The Reactions of Sulfur Atoms. VII. The Ultraviolet Spectrum, the Photolysis, and the Mercury Sensitization of Carbonyl Sulfide

K. S. Sidhu, O. P. Strausz, H. E. Gunning, I. G. Csizmadia

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

Ultrapure gaseous COS exhibits a broad absorption continuum in the near-ultraviolet region which starts at 2550 A and extends to below 2000 A with a rounded maximum at 2225 A. Semiempirical molecular orbital calculations, with the inclusion of the sulfur d orbitals, indicate this continuum to correspond to a π→ π* transition since the lowest lying n → π* type state appears at considerably higher energies. Photolysis in this region affords CO (ψ = 1.81 at 2537 and 2288 A) and sulfur. The primary step yields S atoms at least 74% of which are formed in the excited (1D) state. The mercury photosensitization at 2537 A affords only triplet-ground-state sulfur atoms. Both singlet- and triplet-state atoms abstractively attack COS to form S2 with the rate ratio, S(1D)/S(3P), being ca. 30. The condensed-phase photolysis is similar to that of the gas phase although the relative yields of triplet- and singlet-state atoms may be altered.

Original languageEnglish
Pages (from-to)2412-2417
Number of pages6
JournalJournal of the American Chemical Society
Volume88
Issue number11
DOIs
Publication statusPublished - Jun 1 1966

    Fingerprint

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this