Combining experiment and theory to elucidate the role of supercritical water in sulfide decomposition
Abstract
The cleavage of C-S linkages plays a key role in fuel processing and organic geochemistry. Water is known to affect these processes, and several hypotheses have been proposed, but the mechanism has been elusive. Here we use both experiment and theory to demonstrate that supercritical water reacts with intermediates formed during alkyl sulfide decomposition. During hexyl sulfide decomposition in supercritical water, pentane and CO + CO2 were detected in addition to the expected six carbon products. A multi-step reaction sequence for hexyl sulfide reacting with supercritical water is proposed which explains the surprising products, and quantum chemical calculations provide quantitative rates that support the proposed mechanism. The key sequence is cleavage of one C-S bond to form a thioaldehyde via radical reactions, followed by a pericyclic addition of water to the C[double bond, length as m-dash]S bond to form a geminal mercaptoalcohol. The mercaptoalcohol decomposes into an aldehyde and H2S either directly or via a water-catalyzed 6-membered ring transition state. The aldehyde quickly decomposes into CO plus pentane by radical reactions. The time is ripe for quantitative modelling of organosulfur reaction kinetics based on modern quantum chemistry.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
H2O promoted the decomposition of organic sulfur contents.
“Second, H2O promoted the decomposition of organic sulfur contents.”
From Sulfur transformation mechanism during supercritical water gasification of black liquor (2023) · cites this paper as [60]
Cites
Multiple sulfur isotopes and the evolution of Earth's surface sulfur cycle
Johnston, D. T. (2011) · Earth-Science Reviews · doi:10.1016/j.earscirev.2011.02.003 · Cited by 383 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Sub- and Supercritical Water Liquefaction of Kraft Lignin and Black Liquor Derived Lignin
Lappalainen, J., Baudouin, D., Hornung, U., Schuler, J., Melin, K., Bjelić, S., Vogel, F., Konttinen, J., & Joronen, T. (2020) · Energies · doi:10.3390/en13133309 · Cited by 87 · see citing works
“Free radical reactions are typically used to describe the formation of alkyl polysulfides [146–148], alkyl-tetrahydrothiophene [146,147], 1-alkene and alkyl thiol from n-alkyl sulfides through radical elimination reactions [146] or (n−1)-alkanes [146,150,151].”
BackgroundSulfur transformation mechanism during supercritical water gasification of black liquor
Lu, L., Wei, W., Liu, F., Ge, Z., Jin, H., Chen, Y., & Guo, L. (2023) · Fuel · doi:10.1016/j.fuel.2022.127333 · Cited by 22 · see citing works
On the selective desulphurization of biomass derivatives in supercritical water
Baudouin, D., Xiang, H., & Vogel, F. (2022) · Biomass and Bioenergy · doi:10.1016/j.biombioe.2022.106529 · Cited by 13 · see citing works
- Authors
- Kida, Y., Class, C. A., Concepcion, A. J., Timko, M. T., & Green, W. H.
- Affiliations
- Massachusetts Institute of Technology (US)
- Worcester Polytechnic Institute
- Corresponding author
- Green, William H.
- Venue
- Phys. Chem. Chem. Phys.
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2014
- Volume
- 16
- Issue
- 20
- Pages
- 9220-9228
- ISSN
- 1463-9076 (ISSN-L)
- 1463-9084
- OpenAlex
- W2124075192
- Cited by
- 71
- References
- 1
- Citations by year
- 2026: 3 · 2025: 3 · 2024: 6 · 2023: 7 · 2022: 3 · 2021: 4 · 2020: 7 · 2019: 10 · 2018: 4 · 2017: 7 · 2016: 7 · 2015: 8 · 2014: 2
- FWCI
- 4.15
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Physical Chemistry Chemical Physics (publishedVersion)
- PubMed (publishedVersion)
- Digital Commons @ Butler University (Butler University) (submittedVersion)
- Funders
- Massachusetts Institute of Technology
- Saudi Aramco
- Topics
- Physical Sciences › Engineering › Biomedical Engineering › Subcritical and Supercritical Water Processes
- Physical Sciences › Engineering › Mechanical Engineering › Catalysis and Hydrodesulfurization Studies
- Physical Sciences › Engineering › Computational Mechanics › Heat transfer and supercritical fluids
- Keywords
- supercritical water, alkyl sulfides, C–S bond cleavage, reaction mechanism, thioaldehydes, radical reactions, fuel processing, quantum chemical calculations
- MeSH terms
- Kinetics, Quantum Theory, Sulfides, Water
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
