The enthalpy of hydrophobic hydration, DeltaH(HH), was separately estimated for each apolar segment of amphiphiles and of related compounds. The specimens analyzed in this study were the homologs and analogs of sodium alkyl sulfate, alkyltrimethylammonium bromide, ammonium perfluoroalkylcarboxylate, and polyethylene glycols. The DeltaH(HH) was calculated from the adiabatic compressibility beta of aqueous solution systematically measured for each homologs at varying concentrations and temperatures. Those data reported in the previous paper were utilized. The DeltaH(HH) estimated for each -CH2-, -CF2-, and -OCH2CH2- segments in both hydrophobic and hydrophilic parts of the amphiphiles was found to change depending on its locations in the molecule. The DeltaH(HH) for the first -CH2- unit which is adjacent to the head sulfate group of H(CH2)(n)SO4Na was found to be negligibly small; however, it increases gradually as the position of the unit moves apart from the anionic head group and attains as large as -26.5 kcal/mol for the eighth -CH2-. The change of DeltaH(HH) of -CF2- unit in F(CF2),COONH4 shows the similar tendency to H(CH2)(n)So(4)Na. The value of DeltaH(HH) is as small as -8 kcal/mol for the first -CF2-, however, it increases to -16 kcal/mol for the fifth -CF2-, which is 1.5 times larger than that of the fifth -CH2- of alkyl sulfate. Contrary to this, all the DeltaH(HH) of the methylenes of cationic surfactant ranging from the second to the eighth -CH2- units of H(CH2)(n)N(CH3)(3)Br take a similar value around -8 kcal/mol of -CH2- irrespective of their positions. The first -CH2- unit which is equivalent to that of quaternary ammonium [HCH2](4)NBr shows slightly higher value of -9.0 kcal/mol of the first -CH2- than those for the second to eighth -CH2-. This seems to suggest that the cationic core nitrogen has an enhancing effect on hydrophobic hydration. The hydration enthalpy DeltaH(OEH) of each oxyethylene (OE) unit of polyethylene glycol was also estimated for H(OCH2CH2)pOH (p = 1-4) homologues to see the roles of ether oxygen and hydroxyl groups in hydrophobic hydration. The value of DeltaH(OEH) showed its maximum -13.1 kcal/mol for the OE unit located at the middle of three. The other two units at both ends were found to take the value of -9.9 kcal/mol, smaller than that at the center. This could suggest that the hydrophobic hydration of the ethylene segment is largely enhanced by the neighboring ether oxygens. (C) 2003 Elsevier Inc. All rights reserved.