The spontaneous genesis of hydrocarbons that comprise natural petroleum have been analyzed by chemical thermodynamic-stability theory. The constraints imposed on 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. For the theoretical analysis of this phenomenon, a general, first-principles equation of state has been developed by extending scaled particle theory and by using the technique of the factored partition function of the simplified perturbed hard-chain theory. The chemical potentials and the respective thermodynamic Affinity have been calculated for typical components of the H-C system over a range of pressures between 1 and 100 kbar (1 kbar ‫؍‬ 100 MPa) 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 Ϸ30 kbar, excepting only the lightest, methane. The pressure of 30 kbar corresponds to depths of Ϸ100 km. For experimental verification of the predictions of the theoretical analysis, a special high-pressure apparatus has been designed that permits investigations at pressures to 50 kbar and temperatures to 1,500°C and also allows rapid cooling while maintaining high pressures. The high-pressure genesis of petroleum hydrocarbons has been demonstrated using only the reagents solid iron oxide, FeO, and marble, CaCO 3, 99.9% pure and wet with tripledistilled water. N atural petroleum is a hydrogen-carbon (H-C) system, in distinctly nonequilibrium states, composed of mixtures of highly reduced hydrocarbon molecules, all of very high chemical potential and most in the liquid phase. As such, the phenomenon of the terrestrial existence of natural petroleum in the near-surface crust of the Earth has presented several challenges, most of which have remained unresolved until recently. The primary scientific problem of petroleum has been the existence and genesis of the individual hydrocarbon molecules themselves: how, and under what thermodynamic conditions, can such highly reduced molecules of high chemical potential evolve?The scientific problem of the genesis of hydrocarbons of natural petroleum, and consequentially of the origin of natural petroleum deposits, regrettably has been one too much neglected by competent physicists and chemists; the subject has been obscured by diverse, unscientific hypotheses, typically connected with the rococo hypothesis (1) that highly reduced hydrocarbon molecules of high chemical potentials might somehow evolve from highly oxidized biotic molecules of low chemical potential. The scientific problem of the spontaneous evolution of the hydrocarbon molecules comprising natural petroleum is one of chemical thermodynamic-stability the...

Abstract:Microcanonical thermodynamics [D. H. E. Gross, Microcanonical Thermodynamic Ensembles: Phase Transitions in "Small" Systems. (World Scientific, Singapore, 2001)] allows the application of statistical mechanics both to finite and even small systems and also to the largest, self-gravitating ones. However, one must reconsider the fundamental principles of statistical mechanics especially its key quantity, entropy. Whereas in conventional thermostatistics, the homogeneity and extensivity of the system and the concavity of its entropy are central conditions, these fail for the systems considered here. For example, at phase separation, the entropy, S(E), is necessarily convex to make e S(E)-E/T bimodal in E.Particularly, as inhomogeneities and surface effects cannot be scaled away, one must be careful with the standard arguments of splitting a system into two subsystems, or bringing two systems into thermal contact with energy or particle exchange. Not only the volume part of the entropy must be considered; the addition of any other external constraint, [A. Wehrl, Rev. Mod. Phys. 50, 221 (1978)], such as a dividing surface, or the enforcement of gradients of the energy or particle profile, reduce the page 1 of 23

A thermodynamic argument has been developed which relates the chirality of the constituents of a mixture of enantiomers to the system excess volume, and thereby to its Gibbs free enthalpy. A specific connection is shown between the excess volume and the statistical mechanical partition function. The Kihara-Steiner equations, which describe the geometry of convex hard bodies, have been extended to include also chiral hard bodies. These results have been incorporated into an extension of the Pavlícek-Nezbeda-Boublík equation of state for convex, aspherical, hard-body systems. The Gibbs free enthalpy has been calculated, both for singlecomponent and racemic mixtures, for a wide variety of hard-body systems of diverse volumes and degrees of asphericity, prolateness, and chirality. The results show that a system of chiral enantiomers can evolve to an unbalanced, scalemic mixture, which must manifest optical activity, in many circumstances of density, particle volume, asphericity, and degree of chirality. The real chiral molecules fluorochloroiodomethane, CHFClI, and 4-vinylcyclohexene, C 8 H 12 , have been i nvestigated by Monte Carlo simulation, and observed to manifest, both, positive excess volumes (in their racemic mixtures) which increase with pressure, and thereby the racemic -scalemic transition to unbalanced distributions of enantiomers. The racemic -scalemic transition, responsible for the evolution of an optically active fluid, is shown to be one particular case of the general, complex phase behavior characteristic of "closely-similar" molecules (either chiral or achiral) at high pressures.

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