The Genesis of Hydrocarbons

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The Genesis of Hydrocarbons the Origins
ofPetroleum

• J. F. Kenney
• Russian Academy of Sciences -
• Joint Institute of Physics of the Earth
• Gas Resources Corporation

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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.  J. F.
Kenney, (JFK_at_alum.MIT.edu)Vladimir A.
KutcherovNikolai A. Bendeliani, Vladimir A.
AlekseevProc. Natl. Acad. Sci. U.S.A.
99(17)10976-10981. http//www.GasResources.net
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Dedication In the first instance, this article
is dedicated to the memory of Nikolai
Alexandrovich Kudryavtsev, who first enunciated,
in 1951(1), what has become the modern
Russian-Ukrainian theory of abyssal, abiotic
petroleum origins. After Kudryavtsev, all the
rest followed.
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This article is dedicated generally to the many
geologists, geochemists, geophysicists, and
petroleum engineers of the former U.S.S.R. who,
during the past half century, developed modern
petroleum science. By doing so, they raised their
country from being, in 1946, a relatively
petroleum-poor one, to the greatest petroleum
producing and exporting nation in the world.
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This article is dedicated specifically to the
late Academician Emmanuil Bogdanovich Chekaliuk,
the greatest statistical thermodynamicist ever to
have turned his formidable intellect to the
problem of petroleum genesis. In the Summer of
1976, during the depths of the cold war and at
immeasurable hazard, Academician Chekaliuk chose
to respond, across a gulf of political hostility,
to an unsolicited letter from an unknown American
chief executive officer of a petroleum company
headquartered in Houston, Texas. Thenafter and
for almost fifteen years, Academician Chekaliuk
was my teacher, my collaborator, and my friend.
JFK
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0. Overview1. No more amnesia,-
connected with the constraints of
thermo-dynamics and fossil fuels.2. No more
reticence,- when confronting same, (refer to
article).
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I. The constraints of the 2nd law
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II. The thermodynamic energy spectrum of the H-C
system, and the H-C-O system.
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• The chemical potentials of the elemental
  compo-nents of the H-C system, at STP
• Carbon - graphite diamond
• Hydrogen - gas, H2.

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• The chemical potentials of the n-alkane series of
  the H-C system at STP, from CH4, methane, through
  C20H42, dodecane.

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• The chemical potentials of all the straight-chain
  hydrocarbon components of the H-C system at STP
  n-alkanes, n-alkenes, and
• n-alkynes.

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• The chemical potentials of the straight-chain and
  cyclic hydro-carbons
• n-alkanes, n-al-kenes, n-al-kynes, cyclo-hexanes,
  cyclo-pentanes, and alkylbenzenes, at STP.

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• The chemical potentials of the naturally
  oc-curring compo-nents of the H-C system at STP
  n-alkanes, n-alkenes, cyclohexanes,
  cyclopentanes, and alkyl-benzenes.

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• Chemical potentials of the H-C system, at STP,
  together with represen-tative com-pounds
  invol-ving single and multiple states of
  oxidation, (OH) alcohols and carbohy-drates.

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(1.) The H-C system which constitutes natural
petroleum is a metastable one. At low pressures,
all heavier hydrocarbon molecules are unstable
with respect to methane and the stoichiometric
quantity of hydrogen. All heavier hydrocarbon
molecules are only kinetically stable against
decomposition into methane and hydrogen, -
similarly as is diamond into graphite.(2.)
Methane, or natural gas, does not polymerize
into heavy hydrocarbon molecules at low
pressures, at any temperature. Contrarily,
increasing temperature at low pressures must
increase the rate of decomposition of heavier
hydrocarbons.(3.) Because the chemical
potentials of all biotic molecules lie far below
that of methane, no hydrocarbon molecule heavier
than methane will evolve spontaneously from any
biotic molecule, or combination of such.
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An additional complicationNo benefit is gained
from the predictions of the Le Chatelier - Braun
rules

• Increasing pressure does not drive methane to
  transform into n-hexane and hydrogen.
• Increasing temperature, at low pressures, will
  increase the decomposition of hexane into methane
  and carbon.

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A further complicationThe relative covolumes
inhibit hydrocarbon genesis

• Both the pressure and Gibbs potential depend upon
  a third-order singularity in the reduced density
  1/(1-V/V)3.

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III. Determination of the chemical potentials.
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The theoretical formalismQ QrefQvdW

• The formalism uses a factored partition function
  with a reference system.
• The reference system used is Scaled Particle
  Theory SPT for mixtures of arbitrary convex,
  hard-body fluids fluids, which represents an
  exact statistical mechanical solution.
• The mean-field formalism developed for the
  Simplified Perturbed Hard Chain Theory SPHCT
  formalism is used to account for the attractive,
  van der Waals component of the inter-particle
  potential.

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Application of the formalism of the factored
partition function
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Statistical mechanical analysis

• The exact SPT equation of state for a mixture of
  hard-body particles of Boublík is used for the
  reference system

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The following compositional variables are defined
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The pressure and Gibbs free enthalpy of the
reference system
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The van der Waals components of pressure and
chemical po-tential, from SPHCTpvdW, ?vdW
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CH4 ? 1/nCnH2n1 (n-1)/nH2

• At low pressures, me-thane and the H-C sys-tem
  are robustly stable against genesis of alkane
  compounds.
• At 10kbar, methane is most stable against the
  genesis of heavier H-C compounds.
• At approximately 40kbar, the stability of the
  system inverts, and methane becomes unstable
  relative to alkanes and hydrogen.

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• Gibbs free enthalpy of methane n-alkane
  hydrogen at transition of genesis.

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IV. Experimentalinvestigations

• The spontaneous high-pressure genesis of
  hydro-carbons. Reagents
• FeO, CaCO3, H2O.

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• The reagents were placed into a high-pressure
  cell, brought to pressures up to 50 kbar, and
  2000K. Pressure was maintained while temperature
  was reduced rapidly to ambient.
• The volatile products present in the cell were
  analysed by gas chromatograph.

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• Experimental observation of high-pressure genesis
  of hydro-carbons

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IV. Significance of the theoretical
experimentalresults

• The pressures required for the spontaneous
  genesis of hydrocarbons determines the depth for
  such.

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• Average lapse rates of pressure and temperature
  with depth of the Earth.

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Every ten or fifteen years since the late
1800s, experts have predic-ted that oil
reserves would last only ten more years. These
experts have predicted nine out of the last zero
oil-reserve exhaustions. C. Maurice and C.
Smithson, Doomsday Mythology 10,000 Years of
Economic Crisis, Hoover Institution Press,
Stanford, 1984.
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Five generations of imbecility are
enough.Justice Oliver Wendell Holmes Jr., Buck
vs. Bell, (1927), 274 U.S., 200, 47 S. CT. 584.
(writing for the majority).No more B.S.J. F.
Kenney