The dissertation is devoted to the development of theoretical approaches to the study of the mechanisms and kinetics of reactions of nitroaromatic compounds and cyclic nitroamines, which allows predicting the methods of their effective removal from the environment.
A detailed analysis of different theoretical approximations and solvation models on the accuracy of reduction and oxidation potentials calculation for nitroaromatic compounds and azacyclic compounds is performed. The best approximations provide reproduction of experimental values with an accuracy of 0.1-0.2 eV for these classes of compounds. The MPWB1K/tzvp approximation using SMD(Pauling) model to describe the solvation of molecule and PCM(Pauling) model to describe the solvation of anion radical as well as the M06-2X/6-31+G(d) approximation taking into account the solvation of molecule and anion radical using models SMD(Pauling) and PCM(Bondi), respectively, can be proposed to calculate the reduction potentials for a wide range of nitrocompounds in aqueous solution. The combinations of SMD(UAHF) solvation model for molecule and PCM(Bondi) and SMD (Bondi) models for cation radical with MPW1K functional and 6-31+G(d) basic set were the most accurate for calculating the oxidation potential of azacyclic compounds in acetonitrile and were used to predict the oxidation potentials of a number of azacyclic nitrocompounds with no experimental data.
The adsorption complexes of nitroaromatic compounds TNT (1-methyl-2,4,6-trinitrobenzene), DNT (1-methyl-2,4-dinitrobenzene), DNAN (1-methoxy-2,4-dinitrobenzene), NTO (5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one), ANTA (5-amino-3-nitro-1H-1,2,4-triazole), and nitroamines RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazаcyclooctane), CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.03,11.05,9]dodecane) with hydroxylated surface of α-quartz (001) were modeled. Adsorption was found to reduce the ability of hydrated nitroaromatic compounds and cyclic nitroamines to redox transformations.
