Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory

Abstract

This paper presents an application of mean force kinetic theory (MFT) to the calculation of the self-diffusivity of CO2 in the supercritical fluid regime. Two modifications to the typical application of MFT are employed to allow its application to a system of molecular species. Therefore, the first is the assumption that the inter-particle potential of mean force can be obtained from the molecule center-of-mass pair correlation function, which in the case of CO2 is the C–C pair correlation function. The second is a new definition of the Enskog factor that describes the effect of correlations at the surface of the collision volume. The new definition retains the physical picture that this quantity represents a local density increase, resulting from particle correlations, relative to that in the zero density homogeneous fluid limit. These calculations are facilitated by the calculation of pair correlation functions from molecular dynamics (MD) simulations using the FEPM2 molecular CO2 model. The self-diffusivity calculated from theory is in good agreement with that from MD simulations up to and slightly beyond the density at the location of the Frenkel line. The calculation is compared with and is found to perform similarly well to other commonly used models but hasmore » a greater potential for application to systems of mixed species and to systems of particles with long range interatomic potentials due to electrostatic interactions.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1836999
Report Number(s):
LA-UR=-21-22550
Journal ID: ISSN 0021-9606; TRN: US2300538
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 154; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Kinetic theory; Molecular dynamics; Nonequilibrium statistical mechanics; Particle correlations; Diffusion; Classical statistical mechanics

Citation Formats

Scheiner, Brett Stanford, and Yoon, Tae-Jun. Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory. United States: N. p., 2021. Web. doi:10.1063/5.0045211.
Copy to clipboard
Scheiner, Brett Stanford, & Yoon, Tae-Jun. Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory. United States. https://doi.org/10.1063/5.0045211
Copy to clipboard
Scheiner, Brett Stanford, and Yoon, Tae-Jun. Wed . "Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory". United States. https://doi.org/10.1063/5.0045211. https://www.osti.gov/servlets/purl/1836999.
Copy to clipboard
@article{osti_1836999,
title = {Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory},
author = {Scheiner, Brett Stanford and Yoon, Tae-Jun},
abstractNote = {This paper presents an application of mean force kinetic theory (MFT) to the calculation of the self-diffusivity of CO2 in the supercritical fluid regime. Two modifications to the typical application of MFT are employed to allow its application to a system of molecular species. Therefore, the first is the assumption that the inter-particle potential of mean force can be obtained from the molecule center-of-mass pair correlation function, which in the case of CO2 is the C–C pair correlation function. The second is a new definition of the Enskog factor that describes the effect of correlations at the surface of the collision volume. The new definition retains the physical picture that this quantity represents a local density increase, resulting from particle correlations, relative to that in the zero density homogeneous fluid limit. These calculations are facilitated by the calculation of pair correlation functions from molecular dynamics (MD) simulations using the FEPM2 molecular CO2 model. The self-diffusivity calculated from theory is in good agreement with that from MD simulations up to and slightly beyond the density at the location of the Frenkel line. The calculation is compared with and is found to perform similarly well to other commonly used models but has a greater potential for application to systems of mixed species and to systems of particles with long range interatomic potentials due to electrostatic interactions.},
doi = {10.1063/5.0045211},
journal = {Journal of Chemical Physics},
number = 13,
volume = 154,
place = {United States},
year = {Wed Apr 07 00:00:00 EDT 2021},
month = {Wed Apr 07 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/5.0045211
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The Diffusion of Gases at High Pressures. I. The Self-diffusion Coefficient of Carbon Dioxide
journal, October 1966

  • Takahashi, Shinji; Iwasaki, Hiroji
  • Bulletin of the Chemical Society of Japan, Vol. 39, Issue 10
  • DOI: 10.1246/bcsj.39.2105

Correlations for prediction of molecular diffusivities in liquids
journal, April 1982

  • Hayduk, W.; Minhas, B. S.
  • The Canadian Journal of Chemical Engineering, Vol. 60, Issue 2
  • DOI: 10.1002/cjce.5450600213

Carbon Dioxide's Liquid-Vapor Coexistence Curve And Critical Properties as Predicted by a Simple Molecular Model
journal, August 1995

  • Harris, Jonathan G.; Yung, Kwong H.
  • The Journal of Physical Chemistry, Vol. 99, Issue 31
  • DOI: 10.1021/j100031a034

Shear Viscosity Computed from the Finite-Size Effects of Self-Diffusivity in Equilibrium Molecular Dynamics
journal, October 2018

  • Jamali, Seyed Hossein; Hartkamp, Remco; Bardas, Christos
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 11
  • DOI: 10.1021/acs.jctc.8b00625

Translational and rotational diffusion in liquids. II. Orientational single‐particle correlation functions
journal, May 1974

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 60, Issue 9
  • DOI: 10.1063/1.1681567

Translational and rotational diffusion in liquids. I. Translational single‐particle correlation functions
journal, May 1974

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 60, Issue 9
  • DOI: 10.1063/1.1681566

Testing thermal conductivity models with equilibrium molecular dynamics simulations of the one-component plasma
journal, October 2019

The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids
journal, December 2003

  • Lin, Shiang-Tai; Blanco, Mario; Goddard, William A.
  • The Journal of Chemical Physics, Vol. 119, Issue 22
  • DOI: 10.1063/1.1624057

Rough hard sphere theory of the self‐diffusion constant for molecular liquids
journal, February 1975

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 62, Issue 4
  • DOI: 10.1063/1.430647

Supercritical Carbon Dioxide as a Green Reaction Medium for Catalysis
journal, July 2002

  • Leitner, Walter
  • Accounts of Chemical Research, Vol. 35, Issue 9
  • DOI: 10.1021/ar010070q

On the Use of Excess Entropy Scaling to Describe the Dynamic Properties of Water
journal, August 2010

  • Chopra, Ravi; Truskett, Thomas M.; Errington, Jeffrey R.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 32
  • DOI: 10.1021/jp1049155

Equation of State for Nonattracting Rigid Spheres
journal, July 1969

  • Carnahan, Norman F.; Starling, Kenneth E.
  • The Journal of Chemical Physics, Vol. 51, Issue 2
  • DOI: 10.1063/1.1672048

Behavior of Supercritical Fluids across the “Frenkel Line”
journal, September 2017

A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple‐Point Temperature to 1100 K at Pressures up to 800 MPa
journal, November 1996

  • Span, Roland; Wagner, Wolfgang
  • Journal of Physical and Chemical Reference Data, Vol. 25, Issue 6
  • DOI: 10.1063/1.555991

Free‐Volume Model of the Amorphous Phase: Glass Transition
journal, January 1961

  • Turnbull, David; Cohen, Morrel H.
  • The Journal of Chemical Physics, Vol. 34, Issue 1
  • DOI: 10.1063/1.1731549

Thermodynamic and transport properties of carbon dioxide from molecular simulation
journal, February 2007

  • Nieto-Draghi, Carlos; de Bruin, Theodorus; Pérez-Pellitero, Javier
  • The Journal of Chemical Physics, Vol. 126, Issue 6
  • DOI: 10.1063/1.2434960

Supercritical fluid extraction and fractionation of natural matter
journal, September 2006

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Mean force kinetic theory: A convergent kinetic theory for weakly and strongly coupled plasmas
journal, August 2019

  • Baalrud, Scott D.; Daligault, Jérôme
  • Physics of Plasmas, Vol. 26, Issue 8
  • DOI: 10.1063/1.5095655

Self-diffusion in fluid carbon dioxide at high pressures
journal, September 1998

  • Groß, T.; Buchhauser, J.; Lüdemann, H. -D.
  • The Journal of Chemical Physics, Vol. 109, Issue 11
  • DOI: 10.1063/1.477055

Bond Angle Distributions of Carbon Dioxide in the Gas, Supercritical, and Solid Phases †
journal, March 2009

  • Anderson, Kelly E.; Mielke, Steven L.; Siepmann, J. Ilja
  • The Journal of Physical Chemistry A, Vol. 113, Issue 10
  • DOI: 10.1021/jp808711y

Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids
journal, May 2020

  • Scheiner, Brett; Baalrud, Scott D.
  • The Journal of Chemical Physics, Vol. 152, Issue 17
  • DOI: 10.1063/5.0005435

High pressure nuclear magnetic resonance measurement of spin–lattice relaxation and self‐diffusion in carbon dioxide
journal, August 1992

  • Etesse, Patrick; Zega, James A.; Kobayashi, Riki
  • The Journal of Chemical Physics, Vol. 97, Issue 3
  • DOI: 10.1063/1.463139

Supercritical drying of aerogels using CO2: Effect of extraction time on the end material textural properties
journal, June 2012

Decontamination of uranium oxides from solid wastes by supercritical CO2 fluid leaching method using HNO3–TBP complex as a reactant
journal, October 2004

Modified Free Volume Theory of Self-Diffusion and Molecular Theory of Shear Viscosity of Liquid Carbon Dioxide
journal, April 2005

  • Nasrabad, Afshin Eskandari; Laghaei, Rozita; Eu, Byung Chan
  • The Journal of Physical Chemistry B, Vol. 109, Issue 16
  • DOI: 10.1021/jp044393q

Tetracycline nanoparticles precipitation using supercritical and liquid CO 2 as antisolvents
journal, January 2016

New Method for Prediction of Binary Gas-Phase Diffusion Coefficients
journal, May 1966

  • Fuller, Edward N.; Schettler, Paul D.; Giddings, J. Calvin.
  • Industrial & Engineering Chemistry, Vol. 58, Issue 5
  • DOI: 10.1021/ie50677a007

Dyeing polyester fibres with disperse dyes in supercritical CO2
journal, April 2000

Voids, generic van der Waals equation of state, and transport coefficients of liquids
journal, January 2007

  • Eu, Byung Chan
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 47
  • DOI: 10.1039/b705542k

Diffusion in Carbon Dioxide at Elevated Pressures
journal, October 1955

  • O'Hern, Harold A.; Martin, Joseph J.
  • Industrial & Engineering Chemistry, Vol. 47, Issue 10
  • DOI: 10.1021/ie50550a021

Shear stress relaxation and diffusion in simple liquids by molecular dynamics simulations: Analytic expressions and paths to viscosity
journal, May 2019

  • Heyes, D. M.; Smith, E. R.; Dini, D.
  • The Journal of Chemical Physics, Vol. 150, Issue 17
  • DOI: 10.1063/1.5095501

Excess-entropy scaling in supercooled binary mixtures
journal, August 2020

Generic van der Waals equation of state and statistical mechanical representations of the van der Waals parameters
journal, February 2001

Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids
journal, March 1954

  • Green, Melville S.
  • The Journal of Chemical Physics, Vol. 22, Issue 3
  • DOI: 10.1063/1.1740082

Modified Entropy Scaling of the Transport Properties of the Lennard-Jones Fluid
journal, June 2019

  • Bell, Ian H.; Messerly, Richard; Thol, Monika
  • The Journal of Physical Chemistry B, Vol. 123, Issue 29
  • DOI: 10.1021/acs.jpcb.9b05808

Correlation of diffusion coefficients in dilute solutions
journal, June 1955

SAFT-γ Force Field for the Simulation of Molecular Fluids. 1. A Single-Site Coarse Grained Model of Carbon Dioxide
journal, September 2011

  • Avendaño, Carlos; Lafitte, Thomas; Galindo, Amparo
  • The Journal of Physical Chemistry B, Vol. 115, Issue 38
  • DOI: 10.1021/jp204908d

Thermodynamics, dynamics, and structure of supercritical water at extreme conditions
journal, January 2020

  • Yoon, Tae Jun; Patel, Lara A.; Ju, Taeho
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 28
  • DOI: 10.1039/d0cp02288h

Review of supercritical CO2 power cycle technology and current status of research and development
journal, October 2015

  • Ahn, Yoonhan; Bae, Seong Jun; Kim, Minseok
  • Nuclear Engineering and Technology, Vol. 47, Issue 6
  • DOI: 10.1016/j.net.2015.06.009

System-Size Dependence of Diffusion Coefficients and Viscosities from Molecular Dynamics Simulations with Periodic Boundary Conditions
journal, October 2004

  • Yeh, In-Chul; Hummer, Gerhard
  • The Journal of Physical Chemistry B, Vol. 108, Issue 40
  • DOI: 10.1021/jp0477147

Description of self-diffusion coefficients of gases, liquids and fluids at high pressure based on molecular simulation data
journal, April 2006

Pulsed Breakdown and Plasma-Aided Phenol Polymerization in Supercritical Carbon Dioxide and Sub-Critical Water
journal, November 2009

  • Kiyan, Tsuyoshi; Sasaki, Mitsuru; Ihara, Takeshi
  • Plasma Processes and Polymers, Vol. 6, Issue 11
  • DOI: 10.1002/ppap.200900030

Analysis of the transport coefficients for simple dense fluid: Application of the modified Enskog theory
journal, August 1972

“Two-Phase” Thermodynamics of the Frenkel Line
journal, July 2018

  • Yoon, Tae Jun; Ha, Min Young; Lee, Won Bo
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 16
  • DOI: 10.1021/acs.jpclett.8b01955

Diffusion and viscosity equations of state for a Lennard-Jones fluid obtained from molecular dynamics simulations
journal, September 1997

  • Rowley, R. L.; Painter, M. M.
  • International Journal of Thermophysics, Vol. 18, Issue 5
  • DOI: 10.1007/bf02575252

Self-Diffusion in Gases and Liquids
journal, September 1997

  • Ruckenstein, Eli; Liu, Hongqin
  • Industrial & Engineering Chemistry Research, Vol. 36, Issue 9
  • DOI: 10.1021/ie9701332

Supercritical antisolvent precipitation of micro- and nano-particles
journal, May 1999

Pure and Pseudo-pure Fluid Thermophysical Property Evaluation and the Open-Source Thermophysical Property Library CoolProp
journal, January 2014

  • Bell, Ian H.; Wronski, Jorrit; Quoilin, Sylvain
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 6
  • DOI: 10.1021/ie4033999

Self-Diffusion Coefficients from Entropy Scaling Using the PCP-SAFT Equation of State
journal, August 2018

  • Hopp, Madlen; Mele, Julia; Gross, Joachim
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 38
  • DOI: 10.1021/acs.iecr.8b02406

Lennard-Jones Fluid and Diffusivity:  Validity of the Hard-Sphere Model for Diffusion in Simple Fluids and Application to CO 2
journal, January 2008

  • Ravi, R.; Guruprasad, V.
  • Industrial & Engineering Chemistry Research, Vol. 47, Issue 4
  • DOI: 10.1021/ie071073v

Self-diffusion coefficient equation for polyatomic fluid
journal, December 1999

Probing the link between residual entropy and viscosity of molecular fluids and model potentials
journal, February 2019

Perspective: Excess-entropy scaling
journal, December 2018

  • Dyre, Jeppe C.
  • The Journal of Chemical Physics, Vol. 149, Issue 21
  • DOI: 10.1063/1.5055064

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model
journal, May 2011

  • Huang, Shao-Nung; Pascal, Tod A.; Goddard, William A.
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 6
  • DOI: 10.1021/ct200211b

addendum: A universal scaling law for atomic diffusion in condensed matter
journal, June 2001

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: