Application of the Mason-Schamp equation and ion mobility mass spectrometry to identify structurally related compounds in crude oil.

The various components of crude oil were structurally resolved using an atmospheric-pressure solids analysis probe (ASAP) coupled with ion mobility mass spectrometry (IM-MS). An ASAP source was used to broadly fractionate compounds according to their boiling points, thereby simplifying the resulting mass spectra for easier data interpretation. The m/z-mobility plots obtained by IM-MS analysis of crude oil could be used to find the structural relationship between crude oil molecules. That was demonstrated using ion mobility mass spectra from a homologous series of compounds, differing only by the number of alkyl units, found in crude oil. The peaks from this series were linearly aligned in the plot, suggesting a continuous increase of the collisional cross section with an increase of mass values and hence the absence of significant structural differences within the series. In contrast, peaks in a homologous series differing only in the number of pendant hydrogen atoms were not linearly aligned, suggesting a discontinuous increase of the collisional cross section with an increase of mass values and hence significant structural differences due to the addition or removal of hydrogen. Cases in which a slope change was observed at three- or four-peak intervals may be related to the addition of an aromatic ring to existing structures. Overall, ion mobility mass spectrometry demonstrates a useful tool that can be used to elucidate structural relationships between molecules comprising crude oil.