Entropy maximization method in thermodynamic modelling of organic matter evolution at geodynamic regime changing

Received: September 23, 2020
Institute of Geology and Geochemistry of Combustible Minerals of NAS of Ukraine
Institute of Geology and Geochemistry of Combustible Minerals of NAS of Ukraine
Institute of Geology and Geochemistry of Combustible Minerals of NAS of Ukraine

Purpose. Our research main purpose is to demonstrate the use of entropy maximization method for calculating the geochemical system composition, which consist of solid and gaseous organic substances. Changing the geodynamic situation is the driving force of elements redistribution between compounds in such systems. According to thermodynamic apparatus the main factors influencing this redistribution are pressure, temperature and the initial number of elements. Methods. Gibbs energy minimizing, maximizing the entropy, independent chemical reactions constants, Lagrange's method of undetermined multipliers, Newton–Raphson iterative method. It is well known that the fossilized organic matter, which is mainly represented by many types of kerogen, is an irregular polymer with structure, which cannot be described definitely. To calculate the equilibrium in the kerogen/gas system and obtain reliable results, it is necessary to apply a new model, without using the model structures of kerogen. We have proposed and described in detail a method of applying the Jaynes' formalism and maximizing entropy method to calculate the change in the composition of the kerogen/gas system with geodynamic regimes changing. Software in the Excel macros form and a compiled dynamic library, written in Visual Basic language, was created for calculations. Results. To verify the reliability of the proposed method and algorithm, we calculated the composition of the geochemical system, consisting of type II kerogen, methane to pentane hydrocarbons (including isomers), carbon dioxide, water and hydrogen sulfide. The calculation result is the molar fractions of hydrocarbon components and additive groups that make up kerogen, for different depths of the earth's crust. The calculations were performed for three heat fluxes: 40, 75 and 100 mW/m2, lithostatic pressure taken in account. Scientific novelty. It is established that the geodynamic situation changing in a complex way affects the distribution of elements between gases and kerogen in a closed thermodynamic system; modeling the kerogen/gas system behavior by method of entropy maximization provides results that do not contradict to study the structure of type II kerogen at different stages of maturity; the character of changes in the concentrations of hydrocarbon gases in equilibrium with type II kerogen indicates the inconsistency of the "oil window" hypothesis with the postulates of equilibrium thermodynamics. Practical significance. The entropy maximization method can be successfully used to calculate the composition of various geochemical systems consisting of organic compounds. The method is suitable for determining chemical composition of the irregular polymers, such as kerogen, bitumen, humic, in equilibrium with organic and inorganic gases and liquids.

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