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Keywords
thermodynamic consistency
isobaric
NRTL
Wilson
UNIQUAC
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Abstract
Vapor–liquid equilibrium (VLE) data are essential for the design and optimization of separation processes; however, their reliability remains a challenge, particularly for multicomponent systems, due to inconsistencies in legacy datasets. Here, we analyzed isobaric VLE data at 101.33 kPa for the binary systems chloroform(1) + benzene(2), chloroform(1) + methanol(2), and methanol(1) + benzene(2), as well as for the corresponding ternary system, using data from the Dortmund Data Bank (DDB) and the Korean Data Bank (KDB). Thermodynamic consistency was assessed using the Wisniak-modified Herington test for binaries and the Wisniak (L–W) test for the ternary system, and only consistent datasets were used to estimate thermodynamic parameters. Binary interaction parameters were determined for the Wilson, NRTL, and UNIQUAC models and evaluated through the average absolute deviation in temperature (AADT). The results indicated strong non-ideality, particularly for the chloroform(1) + methanol(2) pair, suggesting hydrogen bonding, whereas chloroform(1) + benzene(2) exhibits near-ideal behavior. On the contrary, the methanol(1) + benzene(2) interactions were highly unfavorable compared to those of the pure components, despite the possibility of association through π–dipole interactions. Additionally, the models Wilson and UNIQUAC showed the best performance for the ternary system (AADT = 0.5849 and 0.6141, respectively), while NRTL had higher deviations (AADT = 0.9896). The study presents a structured thermodynamic evaluation framework for ternary mixtures that integrates consistency testing, dataset selection, parameter optimization, and multi-model validation, thereby enhancing the reliability of VLE predictions in non-ideal multicomponent systems.
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