A direct calorimetric method has been used to determine simultaneously the molar enthalpy, ΔH o , and equilibrium constant, K, for the interaction of quinoline ( Qu) with coal-derived asphaltenes ( A), acid/neutral ( AA) and base ( BA) components of A, silylated asphaltenes ( A(TMS)) and heavy oil ( HO) fractions in solvent C 6H 6. Solvent fractionated A and HO fractions were from three centrifuged-liquid product ( CLP) samples prepared in the 450 kg ( ≈ 1 2 U.S. ton) per day Process Development Unit at Pittsburgh Energy Research Center, at different process conditions from the same feed coal, Kentucky hvAb. For a given system, Qu-A ( AA or BA), Qu-HO, the almost constant value of K and rectilinear variation of ΔH o with the phenolic oxygen content of coal-liquid fractions have been attributed to the dominance of hydrogen-bonding effects, involving phenolic OH, over other types of molecular interactions in solution. In the Qu-A(TMS) system, − ΔH o values increase with decrease in molecular weight of A(TMS), while − ΔS o values increase with increase in aromaticity of the A fraction. The degree of complexation, in absence of OH groups, is much smaller than with the Qu-A system.