Five major nitrogen chemical structures, present in coals of varying ranks, have been quantitatively determined with the use of nitrogen x-ray absorption near-edge spectroscopy (XANES). Similar studies of the sulfur chemical structures of coals have been performed for the last ten years; nitrogen studies on these fossil-fuel samples have only recently been realized. XANES spectra of coals exhibit several distinguishable resonances which can be correlated with characteristic resonances of particular nitrogen chemical structures, thereby facilitating analysis of these complicated systems. Many model compounds have been examined; for some, the relative peak positions are explained in terms of the orbital description of the lone pair of electrons. All features in the XANES spectra of coals have been accounted for; thus, all the major structural groups of nitrogen present in coals have been determined. A wide variety of aromatic nitrogen compounds is found in the coals; no evidence of saturated amine is found. Pyrroles, pyridines, pyridones, and aromatic amines are found in coal; of these, pyrrolic structures are the most prevalent. Pyridine nitrogen is prevalent in all except low-rank coals. The low pyridine content in low-rank (high-oxygen) coals correlates with a large pyridone content. This observation suggests that, with increasing maturation of coal, the pyridone loses its oxygen and is transformed into pyridine. Aromatic amines are present at low levels in coals of all rank. The spectral effects of aromatic amines are shown by comparing the XANES spectra of coal and petroleum asphaltenes.
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