Understanding the mechanism of the sulfur mustard hydrolysis reaction on the atomistic level from experiment and first-principles simulations

Klöffel T, Gordon D, Popiel S, Nawala J, Meyer B, Rodziewicz P (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Process Safety and Environmental Protection Elsevier

Book Volume: 172

Pages Range: 105-112

DOI: 10.1016/j.psep.2023.02.001

Abstract

After World War II, the Baltic Sea was contaminated by dumping unused sulfur mustard (SM) and other chemical warfare agents (CWAs), which now constitutes a huge environmental hazard. We use both experimental and theoretical methods to understand the reactivity of SM in water, in particular the hydrolysis, which is one of the chemical reactions leading to the neutralization of SM. Real conditions present in the Baltic Sea are represented by performing Car-Parrinello molecular dynamics simulations for sulfur mustard in explicit water solution at finite temperature. We study the relative occurrence and stability of various SM conformers in water and analyze the solute–solvent interactions, with special focus on the formation of intra- and intermolecular hydrogen bonds and their lifetime. A missing piece toward the understanding of the sulfonium cation formation and SM hydrolysis reaction is provided by obtaining the activation energy for SM decomposition in water solution from gas chromatography–mass spectrometry (GC-MS) experiments. The complex mechanism of SM hydrolysis is also studied by umbrella sampling simulations to obtain the free energy barrier for the sulfonium cation formation and to provide an atomistic view of the reaction process.

Authors with CRIS profile

Tobias Klöffel-Hüsam Interdisziplinäres Zentrum für Molekulare Materialien (ICMM) Bernd Meyer Professur für Computational Chemistry Pawel Rodziewicz Interdisziplinäres Zentrum für Molekulare Materialien (ICMM)

Involved external institutions

Technische Militärakademie in Warschau PL Poland (PL)

How to cite

APA:

Klöffel, T., Gordon, D., Popiel, S., Nawala, J., Meyer, B., & Rodziewicz, P. (2023). Understanding the mechanism of the sulfur mustard hydrolysis reaction on the atomistic level from experiment and first-principles simulations. Process Safety and Environmental Protection, 172, 105-112. https://doi.org/10.1016/j.psep.2023.02.001

MLA:

Klöffel, Tobias, et al. "Understanding the mechanism of the sulfur mustard hydrolysis reaction on the atomistic level from experiment and first-principles simulations." Process Safety and Environmental Protection 172 (2023): 105-112.

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