Citation

Goud DR, Pardasani D, Purohit AK, Tak VK, Dubey DK. Anal. Chem. 2015; 87(13): 6875-6880.

Copyright

(Copyright © 2015, American Chemical Society)

DOI

10.1021/acs.analchem.5b01283

PMID

26054007

Abstract

Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) are important precursors of extremely toxic chemical warfare agent sulfur mustard and classified respectively into schedule 3.B.12 and 3.B.13 of 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 electro-philic addition reaction of sulfur monochloride and sulfur dichloride towards 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 like 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 = 0.022 x - 0.331 and r2 = 0.992 for working rage of 10 to 500 µg/mL for S2Cl2 and y = 0.007 x - 0.064 and r2= 0.991 for working range of 10 to 100 µg/mL for SCl2 respectively. The intra-day RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and inter-day RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S2Cl2 and SCl2 respectively.

Language: en