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  • Title: Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.
    Author: Vysotsky YB, Belyaeva EA, Fomina ES, Vasylyev AO, Vollhardt D, Fainerman VB, Aksenenko EV, Miller R.
    Journal: J Colloid Interface Sci; 2012 Dec 01; 387(1):162-74. PubMed ID: 22939427.
    Abstract:
    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat capacities for several classes of substituted alkanes. For the calculation of thermodynamic functions of clusterization of dimers, trimers and tetramers of fatty alcohols, thioalcohols, amines, carboxylic acids and cis-unsaturated carboxylic acids two superposition-additive schemes are proposed which ensure the correct superimposition of the molecular graphs, including intermolecular hydrogen-hydrogen interactions in the clusters. The calculations involve the thermodynamic parameters of clusterization obtained earlier by the PM3 method. It is shown that the proposed approach reproduces quite accurately the values calculated earlier and is applicable for the prediction of the thermodynamic parameters of the formation of surfactant monolayers.
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