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Isothermal vapor−liquid equilibrium (VLE) for thiophene + n-hexane at (338.15 and 323.15) K and thiophene + 1-hexene at (333.15 and 323.15) K were measured with a circulation still. Maximum pressure azeotropes were found in the thiophene + n-hexane system. Azeotropic behavior was not found for the thiophene + 1-hexene system. The experimental results were correlated with Wilson model and also compared with original UNIFAC, UNIFAC−Dortmund, and COSMO-RS predictive models. Analyses of liquid and vapor-phase composition were determined with gas chromatograph and refractometer. All VLE measurements passed the three thermodynamic consistency tests used.

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