Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface

Abstract

The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously.