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 spontaneous genesis of hydrocarbons which comprise natural petroleum have been analyzed by chemical thermodynamic stability theory. The constraints imposed upon chemical evolution by the second law of thermodynamics are briefly reviewed; and the effective prohibition of transformation, in the regime of temperatures and pressures characteristic of the near-surface crust of the Earth, of biological molecules into hydrocarbon molecules heavier than methane is recognized.   A general, first-principles equation of state has been developed by extending scaled particle theory (SPT) and by using the technique of the factored partition function of the Simplified Perturbed Hard Chain Theory (SPHCT). The chemical potentials, and the respective thermodynamic Affinity, have been calculated for typical components of the hydrogen-carbon (H-C) system over a range pressures between 1-100 kbar, and at temperatures consistent with those of the depths of the Earth at such pressures. The theoretical analyses establish that the normal alkanes, the homologous hydrocarbon group of lowest chemical potential, evolve only at pressures greater than approximately thirty kbar, excepting only the lightest, methane. The pressure of thirty kbar corresponds to depths of approximately 100 km.   Special high-pressure apparatus has been designed which permits investigations at pressures to 50 kbar and temperatures to 2000 K, and which also allows rapid cooling while maintaining high pressures. The high-pressure genesis of petroleum hydrocarbons has been demonstrated using only the solid reagents iron oxide, FeO, and marble, CaCO3, 99.9% pure and wet with triple-distilled water. 
J. F. Kenney, Vladimir G. Kutcherov, Nikolai A. Bendeliani, Vladimir   A. Alekseev