---
_id: '17278'
abstract:
- lang: eng
  text: An azeotrope is a constant boiling point mixture, and its behavior is important
    for fluid separation processes. Predicting azeotropes from atomistic simulations
    is difficult due to the complexities and convergence problems of Monte Carlo and
    free-energy perturbation techniques. Here, we present a methodology for predicting
    the azeotropes of binary mixtures, which computes the compositional dependence
    of chemical potentials from molecular dynamics simulations using the S0 method
    and employs experimental boiling point and vaporization enthalpy data. Using this
    methodology, we reproduce the azeotropes, or lack thereof, in five case studies,
    including ethanol/water, ethanol/isooctane, methanol/water, hydrazine/water, and
    acetone/chloroform mixtures. We find that it is crucial to use the experimental
    boiling point and vaporization enthalpy for reliable azeotrope predictions, as
    empirical force fields are not accurate enough for these quantities. Finally,
    we use regular solution models to rationalize the azeotropes and reveal that they
    tend to form when the mixture components have similar boiling points and strong
    interactions.
acknowledgement: B.C. thanks Alessandro Laio, who introduced the phenomenon of azeotrope
  and suggested using the S0 method to compute it. B.C. and X.W. thank Felix Wodaczek
  for the insightful comments and suggestions on the manuscript. B.C. and X.W. acknowledge
  the resources provided by the Cambridge Tier-2 system operated by the University
  of Cambridge Research Computing Service, funded by EPSRC Tier-2 capital (Grant No.
  EP/P020259/1).
article_number: '034111'
article_processing_charge: No
article_type: original
arxiv: 1
author:
- first_name: Xiaoyu
  full_name: Wang, Xiaoyu
  id: 8dff9c62-32b0-11ee-9fa8-fc73025e10f3
  last_name: Wang
- first_name: Bingqing
  full_name: Cheng, Bingqing
  id: cbe3cda4-d82c-11eb-8dc7-8ff94289fcc9
  last_name: Cheng
  orcid: 0000-0002-3584-9632
citation:
  ama: Wang X, Cheng B. Integrating molecular dynamics simulations and experimental
    data for azeotrope predictions in binary mixtures. <i>Journal of Chemical Physics</i>.
    2024;161(3). doi:<a href="https://doi.org/10.1063/5.0217232">10.1063/5.0217232</a>
  apa: Wang, X., &#38; Cheng, B. (2024). Integrating molecular dynamics simulations
    and experimental data for azeotrope predictions in binary mixtures. <i>Journal
    of Chemical Physics</i>. AIP Publishing. <a href="https://doi.org/10.1063/5.0217232">https://doi.org/10.1063/5.0217232</a>
  chicago: Wang, Xiaoyu, and Bingqing Cheng. “Integrating Molecular Dynamics Simulations
    and Experimental Data for Azeotrope Predictions in Binary Mixtures.” <i>Journal
    of Chemical Physics</i>. AIP Publishing, 2024. <a href="https://doi.org/10.1063/5.0217232">https://doi.org/10.1063/5.0217232</a>.
  ieee: X. Wang and B. Cheng, “Integrating molecular dynamics simulations and experimental
    data for azeotrope predictions in binary mixtures,” <i>Journal of Chemical Physics</i>,
    vol. 161, no. 3. AIP Publishing, 2024.
  ista: Wang X, Cheng B. 2024. Integrating molecular dynamics simulations and experimental
    data for azeotrope predictions in binary mixtures. Journal of Chemical Physics.
    161(3), 034111.
  mla: Wang, Xiaoyu, and Bingqing Cheng. “Integrating Molecular Dynamics Simulations
    and Experimental Data for Azeotrope Predictions in Binary Mixtures.” <i>Journal
    of Chemical Physics</i>, vol. 161, no. 3, 034111, AIP Publishing, 2024, doi:<a
    href="https://doi.org/10.1063/5.0217232">10.1063/5.0217232</a>.
  short: X. Wang, B. Cheng, Journal of Chemical Physics 161 (2024).
corr_author: '1'
das_tickbox: '1'
dataavailabilitystatement: All simulation setups, analysis scripts, and raw data in
  the study are available in the SI repository https://github.com/Xiaoyu-Wang-Stone/Azeotrope_S0.
date_created: 2024-07-21T22:01:00Z
date_published: 2024-07-14T00:00:00Z
date_updated: 2026-08-07T10:38:59Z
day: '14'
department:
- _id: BiCh
- _id: GradSch
doi: 10.1063/5.0217232
external_id:
  arxiv:
  - '2405.02216'
  isi:
  - '001281819100016'
  pmid:
  - '39007379'
fulldoi: https://doi.org/10.1063/5.0217232
intvolume: '       161'
isi: 1
issue: '3'
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.48550/arXiv.2405.02216
month: '07'
oa: 1
oa_version: Preprint
pmid: 1
publication: Journal of Chemical Physics
publication_identifier:
  eissn:
  - 1089-7690
  issn:
  - 0021-9606
publication_status: published
publisher: AIP Publishing
quality_controlled: '1'
related_material:
  link:
  - relation: software
    url: https://github.com/Xiaoyu-Wang-Stone/Azeotrope_S0
researchdata_availability: no
scopus_import: '1'
status: public
supplementarymaterial: no
title: Integrating molecular dynamics simulations and experimental data for azeotrope
  predictions in binary mixtures
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 161
year: '2024'
...