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Title: Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations

Abstract

Vapor liquid equilibria (VLE) of organic compounds is governed by weak non-covalent interactions. This presents a significant challenge in predicting VLE using a first principles approach where density functional theory is used to model system potential. However, a dispersion corrected approach has significantly improved the performance of traditional density functionals. Here, we predict the VLE for a nonpolar carbon tetrafluoride (R14) and polar 1,1,1,2-tetrafluoroethane (R134a)via first principles Gibbs ensemble Monte Carlo simulations using PBED3 density functional. We find that the saturated liquid density for R14 is slightly under predicted for subcritical temperatures, while for R134a it is under predicted at lower reduced temperatures and over predicted at higher reduced temperatures. In the liquid phase, angle-resolved pair correlation functions indicate slight preference for R143a to align in parallel and antiparallel orientation in the first solvation shell.The vibrational spectra reveal peak broadening in the condensed phase due to solvothermal effects. Altogether, we find thePBED3 functional performance is better for the nonpolar molecule as compared to the polar one.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Mississippi State Univ., MS (United States). Dave C. Swalm School of Chemical Engineering and Center for Advanced Vehicular Systems
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC).
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1461756
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry Select
Additional Journal Information:
Journal Volume: 2; Journal Issue: 36; Journal ID: ISSN 2365-6549
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ab initio calculations; Fluorinated alkanes; FPMC; Vibrational spectroscopy; VLE

Citation Formats

Goel, Himanshu, Windom, Zachary W., Butler, Charles L., and Rai, Neeraj. Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations. United States: N. p., 2017. Web. doi:10.1002/slct.201701972.
Goel, Himanshu, Windom, Zachary W., Butler, Charles L., & Rai, Neeraj. Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations. United States. doi:10.1002/slct.201701972.
Goel, Himanshu, Windom, Zachary W., Butler, Charles L., and Rai, Neeraj. Thu . "Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations". United States. doi:10.1002/slct.201701972. https://www.osti.gov/servlets/purl/1461756.
@article{osti_1461756,
title = {Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations},
author = {Goel, Himanshu and Windom, Zachary W. and Butler, Charles L. and Rai, Neeraj},
abstractNote = {Vapor liquid equilibria (VLE) of organic compounds is governed by weak non-covalent interactions. This presents a significant challenge in predicting VLE using a first principles approach where density functional theory is used to model system potential. However, a dispersion corrected approach has significantly improved the performance of traditional density functionals. Here, we predict the VLE for a nonpolar carbon tetrafluoride (R14) and polar 1,1,1,2-tetrafluoroethane (R134a)via first principles Gibbs ensemble Monte Carlo simulations using PBED3 density functional. We find that the saturated liquid density for R14 is slightly under predicted for subcritical temperatures, while for R134a it is under predicted at lower reduced temperatures and over predicted at higher reduced temperatures. In the liquid phase, angle-resolved pair correlation functions indicate slight preference for R143a to align in parallel and antiparallel orientation in the first solvation shell.The vibrational spectra reveal peak broadening in the condensed phase due to solvothermal effects. Altogether, we find thePBED3 functional performance is better for the nonpolar molecule as compared to the polar one.},
doi = {10.1002/slct.201701972},
journal = {Chemistry Select},
issn = {2365-6549},
number = 36,
volume = 2,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Vapor-liquid coexistence curves (VLCCs) and Clausius-Clapeyron plots for R14 and R134a. Figures A, and C represent VLCCs for R14 and R134a, respectively, and Figures B, and D represent Clausius-Clapeyron plots for R14 and R134a, respectively. The solid black lines depict the experimental data and stars represent the experimentalmore » critical point. The red square symbols represents GEMC simulation data with PBE-D3 functional. The dashed lines show linear fit of the simulated data.« less

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