{"title":"Study on Autocatalytic Decomposition of Dimethyl Sulfoxide (DMSO) III: Investigations Regarding the Main Decomposition","authors":"Yoshikuni Deguchi*, Masafumi Kono, Yuto Koizumi, Yukino Watanabe, Michiya Fujita, Yu-ichiro Izato, Atsumi Miyake","doi":"10.1021/acs.oprd.1c00169","DOIUrl":null,"url":null,"abstract":"<p >It is important to know the entire decomposition mechanism of energetic materials for safety purposes, such as the assessment, control, mitigation, and prevention of thermal hazards. Dimethyl sulfoxide (DMSO) is a common solvent that is widely used in laboratories and industrial applications; however, several severe incidents due to its decomposition have been reported. The decomposition mechanism of DMSO has been studied for several years; however, it has not been sufficiently clear until now. To elucidate the complicated decomposition pathway, analyses of materials from DMSO decomposition were conducted. Several new chemical bonds were found in the decomposition products through gas chromatography–mass spectrometry (GC-MS) analysis, which suggests a radical reaction. Atomic sulfur S(0) or organic divalent sulfur S(II) was found on the inner wall of the vessel after decomposition, which indicates that the sulfur atom in DMSO was reduced during decomposition. In addition to the chemical analyses, a kinetic study was carried out for the data obtained through isothermal heating tests. All of the DMSO samples with or without the studied impurities showed similar activation energies for the main decomposition. Autocatalysts in DMSO decomposition are proposed to work not by accelerating the main decomposition but rather by shortening the induction period. It is proposed that the main decomposition of DMSO occurs via a radical pathway.</p>","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"25 12","pages":"2669–2678"},"PeriodicalIF":3.1000,"publicationDate":"2021-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.oprd.1c00169","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
It is important to know the entire decomposition mechanism of energetic materials for safety purposes, such as the assessment, control, mitigation, and prevention of thermal hazards. Dimethyl sulfoxide (DMSO) is a common solvent that is widely used in laboratories and industrial applications; however, several severe incidents due to its decomposition have been reported. The decomposition mechanism of DMSO has been studied for several years; however, it has not been sufficiently clear until now. To elucidate the complicated decomposition pathway, analyses of materials from DMSO decomposition were conducted. Several new chemical bonds were found in the decomposition products through gas chromatography–mass spectrometry (GC-MS) analysis, which suggests a radical reaction. Atomic sulfur S(0) or organic divalent sulfur S(II) was found on the inner wall of the vessel after decomposition, which indicates that the sulfur atom in DMSO was reduced during decomposition. In addition to the chemical analyses, a kinetic study was carried out for the data obtained through isothermal heating tests. All of the DMSO samples with or without the studied impurities showed similar activation energies for the main decomposition. Autocatalysts in DMSO decomposition are proposed to work not by accelerating the main decomposition but rather by shortening the induction period. It is proposed that the main decomposition of DMSO occurs via a radical pathway.
期刊介绍：
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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