ACID-BASE INTERACTIONS IN WETTING

The study of the ionization of carboxylic acid groups at the interface between organic solids and water demonstrates broad similarities to the ionizations of these groups in homogeneous aqueous solution, but with important systematic differences. Creation of a charged group from a neutral one by protonation or deprotonation (whether -NH3+ from -NH2 or -CO2- from -CO2H) at the interface between surface-functionalized polyethylene and water is more difficult than that in homogeneous aqueous solution. This difference is probably related to the low effective dielectric constant of the interface (epsilon congruent-to 9) relative to water (epsilon congruent-to 80). It is not known to what extent this difference in epsilon (and in other properties of the interphase, considered as a thin solvent phase) is reflected in the stability of the organic ions relative to their neutral forms in the interphase and in solution, and to what extent in differences in the concentration of H+ and OH- in the interphase and in solution. Self-assembled monolayers (SAMs)-especially of terminally functionalized alkanethiols (HS(CH2)(n)X) adsorbed on gold-provide model systems with relatively well-ordered structures that are useful in establishing the fundamentals of ionization of protic acids and bases at the interface between organic solids and water. These systems, coupled with new analytical methods such as photoacoustic calorimetry (PAC) and contact angle titration, may make it possible to disentangle some of the complex puzzles presented by proton-transfer reactions in the environment of the organic solid-water interphase.