A novel equation (Guillaume Y. C. et al. Anal. Chem. 1998, 70, 608) modelin
g the weak polar solute retention in reversed-phase liquid chromatography (
RPLC) was applied to fullerene molecules C-60 and C-70 In RPLC, with an org
anic modifier (OM) /water mobile phase, the fullerene cluster solvation ene
rgies were calculated for OM = methanol, ethanol, propanol, butanol, and pe
ntanol. An enthalpy-entropy compensation revealed that the type of interact
ions between fullerenes and the stationary phase was independent of both th
e fullerene and organic modifier structures. The energetics of OM and OM-wa
ter cluster exchange processes in the mobile phase were investigated in rel
ation to the carbon atom number of the hydrophobic chain of the OM. Two lin
ear correlations were found between the Gibbs free energy changes in the so
lvent exchange processes which confirmed that (i) a reversal elution order
existed for C-60 and C-70 when methanol was changed into ethanol, propanol,
butanol, pentanol and that (ii) the mobile phase was dominant in governing
selectivity changes in nonpolar solutes.