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Heats of formation of gas phase organosulfur molecules, radicals and ions measured by PEPICO, and application of /sup 17/O and /sup 33/S NMR spectroscopy to structure determinations of organosulfur compounds. Progress report, June 1984-March 1985

Technical Report ·
OSTI ID:5528729

The photoionization studies have resulted in the determination of new heats of formation of the following molecules or ions: H/sub 2/S/sub 2/, C/sub 2/H/sub 5/S, C/sub 4/H/sub 9/SH/sup +/, C/sub 3/H/sub 7/S/sup +/. In addition, the dissociation mechanisms of diethyldisulfide and t-butyl sulfide have been investigated. These data clearly show that the ion t-butyl disulfide dissociates via a two component rate indicating that there exists an isomer which is lower in energy than that of t-butyl disulfide. During this contract period, we have also examined in considerable detail the /sup 17/O and /sup 33/S NMR spectral properties of numerous organosulfur compounds in an effort to identify substituent effects and trends which might serve as predictive parameters for the identification and verification of unknown organosulfur compounds. We have found new and convincing /sup 33/S NMR evidence favoring the dipolar description of the sulfinyl bond in sulfoxides. We have successfully established the analytical potential of both /sup 17/O and /sup 33/S NMR as useful methods for determining the composition of mixtures containing various oxidized organosulfur constituents. For the first time, we have applied the /sup 33/S NMR technique to the evaluation of organosulfur components in ''extracted'' coal samples, successfully observing a /sup 33/S resonance consistent with a family of aryl sulfonates. 19 refs., 3 figs., 5 tabs.

Research Organization:
North Carolina Univ., Chapel Hill (USA)
DOE Contract Number:
AS05-80ER10641
OSTI ID:
5528729
Report Number(s):
DOE/ER/10641-T1; ON: DE85010558
Country of Publication:
United States
Language:
English