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Title: Molecular driving forces behind the tetrahydrofuran–water miscibility gap

Abstract

The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of water is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.

Authors:
 [1];  [1];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1327650
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 4; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, and Smith, Jeremy C. Molecular driving forces behind the tetrahydrofuran–water miscibility gap. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.5b09770.
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Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, & Smith, Jeremy C. Molecular driving forces behind the tetrahydrofuran–water miscibility gap. United States. https://doi.org/10.1021/acs.jpcb.5b09770
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Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, and Smith, Jeremy C. Wed . "Molecular driving forces behind the tetrahydrofuran–water miscibility gap". United States. https://doi.org/10.1021/acs.jpcb.5b09770. https://www.osti.gov/servlets/purl/1327650.
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@article{osti_1327650,
title = {Molecular driving forces behind the tetrahydrofuran–water miscibility gap},
author = {Smith, Micholas Dean and Mostofian, Barmak and Petridis, Loukas and Cheng, Xiaolin and Smith, Jeremy C.},
abstractNote = {The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of water is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.},
doi = {10.1021/acs.jpcb.5b09770},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 4,
volume = 120,
place = {United States},
year = {Wed Jan 06 00:00:00 EST 2016},
month = {Wed Jan 06 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acs.jpcb.5b09770
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Works referenced in this record:

Phenyl-bonded phase liquid chromatography of styrene oligomers
journal, January 1984

Synthesis and Characterization of Amphiphilic Polyethers Based on Tetrahydrofuran and Glycidol: Antibacterial Assessment
journal, April 2009

  • Theiler, Stefan; Hövetborn, Thomas; Keul, Helmut
  • Macromolecular Chemistry and Physics, Vol. 210, Issue 8
  • DOI: 10.1002/macp.200800502

Enantiomer recognition of crown ethers and open-chain polyethers containing the trans-tetrahydrofuran-2,5-diylbis(methylene) subunit as the chiral centre
journal, January 1986

  • Naemura, Koichiro; Ebashi, Iwao; Matsuda, Atsushi
  • Journal of the Chemical Society, Chemical Communications, Issue 9
  • DOI: 10.1039/c39860000666

Thermodynamic Studies of Solid Polyethers. III. Poly(tetrahydrofuran), –[–(CH2)4O–;[ndash;n
journal, October 1973

  • Yoshida, Shohei; Suga, Hiroshi; Seki, Syûzô
  • Polymer Journal, Vol. 5, Issue 1
  • DOI: 10.1295/polymj.5.25

THF co-solvent enhances hydrocarbon fuel precursor yields from lignocellulosic biomass
journal, January 2013

  • Cai, Charles M.; Zhang, Taiying; Kumar, Rajeev
  • Green Chemistry, Vol. 15, Issue 11
  • DOI: 10.1039/c3gc41214h

Phase equilibria and excess molar volumes of tetrahydrofuran (1) + deuterium oxide (2)
journal, October 1975

Phase equilibria in the system tetrahydrofuran(1)-water(2)
journal, January 1972

  • Matouš, J.; Novák, J. P.; Šobr, J.
  • Collection of Czechoslovak Chemical Communications, Vol. 37, Issue 8
  • DOI: 10.1135/cccc19722653

The Structure of Liquid Tetrahydrofuran
journal, April 2006

  • Bowron, Daniel T.; Finney, John L.; Soper, Alan K.
  • Journal of the American Chemical Society, Vol. 128, Issue 15
  • DOI: 10.1021/ja0583057

Structural Characteristics of a 0.23 Mole Fraction Aqueous Solution of Tetrahydrofuran at 20 °C
journal, October 2006

  • Bowron, Daniel T.; Finney, John L.; Soper, Alan K.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 41
  • DOI: 10.1021/jp064170v

Excess enthalpies and volumes of water + tetrahydrofuran mixtures at 298.15 K
journal, April 1977

  • Kiyohara, Osamu; Benson, George C.
  • Canadian Journal of Chemistry, Vol. 55, Issue 8
  • DOI: 10.1139/v77-187

Roles of the Ether Oxygen in Hydration of Tetrahydrofuran Studied by IR, NMR, and DFT Calculation Methods
journal, January 2009

  • Mizuno, Kazuko; Masuda, Yohko; Yamamura, Takuya
  • The Journal of Physical Chemistry B, Vol. 113, Issue 4
  • DOI: 10.1021/jp807497d

Nanometer-Scale Phase Separation and Preferential Solvation in THF–Water Mixtures: Ultrafast Electron Hydration and Recombination Dynamics Following CTTS Excitation of I –
journal, October 2011

  • Bragg, Arthur E.; Kanu, Godwin U.; Schwartz, Benjamin J.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz201295a

Dielectric Constant and Refractive Index from 20 to 35° and Density at 25° for the System Tetrahydrofuran—Water 1
journal, December 1953

  • Critchfield, Frank E.; Gibson, John A.; Hall, James L.
  • Journal of the American Chemical Society, Vol. 75, Issue 23
  • DOI: 10.1021/ja01119a509

Liquid–liquid coexistence curves of re-entrant phase transitions beyond the asymptotic range: tetrahydrofuran + water and tetrahydrofuran + heavy water
journal, February 2002

  • Oleinikova, Alla; Weingärtner, Hermann
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 6
  • DOI: 10.1039/b109349e

Simulation of the liquid–liquid coexistence of the tetrahydrofuran+water mixture in the Gibbs ensemble
journal, July 2001

Percolation of water in aqueous solution and liquid–liquid immiscibility
journal, August 2002

  • Oleinikova, A.; Brovchenko, I.; Geiger, A.
  • The Journal of Chemical Physics, Vol. 117, Issue 7
  • DOI: 10.1063/1.1493183

Additive and Classical Drude Polarizable Force Fields for Linear and Cyclic Ethers
journal, March 2007

  • Vorobyov, Igor; Anisimov, Victor M.; Greene, Shannon
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 3
  • DOI: 10.1021/ct600350s

Enzymatic conversion of lignocellulose into fermentable sugars: challenges and opportunities
journal, October 2007

  • Jørgensen, Henning; Kristensen, Jan Bach; Felby, Claus
  • Biofuels, Bioproducts and Biorefining, Vol. 1, Issue 2
  • DOI: 10.1002/bbb.4

Reply to ‘Comment on “Theory of the evaporation/condensation transition of equilibrium droplets in finite volumes”’
journal, September 2003

Optimization of parameters for molecular dynamics simulation using smooth particle-mesh Ewald in GROMACS 4.5
journal, April 2011

  • Abraham, Mark J.; Gready, Jill E.
  • Journal of Computational Chemistry, Vol. 32, Issue 9
  • DOI: 10.1002/jcc.21773

GROMACS: Fast, flexible, and free
journal, January 2005

  • Van Der Spoel, David; Lindahl, Erik; Hess, Berk
  • Journal of Computational Chemistry, Vol. 26, Issue 16
  • DOI: 10.1002/jcc.20291

GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008

  • Hess, Berk; Kutzner, Carsten; van der Spoel, David
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 3
  • DOI: 10.1021/ct700301q

GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit
journal, February 2013

Molecular dynamics with coupling to an external bath
journal, October 1984

  • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
  • The Journal of Chemical Physics, Vol. 81, Issue 8
  • DOI: 10.1063/1.448118

Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

P-LINCS:  A Parallel Linear Constraint Solver for Molecular Simulation
journal, December 2007

  • Hess, Berk
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 1
  • DOI: 10.1021/ct700200b

LINCS: A linear constraint solver for molecular simulations
journal, September 1997

Settle: An analytical version of the SHAKE and RATTLE algorithm for rigid water models
journal, October 1992

  • Miyamoto, Shuichi; Kollman, Peter A.
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130805

The Statistical Thermodynamics of Multicomponent Systems
journal, July 1945

  • McMillan, William G.; Mayer, Joseph E.
  • The Journal of Chemical Physics, Vol. 13, Issue 7
  • DOI: 10.1063/1.1724036

Thermodynamics of Hydrogen Bonding in Hydrophilic and Hydrophobic Media
journal, March 2006

  • van der Spoel, David; van Maaren, Paul J.; Larsson, Per
  • The Journal of Physical Chemistry B, Vol. 110, Issue 9
  • DOI: 10.1021/jp0572535

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

Computer simulation and mode coupling theory study of the effects of specific solute–solvent interactions on diffusion: Crossover from a sub-slip to a super-stick limit of diffusion
journal, March 1999

  • Srinivas, Groundla; Bhattacharyya, Sarika; Bagchi, Biman
  • The Journal of Chemical Physics, Vol. 110, Issue 9
  • DOI: 10.1063/1.478292

Theory of closed-loop phase diagrams in binary fluid mixtures
journal, October 1980

A Theory of Liquid Structure
journal, November 1937

  • Hirschfelder, Joseph; Stevenson, David; Eyring, Henry
  • The Journal of Chemical Physics, Vol. 5, Issue 11
  • DOI: 10.1063/1.1749960

Theory of multiple phase separations in binary mixtures: Phase diagrams, thermodynamic properties, and comparisons with experiments
journal, February 1983

  • Goldstein, Raymond E.; Walker, James S.
  • The Journal of Chemical Physics, Vol. 78, Issue 3
  • DOI: 10.1063/1.444839
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    • Reaction Chemistry & Engineering, Vol. 5, Issue 4
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    Structures, intermolecular interactions, and chemical hardness of binary water–organic solvents: a molecular dynamics study
    journal, September 2018

    • Aguilera-Segura, Sonia M.; Di Renzo, Francesco; Mineva, Tzonka
    • Journal of Molecular Modeling, Vol. 24, Issue 10
    • DOI: 10.1007/s00894-018-3817-2

    Molecular dynamics simulation of a binary mixture near the lower critical point
    journal, July 2016

    • Pousaneh, Faezeh; Edholm, Olle; Maciołek, Anna
    • The Journal of Chemical Physics, Vol. 145, Issue 1
    • DOI: 10.1063/1.4954768
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