The Thermodynamic Stability of the Hydrogen-Carbon System:
The Genesis of Hydrocarbons and the Origin of Petroleum
Summary of the Article
By J. F. Kenney
(JFK@alum.MIT.edu)
Gas Resources Corporation
Russian Academy of Sciences - Joint Institute of Earth Physics
By Vladimir A. Kutcherov
Russian State University of Oil and Gas
By Nikolai A. Bendeliani and Vladimir A. Alekseev
Russian Academy of Sciences - Institute for High Pressure Physics
Experiment in a laboratory on how oil is formed
Petroleum is generated because of high pressure and high temperature such as 50 kbar and temperatures to 1500°Celsius, and which also allows rapid cooling while maintaining high pressures. [28] The importance of this latter ability cannot be overstated; for, in order to examine the spontaneous reaction products, the system must be rapidly quenched to "freeze in" their high-pressure, high-temperature distribution.
Experiments to demonstrate the high-pressure genesis of petroleum hydrocarbons have been carried out. No biotic compounds or hydrocarbons were admitted to the reaction chamber. Conservative measures were used. The initial carbon compound, CaCO 3, is more oxidized and of lower chemical potential. All of which rendered the system more resistant to the reduction of carbon to form heavy alkanes, than it would be under conditions of the mantle of the Earth. Although there has been observed igneous CaCO 3(carbonatite) of mantle origin, carbon should be more reasonably expected to exist in the mantle of the Earth as an element in its dense phases.
Pressure in the reaction cell, as described in [25] of volume 0.6 cm 3, was measured by a pressure gauge calibrated using data of the phase transitions of Bi, Tl, and PbTe. The cell was heated by a cylindrical graphite heater; its temperature was measured using a chromel-alumel thermocouple and was regulated within the range ±5°C. Both stainless steel and platinum reaction cells were used; all were constructed to prevent contamination by air and to provide impermeability during and after each experimental run.
The reaction cell was brought from 1 bar to 50 kbar gradually, at a rate of 2 kbar/min, and from room temperature to the elevated temperatures of investigation at the rate of 100 K/min. The cell and reaction chamber were held for at least an hour at each temperature for which measurements were taken in order to allow the H-C system to come to thermodynamic equilibrium. The samples were thereafter quenched rapidly at the rate of 700°Celsius/sec to 50 °Celsius, and from 50°Celsius to room temperature over several minutes, while maintaining the high pressure of investigation. The pressure was then reduced gradually to 1 bar at the rate of 1 kbar/min. The reaction cell was then gently heated to desorb the hydrocarbons for mass spectrometer analysis, using an HI-120 1B mass spectrometer equipped with an automatic system of computerized spectrum registration. A specially-designed high-temperature gas probe allowed sampling the cell while maintaining its internal pressure.
At pressures below 10 kbar, no hydrocarbons heavier than methane were present. Hydrocarbon molecules begin to evolve above 30 kbar. At 50 kbar and at the temperature of 1500°Celsius, the system spontaneously evolved methane, ethane, n-propane, 2-methylpropane, 2, 2-dimethylpropane, n-butane, 2-methylbutane, n-pentane, 2-methylpentane, n-hexane, and n-alkanes through Celsius 10 H22, ethene, n-propene, n-butene, and n-pentene, in distributions characteristic of natural petroleum. That the extent of hydrocarbon evolution becomes relatively stable as a function of temperature above approximately 900°C, both for the absolute abundance of the individual hydrocarbon species as well as for their relative abundances, argues that the distributions observed represent thermodynamic equilibrium for the H-C system. That the evolved hydrocarbons remain stable over a range of temperatures increasing by more than 300 K demonstrates the third prediction of the theoretical analysis: Hydrocarbon molecules heavier than methane do not decompose with increasing temperature in the high-pressure regime of their genesis.
The pressure of 30 kbar, which causes ethane and heavier hydrocarbon compounds to evolve, exists at a depth of more than 100 km. The results of the theoretical analysis shown in Fig. 2 clearly establish that the evolution of the molecular components of natural petroleum occur at depth at least as great as those of the mantle of the Earth, as shown graphically in Figure 4 in which are represented the thermal and pressure lapse rates in the depths of the Earth.
Editor's note: To see the Figures indicated above, log onto http://www.gasresources.net and look for the article entitled "The Evolution of Multicomponent Systems at High Pressures: VI. the Thermodynamic Stability of the Hydrogen-Carbon System: The Genesis of Hydrocarbons and the Origin of Petroleum."
The genesis of natural petroleum must occur at depths not less than approximately 100 km, - well into the mantle of the Earth. The experimental observations reported in Section 7 confirm theoretical predictions of Section 5, and demonstrate how the iron compounds interact under high pressures to reduce water, of which the hydrogen combines with available carbon to produce heavy hydrocarbon compounds.
Editor's note: To see Sections 5 and 7 in the original article go to http://www.gasresources.net and go to the same titled article as indicated above in previous Ed's note.
Significantly, these theoretical results are consistent with, and complement, the analysis of the genesis of the phenomenon of optical activity in abiotic fluids, including natural petroleum, previously reported. (14) In the past, observation of optical activity in natural petroleum had been spuriously claimed as evidence of a biological connection.
Editor's note: See Figure 4 for pressure and temperature in the depths of the Earth.
In 1951, the Russian geologist Nikolai Kudryavtsev (33) enunciated what has become the modern Russian-Ukrainian theory of deep, abiotic petroleum origins, a fundamental tenet of which is that natural petroleum is a primordial, abiotic material, erupted from great depth. Kudryavtsev was soon joined by many prominent Russian geologists, geochemists, geophysicists, and petroleum engineers who together developed the extensive body of knowledge which now forms modern petroleum science.
Modern petroleum science has heretofore been a geologists' theory, supported by many observations, drawn into a comprehensive pattern, and argued by persuasion. By contrast, a physicist's theory uses only a minimum of data, applies fundamental physical laws, using the principles of mathematics, and argues by compulsion. The theoretical results here reported, use only the fundamental laws of physics and thermodynamics, and establish the provenance of modern petroleum science in the rigorous mainstream of modern physics and chemistry. The experimental results here reported, confirm unequivocally those theoretical conclusions, which may now be taken as foundations of the modern theory of deep, abiotic petroleum origins.
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Editor's note: For the first 27 citations, please see the article at http://www.gasresources.net