Vapor–liquid equilibrium of formaldehyde mixtures: New data and model revision

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Abstract
A physicochemical model for vapor–liquid equilibria and enthalpies in formaldehyde‐containing mixtures is revised and extended using recently published NMR spectroscopic data on chemical equilibria in aqueous and methanolic formaldehyde solutions as well as new vapor–liquid equilibrium data for the system formaldehyde–water at temperatures up to 413 K (pressures up to 450 kPa), which were taken in this work with a new apparatus. Furthermore, the model is revised so that it can be extended straight‐forwardly to explicitly account for reaction kinetic effects based on results from other recent NMR spectroscopic studies. The model is tested over the entire temperature range (293–413 K), where reliable experimental data on vapor–liquid equilibria are available, and against calorimetric data. Typical relative deviations between experimental data and the correlation are about 5% for vapor–liquid partition coefficients and 2% for the pressure. Deviations between calculated and measured enthalpies of vaporization are generally below 2%.

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