Abstract
The recent resolution of the controversy surrounding asphaltene molecular weight coupled with increasing understanding of their molecular structure has enabled the understanding of asphaltene behavior. It has been shown previously that larger ring systems require more alkane substituents to maintain a balance between ring-stacking propensity vs. steric repulsion. Here, stacking and its disruption in asphaltenes and aromatic ring systems are explored using high-resolution transmission electron microscopy (HRTEM). The TEM images are consistent with the presence of aromatic ring systems of ~1 nm diameter for petroleum asphaltenes and 0.7 nm for coal asphaltenes. It is shown that molecularly disparate asphaltenes exhibit stacking invariants. Solubility data herein suggest these stacking invariants naturally follow from the solubility classification of asphaltenes.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Crick, F. (1988). What Mad Pursuit, a personal View of Scientific Discovery, Basic Books, New York.
Chilingarian, G.V. and T.F. Yen (eds.) (1978). Bitumens, Asphalts, and Tar Sands. Elsevier Scientific Publishing, New York.
Bunger, J.W. and N.C. Li (eds.), (1984). Chemistry of Asphaltenes. American Chemical Society, Washington, DC.
Sheu, E. Y. and O.C. Mullins (eds.) (1995). Asphaltenes: Fundamentals and Applications. Plenum, New York.
Mullins, O.C. and E.Y. Sheu (eds.) (1998). Structures and Dynamics of Asphaltenes. Plenum, New York.
Groenzin, H. and O.C. Mullins (1999). Asphaltene molecular size and structure, J. Phys. Chem. A.. 103, 11237.
Groenzin, H. and O.C. Mullins (2000). Molecular sizes of asphaltenes from different origin, Energy Fuels 14, 677.
Boduszynski, M.M. (1988). Composition of heavy petroleums. 2. Molecular characterization, Energy Fuels 2, 597.
Miller, J.T., R.B. Fisher, P. Thiyagarajan, R.E. Winans, and J.E. Hunt (1998). Subfractionation and characterization of mayan asphaltene, Energy Fuels 12, 1290.
Buenrostro-Gonzalez, E., H. Groenzin, C. Lira-Galeana, and O.C. Mullins (2001). The overriding chemical principles that define asphaltenes, Energy Fuels 15, 972.
Hortal, A.R., B. Martinez-Haya, M.D. Lobato, J.M. Pedrosa, and S. Lago (2006). On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments, J. Mass Spec. 41, 960–968.
Sheu, E.Y., M.M. De Tar, and D.A. Storm (1991). Rheological properties of vacuum residue fractions in organic solvents, Fuel 70, 1151.
George, G.N. and M.L. Gorbaty (1989). Sulfur K-edge x-ray absorption spectroscopy of petroleum asphaltenes and model compounds, J. Am. Chem. Soc. 111, 3182.
Kelemen, S.R., G.N. George, and M.L. Gorbaty (1990). Direct determination and quantification of sulphur forms in heavy petroleum and coals : 1. The X-ray photoelectron spectroscopy (XPS) approach, Fuel 69, 939.
Waldo, G.S., O.C. Mullins, J.E. Penner-Hahn, and S.P. Cramer (1992). Determination of the chemical environment of sulfur in petroleum asphaltenes by X-ray absorption spectroscopy, Fuel 71, 53.
Mitra-Kirtley, S., O.C. Mullins, J. van Elp, S.J. George, J. Chen, and S.P. Cramer (1993). Determination of the nitrogen chemical structures in petroleum asphaltenes using XANES spectroscopy, J. Am. Chem. Soc. 115, 252.
Bergmann, U., H. Groenzin, O.C. Mullins, P. Glatzel, J. Fetzer, and S.P. Cramer (2003). Carbon K-edge X-ray Raman speetroscopy supports simple yet powerful description of aromatic hydrocarbons and asphaltenes, Chem. Phys. Lett. 369, 184.
Gordon, M.L., D. Tulumello, G. Cooper, A.P. Hitchcock, P. Glatzel, O.C. Mullins, S.P. Cramer, and U. Bergmann (2003). Inner shell excitation speetroscopy of fused aromatic molecules by electron energy loss and X-ray Raman techniques, J. Phys. Chem. A. 107(41), 8512.
Ruiz-Morales, Y. (2002). HOMO-LUMO gap as an index of molecular size and structure for polycyclic aromatic hydrocarbons (PAHs) and asphaltenes: a theoretical study, J. Phys. Chem. A. 106(46), 11283.
Millward, G.R. and D.A. Jefferson (1978). In: P.A.Thrower (ed.), Chemistry and Physics of Carbon. Marcel Dekker, New York, Vol. 14 pp. 1–78.
Furuta, T., Y. Yamashita, and M. Shiraishi (1989). Tanso 140, 241–247.
Davis, K.A., R.H. Hurt N.Y.C. Yang, and T.H. Headley (1995). Combust. Flame 100, 31–40.
Palotás, Á.B., L.C. Rainey, A.F. Sarofim, J.B.V. Sande, and P. Ciambelli (1996). Effect of oxidation on the microstructure of carbon blacks, Energy Fuels 10, 254–259.
Sharma, A., T. Kyotani, and A. Tomita (1999). A new quantitative approach for microstructural analysis of coal char using HRTEM images, Fuel, 78, 1203–1212.
Sharma, A., T. Kyotani, and A. Tomita (2000). Comparison of structural parameters of PF carbon from XRD and HRTEM techniques, Carbon 38, 1977–1984.
Sharma, A., T. Kyotani, and A. Tomita (2000). Direct observation of layered structure of coals by a transmission electron microscope, Energy Fuels 14, 515–516.
Sharma, A., T. Kyotani, and A. Tomita (2000). Direct observation of raw coals in lattice fringe mode using high-resolution transmission electron microscopy, Energy Fuels 14, 1219–1225.
Sharma, A., T. Kyotani, and A. Tomita (2001). Quantitative evaluation of structural transformations in raw coals on heat-treatment using HRTEM technique, Fuel 80, 1467–1473.
Sharma, A., H. Kadooka, T. Kyotani, and A. Tomita (2002). Effect of microstructural changes on gasification reactivity of coal chars during Low temperature gasification, Energy Fuels 16, 54–61.
Aso, H., K. Matsuoka, A. Sharma, and A. Tomita (2004). Evaluation of size of graphene sheet in anthracite by a temperature-programmed oxidation method, Energy Fuels 18, 1309–1314.
Aso, H., K. Matsuoka, A. Sharma, and A. Tomita (2004). Structural analysis of PVC and PFA carbons prepared at 500–1000 °C based on elemental composition, XRD, and HRTEM, Carbon 42, 2963–2973.
Oberlin, A. (1989). In: P.A. Thrower (ed.), Chemistry and Physics of Carbon. Marcel Dekker, New York, Vol. 22, p. 1.
Oberlin, A., S. Bonnamy, and P.G. Rouxhet (1999). In: P.A. Thrower and L.R Radovic (eds.), Chemistry and Physics of Carbon. Marcel Dekker, New York, Vol. 26, p. 1.
Sharma, A., H. Groenzin, O.C. Mullins, and A. Tomita (2002). Probing order in asphaltenes and aromatic ring systems by HRTEM, Energy Fuels 16(2), 490.
Zajac, G.W., N.K. Sethi, and J.T. Joseph (1994). Molecular imaging of petroleum asphaltenes by scanning tunneling microscopy, Scan. Micros. 8, 463.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2007 Springer
About this chapter
Cite this chapter
Sharma, A., Mullins, O.C. (2007). Insights into Molecular and Aggregate Structures of Asphaltenes Using HRTEM. In: Mullins, O.C., Sheu, E.Y., Hammami, A., Marshall, A.G. (eds) Asphaltenes, Heavy Oils, and Petroleomics. Springer, New York, NY. https://doi.org/10.1007/0-387-68903-6_8
Download citation
DOI: https://doi.org/10.1007/0-387-68903-6_8
Publisher Name: Springer, New York, NY
Print ISBN: 978-0-387-31734-2
Online ISBN: 978-0-387-68903-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)