The Constraints of the Laws of Thermodynamics upon the Evolution of Hydrocarbons: The Prohibition of Hydrocarbon Genesis at Low Pressures

Summary of the article

By J. F. Kenney
Joint Institute of The Physics of the Earth - Russian Academy of Sciences
Gas Resources Corporation, 11811 North Freeway, Houston, TX 77060, U.S.A.

By I. K. Karpov
Institute of Geochemistry - Russian Academy of Sciences
Favorskii Street 1a, Irkutsk, 664.033 RUSSIA

By Ac. Ye. F. Shnyukov
National Academy of Sciences of Ukraine
Khmelnitskogo Street 15 B, 01650 Kiev, Ukraine

By V. A. Krayushkin

By I. I. Chebanenko

By V. P. Klochko
Institute of Geological Sciences - National Academy of Sciences of UKRAINE
O. Gonchara Street 55-B, 01054 Kiev, Ukraine

This first article, which deals with the general subject of the modern Russian-Ukrainian theory of abyssal (bottomless pit), abiotic petroleum origins does not specifically address that body of knowledge. Instead it discusses the reasons which led physicists, chemists, thermodynamicists, and chemical, mechanical, and petroleum engineers to reject the hypothesis that highly-reduced hydrocarbon molecules of high chemical potentials might somehow evolve spontaneously from highly-oxidized biological molecules of low chemical potentials, and reviews briefly the fundamental scientific reasons for the failure of the 18th Century hypothesis[1] of a biological origin of petroleum.

Fundamentally, Russian petroleum science adheres to the fundamental laws of physics and chemistry. Moreover, the second law of thermodynamics completely disputes the biological theory proposed in the 18th Century.

Some everyday examples of the second law of thermodynamics include heat flowing from a hotter body to a colder one, until they become equal; the flow of heat then ceases. The process never reverses.

A drop of cream placed in coffee diffuses throughout the other, until such time as their respective densities become equally uniform throughout the volume at which time the diffusive flow ceases; the process never reverses.

This is true for chemical processes also, when any two chemical species capable of reacting (reagents) are placed in contact, and no other action is taken upon them, chemical reaction proceeds, until such time as the reagents have reached their equilibrium chemical state; at which time the reaction ceases; the process never reverses.

The properties of natural petroleum (oil) and the prohibition by the second law of thermodynamics of its spontaneous genesis from highly-oxidized biological molecules of low chemical potentials, were understood in the second half of the 19th century by physicists, chemists and thermodynamicists, such as Berthelot, Sokolov, Biasson, and Mendeleev. However, the problem of how, and in what regime of temperature and pressure, do hydrogen and carbon combine to form the particular H-C system manifested by natural petroleum, remained. However, the resolution of this problem had to wait a century for the development of modern atomic and molecular theory, quantum statistical mechanics, and many-body theory. This question has now been resolved theoretically by determination of the chemical potentials and the thermodynamic affinity of the H-C system, using modern quantum statistical mechanics, and has also now been demonstrated experimentally with specially designed high-pressure apparatus, and is described in the following articles.

1.     M. V. Lomonosov, Slovo o reshdinii metallov ot tryaseniya zemli, Akadimii Nauk, St. Petersburg, 1757.

2.     R. J. E. Clausius, The Mechanical Theory of Heat, Berlin, 1850.

3.     R. J. E. Clausius, "The Mechanical Theory of Heat", Phil. Mag., 1862, xxiv, 201.

4.     T. De Donder, L'Affinité, Gautier-Villars, Paris, 1936.

5.     T. De Donder and P. Van Rysselberghe, The Thermodynamic Theory of Affinity, Stanford University Press, Menlo Park, 1936.

6.     I. Prigogine and R. Defay, Chemical Thermodynamics, Longmans, London, 1954.

7.     D. Kondepudi and I. Prigogine, Modern Thermodynamics: From Heat Engines to Dissipative Structures, John Wiley & Sons, New York, 1998.

8.     J. N. Bronsted and J. Koefoed, J. Kgl. Danske, Vedenskab Selskab, Mat.-Phys. Medd., 1946, 22, 1.

9.     J. Hijmans, "Phenomenological formulation of the principle of corresponding states for liquids consisting of chain molecules," Physica, 1961, 27, 433-447.

10.     I. Prigogine, A. Bellemans and C. J. Naar-Colin, "Theorem of corresponding states for polymers," J. Chem. Phys., 1957, 26, 751.

11.     U. S. Bureau of Standards, Selected properties of hydrocarbons, A.P.I. Project 41, 1946-1952.

12.     A. S. Eigenson, "On quantitative study of the formation of technogenic and natural hydrocarbons using methods of mathematical modeling", Khimiya i Teknologiya Topliv i Masel, 1990, 12 , 19-254.

13.     A. S. Eigenson, "On quantitative study of the formation of technogenic and natural hydrocarbons using methods of mathematical modeling," Khimiya i Teknologiya Topliv i Masel, 1991, 5, 19-26.

14.     A. S. Eigenson, "Quantitative study of some notions about catagenesis which is a main stage of biogenic oil-gas formation," Khimiya i Teknologiya Topliv i Masel, 1996, 6, 31-36.

Editor's note: To understand the chemical and mathematical components of this article, I recommend reading the original article at http://www.gasresources.net It also provides diagrams and charts that this summary can't.