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Title: Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids

Abstract

Phosphonium based phase-separable ionic liquids (PSILs) are promising green solvents for dissolution of cellulose and lignin, a necessary step for conversion of biomass to fuels and chemicals. The knowledge of interfacial behavior of ionic liquid/solvent systems is critical for designing efficient separation processes. Here, molecular dynamics simulations are carried out for aqueous interface of tetraalkylphosphonium ionic liquids with chloride and acetate as anions to investigate IL miscibility with water. The transition zone from miscible to immiscible behavior was observed for alkyl chain lengths of 6 to 8. Emulsion phase was observed for [P8888]+ ion and multiple IL/water interface was observed for [P12121212]+ phosphonium cation. IL/water interface is observed to be enriched with solvated anions with phosphorous atom oriented towards the aqueous phase. The potential of mean force calculations suggest that as the alkyl chain of the phosphonium cations increase, so does the driving force for aggregation of cations in the aqueous phase. Due to the difference in the molecular shape and size, anions are better solvated by the water molecules, and these ions diffuse into the aqueous phase. Furthermore, the analysis of selected pair interactions provides insights into the nature of intermolecular forces and the role of the alkyl sidemore » chains on the interfacial properties.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Mississippi State Univ., Mississippi State, MS (United States)
Publication Date:
Research Org.:
Mississippi State Univ., Mississippi State, MS (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1566770
Alternate Identifier(s):
OSTI ID: 1506557; OSTI ID: 1529933
Grant/Contract Number:  
SC0018211; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
AIP Advances
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2158-3226
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionic liquid; Miscibility; Molecular dynamics; Interfacial properties; Potential of mean force

Citation Formats

Venkatesan, Shanmuga S., Huda, Md. Masrul, and Rai, Neeraj. Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids. United States: N. p., 2019. Web. doi:10.1063/1.5090775.
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Venkatesan, Shanmuga S., Huda, Md. Masrul, & Rai, Neeraj. Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids. United States. https://doi.org/10.1063/1.5090775
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Venkatesan, Shanmuga S., Huda, Md. Masrul, and Rai, Neeraj. Thu . "Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids". United States. https://doi.org/10.1063/1.5090775. https://www.osti.gov/servlets/purl/1566770.
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@article{osti_1566770,
title = {Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids},
author = {Venkatesan, Shanmuga S. and Huda, Md. Masrul and Rai, Neeraj},
abstractNote = {Phosphonium based phase-separable ionic liquids (PSILs) are promising green solvents for dissolution of cellulose and lignin, a necessary step for conversion of biomass to fuels and chemicals. The knowledge of interfacial behavior of ionic liquid/solvent systems is critical for designing efficient separation processes. Here, molecular dynamics simulations are carried out for aqueous interface of tetraalkylphosphonium ionic liquids with chloride and acetate as anions to investigate IL miscibility with water. The transition zone from miscible to immiscible behavior was observed for alkyl chain lengths of 6 to 8. Emulsion phase was observed for [P8888]+ ion and multiple IL/water interface was observed for [P12121212]+ phosphonium cation. IL/water interface is observed to be enriched with solvated anions with phosphorous atom oriented towards the aqueous phase. The potential of mean force calculations suggest that as the alkyl chain of the phosphonium cations increase, so does the driving force for aggregation of cations in the aqueous phase. Due to the difference in the molecular shape and size, anions are better solvated by the water molecules, and these ions diffuse into the aqueous phase. Furthermore, the analysis of selected pair interactions provides insights into the nature of intermolecular forces and the role of the alkyl side chains on the interfacial properties.},
doi = {10.1063/1.5090775},
journal = {AIP Advances},
number = 4,
volume = 9,
place = {United States},
year = {Thu Apr 11 00:00:00 EDT 2019},
month = {Thu Apr 11 00:00:00 EDT 2019}
}
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Publisher's Version of Record
https://doi.org/10.1063/1.5090775
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Cited by: 8 works
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Figures / Tables:

FIG. 1 FIG. 1: Molecular structure of a representative phosphonium ion [P4444]+ and [CH3COO]− (acetate) ion.
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CHEMISTRY: Ionic Liquids--Solvents of the Future?
journal, October 2003

The distillation and volatility of ionic liquids
journal, February 2006

  • Earle, Martyn J.; Esperança, José M. S. S.; Gilea, Manuela A.
  • Nature, Vol. 439, Issue 7078
  • DOI: 10.1038/nature04451

Vapor–Liquid Coexistence and Critical Behavior of Ionic Liquids via Molecular Simulations
journal, May 2011

  • Rai, Neeraj; Maginn, Edward J.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 12
  • DOI: 10.1021/jz200526z

Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions
journal, January 2008

  • Fukaya, Yukinobu; Hayashi, Kensaku; Wada, Masahisa
  • Green Chem., Vol. 10, Issue 1
  • DOI: 10.1039/b713289a

Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids
journal, January 1992

  • Wilkes, John S.; Zaworotko, Michael J.
  • Journal of the Chemical Society, Chemical Communications, Issue 13
  • DOI: 10.1039/c39920000965

Distillable Acid-Base Conjugate Ionic Liquids for Cellulose Dissolution and Processing
journal, May 2011

  • King, Alistair W. T.; Asikkala, Janne; Mutikainen, Ilpo
  • Angewandte Chemie International Edition, Vol. 50, Issue 28
  • DOI: 10.1002/anie.201100274

Amphiphilic and Phase-Separable Ionic Liquids for Biomass Processing
journal, March 2014

  • Holding, Ashley J.; Heikkilä, Mikko; Kilpeläinen, Ilkka
  • ChemSusChem, Vol. 7, Issue 5
  • DOI: 10.1002/cssc.201301261

Uranyl Coordination Environment in Hydrophobic Ionic Liquids:  An in Situ Investigation
journal, April 2003

  • Visser, Ann E.; Jensen, Mark P.; Laszak, Ivan
  • Inorganic Chemistry, Vol. 42, Issue 7
  • DOI: 10.1021/ic026302e

Identical extraction behavior and coordination of trivalent or hexavalent f-element cations using ionic liquid and molecular solvents
journal, January 2005

  • Cocalia, Violina A.; Jensen, Mark P.; Holbrey, John D.
  • Dalton Transactions, Issue 11
  • DOI: 10.1039/b502016f

Traditional Extractants in Nontraditional Solvents:  Groups 1 and 2 Extraction by Crown Ethers in Room-Temperature Ionic Liquids †
journal, October 2000

  • Visser, Ann E.; Swatloski, Richard P.; Reichert, W. Matthew
  • Industrial & Engineering Chemistry Research, Vol. 39, Issue 10
  • DOI: 10.1021/ie000426m

Influence of Structural Variation in Room-Temperature Ionic Liquids on the Selectivity and Efficiency of Competitive Alkali Metal Salt Extraction by a Crown Ether
journal, August 2001

  • Chun, Sangki; Dzyuba, Sergei V.; Bartsch, Richard A.
  • Analytical Chemistry, Vol. 73, Issue 15
  • DOI: 10.1021/ac010061v

Solvent extraction of strontium nitrate by a crown ether using room-temperature ionic liquids †
journal, January 1999

  • Dai, Sheng; Ju, Y. H.; Barnes, C. E.
  • Journal of the Chemical Society, Dalton Transactions, Issue 8
  • DOI: 10.1039/a809672d

Extraction of Cesium Ions from Aqueous Solutions Using Calix[4]arene-bis( tert -octylbenzo-crown-6) in Ionic Liquids
journal, June 2004

  • Luo, Huimin; Dai, Sheng; Bonnesen, Peter V.
  • Analytical Chemistry, Vol. 76, Issue 11
  • DOI: 10.1021/ac049949k

What's happening at the liquid—liquid interface in solvent extraction chemistry?
journal, January 1993

Extraction of Biomolecules Using Phosphonium-Based Ionic Liquids + K3PO4 Aqueous Biphasic Systems
journal, April 2010

  • Louros, Cláudia L. S.; Cláudio, Ana Filipa M.; Neves, Catarina M. S. S.
  • International Journal of Molecular Sciences, Vol. 11, Issue 4
  • DOI: 10.3390/ijms11041777

Investigation of aqueous biphasic systems formed from solutions of chaotropic salts with kosmotropic salts (salt–salt ABS)
journal, January 2007

  • Bridges, Nicholas J.; Gutowski, Keith E.; Rogers, Robin D.
  • Green Chem., Vol. 9, Issue 2
  • DOI: 10.1039/b611628k

Controlling the Aqueous Miscibility of Ionic Liquids:  Aqueous Biphasic Systems of Water-Miscible Ionic Liquids and Water-Structuring Salts for Recycle, Metathesis, and Separations
journal, June 2003

  • Gutowski, Keith E.; Broker, Grant A.; Willauer, Heather D.
  • Journal of the American Chemical Society, Vol. 125, Issue 22
  • DOI: 10.1021/ja0351802

Salting-out in Aqueous Solutions of Ionic Liquids and K3PO4: Aqueous Biphasic Systems and Salt Precipitation
journal, July 2007

  • Najdanovic-Visak, Vesna; Lopes, José; Visak, Zoran
  • International Journal of Molecular Sciences, Vol. 8, Issue 8
  • DOI: 10.3390/i8080736

Design and synthesis of hydrophobic and chiral anions from amino acids as precursor for functional ionic liquids
journal, January 2006

  • Fukumoto, Kenta; Ohno, Hiroyuki
  • Chemical Communications, Issue 29
  • DOI: 10.1039/b606613e

LCST-Type Phase Changes of a Mixture of Water and Ionic Liquids Derived from Amino Acids
journal, March 2007

  • Fukumoto, Kenta; Ohno, Hiroyuki
  • Angewandte Chemie International Edition, Vol. 46, Issue 11
  • DOI: 10.1002/anie.200604402

Material design of ionic liquids to show temperature-sensitive LCST-type phase transition after mixing with water
journal, January 2011

  • Kohno, Yuki; Arai, Hiroki; Saita, Shohei
  • Australian Journal of Chemistry, Vol. 64, Issue 12
  • DOI: 10.1071/ch11278

Theory and Computer Simulations of Solvation and Chemical Reactions at Liquid Interfaces
journal, May 1995

Recent Advances in Molecular Simulations of Ion Solvation at Liquid Interfaces
journal, April 2006

  • Chang, Tsun-Mei; Dang, Liem X.
  • Chemical Reviews, Vol. 106, Issue 4
  • DOI: 10.1021/cr0403640

Importance of Interfacial Phenomena and Synergistic Effects in Lanthanide Cation Extraction by Dithiophosphinic Ligands:  A Molecular Dynamics Study
journal, September 2003

  • Coupez, Bernard; Boehme, Christian; Wipff, Georges
  • The Journal of Physical Chemistry B, Vol. 107, Issue 35
  • DOI: 10.1021/jp034748q

Demixing of Binary Water−Chloroform Mixtures Containing Ionophoric Solutes and Ion Recognition at a Liquid−Liquid Interface:  A Molecular Dynamics Study
journal, December 1998

  • Muzet, N.; Engler, E.; Wipff, G.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 52
  • DOI: 10.1021/jp981869v

Simulation of interfaces between room temperature ionic liquids and other liquids
journal, January 2005

  • Lynden-Bell, R. M.; Kohanoff, J.; Del Popolo, M. G.
  • Faraday Discussions, Vol. 129
  • DOI: 10.1039/b405514d

Aqueous Interfaces with Hydrophobic Room-Temperature Ionic Liquids:  A Molecular Dynamics Study
journal, October 2005

  • Chaumont, A.; Schurhammer, R.; Wipff, G.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 40
  • DOI: 10.1021/jp052854h

The [BMI][Tf 2 N] Ionic Liquid/Water Binary System:  A Molecular Dynamics Study of Phase Separation and of the Liquid−Liquid Interface
journal, July 2006

  • Sieffert, N.; Wipff, G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 26
  • DOI: 10.1021/jp061849q

Molecular dynamics simulations of the aqueous interface with the [BMI][PF6] ionic liquid: comparison of different solvent models
journal, January 2006

  • Chevrot, G.; Schurhammer, R.; Wipff, G.
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 36
  • DOI: 10.1039/b608218a

Molecular dynamics simulations of imidazolium-based ionic liquid/water mixtures: Alkyl side chain length and anion effects
journal, July 2010

A Simulation Study of Water−Dialkylimidazolium Ionic Liquid Mixtures
journal, October 2003

  • Hanke, C. G.; Lynden-Bell, R. M.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 39
  • DOI: 10.1021/jp034221d

The effect of hydrophobic alkyl chain length on the mechanical properties of latex particle hydrogels
journal, January 2017

  • Gao, Yang; Duan, Lijie; Guan, Shuang
  • RSC Advances, Vol. 7, Issue 71
  • DOI: 10.1039/c7ra07983d

The role of hydrophobic alkyl chains in the physicochemical properties of poly(β-amino ester)/DNA complexes
journal, February 2015

  • Rata-Aguilar, Azahara; Segovia-Ramos, Nathaly; Jódar-Reyes, Ana Belén
  • Colloids and Surfaces B: Biointerfaces, Vol. 126
  • DOI: 10.1016/j.colsurfb.2014.11.048

Molecular Force Field for Ionic Liquids III:  Imidazolium, Pyridinium, and Phosphonium Cations; Chloride, Bromide, and Dicyanamide Anions
journal, October 2006

  • Canongia Lopes, José N.; Pádua, Agílio A. H.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp063901o

Structure and dynamics of acetate anion-based ionic liquids from molecular dynamics study
journal, August 2010

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: 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

Comparison of simple potential functions for simulating liquid water
journal, July 1983

  • Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D.
  • The Journal of Chemical Physics, Vol. 79, Issue 2
  • DOI: 10.1063/1.445869

PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009

  • Martínez, L.; Andrade, R.; Birgin, E. G.
  • Journal of Computational Chemistry, Vol. 30, Issue 13
  • DOI: 10.1002/jcc.21224

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

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

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984

Polymorphic transitions in single crystals: A new molecular dynamics method
journal, December 1981

  • Parrinello, M.; Rahman, A.
  • Journal of Applied Physics, Vol. 52, Issue 12
  • DOI: 10.1063/1.328693

Constant pressure molecular dynamics for molecular systems
journal, December 1983

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

A smooth particle mesh Ewald method
journal, November 1995

  • Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L.
  • The Journal of Chemical Physics, Vol. 103, Issue 19
  • DOI: 10.1063/1.470117

VMD: Visual molecular dynamics
journal, February 1996

Thermophysical properties of pure and water-saturated tetradecyltrihexylphosphonium-based ionic liquids
journal, June 2011

  • Neves, Catarina M. S. S.; Carvalho, Pedro J.; Freire, Mara G.
  • The Journal of Chemical Thermodynamics, Vol. 43, Issue 6
  • DOI: 10.1016/j.jct.2011.01.016

Study of thermodynamic and transport properties of phosphonium-based ionic liquids
journal, July 2013

  • Deive, Francisco J.; Rivas, Miguel A.; Rodríguez, Ana
  • The Journal of Chemical Thermodynamics, Vol. 62
  • DOI: 10.1016/j.jct.2013.02.012

Densities and Derived Thermodynamic Properties of Ionic Liquids. 3. Phosphonium-Based Ionic Liquids over an Extended Pressure Range
journal, January 2006

  • Esperança, José M. S. S.; Guedes, Henrique J. R.; Blesic, Marijana
  • Journal of Chemical & Engineering Data, Vol. 51, Issue 1
  • DOI: 10.1021/je050358g

Surface tension and refractive index of pure and water-saturated tetradecyltrihexylphosphonium-based ionic liquids
journal, February 2013

  • Almeida, Hugo F. D.; Lopes-da-Silva, José A.; Freire, Mara G.
  • The Journal of Chemical Thermodynamics, Vol. 57
  • DOI: 10.1016/j.jct.2012.09.004

Surface tension of the most popular models of water by using the test-area simulation method
journal, April 2007

  • Vega, C.; de Miguel, E.
  • The Journal of Chemical Physics, Vol. 126, Issue 15
  • DOI: 10.1063/1.2715577

Computer simulation of liquid/liquid interfaces. I. Theory and application to octane/water
journal, December 1995

  • Zhang, Yuhong; Feller, Scott E.; Brooks, Bernard R.
  • The Journal of Chemical Physics, Vol. 103, Issue 23
  • DOI: 10.1063/1.469927

Molecular dynamics simulations of lung surfactant lipid monolayers
journal, December 2008

Pressure−Area Isotherm of a Lipid Monolayer from Molecular Dynamics Simulations
journal, December 2007

  • Baoukina, Svetlana; Monticelli, Luca; Marrink, Siewert J.
  • Langmuir, Vol. 23, Issue 25
  • DOI: 10.1021/la702286h

Comparing Experimental and Simulated Pressure-Area Isotherms for DPPC
journal, April 2008

g_wham—A Free Weighted Histogram Analysis Implementation Including Robust Error and Autocorrelation Estimates
journal, November 2010

  • Hub, Jochen S.; de Groot, Bert L.; van der Spoel, David
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 12
  • DOI: 10.1021/ct100494z

Influence of Electronic Polarization on the Structure of Ionic Liquids
journal, August 2018

Polarization Effects in Binary [BMIM + ][BF 4 – ]/1,2-Dichloroethane, Acetone, Acetonitrile, and Water Electrolytes
journal, March 2018

Simulation and measurement of water-induced liquid-liquid phase separation of imidazolium ionic liquid mixtures
journal, October 2018

  • Rocha, M. Alejandra; Zhang, Yong; Maginn, Edward J.
  • The Journal of Chemical Physics, Vol. 149, Issue 16
  • DOI: 10.1063/1.5054786

Chemical and Radiation Stability of Ionic Liquids: A Computational Screening Study
journal, November 2016

  • Ilawe, Niranjan V.; Fu, Jia; Ramanathan, Shriram
  • The Journal of Physical Chemistry C, Vol. 120, Issue 49
  • DOI: 10.1021/acs.jpcc.6b08138

An improvement in the theory of regular solutions
journal, December 1979

  • Hildebrand, J. H.
  • Proceedings of the National Academy of Sciences, Vol. 76, Issue 12
  • DOI: 10.1073/pnas.76.12.6040

LCST-Type Phase Changes of a Mixture of Water and Ionic Liquids Derived from Amino Acids
journal, March 2007

Distillable Acid-Base Conjugate Ionic Liquids for Cellulose Dissolution and Processing
journal, May 2011

  • King, Alistair W. T.; Asikkala, Janne; Mutikainen, Ilpo
  • Angewandte Chemie, Vol. 123, Issue 28
  • DOI: 10.1002/ange.201100274

Design and Synthesis of Hydrophobic and Chiral Anions from Amino Acids as Precursor for Functional Ionic Liquids.
journal, November 2006

A molecular dynamics method for simulations in the canonical ensemble
journal, January 2002

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