title: Method for Derivatization and Detection of Chemical Weapons Convention Related Sulfur Chlorides via Electrophilic Addition with 3-Hexyne.
abstract: Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) 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 S2Cl2 and 2.3 μg/mL, 7.7 μg/mL for SCl2, 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 S2Cl2 and y = 0.007x - 0.064 and r(2) = 0.991 for the working range of 10 to 100 μg/mL for SCl2, 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 S2Cl2 and SCl2, respectively.
authors.affiliation: Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
authors.forename: D Raghavender
authors.initials: DR
authors.lastname: Goud
authors.affiliation: Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
authors.forename: Deepak
authors.initials: D
authors.lastname: Pardasani
authors.affiliation: Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
authors.forename: Ajay Kumar
authors.initials: AK
authors.lastname: Purohit
authors.affiliation: Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
authors.forename: Vijay
authors.initials: V
authors.lastname: Tak
authors.affiliation: Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
authors.forename: Devendra Kumar
authors.initials: DK
authors.lastname: Dubey
mesh_terms: D002619:Chemical Warfare Agents / Q000032:analysis*; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D002619:Chemical Warfare Agents; D013457:Sulfur Compounds; C053578:sulfur monochloride