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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 [P 8888] + ion and multiple IL/water interface was observed for [P 12121212] + 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 rolemore » of the alkyl side chains on the interfacial properties.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC)
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.
Venkatesan, Shanmuga S., Huda, Md. Masrul, & Rai, Neeraj. Molecular insights into ionic liquid/aqueous interface of phosphonium based phase-separable ionic liquids. United States. doi:10.1063/1.5090775.
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. doi:10.1063/1.5090775. https://www.osti.gov/servlets/purl/1566770.
@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 = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

FIG. 1 FIG. 1: Molecular structure of a representative phosphonium ion [P4444]+ and [CH3COO] (acetate) ion.

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Works referenced in this record:

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