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Molecular Characterization of Volatiles and Petrochemical Base Oils by Photo-Ionization GC×GC-TOF-MS

Abstract

The characterization of organic mixtures by comprehensive two-dimensional gas chromatography (GC×GC) coupled to electron impact (EI) ionization time-of-flight mass spectrometry (TOF-MS) allows the detection of thousands of compounds. However, owing to the exhaustive fragmentation following EI ionization, despite the use of mass spectral libraries, a majority of the compounds remains unidentified because of the lack of parent ion preservation. Thus, soft-ionization energies leading to organic compounds being ionized with limited or no fragmentation, retaining the molecular ion, has been of interest for many years. In this study, photoionization (PI) was evaluated as the ion source for GC×GC-TOF-MS measurements. First, capabilities and limitations of PI were tested using an authentic mixture of compounds of several chemical classes. Ionization energy exhibited by PI, equivalent to 10.8 eV, resulted in significant retention of molecular ion information; [M]+• for alkanes, ketones, FAMEs, aromatics, [M–H]+• for chloroalkanes, and [M–H2O]+• for alcohols. Second, considering the potential of PI for hydrocarbons, base oils, complex mixtures of saturated and unsaturated hydrocarbons blended for finished lubricant formulations, were extensively evaluated. Several chemical classes of hydrocarbons were positively identified including a large number of isomeric compounds, both aliphatics and cyclics. Interestingly, branched-alkanes were ionized with lower excess internal energy, not only retaining the molecular ions but also exhibiting unique fragmentation patterns. The results presented herein offer a unique perspective into the detailed molecular characterization of base oils. Such unprecedented identification power of PI coupled with GC×GC-TOF-MS is the first report covering volatiles to low-volatile organic mixtures.

For more information: https://pubs.acs.org/doi/pdf/10.1021/acs.analchem.7b00124

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