Transformations of organic compounds in supercritical fluid solvents: From experiments to kinetics,thermodynamics, simulation,and practical applications

The results of fundamental studies performed by the author on the reactivity of supercritical fluid solvents are systematized and generalized; practical applications of these solvents are considered. Methods for performing kinetic and physicochemical experiments, processing the data, constructing kinetic models, and calculating the thermodynamics of nonideal supercritical fluids (the parameters of critical points, binodal and spinodal lines, and critical point drifts; the thermophysical properties of reaction mixtures under supercritical conditions; etc.) are described. Attention is focused on the effect of supercritical fluid pressure on the rate constants of chemical reactions. The kinetics and mechanisms of the reactions of 2-propanol dehydration and decomposition of aliphatic nitro compounds in supercritical water and the isomerization of terpene compounds (α-pinene, β-pinene, and turpentine) in supercritical lower alcohols are studied. The formation of nanoparticles in supercritical fluid solvents and the treatment of ultradisperse diamonds in supercritical water are considered. The results formed the basis for the simulation and calculation of acetic acid and phenol oxidation processes in supercritical water and the Fischer-Tropsch synthesis in a supercritical solvent and for the development of a pilot plant for the complete oxidation of trinitroglycerol and diethylene glycol dinitrate in supercritical water.