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:
-
- 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:
- Journal Article: 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.
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
Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, and Smith, Jeremy C. 2016.
"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.
@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},
url = {https://www.osti.gov/biblio/1327650},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
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}
}
Web of Science
Works referenced in this record:
Phenyl-bonded phase liquid chromatography of styrene oligomers
journal, January 1984
- Lai, Shih-Tse; Sangermano, Louis; Locke, David C.
- Journal of Chromatography A, Vol. 312
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
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
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
Coupling metal halides with a co-solvent to produce furfural and 5-HMF at high yields directly from lignocellulosic biomass as an integrated biofuels strategy
journal, January 2014
- Cai, Charles M.; Nagane, Nikhil; Kumar, Rajeev
- Green Chem., Vol. 16, Issue 8
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
Phase equilibria and excess molar volumes of tetrahydrofuran (1) + deuterium oxide (2)
journal, October 1975
- Lejček, P.; Matouš, J.; Novák, J. P.
- The Journal of Chemical Thermodynamics, Vol. 7, Issue 10
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
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
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
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
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
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
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
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
Simulation of the liquid–liquid coexistence of the tetrahydrofuran+water mixture in the Gibbs ensemble
journal, July 2001
- Brovchenko, I.; Guillot, B.
- Fluid Phase Equilibria, Vol. 183-184
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
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
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
Reply to ‘Comment on “Theory of the evaporation/condensation transition of equilibrium droplets in finite volumes”’
journal, September 2003
- Binder, K.
- Physica A: Statistical Mechanics and its Applications, Vol. 327, Issue 3-4
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
GROMACS: Fast, flexible, and free
journal, January 2005
- Van Der Spoel, David; Lindahl, Erik; Hess, Berk
- Journal of Computational Chemistry, Vol. 26, Issue 16
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
GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit
journal, February 2013
- Pronk, Sander; Páll, Szilárd; Schulz, Roland
- Bioinformatics, Vol. 29, Issue 7
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
Canonical sampling through velocity rescaling
journal, January 2007
- Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
- The Journal of Chemical Physics, Vol. 126, Issue 1
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
LINCS: A linear constraint solver for molecular simulations
journal, September 1997
- Hess, Berk; Bekker, Henk; Berendsen, Herman J. C.
- Journal of Computational Chemistry, Vol. 18, Issue 12
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
The Statistical Thermodynamics of Multicomponent Systems
journal, July 1945
- McMillan, William G.; Mayer, Joseph E.
- The Journal of Chemical Physics, Vol. 13, Issue 7
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
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
Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol, ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding
journal, April 2013
- Zhang, Ning; Li, Weizhong; Chen, Cong
- Molecular Physics, Vol. 111, Issue 7
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
Theory of closed-loop phase diagrams in binary fluid mixtures
journal, October 1980
- Walker, James S.; Vause, Chester A.
- Physics Letters A, Vol. 79, Issue 5-6
A Theory of Liquid Structure
journal, November 1937
- Hirschfelder, Joseph; Stevenson, David; Eyring, Henry
- The Journal of Chemical Physics, Vol. 5, Issue 11
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
Works referencing / citing this record:
Multistep synthesis of a valsartan precursor in continuous flow
journal, July 2019
- Hiebler, Katharina; Soritz, Sebastian; Gavric, Kristian
- Journal of Flow Chemistry
Development of a multistep reaction cascade for the synthesis of a sacubitril precursor in continuous flow
journal, December 2019
- Hiebler, Katharina; Dertnig, Carina; Soritz, Sebastian
- Journal of Flow Chemistry, Vol. 10, Issue 1
Structural anomaly and dynamic heterogeneity in cycloether/water binary mixtures: Signatures from composition dependent dynamic fluorescence measurements and computer simulations
journal, March 2016
- Indra, Sandipa; Guchhait, Biswajit; Biswas, Ranjit
- The Journal of Chemical Physics, Vol. 144, Issue 12
Elucidating the role of solvents in acid catalyzed dehydration of biorenewable hydroxy-lactones
journal, January 2020
- Shrivastav, Gourav; Khan, Tuhin S.; Agarwal, Manish
- Reaction Chemistry & Engineering, Vol. 5, Issue 4
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
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