Sulfur K-edge x-ray absorption spectroscopy of petroleum asphaltenes and model compounds

The utility of sulfur K-edge X-ray absorption spectroscopy for the determination and quantification of sulfur forms in petroleum asphaltenes has been investigated. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra were obtained for a selected group of model compounds and for several petroleum asphaltene samples. For the model compounds the sulfur XANES was found to vary widely from compound to compound and to provide a fingerprint for the form of sulfur involved. The use of third derivatives of the spectra enabled discrimination of mixtures of sulfidic and thiophenic model compounds and allowed approximate quantification of the amount of each component in the mixtures and in the asphaltene samples. These results represent the first demonstration that nonvolatile sulfur forms can be distinguished and approximately quantified by direct measurement.