PNNL

Abstract

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M+) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M+ will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS+). Oxide products were also observed for many M+ but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker C=S bond that makes MS+ formation more favorable. Increasing the reaction gas pressure from 2.6 to 4.0 mTorr generally resulted in greater MS+ production, including the secondary product MS2+ for a few cations. The early lanthanide series ions (La+, Ce+, Pr+ and Nd+) produced greater quantities of MO+ at the higher pressure, although MS+ products were still the dominant product. DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy > 90%; however, model predictions were less accurate for the minor and higher order products (