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CORRELATION OF BOILING POINT, MOLECULAR WEIGHT AND COMPOSITION
BY MASS SPECTROMETRY: THE DEVELOPMENT OF CHEMICAL DEPENDENT
EQUATIONS
Yuri E. Corilo 1, 2*, Priscila M. Lalli 2, Steven M. Rowland 2, Logan C. Krajewski 1, Alan G.
Marshall1, 3 and Ryan P. Rodgers 1, 2, 3
1
National High Magnetic Field Laboratory, Florida State University, 1800 East Paul
Dirac Drive, Tallahassee, Florida 32310-4005. 2Future Fuels Institute, 1800 East Paul
Dirac Drive, Tallahassee, Florida 32310-4005.
3
Department of Chemistry and
Biochemistry, Florida State University, 95 Chieftain Way Tallahassee, Florida, 32306.
Abstract – Limit 400 words, including spacing (380 words)
Boduszynski et al. demonstrated a clear correlation between the molecular weight of different
crude oils, their atmospheric equivalent boiling point, and H/C ratios [1]. However, accurate and
comprehensive molecular characterization of petroleum by the combination of atmospheric
pressure ionization techniques and ultrahigh resolution Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry (FT-ICR MS) provides an opportunity for a more detailed
evaluation of Boduszynski’s original equations and its extension beyond hydrocarbons to other
heteroatom classes. Because Boduszynski’s original work was limited to the most abundant
hydrocarbons, we performed the initial FT-ICR MS evaluation with hydrocarbon (HC) class
species
(mostly
polycyclic
aromatic
hydrocarbons)
from
(+)
atmospheric
pressure
photoionization FT ICR mass spectra for all eight distillate cuts (initial boiling point to 700 oC).
The number-weighted average boiling point was calculated from the peak heights of all of the
mass spectral peaks identified as HC class species. The resulting values were then compared
to the mid-point of the boiling point range for the boiling cuts and they agreed within a 5%
margin of error. However, FT-ICR analytical figures of merit (resolution and mass accuracy)
enable evaluation of other heteroatom classes. In addition, the combination of a broad range of
ionization sources and chromatographic separations techniques allow us to target specific
chemical functionalities. Such a strategy facilitated creation of an updated, class dependent
Boduszynski equation to account for all deviations of the predicted boiling points relative to the
hydrocarbon class, to reflect the influence of the heteroatoms and varied chemical
functionalities accessible by FT-ICR MS. Work supported by NSF Division of Materials
CORRELATION OF BOILING POINT, MOLECULAR WEIGHT AND COMPOSITION
BY MASS SPECTROMETRY: THE DEVELOPMENT OF CHEMICAL DEPENDENT
EQUATIONS
Research through DMR-11-57490, the Florida State University Future Fuels Institute, and the
State of Florida.
[1] Altgelt, K. H.; Boduszynski, M. M., Energy & Fuels 1992, 6, 68-72.