Probing the kinetics for thiol desulfurization: The reactions of 2-methyl-2-propanethiol on Mo(110)

Journal Article · Thu May 28 04:00:00 EDT 1992 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100190a073· OSTI ID:555062

Wiegand, B C; Uvdal, P; Friend, C M ^[1]

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1. Harvard Univ., Cambridge, MA (United States)

The reactions of 2-methyl-2-propanethiol on Mo(110) were studied using temperature programmed reaction, high resolution electron energy loss, and X-ray photoelectron spectroscopies. The sulfur-hydrogen bond breaks upon adsorption at 120 K, yielding adsorbed 2-methyl-2-propyl thiolate and hydrogen. Thiolate hydrogenolysis produces isobutane, while cleavage of the C-S and selective C-H bond breaking {beta} to the sulfur yields isobutene. Nonselective decomposition to adsorbed carbon, sulfur, and gaseous dihydrogen is a competing channel. At reaction saturation, the selectivity for hydrocarbon for hydrocarbon formation patterns is 80%. The specific butane and butene isomers were identified on the basis of the differences in the fragmentation patterns of the various isomers when an electron energy of 27 eV was used in the mass spectrometer. The isometric selectivity corroborates the authors general mechanism for thiolate reaction. Isobutane formation preceded ethane formation for a 2-methyl-2-propanethiol/ethanethiol mixture. The kinetics for 2-methyl-2-propyl thiolate desulfurization were found to increase with increasing 2-methyl-2-propyl thiolate coverage. 38 refs., 6 figs., 4 tabs.

• Sponsoring Organization: USDOE
• DOE Contract Number: FG02-84ER13289
• OSTI ID: 555062
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 11 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL REACTION KINETICS
DESULFURIZATION
MOLYBDENUM
ORGANIC COMPOUNDS
SURFACES
TEMPERATURE RANGE 0065-0273 K
THIOLS