Improved Resolution of Hydrocarbon Structures and Constitutional Isomers in Complex Mixtures Using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry

Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography/mass spectrometry (GC/MS) techniques. This work uses vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally “unresolved complex mixture” by separating components by GC retention time, <i>t</i>_R, and mass-to-charge ratio, <i>m</i>/<i>z</i>, which are used to determine carbon number, <i>N</i>_C, and the number of rings and double bonds, <i>N</i>_DBE. Constitutional isomers are resolved on the basis of <i>t</i>_R, enabling the most complete quantitative analysis to date of structural isomers in an environmentally relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. The classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture

Evaluation of a New Vocus Reagent-Ion Source and Focusing Ion-Molecule Reactor for use in Proton-Transfer-Reaction Mass Spectrometry

<div>We evaluate the performance of a new chemical ionization source called Vocus, consisting of a discharge reagent-ion source and focusing ion-molecule reactor (FIMR) for use in protontransfer-reaction time-of-flight mass spectrometry (PTR-TOF) measurements of volatile organic compounds (VOCs) in air. The reagent ion source uses a low-pressure discharge. The FIMR consists of a glass tube with a resistive coating, mounted inside a radio-frequency (RF) quadrupole. The axial electric field is used to enhance ion collision energies and limit cluster ion formation. The RF field focuses ions to the central axis of the reactor and improves the detection efficiency of product ions. Ion trajectory calculations demonstrate the mass-dependent focusing of ions and enhancement of the ion collision energy by the RF field, in particular for the lighter ions. Product ion signals are increased by a factor of 10 when the RF field is applied (5,000-18,000 cps ppbv^-1), improving measurement precision and detection limits while operating at very similar reaction conditions as traditional PTR instruments. Due to the high water mixing ratio in the FIMR, we observe no dependence of the sensitivity on ambient sample humidity. In this work, the Vocus is interfaced to a TOF mass analyzer with a mass resolving power up to 14,000, which allows clear separation of isobaric ions, observed at nearly every nominal mass when measuring ambient air. Measurement response times are determined for a range of ketones with saturation vapor concentrations down to 5×10⁴ μg m^-3 and compare favorably with previously published results for a PTR-MS instrument.</div