Correlation of the hydrocarbon components structural elements of the Eastern Carpathians argillites by the Jaynes' formalism
Abstract
Purpose. On the territory of the Ukrainian Eastern Carpathians there are sedimentary rocks characterized by a great content of hydrocarbons. Among them, the so-called "menilite shale" deserves special attention. In reality, "menilite shale" is black and dark gray argillites. They form the bulk of the Menilite suite of oligocene of the Precarpathian Foredeep Inner zone and the Plicate Carpathians.
These argillites represent a convenient and easily accessible object for study, as there are numerous exits of these rocks on the surface in the Eastern Carpathians. The menilite suite is a massive formation, the thickness of which sometimes reaches1500 m.
Our aim is to study the structure of the bitumen of the menilite suite argillites and to calculate redistribution of structural elements in hydrocarbons, which occurs with increasing temperature.
Method. In order to perform the work, we have applied methods of equilibrium thermodynamics and Jaynes' formalism. The basis for algorithms creating was thermodynamics of maximum entropy, which combines techniques from Claude Shannon's information theory, Bayesian probability, and the principle of maximum entropy.
Based on Jaines's formalism, we have developed a method for determining the quantity of structural elements in black argillites bitumen. Output data for calculation was layers temperature and elemental composition of the sample. The calculations were carried out within the temperature range 300-600 K (27-327 °С).
Results. The result of calculation is the distribution of atoms, which composes bitumen in functional groups, depending on the temperature. It is established that with increasing temperature the value of Gibbs free energy increases with linear dependence, along with nonlinear growth of entropy.
As the temperature rises, relative amount of the methyl group (-CH3) decreases, together with the increase in the number of other components of alkanes.
It has also been established that the process of cyclization of hydrocarbon compounds takes place with the submergence of the rock. It is shown that among the sulfur-containing groups the content of cyclic sulfur is increasing most rapidly with increasing temperature.
As the temperature increases, a significant rise in the relative proportion of the nitrile group is observed. Simultaneously, the process of aliphatic structures destruction containing Nitrogen (for example a primary amino group) is occurring.
Scientific novelty and practical significance. We show that the Jaynes' formalism can be successfully applied to establishing redistribution of atomic groups of fossil hydrocarbons, which occurs in changing geological conditions – submergence and emergence. Flexibility of the method allows us to expand the list of conditions, including adding other structural units or individual components: gases, liquid hydrocarbons, etc.
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