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Title: Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations

Abstract

Vapor liquid equilibria (VLE) of organic compounds is governed by weak non-covalent interactions. This presents a significant challenge in predicting VLE using a first principles approach where density functional theory is used to model system potential. However, a dispersion corrected approach has significantly improved the performance of traditional density functionals. Here, we predict the VLE for a nonpolar carbon tetrafluoride (R14) and polar 1,1,1,2-tetrafluoroethane (R134a)via first principles Gibbs ensemble Monte Carlo simulations using PBED3 density functional. We find that the saturated liquid density for R14 is slightly under predicted for subcritical temperatures, while for R134a it is under predicted at lower reduced temperatures and over predicted at higher reduced temperatures. In the liquid phase, angle-resolved pair correlation functions indicate slight preference for R143a to align in parallel and antiparallel orientation in the first solvation shell.The vibrational spectra reveal peak broadening in the condensed phase due to solvothermal effects. Altogether, we find thePBED3 functional performance is better for the nonpolar molecule as compared to the polar one.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
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  1. Mississippi State Univ., MS (United States). Dave C. Swalm School of Chemical Engineering and Center for Advanced Vehicular Systems
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
OSTI Identifier:
1461756
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry Select
Additional Journal Information:
Journal Volume: 2; Journal Issue: 36; Journal ID: ISSN 2365-6549
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ab initio calculations; Fluorinated alkanes; FPMC; Vibrational spectroscopy; VLE

Citation Formats

Goel, Himanshu, Windom, Zachary W., Butler, Charles L., and Rai, Neeraj. Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations. United States: N. p., 2017. Web. doi:10.1002/slct.201701972.
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Goel, Himanshu, Windom, Zachary W., Butler, Charles L., & Rai, Neeraj. Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations. United States. https://doi.org/10.1002/slct.201701972
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Goel, Himanshu, Windom, Zachary W., Butler, Charles L., and Rai, Neeraj. Thu . "Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations". United States. https://doi.org/10.1002/slct.201701972. https://www.osti.gov/servlets/purl/1461756.
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@article{osti_1461756,
title = {Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations},
author = {Goel, Himanshu and Windom, Zachary W. and Butler, Charles L. and Rai, Neeraj},
abstractNote = {Vapor liquid equilibria (VLE) of organic compounds is governed by weak non-covalent interactions. This presents a significant challenge in predicting VLE using a first principles approach where density functional theory is used to model system potential. However, a dispersion corrected approach has significantly improved the performance of traditional density functionals. Here, we predict the VLE for a nonpolar carbon tetrafluoride (R14) and polar 1,1,1,2-tetrafluoroethane (R134a)via first principles Gibbs ensemble Monte Carlo simulations using PBED3 density functional. We find that the saturated liquid density for R14 is slightly under predicted for subcritical temperatures, while for R134a it is under predicted at lower reduced temperatures and over predicted at higher reduced temperatures. In the liquid phase, angle-resolved pair correlation functions indicate slight preference for R143a to align in parallel and antiparallel orientation in the first solvation shell.The vibrational spectra reveal peak broadening in the condensed phase due to solvothermal effects. Altogether, we find thePBED3 functional performance is better for the nonpolar molecule as compared to the polar one.},
doi = {10.1002/slct.201701972},
journal = {Chemistry Select},
number = 36,
volume = 2,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2017},
month = {Thu Dec 21 00:00:00 EST 2017}
}
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Journal Article:
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https://doi.org/10.1002/slct.201701972
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Figures / Tables:

Figure 1 Figure 1: Vapor-liquid coexistence curves (VLCCs) and Clausius-Clapeyron plots for R14 and R134a. Figures A, and C represent VLCCs for R14 and R134a, respectively, and Figures B, and D represent Clausius-Clapeyron plots for R14 and R134a, respectively. The solid black lines depict the experimental data and stars represent the experimentalmore » critical point. The red square symbols represents GEMC simulation data with PBE-D3 functional. The dashed lines show linear fit of the simulated data.« less
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Works referenced in this record:

Cassandra: An open source Monte Carlo package for molecular simulation
journal, April 2017

  • Shah, Jindal K.; Marin-Rimoldi, Eliseo; Mullen, Ryan Gotchy
  • Journal of Computational Chemistry, Vol. 38, Issue 19
  • DOI: 10.1002/jcc.24807

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Effective potentials for liquid simulation of the alternative refrigerants HFC-134a (CF3CH2F) and HFC-125 (CF3CHF2)
journal, January 1997

A multi-scale approach to characterize pure CH 4 , CF 4 , and CH 4 /CF 4 mixtures
journal, April 2015

  • Chattoraj, Joyjit; Risthaus, Tobias; Rubner, Oliver
  • The Journal of Chemical Physics, Vol. 142, Issue 16
  • DOI: 10.1063/1.4919079

High-pressure neutron diffraction on fluid carbon tetrafluoride and interpretation by reverse Monte Carlo simulations
journal, December 1997

  • Waldner, I.; Bassen, A.; Bertagnolli, H.
  • The Journal of Chemical Physics, Vol. 107, Issue 24
  • DOI: 10.1063/1.474183

HFC 134a as a substitute refrigerant for CFC 12
journal, November 1988

Microwave Spectroscopy of the Ground, ν18, 2ν18, and ν11Vibrational States of CF3CFH2
journal, June 1999

  • Ilyushin, V. V.; Alekseev, E. A.; Dyubko, S. F.
  • Journal of Molecular Spectroscopy, Vol. 195, Issue 2
  • DOI: 10.1006/jmsp.1999.7825

Molecular Dynamics Studies on the Partially Miscible Binary Liquid Mixture Methane/Tetrafluoromethane Based on Lennard-Jones (12-6) Potentials
journal, May 1977

  • Hoheisel, Claus
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 81, Issue 5
  • DOI: 10.1002/bbpc.19770810504

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Vapor–Liquid Coexistence Curves for Methanol and Methane Using Dispersion-Corrected Density Functional Theory
journal, October 2011

  • McGrath, Matthew J.; Kuo, I. -F. Will; Ghogomu, Julius N.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 40
  • DOI: 10.1021/jp205072v

Infrared absorption cross sections for 1,1,1,2-tetrafluoroethane
journal, January 2015

Configurational bias Monte Carlo: a new sampling scheme for flexible chains
journal, January 1992

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Microscopic structure of liquid 1-1-1-2-tetrafluoroethane (R134a) from Monte Carlo simulation
journal, January 2010

  • Do, Hainam; Wheatley, Richard J.; Hirst, Jonathan D.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 40
  • DOI: 10.1039/c0cp00620c

Rotational and Vibrational Spectroscopy and Ideal Gas Heat Capacity of HFC 134a (CF 3 CFH 2 )
journal, March 1997

  • Xu, Li-Hong; Andrews, Anne M.; Cavanagh, Richard R.
  • The Journal of Physical Chemistry A, Vol. 101, Issue 12
  • DOI: 10.1021/jp9640383

Possible greenhouse effects of tetrafluoromethane and carbon dioxide emitted from aluminum production
journal, August 1996

Maximally localized generalized Wannier functions for composite energy bands
journal, November 1997

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Infrared and Raman spectra of fluorinated ethanes part XVIII. 1, 1, 1, 2-Tetrafluoroethane
journal, August 1965

CH-Stretching Overtone Spectroscopy of 1,1,1,2-Tetrafluoroethane
journal, June 2005

  • Saar, Brian G.; Steeves, Adam H.; Thoman, John W.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 24
  • DOI: 10.1021/jp058060k

HPFP, a Model Propellant for pMDIs
journal, January 2003

  • Rogueda, Philippe G. A.
  • Drug Development and Industrial Pharmacy, Vol. 29, Issue 1
  • DOI: 10.1081/DDC-120016682

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

A review of uses, environmental hazards and recovery/recycle technologies of perfluorocarbons (PFCs) emissions from the semiconductor manufacturing processes
journal, March 2002

  • Tsai, Wen-Tien; Chen, Horng-Ping; Hsien, Wu-Yuan
  • Journal of Loss Prevention in the Process Industries, Vol. 15, Issue 2
  • DOI: 10.1016/S0950-4230(01)00067-5

Performance comparison between the combined R134a/CO 2 heat pump and cascade R134a/CO 2 heat pump for space heating
journal, February 2017

Continuous Fractional Component Monte Carlo:  An Adaptive Biasing Method for Open System Atomistic Simulations
journal, May 2007

  • Shi, Wei; Maginn, Edward J.
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 4
  • DOI: 10.1021/ct7000039

Perfluoroalkanes:  Conformational Analysis and Liquid-State Properties from ab Initio and Monte Carlo Calculations
journal, April 2001

  • Watkins, Edward K.; Jorgensen, William L.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 16
  • DOI: 10.1021/jp004071w

The infrared and Raman spectra of CF3CH2I, CF3CH2Br, and CF3CH2F
journal, January 1963

  • Edgell, Walter F.; Riethof, Thomas R.; Ward, Charlotte
  • Journal of Molecular Spectroscopy, Vol. 11, Issue 1-6
  • DOI: 10.1016/0022-2852(63)90010-9

Experimental evaluation of a R134a/CO 2 cascade refrigeration plant
journal, December 2014

Investigation of Exchange Energy Density Functional Accuracy for Interacting Molecules
journal, August 2009

  • Murray, Éamonn D.; Lee, Kyuho; Langreth, David C.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct900365q

Exergy analysis of R413A as replacement of R12 in a domestic refrigeration system
journal, November 2010

Global warming potentials and radiative efficiencies of halocarbons and related compounds: A comprehensive review: HALOCARBON REVIEW
journal, April 2013

  • Hodnebrog, Ø.; Etminan, M.; Fuglestvedt, J. S.
  • Reviews of Geophysics, Vol. 51, Issue 2
  • DOI: 10.1002/rog.20013

Energy and environmental comparison of two-stage solutions for commercial refrigeration at low temperature: Fluids and systems
journal, January 2015

Optimized density functionals from the extended G2 test set
journal, June 1998

  • Schmider, Hartmut L.; Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 108, Issue 23
  • DOI: 10.1063/1.476438

Ideal gas thermodynamic properties of six fluoroethanes
journal, April 1975

  • Chen, S. S.; Rodgers, A. S.; Choo, J.
  • Journal of Physical and Chemical Reference Data, Vol. 4, Issue 2
  • DOI: 10.1063/1.555521

Absorption system based on the refrigerant R134a
journal, July 1995

Experimental Study of R134a, R406A and R600a Blends as Alternative To Freon 12
journal, January 2013

  • Akintunde, M. A., Akintunde, M. A.
  • IOSR Journal of Mechanical and Civil Engineering, Vol. 7, Issue 1
  • DOI: 10.9790/1684-0714046

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Simulating Fluid-Phase Equilibria of Water from First Principles †
journal, January 2006

  • McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 2
  • DOI: 10.1021/jp0535947

Calculation of the Gibbs free energy of solvation and dissociation of HCl in water via Monte Carlo simulations and continuum solvation models
journal, January 2013

  • McGrath, Matthew J.; Kuo, I-F. Will; Ngouana W., Brice F.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 32
  • DOI: 10.1039/c3cp51762d

Molecular Simulation for Thermodynamic Properties and Process Modeling of Refrigerants
journal, May 2014

  • Smith, William R.; Figueroa-Gerstenmaier, Susana; Skvorova, Magda
  • Journal of Chemical & Engineering Data, Vol. 59, Issue 10
  • DOI: 10.1021/je500260d

An improved determination of the molecular dipole moment of HFC-134a: microwave Stark spectra and ab initio calculations
journal, March 2003

  • Puzzarini, Cristina; Dore, Luca; Cludi, Lino
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 8
  • DOI: 10.1039/b300260h

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Ab Initio Calculations of Vibrational Frequencies and Infrared Intensities for Global Warming Potential of CFC Substitutes: CF3CH2F (HFC-134a)
journal, March 1995

  • Papasavva, Stella; Tai, Stephanie; Esslinger, Amy
  • The Journal of Physical Chemistry, Vol. 99, Issue 11
  • DOI: 10.1021/j100011a006

Molecular simulation of the binary mixture of 1–1–1–2–tetrafluoroethane and carbon dioxide
journal, January 2011

  • Do, Hainam; Wheatley, Richard J.; Hirst, Jonathan D.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 34
  • DOI: 10.1039/c1cp21419e

Higher-accuracy van der Waals density functional
journal, August 2010

High resolution FTIR spectroscopy of 1,1,1,2-tetrafluoroethane:
journal, March 2003

  • Thompson, Christopher D.; Robertson, Evan G.; Evans, Corey J.
  • Journal of Molecular Spectroscopy, Vol. 218, Issue 1
  • DOI: 10.1016/S0022-2852(02)00079-6

Liquid Water from First Principles:  Investigation of Different Sampling Approaches
journal, August 2004

  • Kuo, I-Feng W.; Mundy, Christopher J.; McGrath, Matthew J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 34
  • DOI: 10.1021/jp047788i

First principles Monte Carlo simulations of aggregation in the vapor phase of hydrogen fluoride
journal, January 2010

  • McGrath, Matthew J.; Ghogomu, Julius. N.; Mundy, Christopher J.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 27
  • DOI: 10.1039/b924506e

Gibbs ensemble simulation of HCFC/HFC mixtures by effective Stockmayer potential
journal, June 1999

Vapour-liquid equilibria for dipolar two-centre Lennard-Jones fluids by Gibbs-Duhem integration
journal, August 1997

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986

Phase equilibria by simulation in the Gibbs ensemble: Alternative derivation, generalization and application to mixture and membrane equilibria
journal, March 1988

Transferable Potentials for Phase Equilibria. 9. Explicit Hydrogen Description of Benzene and Five-Membered and Six-Membered Heterocyclic Aromatic Compounds
journal, September 2007

  • Rai, Neeraj; Siepmann, J. Ilja
  • The Journal of Physical Chemistry B, Vol. 111, Issue 36
  • DOI: 10.1021/jp073586l

High-resolution IR spectroscopy of jet-cooled CF3CH2F
journal, January 1995

  • McNaughton, Don; Evans, Corey; Robertson, Evan G.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 12
  • DOI: 10.1039/ft9959101723

Theoretical and experimental investigation of a combined R134a and transcritical CO2 heat pump for space heating
journal, December 2016

Vapor Liquid Equilibria of Hydrofluorocarbons Using Dispersion-Corrected and Nonlocal Density Functionals
journal, June 2016

  • Goel, Himanshu; Butler, Charles L.; Windom, Zachary W.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 7
  • DOI: 10.1021/acs.jctc.6b00305

Microscopic and Thermodynamic Properties of the HFA134a−Water Interface:  Atomistic Computer Simulations and Tensiometry under Pressure
journal, October 2006

  • Peguin, Robson P. S.; Selvam, Parthiban; da Rocha, Sandro R. P.
  • Langmuir, Vol. 22, Issue 21
  • DOI: 10.1021/la0608157

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

Van der Waals Density Functional for General Geometries
journal, June 2004

Vibrational Fundamentals of CF 3 CH 2 X Molecules
journal, January 1970

Resolution of the uncertainties in the radiative forcing of HFC-134a
journal, July 2005

  • Forster, Piers M. de F.; Burkholder, J. B.; Clerbaux, C.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 93, Issue 4
  • DOI: 10.1016/j.jqsrt.2004.08.038

Derivation of an Optimized Potential Model for Phase Equilibria (OPPE) for Sulfides and Thiols
journal, May 2000

  • Delhommelle, J.; Tschirwitz, C.; Ungerer, P.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 19
  • DOI: 10.1021/jp994064b

Computing vibrational spectra from ab initio molecular dynamics
journal, January 2013

  • Thomas, Martin; Brehm, Martin; Fligg, Reinhold
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 18
  • DOI: 10.1039/c3cp44302g

Predicting the Phase Equilibria of Mixtures of Hydrogen Fluoride with Water, Difluoromethane (HFC-32), and 1,1,1,2-Tetrafluoroethane (HFC-134a) Using a Simplified SAFT Approach
journal, March 1997

  • Galindo, Amparo; Whitehead, Paul J.; Jackson, George
  • The Journal of Physical Chemistry B, Vol. 101, Issue 11
  • DOI: 10.1021/jp962675n

Structural investigations of fluid carbon tetrafluoride by statistical mechanical calculations and Monte Carlo simulation
journal, April 1998

  • Bassen, A.; Waldner, I.; Bertagnolli, H.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 102, Issue 4
  • DOI: 10.1002/bbpc.19981020404

Mie Potentials for Phase Equilibria Calculations: Application to Alkanes and Perfluoroalkanes
journal, November 2009

  • Potoff, Jeffrey J.; Bernard-Brunel, Damien A.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 44
  • DOI: 10.1021/jp9072137

Development of an all-atoms force field from ab initio calculations for alternative refrigerants
journal, July 2003

Left-right correlation energy
journal, March 2001

A study of solid and liquid carbon tetrafluoride using the constant pressure molecular dynamics technique
journal, June 1983

  • Nosé, Shuichi; Klein, Michael L.
  • The Journal of Chemical Physics, Vol. 78, Issue 11
  • DOI: 10.1063/1.444641

Infrared band strengths of HFC-134a vapour
journal, March 1996

  • Newnham, D.; Ballard, J.; Page, M.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 55, Issue 3
  • DOI: 10.1016/0022-4073(95)00164-6

Theoretical investigation on the combined and cascade CO2/R134a heat pump systems for space heating
journal, September 2017

Prediction of Phase Equilibria for Refrigerant Mixtures of Difluoromethane (HFC-32), 1,1,1,2-Tetrafluoroethane (HFC-134a), and Pentafluoroethane (HFC-125a) Using SAFT-VR
journal, September 1998

  • Galindo, Amparo; Gil-Villegas, Alejandro; Whitehead, Paul J.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 39
  • DOI: 10.1021/jp9809437

Nonlocal van der Waals Density Functional Made Simple
journal, August 2009

Vapor–liquid equilibria of water from first principles: comparison of density functionals and basis sets
journal, November 2006

All-Atom Force Field for the Prediction of Vapor−Liquid Equilibria and Interfacial Properties of HFA134a
journal, January 2009

  • Peguin, Robson P. S.; Kamath, Ganesh; Potoff, Jeffrey J.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 1
  • DOI: 10.1021/jp806213w
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