Method for Derivatization and Detection of Chemical Weapons Convention Related Sulfur Chlorides via Electrophilic Addition with 3-Hexyne

Abstract

Sulfur monochloride (S 2 Cl 2 ) and sulfur dichloride (SCl 2 ) are important precursors of the extremely toxic chemical warfare agent sulfur mustard and classified, respectively, into schedule 3.B.12 and 3.B.13 of the Chemical Weapons Convention (CWC). Hence, their detection and identification is of vital importance for verification of CWC. These chemicals are difficult to detect directly using chromatographic techniques as they decompose and do not elute. Until now, the use of gas chromatographic approaches to follow the derivatized sulfur chlorides is not reported in the literature. The electrophilic addition reaction of sulfur monochloride and sulfur dichloride toward 3-hexyne was explored for the development of a novel derivatization protocol, and the products were subjected to gas chromatography−mass spectrometric (GC-MS) analysis. Among various unsaturated reagents like alkenes and alkynes, symmetrical alkyne 3-hexyne was optimized to be the suitable derivatizing agent for these analytes. Acetonitrile was found to be the suitable solvent for the derivatization reaction. The sample preparation protocol for the identification of these analytes from hexane spiked with petrol matrix was also optimized. Liquid−liquid extraction followed by derivatization was employed for the identification of these analytes from petrol matrix. Under the established conditions, the detection and quantification limits are 2.6 μg/mL, 8.6 μg/mL for S 2 Cl 2 and 2.3 μg/mL, 7.7 μg/mL for SCl 2 , respectively, in selected ion monitoring (SIM) mode. The calibration curve had a linear relationship with y = 0.022x − 0.331 and r 2 = 0.992 for the working range of 10 to 500 μg/mL for S 2 Cl 2 and y = 0.007x − 0.064 and r 2 = 0.991 for the working range of 10 to 100 μg/mL for SCl 2 , respectively. The intraday RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and interday RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S 2 Cl 2 and SCl 2 , respectively.

Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

“…Should the reaction be scaled up in the laboratory, trapping S 2 Br 2 by its hydrolysis in a water bath as it forms could be an appropriate measure to prevent its release into the atmosphere. In the current context, at least some of the S 2 Br 2 generated during RASP could also react with phenolic sites as well [51].…”

Derivatization and rapid GC-MS screening of chlorides relevant to the Chemical Weapons Convention in organic liquid samples

“…In 2015 the derivatization of SCl 2 , as well as of sulfur monochloride (S 2 Cl 2 ) using the electrophilic addition reaction with 3-hexyne was published. 16 The reaction products were analyzed by GC-MS. For some reasons, the third sulfur chloride of the Schedule 3, thionyl chloride (SOCl 2 ), was not analyzed.…”