Professional Documents
Culture Documents
Communicated by Howard Reiss, University of California, Los Angeles, CA, June 24, 2002 (received for review April 3, 2002)
The spontaneous genesis of hydrocarbons that comprise natural of rocks where petroleum might be found or of microorganisms
petroleum have been analyzed by chemical thermodynamic-stability observed in crude oil.
theory. The constraints imposed on chemical evolution by the second This paper is organized into five parts. The first section reviews
law of thermodynamics are briefly reviewed, and the effective pro- briefly the formalism of modern thermodynamic-stability theory,
hibition of transformation, in the regime of temperatures and pres- the theoretical framework for the analysis of the genesis of hydro-
sures characteristic of the near-surface crust of the Earth, of biological carbons and the H–C system, as similarly for any system.
molecules into hydrocarbon molecules heavier than methane is rec- The second section examines, applying the constraints of ther-
ognized. For the theoretical analysis of this phenomenon, a general, modynamics, the notion that hydrocarbons might evolve sponta-
first-principles equation of state has been developed by extending neously from biological molecules. Here are described the spectra
scaled particle theory and by using the technique of the factored of chemical potentials of hydrocarbon molecules, particularly the
partition function of the simplified perturbed hard-chain theory. The naturally occurring ones present in petroleum. Interpretation of the
chemical potentials and the respective thermodynamic Affinity have significance of the relative differences between the chemical po-
been calculated for typical components of the H–C system over a tentials of the hydrocarbon system and those of biological mole-
range of pressures between 1 and 100 kbar (1 kbar ⴝ 100 MPa) and cules, applying the dictates of thermodynamic-stability theory,
at temperatures consistent with those of the depths of the Earth at disposes of any hypothesis of an origin for hydrocarbon molecules
such pressures. The theoretical analyses establish that the normal from biological matter, excepting only the lightest, methane.
alkanes, the homologous hydrocarbon group of lowest chemical In the third section is described a first-principles, statistical
potential, evolve only at pressures greater than ⬇30 kbar, excepting mechanical formalism, developed from an extended representation
only the lightest, methane. The pressure of 30 kbar corresponds to of scaled particle theory (SPT) appropriate for mixtures of aspheri-
depths of ⬇100 km. For experimental verification of the predictions cal hard-body molecules combined with a mean-field representa-
of the theoretical analysis, a special high-pressure apparatus has been tion of the long-range, attractive component of the intermolecular
designed that permits investigations at pressures to 50 kbar and potential.
temperatures to 1,500°C and also allows rapid cooling while main- In the fourth section, the thermodynamic Affinity developed
taining high pressures. The high-pressure genesis of petroleum hy- using this formalism establishes that the hydrocarbon molecules
drocarbons has been demonstrated using only the reagents solid iron peculiar to natural petroleum are high-pressure polymorphs of
oxide, FeO, and marble, CaCO3, 99.9% pure and wet with triple- the H–C system, similarly as diamond and lonsdaleite are to
distilled water. graphite for the elemental carbon system, and evolve only in
thermodynamic regimes of pressures greater than 25–50 kbar (1
kbar ⫽ 100 MPa).
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
The fifth section reports the experimental results obtained using
equipment specially designed to test the predictions of the previous
potential and most in the liquid phase. As such, the phenomenon sections. Application of pressures to 50 kbar and temperatures to
of the terrestrial existence of natural petroleum in the near-surface 1,500°C upon solid (and obviously abiotic) CaCO3 and FeO wet
crust of the Earth has presented several challenges, most of which with triple-distilled water, all in the absence of any initial hydro-
have remained unresolved until recently. The primary scientific carbon or biotic molecules, evolves the suite of petroleum fluids:
problem of petroleum has been the existence and genesis of the methane, ethane, propane, butane, pentane, hexane, branched
individual hydrocarbon molecules themselves: how, and under what isomers of those compounds, and the lightest of the n-alkene series.
thermodynamic conditions, can such highly reduced molecules of
1. Thermodynamic Stability and the Evolution of
high chemical potential evolve?
Multicomponent Systems
The scientific problem of the genesis of hydrocarbons of natural
petroleum, and consequentially of the origin of natural petroleum Central to any analysis of chemical stability is the thermody-
deposits, regrettably has been one too much neglected by compe- namic Affinity, A({i}), which determines the direction of
tent physicists and chemists; the subject has been obscured by evolution of a system in accordance with the second law of
diverse, unscientific hypotheses, typically connected with the ro- thermodynamics as expressed by De Donder’s inequality, dQ⬘ ⫽
coco hypothesis (1) that highly reduced hydrocarbon molecules of Ad ⱖ 0 (2). The Affinity of an n-component, multiphase system
high chemical potentials might somehow evolve from highly oxi- of p phases involving r chemical reactions is given as
dized biotic molecules of low chemical potential. The scientific
problem of the spontaneous evolution of the hydrocarbon mole- Abbreviations: STP, standard temperature and pressure; SPT, scaled particle theory; SPHCT,
cules comprising natural petroleum is one of chemical thermody- simplified perturbed hard-chain theory.
namic-stability theory. This problem does not involve the properties §To whom reprint requests should be addressed. E-mail: JFK@alum.mit.edu.
in which i, and i, are the chemical potential and stoichio-
metric coefficients of the ith component in the th reaction,
respectively; ␣ designates the respective phase.
The second law states that the internal production of entropy
is always positive for every spontaneous transformation. There-
fore, the thermodynamic Affinity (Eq. 1) must always be posi-
tive, and the direction of evolution of any system must always
obey the inequalities:
冦 冘 冘冘冘
冧
r p n
1 1
A d ⫽ ⫺ i,i␣共p, T, 兵nj其兲d
T T
dSint ⫽ ⫽1 ␣⫽1 i⫽1 ⱖ 0.
冘
k
FkdXk
[2]
The inequalities in Eq. 2 express the irreversibility of spontaneous
transitions and state that for a spontaneous evolution of a system
from any state, A, to any other state, B, the free enthalpy of state
B must be less than that of state A, and at no point between the two
may the free enthalpy be greater than that of state A or less than Fig. 1. Molar Gibbs energies of formation, ⌬Gf, of the naturally occurring
that of state B. hydrocarbons at STP (5).
The sum of the products on the second line of inequality in Eq.
2, of the thermodynamic Affinities and the differential of the
variables of extent, d, is always positive, and the circumstance for 2. The Thermodynamic Energy Spectrum of the H–C System
which the change of internal entropy is zero defines equilibrium, and the Effective Prohibition of Low-Pressure Genesis
from which there is no spontaneous evolution. This is De Donder’s of Hydrocarbons
inequality. The thermodynamic energy spectrum of the chemical potentials
The sum of products on the second line of inequality in Eq. 2 (molar Gibbs energies of formation, ⌬Gf) of the H–C system at
deserves particular note. In the second line of Eq. 2, Fk and dXk are standard temperature and pressure [(STP, 298.15 K; 1 atm
general thermodynamic forces and flows, respectively, and subsume (1 atm ⫽ 101.3 kPa)] is available from tables of chemical data
Newton’s rule, Fᠬ ⫽ maᠬ , as a special case (3, 4). The expression in the (5). The chemical potentials of naturally occurring members of
second line of Eq. 2 states further that for any circumstance for the of the H–C system at STP are shown graphically in Fig. 1.
which the Affinity does not vanish, there exists a generalized Examination of the energy spectrum of these chemical potentials
thermodynamic force that drives the system toward equilibrium. of the H–C system establishes at once that, at STP, the chemical
The constraints of this expression assure that an apple, having potentials of the entire hydrocarbon system are remarkable for
disconnected from its bough, does not fall, say, half way to the both their characteristic increase with degree of polymerization
ground and there stop (a phenomenon not prohibited by the first as well as their linear, and almost constant, magnitude of such
law) but must continue to fall until the ground. These constraints increase with carbon number. With increasing polymerization,
force a chemically reactive system to evolve always toward the state the n-alkane molecules manifest increased chemical potential of
of lowest thermodynamic Affinity. very approximately 2.2 kcal per added carbon atom or CH2 unit.
Thus, the evolution of a chemically reactive, multicomponent (There exist also branched isomers, the chemical potentials of
system may be determined at any temperature, pressure, or com- which differ from such of the normal configuration by, typically,
position whenever the chemical potentials of its components are 2–4%.) Such increase in chemical potential with increased
known. To ascertain the thermodynamic regime of the sponta- degree of polymerization contrasts strongly with the thermody-
neous evolution of hydrocarbons, their chemical potentials must namic spectrum of the highly oxidized biotic carbon (‘‘organic’’)
be determined. compounds of the hydrogen–carbon–oxygen (H–C–O) system,
No consideration has been given in the foregoing discussion of which manifest consistently decreasing chemical potentials with
chemical thermodynamic stability to the rate of increase of the increasing polymerization. This latter property allows the
variables of extent, d. Such is the subject of chemical kinetics, not high degree of polymerization and complexity of the biotic
PHYSICS
stability theory. The rate at which a reaction might occur cannot compounds.
alter its direction as determined by the second law of thermody- Examination of the H–C–O system of oxidized carbon com-
namics; otherwise the second law would not exist. The evolution of pounds establishes that the chemical potentials of almost all biotic
a system can admit intermediate states, in which one (or more) compounds lie far below that of methane, the least energetic of the
intermediate product might possess a chemical potential consider- reduced hydrocarbon compounds, typically by several hundred
ably greater than that of any of the initial reagents. The presence kcal兾mol. Although there exist biotic molecules of unusually high
of a selected catalyst can enhance a fast reaction, and if the system chemical potential such as -carotene (C40H56), vitamin D
CHEMISTRY
is removed rapidly from thermodynamic environment at which such (C38H44O), and some of the pheromone hormones, such com-
reactions proceeding to the final state occur, the intermediate pounds are relatively rare by abundance. They are produced by
product(s) can be separated. The petrochemical industry routinely biological systems only when the producing entity is alive (and at
operates such processes. However, such complex industrial pro- formidable metabolic cost to the producing entity), and the pro-
cesses are not mimicked spontaneously in the natural world. duction ceases with the death of the entity. Such compounds are not
p ref ⫽ kBT 1 ⫹ 冋 冉
⫹
rs
共1 ⫺ 兲 共1 ⫺ 兲 2⫹
qs2共1 ⫺ 2兲 ⫹ 5rs2
3共1 ⫺ 兲3
冊册
⫽ 共pIG ⫹ phc兲, [6]
r⫽ 冘
i
x i R̃ i , q⫽ 冘
i
x i R̃ i2 , s⫽ 冘i
x i S̃ i ,
⫽ 冘i
x i Ṽ i , ⫽ 冘
i
x i Ṽ i ⫽ . 冎 [7]
冋冘 冉 冊 冉 冊 册
and pressures, the evolution of methane will dominate and
共nii3兲 I ⫹ J ⫹ K2 effectively exhaust the H–C system of its elemental components.
G ref ⫽ NkBT xi ln ⫹ ⫺ c3 ln共1 ⫺ 兲 ,
V 共1 ⫺ 兲3 Because methane is the sole hydrocarbon specie that is thermo-
i
dynamically stable at low pressures, the chemical Affinities of
[9]
each of the heavier species have been calculated in comparison
in which I ⫽ 2c1 ⫺ c3, J ⫽ ⫺1兾2(3c1 ⫺ 3c2 ⫺ 5c3), and K ⫽ 1兾6(3c1 ⫺ with methane. Accordingly, the chemical Affinity calculated for
3c2 ⫺ 3c3). When these identities are used, the contribution of the the thermodynamic stability of, for example, the methane 7
reference system to the pressure and the free enthalpy become (n-octane ⫹ hydrogen) system is that for the reaction CH4 3
simplified functions of the packing-fraction, , and the geometric 1兾8 C8H18⫹ 7兾8 H2.
compositional variables, ␣ and ␥. The chemical potentials of the hydrocarbon and methane
The contributions to the pressure and the chemical potentials molecules and the resulting thermodynamic Affinities of the
from the long-range van der Waals component of the intermolec- (methane 3 hydrocarbon ⫹ hydrogen) system have been eval-
ular potential are described using the formalism of the SPHCT uated for the n-alkanes from methane through C20H42. In Fig. 2
(17–19). The SPHCT uses the mean-field technique (20) of the are shown the Gibbs energies for the set of hydrocarbons
Bethe–Peierls–Prigogine ‘‘lattice-gas’’ model, in which has been methane (CH4) and the n-alkanes, ethane (n-C2H6), hexane
PHYSICS
applied the shape-independent scattering formalism (21). As dem- (n-C6H14), and decane (n-C10H22). These thermodynamic vari-
onstrated previously (22) at elevated pressures, the pressure and ables have been determined at pressures ranging from 1 to
chemical potential are dominated by their respective hard-core 100,000 bar and at the supercritical temperature 1,000 K, the
components, and the attractive component is several orders of temperature of which corresponds conservatively to the geolog-
magnitude smaller and of little consequence. The representation of ical regime characterized by the respective pressures of transition.
the attractive components of the pressure and chemical potential The values of the SPHCT parameters, c, , and Y, for the
used has been that developed for the SPHCT by Sandler (23), individual compounds that have been used were taken from van
CHEMISTRY
Donohue and Prausnitz (19), and Lee and Chao (24) using the Pelt et al. (27), and the reference values of the chemical
mixing rules of Kim et al. (25). The Prigogine shape c factors used potentials of the pure component were taken from standard
by the SPHCT are related to the Boublı́k geometric parameters reference tables (3).
such that ci ⫽ (1 ⫹ 3R̃iS̃i兾Ṽi) and V *i ⫽ Ṽi(1 ⫹ ␣i). The values of V i The results of the analysis are shown graphically for the temper-
and ␣i were taken from van Pelt et al. (26). The chemical potential ature 1,000 K in Fig. 2. These results demonstrate clearly that all
1. Lomonosov, M. V. (1757) Slovo o Reshdinii Metallov ot Tryaseniya Zemli (Akadimii Nauk, 18. Beret, S. & Prausnitz, J. M. (1975) AIChE J. 21, 1123–1132.
St. Petersburg). 19. Donohue, M. D. & Prausnitz, J. M. (1978) AIChE J. 24, 849–860.
2. De Donder, T. (1936) L’Affinité (Gautier-Villars, Paris). 20. Bethe, H. A. & Kirkwood, J. G. (1939) J. Chem. Phys. 7, 578–582.
3. Kondepudi, D. & Prigogine, I. (1998) Modern Thermodynamics: From Heat Engines to 21. Huang, K. & Yang, C. N. (1957) Phys. Rev. 105, 767–775.
Dissipative Structures (Wiley, New York). 22. Kenney, J. F. (1998) Fluid Phase Equilibria 148, 21–47.
4. Prigogine, I. & Defay, R. (1954) Chemical Thermodynamics (Longmans, London). 23. Sandler, S. I. (1985) Fluid Phase Equilibria 19, 233–257.
5. U.S. Bureau of Standards (1946–1952) Selected Properties of Hydrocarbons, A.P.I. Project 41 24. Lee, R. J. & Chao, K. C. (1987) Mol. Phys. 61, 1431–1442.
(U.S. Bureau of Standards, Washington, DC). 25. Kim, C.-H., Vimalchand, P., Donohue, P. & Sandler, S. I. (1986) AIChE J. 32, 1726–1734.
6. Pavlı́cek, J., Nezbeda, I. & Boublı́k, T. (1979) Czech. J. Phys. B29, 1061–1070. 26. van Pelt, A., Peters, C. J. & de Swaan Arons, J. (1991) J. Chem. Phys. 95, 7569–7575.
PHYSICS
7. Boublı́k, T. (1981) Mol. Phys. 42, 209–216. 27. van Pelt, A., Peters, C. J. & de Swaan Arons, J. (1992) Fluid Phase Equilibria 74, 67–83.
8. Prigogine, I. (1957) Molecular Theory of Solutions (North–Holland, Amsterdam). 28. Nikolaev, N. A. & Shalimov, M. D. (1999) Patent RF 1332598, MKE 601; (1999) Bull. Izobretenii
9. Bogolyubov, N. N. (1946) Problems of a Dynamical Theory in Statistical Mechanics (GITTL, Moscow). (Russia) 7, 257, 23兾20.
10. Feynman, R. P. (1972) Statistical Mechanics: A Set of Lectures (Addison–Wesley, New York). 29. Chekaliuk, E. B. (1975) in Regularities of Formation of Commercial Oil and Gas Fields (Naukova
11. Yukhnovskii, I. R. (1987) Phase Transitions of the Second Order: The Method of Collective Dumka, Kiev, Ukraine), pp. 66–76.
Variables (World Scientific, Singapore). 30. Kenney, J. F. (1993) Bull. A. P. S. 38, 1508.
12. Reiss, H., Frisch, H. L. & Lebowitz, J. L. (1959) J. Chem. Phys. 31, 369–380. 31. Kenney, J. F. (1995) in Joint XV AIR兾APT International Conference on High-Pressure Physics and
13. Reiss, H., Frisch, H. L. & Lebowitz, J. L. (1964) in The Equilibrium Theory of Classical Fluids, Technology (Warsaw), pp. 843–845.
eds. Frisch, H. L. & Lebowitz, J. L. (W. A. Benjamin, New York), pp. II-299–II-302. 32. Kenney, J. F. (1997) in The Prospects for Oil and Gas Potential of the Crystalline Basement in the
14. Reiss, H. (1965) in Advances in Chemical Physics, ed. Prigogine, I. (Interscience, New York), Vol. Territory of Tatarstan and Volga-Kama Region, ed. Romanov, G. V. (Russian Academy of
9, pp. 1–84. Sciences, Kazan, Russia), pp. 43–52.
CHEMISTRY
15. Reiss, H. (1977) in Statistical Mechanics and Statistical Methods in Theory and Application: A 33. Chekaliuk, E. B. (1971) The Thermodynamic Basis for the Theory of the Abiotic Genesis of
Tribute to Elliott W. Montroll, ed. Landman, U. (Plenum, London), pp. 99–140. Petroleum (Naukova Dumka, Kiev, Ukraine).
16. Kenney, J. F. & Deiters, U. K. (2000) Phys. Chem. Chem. Phys. 2, 3163–3174. 34. Chekaliuk, E. B. & Kenney, J. F. (1991) Proc. Am. Phys. Soc. 36, 347.
17. Vera, J. H. & Prausnitz, J. M. (1972) Chem. Eng. J. 3, 113. 35. Kudryavtsev, N. A. (1951) Petroleum Econ. (Neftianoye Khozyaistvo) 9, 17–29.