Quantum chemical analysis of the thermodynamics of 2D cluster formation of n-carboxylic acids at the air/water interface

Within the framework of PM3 molecular orbital approximation the thermodynamic function characteristics for the formation and Geometrical structure of monomers, dimers, trimers, and tetramers of nondissociated n-carboxylic acids CnH2n+1COOH with n = 5- 15 are calculated. It is shown that spontaneous aggregation of homologous fatty acids for the homologues with carbon atoms numbers n >= 13 at the air/water interface can take place, leading to the formation of infinite plane rectangular clusters, whereas for the homologues with it < 11 spontaneous decomposition of large aggregates is energetically preferable. At the same time, the formation of trimers is more probable for the lower homologues (8 < n < 13). These results agree well both with the experimental data reported by various authors and with thermodynamic models developed earlier for Soluble and insoluble monolayers. The slopes of the regressions calculated for the dependencies of the thermodynamic parameters on the alkyl chain length for all the clusters considered are all equal to each other. This fact indicates that the contributions of the CH2 groups to the thermodynamic characteristics of alcohols and acids are the same, and the differences in the formation of clusters by these substances should be attributed only to the differences in the structure and interactions of relevant functional groups. Therefore, it enables one to describe both acids and alcohols within the framework of the developed method, and it makes it possible to extend the proposed approach onto other classes of amphiphilic compounds.