A fundamental understanding of the inter- and intramolecular interactions of organic molecules and organic molecules with a mineral matrix is needed for the production of liquid oil products from solid fossil fuel material s such as the extraction of tar sand bitumen, the conversion of kerogen in oil shale to shale oil and the liquefaction of coal. An exploratory investigation was conducted using the advanced NMR technique CRAMPS (combined rotation and multiple-pulse spectrometry) to provide information on the types of organic functionality via hydrogen types present on the surface of tar sand residues. These residues were obtained from (1) solvent extraction using solvents of different polarity, (2) isothermal pyrolysis at four temperatures, and (3) non isothermal pyrolysis at three temperatures. The solvents hexane, toluene, and methylene chloride were used to extract the bitumen from the native tar sand. All three solvents removed essentially all of the bitumen from the mineral matrix. However, the solid-state 1H NMR and diffuse reflectance infrared have shown the presence of a small amount of organic material still in contact with the mineral matrix. As would be expected. tar sand residues after extraction with methylene chloride, the most polar solvent, contain less organic material than the tar sand residues obtained after solvent extraction with hexane, the least polar of the solvents. The hydrogen spectra of the tar sand residues show a greater amount of aromatic hydrogens than aliphatic hydrogens presumably because of heteroaromatics, ,which would interact more strongly with the mineral matrix. Of interest were the relatively large amounts of hydrogen causer by (1) alkyl hydrogens adjacent to ketone carbonyl functionality. (2) hydrogens of methylene groups bridged between aromatic rings, and/or (3) hydrogens of methyl and ethyl substituents on aromatic rings. The infrared data on the extracted tar sand residue also show a relatively large amount of ketone functionality. The 1H CRAMPS spectra of the tar sand residues obtained from the isothermal and non isothermal pyrolysis of the native tar sand show that a relatively large amount of bitumen still remains with the mineral matrix even at a temperature of 380°C (716°F). Above 400°C (752°F) the 1H spectra changed dramatically but still do not have the 1H resolution that was apparent in the spectra of the tar sand residues from solvent extraction. The major change in the 1H spectra of the tar sand residues after pyrolysis above 400°C was the loss of paraffinic hydrogens. The application of solid-state 1H NMR technique to the study of the bitumen-mineral interaction is still in its infancy. However, it has been shown that the technique is sensitive enough to detect different hydrogen types on or near the surface of the mineral matrix and that the hydrogen types can be quantified. Also shown is that the technique can be successfully used to follow the pyrolysis process not from the stand point of observing the liquid products produced but of monitoring the changes that occur in the solid residue as the temperature is changed.