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Title: Electrostatic and induction effects in the solubility of water in alkanes

Abstract

Experiments show that at 298 K and 1 atm pressure, the transfer free energy, μex, of water from its vapor to liquid normal alkanes CnH2n+2 (n=5…12) is negative. Earlier it was found that with the united-atom TraPPE model for alkanes and the SPC/E model for water, one had to artificially enhance the attractive alkane-water cross interaction to capture this behavior. Here we revisit the calculation of μex using the polarizable AMOEBA and the non-polarizable Charmm General (CGenFF) forcefields. We test both the AMOEBA03 and AMOEBA14 water models; the former has been validated with the AMOEBA alkane model while the latter is a revision of AMOEBA03 to better describe liquid water. We calculate μex using the test particle method. With CGenFF, μex is positive and the error relative to experiments is about 1.5 kBT. With AMOEBA, μex is negative and deviations relative to experiments are between 0.25 kBT (AMOEBA14) and 0.5 kBT (AMOEBA03). Quantum chemical calculations in a continuum solvent suggest that zero point effects may account for some of the deviation. In conclusion, forcefield limitations notwithstanding, electrostatic and induction effects, commonly ignored in consideration of water-alkane interactions, appear to be decisive in the solubility of water in alkanes.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Rice University, Houston, TX (United States). Chemical and Biomolecular Engineering
  2. Ames Laboratory, Ames, IA (United States). Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1497880
Grant/Contract Number:  
AC02-07CH11358; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Asthagiri, D., Parambathu, Arjun Valiya, Ballal, Deepti, and Chapman, Walter G. Electrostatic and induction effects in the solubility of water in alkanes. United States: N. p., 2017. Web. doi:10.1063/1.4997916.
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Asthagiri, D., Parambathu, Arjun Valiya, Ballal, Deepti, & Chapman, Walter G. Electrostatic and induction effects in the solubility of water in alkanes. United States. https://doi.org/10.1063/1.4997916
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Asthagiri, D., Parambathu, Arjun Valiya, Ballal, Deepti, and Chapman, Walter G. Mon . "Electrostatic and induction effects in the solubility of water in alkanes". United States. https://doi.org/10.1063/1.4997916. https://www.osti.gov/servlets/purl/1497880.
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@article{osti_1497880,
title = {Electrostatic and induction effects in the solubility of water in alkanes},
author = {Asthagiri, D. and Parambathu, Arjun Valiya and Ballal, Deepti and Chapman, Walter G.},
abstractNote = {Experiments show that at 298 K and 1 atm pressure, the transfer free energy, μex, of water from its vapor to liquid normal alkanes CnH2n+2 (n=5…12) is negative. Earlier it was found that with the united-atom TraPPE model for alkanes and the SPC/E model for water, one had to artificially enhance the attractive alkane-water cross interaction to capture this behavior. Here we revisit the calculation of μex using the polarizable AMOEBA and the non-polarizable Charmm General (CGenFF) forcefields. We test both the AMOEBA03 and AMOEBA14 water models; the former has been validated with the AMOEBA alkane model while the latter is a revision of AMOEBA03 to better describe liquid water. We calculate μex using the test particle method. With CGenFF, μex is positive and the error relative to experiments is about 1.5 kBT. With AMOEBA, μex is negative and deviations relative to experiments are between 0.25 kBT (AMOEBA14) and 0.5 kBT (AMOEBA03). Quantum chemical calculations in a continuum solvent suggest that zero point effects may account for some of the deviation. In conclusion, forcefield limitations notwithstanding, electrostatic and induction effects, commonly ignored in consideration of water-alkane interactions, appear to be decisive in the solubility of water in alkanes.},
doi = {10.1063/1.4997916},
journal = {Journal of Chemical Physics},
number = 7,
volume = 147,
place = {United States},
year = {Mon Aug 21 00:00:00 EDT 2017},
month = {Mon Aug 21 00:00:00 EDT 2017}
}
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https://doi.org/10.1063/1.4997916
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Cited by: 6 works
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Figures / Tables:

Table I Table I: Simulation cell density and number of particles. The density ρa is obtained from the NIST database.20 N is the number of molecules in the system.
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    Miscibility at the immiscible liquid/liquid interface: A molecular dynamics study of thermodynamics and mechanism
    journal, January 2018

    • Karnes, John J.; Benjamin, Ilan
    • The Journal of Chemical Physics, Vol. 148, Issue 3
    • DOI: 10.1063/1.5012506
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      Figure 5 (p. 7)figure
      Table II (p. 9)table
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