caa a22 4500 605513503 CHVBK 20210128100700.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00894-015-2577-5 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2577-5 Theoretical predictions of thermodynamic parameters of adsorption of nitrogen containing environmental contaminants on kaolinite [Elektronische Daten] [Andrea Scott, Elizabeth Burns, Brandon Lafferty, Frances Hill] In this study thermodynamic parameters of adsorption of nitrogen containing environmental contaminants (NCCs, 2,4,6, trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-one-1,2,4-triazol-5-one (NTO)) interacting with the tetrahedral and octahedral surfaces of kaolinite were predicted. Adsorption complexes were investigated using a density functional theory and both periodic and cluster approach. The complexes, modeled using the periodic boundary conditions approach, were fully optimized at the BLYP-D2 level to obtain the structures and adsorption energies. The relaxed kaolinite-NCCs structures were used to prepare cluster models to calculate thermodynamic parameters and partition coefficients at the M06-2X-D3 and BLYP-D2 levels from the gas phase. The entropy effect on the Gibbs free energies of adsorption of NCCS on kaolinite was also studied and compared with available experimental data. The results showed that in all calculated models, the NCCs molecules are physisorbed and they favor a parallel orientation toward both kaolinite surfaces. It was found that all calculated NCCs compounds are more stable on the octahedral than on the tetrahedral surface of kaolinite. The Gibbs free energies and partition coefficients were also predicted for interactions of NCCs with Na-kaolinite from aqueous solution. Calculations revealed adsorption of NCCs is effective from the gas phase on both cation free kaolinite surfaces and on Na-kaolinite from aqueous solution at room temperature. Theoretical data were validated against experimental results, and the reasons for small differences between calculated and measured partition coefficients are discussed. Springer-Verlag Berlin Heidelberg (outside the USA), 2015 Binding nationallicence Clay nationallicence Distribution nationallicence Modeling nationallicence Nitroaromatic nationallicence Scott Andrea U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut Burns Elizabeth Badger Technical Services, LLC, 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut Lafferty Brandon U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut Hill Frances U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/2(2015-02-01), 1-16 1610-2940 21:2<1 2015 21 894 https://doi.org/10.1007/s00894-015-2577-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2577-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Scott Andrea U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut NATIONALLICENCE 700 1- Burns Elizabeth Badger Technical Services, LLC, 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut NATIONALLICENCE 700 1- Lafferty Brandon U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut NATIONALLICENCE 700 1- Hill Frances U. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., 39180, Vicksburg, MS, USA aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/2(2015-02-01), 1-16 1610-2940 21:2<1 2015 21 894