& Retention factors (log k w ) in pure water were calculated for a homologous series of alkylbenzenes, PAHs, and aromatic monosubstituted derivatives for column C18, C8, and C4, using the numerical method based on the linear form of the Os´cik's equation, which were correlated with the log k w values determined by the linear extrapolation method from the log k dependence on methanol volume fraction in binary eluent. The chromatographic parameters (log k w ), being the hydrophobicity measure, were compared with the experimental partition coefficients in n-octanol=water system (log P). The author examined the contribution of the substituents (ÀCH 2 À, ÀOH, ÀCl, ÀNO 2 , and ÀCHO) in the substance retention in pure water for columns of different hydrocarbon chain length of the bonded phase. Moreover, the transfer thermodynamics of the particular functional groups from water to the stationary phase, as well as the influence of the kind of the stationary phase on the thermodynamics of this process were studied. For this purpose the standard free enthalpy (DG o ) of the functional groups transfer from water to the stationary phase and from the gas to stationary one was calculated.