skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Photoionization studies of organosulfur transient species

Abstract

Photoionization mass spectrometric studies of the transient species CH{sub 2}SH, CH{sub 3}S, CH{sub 2}S, and HCS have established the heats of formation of these species and their cations, thereby resolving a serious discrepancy between other recent experiments and ab initio calculations in favor of the latter. The isomers CH{sub 2}SH (CD{sub 2}SH) and CH{sub 3}S (CD{sub 3}S) were prepared in situ by reaction of F atoms with CH{sub 3}SH (CD{sub 3}SH). Similar successive abstractions, as well as pyrolysis of suitable precursors, were used to generate CH{sub 2}S and HCS. The adiabatic ionization potentials obtained, together with relevant appearance potentials and some auxiliary data, were sufficient to establish the heats of formation for the cited species. Together with confirmatory data obtained from dissociative ionization of CH{sub 3}SSCH{sub 3} into various fragments, thermochemical properties of these important intermediates occurring in the combustion of sulfur-containing hydrocarbon fuels were derived.

Authors:
;
Publication Date:
Research Org.:
Argonne National Lab., IL (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
10132759
Report Number(s):
ANL/CHM/PP-76968
ON: DE94008140
DOE Contract Number:  
W-31109-ENG-38
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: [1994]
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; ORGANIC SULFUR COMPOUNDS; TRANSIENTS; FORMATION HEAT; PHOTOIONIZATION; MASS SPECTROSCOPY; REACTION INTERMEDIATES; AIR POLLUTION; POLLUTANTS; DEUTERATION; COMBUSTION; THIOLS; IONIZATION POTENTIAL; 400800; 400201; 540120; COMBUSTION, PYROLYSIS, AND HIGH-TEMPERATURE CHEMISTRY; CHEMICAL AND PHYSICOCHEMICAL PROPERTIES; CHEMICALS MONITORING AND TRANSPORT

Citation Formats

Ruscic, B., and Berkowitz, J.. Photoionization studies of organosulfur transient species. United States: N. p., 1994. Web. doi:10.2172/10132759.
Ruscic, B., & Berkowitz, J.. Photoionization studies of organosulfur transient species. United States. doi:10.2172/10132759.
Ruscic, B., and Berkowitz, J.. Tue . "Photoionization studies of organosulfur transient species". United States. doi:10.2172/10132759. https://www.osti.gov/servlets/purl/10132759.
@article{osti_10132759,
title = {Photoionization studies of organosulfur transient species},
author = {Ruscic, B. and Berkowitz, J.},
abstractNote = {Photoionization mass spectrometric studies of the transient species CH{sub 2}SH, CH{sub 3}S, CH{sub 2}S, and HCS have established the heats of formation of these species and their cations, thereby resolving a serious discrepancy between other recent experiments and ab initio calculations in favor of the latter. The isomers CH{sub 2}SH (CD{sub 2}SH) and CH{sub 3}S (CD{sub 3}S) were prepared in situ by reaction of F atoms with CH{sub 3}SH (CD{sub 3}SH). Similar successive abstractions, as well as pyrolysis of suitable precursors, were used to generate CH{sub 2}S and HCS. The adiabatic ionization potentials obtained, together with relevant appearance potentials and some auxiliary data, were sufficient to establish the heats of formation for the cited species. Together with confirmatory data obtained from dissociative ionization of CH{sub 3}SSCH{sub 3} into various fragments, thermochemical properties of these important intermediates occurring in the combustion of sulfur-containing hydrocarbon fuels were derived.},
doi = {10.2172/10132759},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1994},
month = {3}
}