Skip to main content
  • Submit
  • About
    • Editorial Board
    • PNAS Staff
    • FAQ
    • Rights and Permissions
    • Site Map
  • Contact
  • Journal Club
  • Subscribe
    • Subscription Rates
    • Subscriptions FAQ
    • Open Access
    • Recommend PNAS to Your Librarian
  • Log in
  • My Cart

Main menu

  • Home
  • Articles
    • Current
    • Latest Articles
    • Special Features
    • Colloquia
    • Collected Articles
    • PNAS Classics
    • Archive
  • Front Matter
  • News
    • For the Press
    • Highlights from Latest Articles
    • PNAS in the News
  • Podcasts
  • Authors
    • Information for Authors
    • Purpose and Scope
    • Editorial and Journal Policies
    • Submission Procedures
    • For Reviewers
    • Author FAQ
  • Submit
  • About
    • Editorial Board
    • PNAS Staff
    • FAQ
    • Rights and Permissions
    • Site Map
  • Contact
  • Journal Club
  • Subscribe
    • Subscription Rates
    • Subscriptions FAQ
    • Open Access
    • Recommend PNAS to Your Librarian

User menu

  • Log in
  • My Cart

Search

  • Advanced search
Home
Home

Advanced Search

  • Home
  • Articles
    • Current
    • Latest Articles
    • Special Features
    • Colloquia
    • Collected Articles
    • PNAS Classics
    • Archive
  • Front Matter
  • News
    • For the Press
    • Highlights from Latest Articles
    • PNAS in the News
  • Podcasts
  • Authors
    • Information for Authors
    • Purpose and Scope
    • Editorial and Journal Policies
    • Submission Procedures
    • For Reviewers
    • Author FAQ

New Research In

Physical Sciences

Featured Portals

  • Physics
  • Chemistry
  • Sustainability Science

Articles by Topic

  • Applied Mathematics
  • Applied Physical Sciences
  • Astronomy
  • Computer Sciences
  • Earth, Atmospheric, and Planetary Sciences
  • Engineering
  • Environmental Sciences
  • Mathematics
  • Statistics

Social Sciences

Featured Portals

  • Anthropology
  • Sustainability Science

Articles by Topic

  • Economic Sciences
  • Environmental Sciences
  • Political Sciences
  • Psychological and Cognitive Sciences
  • Social Sciences

Biological Sciences

Featured Portals

  • Sustainability Science

Articles by Topic

  • Agricultural Sciences
  • Anthropology
  • Applied Biological Sciences
  • Biochemistry
  • Biophysics and Computational Biology
  • Cell Biology
  • Developmental Biology
  • Ecology
  • Environmental Sciences
  • Evolution
  • Genetics
  • Immunology and Inflammation
  • Medical Sciences
  • Microbiology
  • Neuroscience
  • Pharmacology
  • Physiology
  • Plant Biology
  • Population Biology
  • Psychological and Cognitive Sciences
  • Sustainability Science
  • Systems Biology

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, Vladimir A. Kutcherov, Nikolai A. Bendeliani, and Vladimir A. Alekseev
PNAS August 20, 2002 99 (17) 10976-10981; https://doi.org/10.1073/pnas.172376899
J. F. Kenney
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
Vladimir A. Kutcherov
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
Nikolai A. Bendeliani
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
Vladimir A. Alekseev
  • Find this author on Google Scholar
  • Find this author on PubMed
  • Search for this author on this site
  1. Communicated by Howard Reiss, University of California, Los Angeles, CA (received for review April 3, 2002)

  • Article
  • Figures & SI
  • Info & Metrics
  • PDF
Loading

Abstract

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 ≈30 kbar, excepting only the lightest, methane. The pressure of 30 kbar corresponds to depths of ≈100 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, CaCO3, 99.9% pure and wet with triple-distilled water.

Footnotes

    • ↵§ To whom reprint requests should be addressed. E-mail: JFK{at}alum.mit.edu.

  • Abbreviations

    • STP, standard temperature and pressure

    • SPT, scaled particle theory

    • SPHCT, simplified perturbed hard-chain theory

    • Received April 3, 2002.
    • Accepted June 24, 2002.
    • Copyright © 2002, The National Academy of Sciences
    View Full Text
    PreviousNext
    Back to top
    Article Alerts
    Email Article

    Thank you for your interest in spreading the word on PNAS.

    NOTE: We only request your email address so that the person you are recommending the page to knows that you wanted them to see it, and that it is not junk mail. We do not capture any email address.

    Enter multiple addresses on separate lines or separate them with commas.
    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
    (Your Name) has sent you a message from PNAS
    (Your Name) thought you would like to see the PNAS web site.
    Citation Tools
    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, Vladimir A. Kutcherov, Nikolai A. Bendeliani, Vladimir A. Alekseev
    Proceedings of the National Academy of Sciences Aug 2002, 99 (17) 10976-10981; DOI: 10.1073/pnas.172376899

    Citation Manager Formats

    • BibTeX
    • Bookends
    • EasyBib
    • EndNote (tagged)
    • EndNote 8 (xml)
    • Medlars
    • Mendeley
    • Papers
    • RefWorks Tagged
    • Ref Manager
    • RIS
    • Zotero
    Request Permissions
    Share
    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, Vladimir A. Kutcherov, Nikolai A. Bendeliani, Vladimir A. Alekseev
    Proceedings of the National Academy of Sciences Aug 2002, 99 (17) 10976-10981; DOI: 10.1073/pnas.172376899
    del.icio.us logo Digg logo Reddit logo Twitter logo CiteULike logo Facebook logo Google logo Mendeley logo
    • Tweet Widget
    • Facebook Like
    • Mendeley logo Mendeley
    Proceedings of the National Academy of Sciences: 116 (8)
    Current Issue

    Submit

    Sign up for Article Alerts

    Jump to section

    • Article
      • Abstract
      • 1. Thermodynamic Stability and the Evolution of Multicomponent Systems
      • 2. The Thermodynamic Energy Spectrum of the H–C System and the Effective Prohibition of Low-Pressure Genesis of Hydrocarbons
      • 3. Calculation of the Thermodynamic Affinity Using SPT and the Formalism of the Simplified Perturbed Hard-Chain Theory (SPHCT)
      • 4. The Evolution of the Normal Alkanes, Ethane, Hexane, and Decane from Methane at High Pressures
      • 5. Experimental Demonstration of Hydrocarbon Genesis Under Thermodynamic Conditions Typical of the Depths of the Earth
      • 6. Discussion and Conclusions
      • Acknowledgments
      • Footnotes
      • Abbreviations
      • References
    • Figures & SI
    • Info & Metrics
    • PDF

    You May Also be Interested in

    News Feature: Cities serve as testbeds for evolutionary change
    Urban living can pressure flora and fauna to adapt in intriguing ways. Biologists are starting to take advantage of this convenient laboratory of evolution.
    Image credit: Kristin Winchell (Washington University in St. Louis, St. Louis).
    Several aspects of the proposal, which aims to expand open access, require serious discussion and, in some cases, a rethink.
    Opinion: “Plan S” falls short for society publishers—and for the researchers they serve
    Several aspects of the proposal, which aims to expand open access, require serious discussion and, in some cases, a rethink.
    Image credit: Dave Cutler (artist).
    Featured Profile
    PNAS Profile of NAS member and biochemist Hao Wu
     Nonmonogamous strawberry poison frog (Oophaga pumilio).  Image courtesy of Yusan Yang (University of Pittsburgh, Pittsburgh).
    Putative signature of monogamy
    A study suggests a putative gene-expression hallmark common to monogamous male vertebrates of some species, namely cichlid fishes, dendrobatid frogs, passeroid songbirds, common voles, and deer mice, and identifies 24 candidate genes potentially associated with monogamy.
    Image courtesy of Yusan Yang (University of Pittsburgh, Pittsburgh).
    Active lifestyles. Image courtesy of Pixabay/MabelAmber.
    Meaningful life tied to healthy aging
    Physical and social well-being in old age are linked to self-assessments of life worth, and a spectrum of behavioral, economic, health, and social variables may influence whether aging individuals believe they are leading meaningful lives.
    Image courtesy of Pixabay/MabelAmber.

    More Articles of This Classification

    Physical Sciences

    • Observing a previously hidden structural-phase transition onset through heteroepitaxial cap response
    • Observation of chiral surface excitons in a topological insulator Bi2Se3
    • Froghoppers jump from smooth plant surfaces by piercing them with sharp spines
    Show more

    Chemistry

    • Consecutive feedback-driven constitutional dynamic networks
    • Design–functionality relationships for adhesion/growth-regulatory galectins
    • Homogeneous electrocatalytic oxidation of ammonia to N2 under mild conditions
    Show more

    Physics

    • Observing a previously hidden structural-phase transition onset through heteroepitaxial cap response
    • Structural hierarchy confers error tolerance in biological materials
    • Unraveling materials Berry curvature and Chern numbers from real-time evolution of Bloch states
    Show more

    Related Content

    • Scopus
    • PubMed
    • Google Scholar

    Cited by...

    • On the Origins of Deep Hydrocarbons
    • The Chemistry of Carbon in Aqueous Fluids at Crustal and Upper-Mantle Conditions: Experimental and Theoretical Constraints
    • Laboratory Simulations of Abiotic Hydrocarbon Formation in Earth's Deep Subsurface
    • Stability of hydrocarbons at deep Earth pressures and temperatures
    • Generation of methane in the Earth's mantle: In situ high pressure-temperature measurements of carbonate reduction
    • Scopus (91)
    • Google Scholar

    Similar Articles

    Site Logo
    Powered by HighWire
    • Submit Manuscript
    • Twitter
    • Facebook
    • RSS Feeds
    • Email Alerts

    Articles

    • Current Issue
    • Latest Articles
    • Archive

    PNAS Portals

    • Classics
    • Front Matter
    • Teaching Resources
    • Anthropology
    • Chemistry
    • Physics
    • Sustainability Science

    Information

    • Authors
    • Editorial Board
    • Reviewers
    • Press
    • Site Map

    Feedback    Privacy/Legal

    Copyright © 2019 National Academy of Sciences. Online ISSN 1091-6490