Affinity of Amphiphilic Molecules to Air/Water Surface.

Abstract

The affinity of amphiphiles to the water/air surface was modeled by adapting Eberhart's equation. The proposed method successfully describes surface tension for all amphiphilic structures, including alkanols, carboxylic acids, nonionic, ionic, and Gemini surfactants. The model is more effective than conventional analysis for amphiphiles with multiple ionic states. The prediction was consistently validated at different temperatures and nonaqueous solvents. The modeling results show a linear correlation between surface affinity and hydrophobicity/hydrophilicity. For alkanols, the affinity increment is 2.84 kJ/mol per CH2 group, the same as the reported hydrophobic energy from monomer to aggregate for nonionic surfactants. For carboxylic acids, the affinity increment per CH2 group is 3.18 kJ/mol, incorporating the degree of acid dissociation. The affinity-hydrophilicity correlation is approximately -0.22 kJ/mol per oxyethylene group. The affinity constant can be obtained for all classes of amphiphiles to clarify the relationship between the molecular structure and surface activity.