Dipole moments in Langmuir monolayers from aromatic carboxylic acids

Abstract

The three-layer capacitor model proposed by Demchak and Fort [J. Colloid Interface Sci. 46 (1974) 191] is employed to relate measured surface potentials of Langmuir monolayers from a series of polyphenyl carboxylic acids to molecular dipole moments calculated using semiempirical quantum methods. The effective dielectric constant at the air/monolayer interface is 3.0±0.6, very close to that estimated for aliphatic compounds. Good agreement between theory and experiment is obtained by adopting a dielectric constant of 6.4 for the monolayer/water interface and a contribution from the water reorientation of −0.064±0.006 D, which shows that the parameters in the DF model are essentially the same as for aliphatic amphiphiles, such as esters, acids, alcohols and ethers.