the first band; where two alkyl groups are bound to the same carbon atom (unsymmetrical substitution) or to different carbon atoms (symmetrical substitution), the wave number of the first band is very slightly different. The first band of these derivatives is tentatively assigned to an electronic excitation corresponding to the transition 1A1→1B1, predicted for the ethylene molecule. Usually one, but never more than three bands of this system could be seen because of overlapping with another group of bands of higher intensity. All of the sixteen olefines have this same intensity change, showing the existence of another electronic excitation. A third group of bands corresponding to a third electronic excitation can be seen clearly in the spectra of four hydrocarbons and may possibly be present but overlapping the lower frequency group in the other compounds. The bands are too broad and diffuse to admit of analysis of vibrational structure but certain recurring separations, which are probably related to the 1350 cm—1 vibrational frequency of ethylene, are evident. In the molecules of higher symmetry, where fewer transitions are permitted by the selection rules, there is less overlapping and therefore more discrete bands can be seen.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1749788