<p>This work investigates the ternary liquid system butan-1-ol + benzene + acetophenone, together with its corresponding binary mixtures. The system exhibits complex non-ideal behavior arising from pronounced differences in polarity, molecular size, shape, and intermolecular interactions among the components. To gain insight into these effects, thermophysical and thermodynamic properties were determined experimentally and analyzed across the full composition range. Density (ρ) and speed of sound (<i>u</i>) were measured at (293.15, 303.15, 313.15, 323.15, and 333.15) K and ambient pressure for the ternary system for the first time, with the same methodology applied to the binary subsystems. From these measurements, excess molar volumes (<InlineEquation ID="IEq1"> <EquationSource Format="TEX">${V}_{m}^{E}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mi>V</mi> <mrow> <mi>m</mi> </mrow> <mi>E</mi> </msubsup> </math></EquationSource> </InlineEquation>) and excess isentropic compressibilities (<InlineEquation ID="IEq2"> <EquationSource Format="TEX">${\kappa }_{S}^{E}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mi>κ</mi> <mrow> <mi>S</mi> </mrow> <mi>E</mi> </msubsup> </math></EquationSource> </InlineEquation>) were evaluated and correlated using Redlich–Kister polynomial for the binaries and the Cibulka equation for the ternary data. The Jouyban–Acree model accurately reproduced the composition and temperature dependence of the measured and derived properties using a compact set of parameters. The experimentally determined ternary excess properties were further compared with predictions based on symmetric (Kohler, Muggianu) and asymmetric (Hillert, Toop) binary-contribution models. Among these, the Hillert formulation yielded the most reliable agreement with experiment, particularly when acetophenone was treated as the asymmetric component, consistent with its distinct polarity and electronic structure compared to butan-1-ol and benzene. To substantiate the origin and extent of asymmetry, the Chou’s General Solution model was additionally applied. The Chou analysis independently identified acetophenone as the dominant asymmetric contributor, thereby confirming that the Hillert model provides the physically and mathematically most appropriate representation of the ternary system. This outcome reflects the fact that the Hillert model can be interpreted as a limiting case of the Chou formulation, explaining the strong internal consistency between the two approaches.</p>

Excess Thermodynamic Properties of Binary and Ternary Mixtures of Butan-1-ol, Benzene, and Acetophenone: An Experimental and Modeling Approach

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发表日期：

2026年2月17日

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Rozafa Krasniqi,
Arbër Zeqiraj,
Fisnik Aliaj

摘要

This work investigates the ternary liquid system butan-1-ol + benzene + acetophenone, together with its corresponding binary mixtures. The system exhibits complex non-ideal behavior arising from pronounced differences in polarity, molecular size, shape, and intermolecular interactions among the components. To gain insight into these effects, thermophysical and thermodynamic properties were determined experimentally and analyzed across the full composition range. Density (ρ) and speed of sound (u) were measured at (293.15, 303.15, 313.15, 323.15, and 333.15) K and ambient pressure for the ternary system for the first time, with the same methodology applied to the binary subsystems. From these measurements, excess molar volumes ( ${V}_{m}^{E}$ $V_{m}^{E}$ ) and excess isentropic compressibilities ( ${\kappa }_{S}^{E}$ $κ_{S}^{E}$ ) were evaluated and correlated using Redlich–Kister polynomial for the binaries and the Cibulka equation for the ternary data. The Jouyban–Acree model accurately reproduced the composition and temperature dependence of the measured and derived properties using a compact set of parameters. The experimentally determined ternary excess properties were further compared with predictions based on symmetric (Kohler, Muggianu) and asymmetric (Hillert, Toop) binary-contribution models. Among these, the Hillert formulation yielded the most reliable agreement with experiment, particularly when acetophenone was treated as the asymmetric component, consistent with its distinct polarity and electronic structure compared to butan-1-ol and benzene. To substantiate the origin and extent of asymmetry, the Chou’s General Solution model was additionally applied. The Chou analysis independently identified acetophenone as the dominant asymmetric contributor, thereby confirming that the Hillert model provides the physically and mathematically most appropriate representation of the ternary system. This outcome reflects the fact that the Hillert model can be interpreted as a limiting case of the Chou formulation, explaining the strong internal consistency between the two approaches.