Configurational-bias Monte Carlo simulations in the Gibbs and isobaric-isothermal ensembles using the, transferable potentials for phase equilibria force field were carried out to investigate the thermophysical properties of, mixtures containing supercritical carbon dioxide and methanol. The binary vapor-liquid coexistence curves were calculated at 333.15 and 353.15 K and are in excellent agreement with,experimental measurements. The self-association of methanol in supercritical carbon dioxide was investigated over a range, of temperatures and pressures near the mixture critical point. The temperature dependence of the equlibrium constants for the formation of hydrogen-bonded aggregates (from dimer to heptamer) allowed for the determination of the enthalpy of hydrogen bonding, DeltaH(HB), in supercritical carbon dioxide with values for DeltaH(HB) of about 15 kJ mol(-1) falling within the range of previously proposed values. No strong pressure dependence was observed for the formation of aggregates. Apparently the decrease of the entropic penalty and of the enthalpic benefit upon increasing pressure or solvent density mostly cancel each other's effect on aggregate formation. (C) 2004 American Institute of Physics.