Quantitative response in ion mobility spectrometry with atmospheric pressure chemical ionization in positive polarity as a function of moisture and temperature

Abstract

Response of an ion mobility spectrometer at ambient pressure was quantitatively determined for fourteen chemicals from five chemical families spanning a range of proton affinities and temperature from 30 to 175 °C with moisture from 1 to 1 × 104 ppmv in purified air. Peak intensities, drift times and reduced mobility coefficients were determined for hydrated protons from a63Ni ion source and for protonated monomers and proton bound dimers of alcohols, aldehydes, acetates, ketones, and organophosphates. These measurements permitted the determination of response factors with atmospheric pressure chemical ionization and the influence of moisture and temperature on APCI response with correlation to computational models of hydration values. The formation of protonated monomers and proton bound dimers was described by heats of formation for a displacement reaction of water on H+(H2O)n by an analyte vapor and favorably matched results from density functional theory (DFT) with the 6-311 + G(dp) basis set. Response factors worsened with increased moisture and decreased temperature for compounds of medium, and more so, of low proton affinities. Findings here provide a broad measure and understanding for quantitative response in ion mobility spectrometers for substances for combinations of moisture and temperature.