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The Evolution of Multi-component Systems at
High Pressures: VI. The Thermodynamic Stability of the Hydrogen-Carbon
System: The Genesis of Hydrocarbons and the Origin of Petroleum.
J. F. Kenney, V. G. Kutcherov, N. A. Bendeliani, V. A. Alekseev, (2002),
Proceedings of the National Academy of Sciences (U.S.A.), 99/17,
10976-10981.
PDF version
Abstract:
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.
For the theoretical analysis of this
phenomenon, 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.
For experimental verification of the
predictions of the theoretical analysis, special high-pressure apparatus has
been designed which permits investigations at pressures to 50 kbar and
temperatures to 1500°C, 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
solid iron oxide, FeO, and marble, CaCO3, 99.9% pure, wet with
triple-distilled water.
Natural petroleum is a hydrogen-carbon [H-C]
system, in distinctly non-equilibrium states, composed of mixtures of highly
reduced, hydrocarbon molecules, all of very high chemical potential, 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, has regrettably 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 theory. This problem does not involve the
properties of rocks where petroleum might be found, nor of microorganisms
observed in crude oil.
This paper is organized into five parts. The
first section reviews briefly the formalism of modern thermodynamic
stability theory, the theoretical framework for the analysis of the genesis
of hydrocarbons and the H-C system, - as similarly for any system.
The second section examines, applying the
constraints of thermodynamics, the notion that hydrocarbons might evolve
spontaneously from biological molecules. Here are described the spectra of
chemical potentials of hydrocarbon molecules, particularly the
naturally-occurring ones present in petroleum. Interpretation of the
significance of the relative differences between the chemical potentials of
the hydrocarbon system and those of biological molecules, applying the
dictates of thermodynamic stability theory, disposes of any hypothesis of an
origin for hydrocarbon molecules from biological matter, excepting only the
lightest, methane.
In the third section is described a
first-principles, statistical mechanical formalism, developed from an
extended representation of scaled particle theory appropriate for mixtures
of aspherical, hard-body molecules, combined with a mean-field
representation of the long-range, attractive component of the intermolecular
potential.
In the fourth section, the thermodynamic
Affinity developed using this formalism establishes that the hydrocarbon
molecules peculiar to natural petroleum are high-pressure polymorphs of the
H-C system, similarly as diamond and lonsdalite are to graphite for the
elemental carbon system, and evolve only in thermodynamic regimes of
pressures greater than 25-50 kbar.
The fifth section reports the experimental
results obtained using equipment specially-designed to test the predictions
of the previous sections. Application of pressures to 50 kbar and
temperatures to 1500°C upon solid (and obviously abiotic) CaCO3
and FeO, wet with triple-distilled water, all in the absence of any initial
hydrocarbon or biotic molecules, evolves the suite of petroleum fluids:
methane, ethane, propane, butane, pentane, hexane, branched isomers of those
compounds, and the lightest of the n-alkene series.
The synthesis of hydrocarbons from abiotic
reagents at pressures to 5 Gpa.
V. G. Kutcherov, N. A. Bendeliani, V. A. Alekseev, J. F. Kenney, (2002),
Proceedings of the National Academy of Sciences of Russia, 387/6,
789-792.
PDF version
The Evolution of Multicomponent Systems at
High Pressures: IV. The Genesis of Optical Activity in High-density, Abiotic
Fluids.
J. F. Kenney, U. K. Deiters, (2001), Physical Chemistry - Chemical
Physics, 2, 3163-3174.
PDF version
Abstract:
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.
For the theoretical analysis of this
phenomenon, 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.
For experimental verification of the
predictions of the theoretical analysis, special high-pressure apparatus has
been designed which permits investigations at pressures to 50 kbar and
temperatures to 1500°C, 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
solid iron oxide, FeO, and marble, CaCO3, 99.9% pure, wet with
triple-distilled water.
Natural petroleum is a hydrogen-carbon [H-C]
system, in distinctly non-equilibrium states, composed of mixtures of highly
reduced, hydrocarbon molecules, all of very high chemical potential, 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, has regrettably 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 theory. This problem does not involve the
properties of rocks where petroleum might be found, nor of microorganisms
observed in crude oil.
This paper is organized into five parts. The
first section reviews briefly the formalism of modern thermodynamic
stability theory, the theoretical framework for the analysis of the genesis
of hydrocarbons and the H-C system, - as similarly for any system.
The second section examines, applying the
constraints of thermodynamics, the notion that hydrocarbons might evolve
spontaneously from biological molecules. Here are described the spectra of
chemical potentials of hydrocarbon molecules, particularly the
naturally-occurring ones present in petroleum. Interpretation of the
significance of the relative differences between the chemical potentials of
the hydrocarbon system and those of biological molecules, applying the
dictates of thermodynamic stability theory, disposes of any hypothesis of an
origin for hydrocarbon molecules from biological matter, excepting only the
lightest, methane.
In the third section is described a
first-principles, statistical mechanical formalism, developed from an
extended representation of scaled particle theory appropriate for mixtures
of aspherical, hard-body molecules, combined with a mean-field
representation of the long-range, attractive component of the intermolecular
potential.
In the fourth section, the thermodynamic
Affinity developed using this formalism establishes that the hydrocarbon
molecules peculiar to natural petroleum are high-pressure polymorphs of the
H-C system, similarly as diamond and lonsdalite are to graphite for the
elemental carbon system, and evolve only in thermodynamic regimes of
pressures greater than 25-50 kbar.
The fifth section reports the experimental
results obtained using equipment specially-designed to test the predictions
of the previous sections. Application of pressures to 50 kbar and
temperatures to 1500°C upon solid (and obviously abiotic) CaCO3
and FeO, wet with triple-distilled water, all in the absence of any initial
hydrocarbon or biotic molecules, evolves the suite of petroleum fluids:
methane, ethane, propane, butane, pentane, hexane, branched isomers of those
compounds, and the lightest of the n-alkene series.
The Evolution of Multi-component Systems at
High Pressures: II. The Alder-Wainwright, High-Density, Gas-Solid Phase
Transition of the Hard-Sphere Fluid.
J. F. Kenney, (1999), Physical Chemistry - Chemical Physics, 1,
3277-3285.
PDF version
Abstract:
The thermodynamic stability of the
hard-sphere gas has been examined, using the formalism of scaled particle
theory [SPT], and by applying explicitly the conditions of stability
required by both the second and third laws of thermodynamics. The
temperature and volume limits to the validity of SPT have also been
examined. It is demonstrated that scaled particle theory predicts absolute
limits to the stability of the fluid phase of the hard-sphere system, at all
temperatures within its range of validity. Because scaled particle theory
describes fluids equally well as dilute gases or dense liquids, the limits
set upon the system stability by SPT must represent limits for the existence
of the fluid phase and transition to the solid. The reduced density at the
stability limits determined by SPT is shown to agree exactly with those of
that estimated for the Alder-Wainwright, supercritical, high-density
gas-solid phase transition in a hard-sphere system, at a specific
temperature, and closely over a range of more than 1,000K. The temperature
dependence of the gas-solid phase stability limits has been examined over
the range 0.01K-10,000K. It is further shown that SPT describes correctly
the variation of the entropy of a hard-core fluid at low temperatures,
requiring its entropy to vanish as T -> 0 by undergoing a gas-solid
phase transition at finite temperature and all pressures.[†]
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History of Banking Fraud:
The Coming Battle
By M. W. WALBERT
The Coming Battle
documents from Congressional records, newspaper reports and writings by
the founding fathers and others a chronology of events long forgotten that
shaped our fledgling nation from 1776 to 1899. Read about the manipulation
of our money and its supply, the intentional creation of recessions,
depressions and panics, manipulation of the stock markets, and the
demonetization of silver.
Secrets of the Federal Reserve
by Eustace Mullins
Eustace Mullins' carefully
researched and documented treatise picks up from Walbert's expose' of
control of the money supply and the economy and
brings it to the mid 1980's.
The
World Order
How control of the world's money has inexorably led to an ever tighter
grip on control of the world's people.
Uranium Wars by Leuren Moret
How control of the world's people has inexorably led to wider use of
depopulation methods which include spreading radioactivity in food,
water, air, and the human genome.
Taking Back Your Power
by Allen Aslan Heart
WHAT CAN YOU DO? Stop playing THEIR game. Take back
your power. Stop paying taxes that are not legal or lawful. Stop paying
bills you don't really owe. Stop using THEIR money. There ARE ways if you
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© 2007, Allen Aslan Heart / White Eagle Soaring of the Little Shell Pembina Band,
a
Treaty
Tribe of the Ojibwe Nation
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