Quantitative Approaches for the Determination of Volatile Organic Compounds (VOC) and Its Performance Assessment in Terms of Solvent Types and the Related Matrix Effects

For the quantitative analysis of volatile organic compounds (VOC), the use of a proper solvent is crucial to reduce the chance of biased results or effect of interference either in direct analysis by a gas chromatograph (GC) or with thermal desorption analysis due to matrix effects, e.g., the existence of a broad solvent peak tailing that overlaps early eluters. In this work, the relative performance of different solvents has been evaluated using standards containing 19 VOCs in three different solvents (methanol, pentane, and hexane). Comparison of the response factor of the detected VOCs confirms their means for methanol and hexane higher than that of pentane by 84% and 27%, respectively. In light of the solvent vapor pressure at the initial GC column temperature ($35^{\circ}C$), the enhanced sensitivity in methanol suggests the potential role of solvent vapor expansion in the hot injector (split ON) which leads to solvent trapping on the column. In contrast, if the recurrent relationships between homologues were evaluated using an effective carbon number (ECN) additivity approach, the comparability assessed in terms of percent difference improved on the order of methanol (26.5%), hexane (6.73%), and pentane (5.24%). As such, the relative performance of GC can be affected considerably in the direct injection-based analysis of VOC due to the selection of solvent.