Vapor-Liquid Equilibrium in the Systems Argon-Oxygen and Ammonia-Water Measurements and Modeling for Industrial and Planetary Applications

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Jupiter

Scientific paper

This work presents an integrated approach for characterizing binary vapor-liquid equilibrium (VLE) through a combination of experimental measurements and thermodynamic modeling for low to medium pressure binary VLE. We focus on two dissimilar mixtures: the non-polar argon-oxygen system of importance for industrial air separation processes and the polar ammonia-water system of interest for understanding the atmospheres of Jupiter, Saturn, Uranus, and Neptune. Experimental measurements of pressure, temperature, and phase composition at equilibrium were made for the argon-oxygen system at temperatures from 92K to 115K with a cryogenic VLE apparatus. A second custom-built apparatus was used to measure VLE in the ammonia-water system from 276K to 285K. Our new data, along with existing literature data, were critically evaluated and tested for thermodynamic consistency. A thermodynamic model of the argon-oxygen system from 90K to 120K was developed using an activity coefficient approach to describe nonidealities in the liquid and the virial equation of state to characterize vapor phase nonidealities. The model employs maximum likelihood parameter fitting which takes into account uncertainties in all measured quantities and maximizes the likelihood that the model describes the true behavior of the mixture. For the ammonia-water study a new extension of the thermodynamic model to polar mixtures is presented. Our model has built-in temperature dependence for reliable extrapolation to temperatures beyond the range of the available data. The model constants can be used in a simple iterative procedure to calculate the liquid and vapor compositions of the mixture at specified temperature and pressure. As a demonstration, our ammonia-water model is used to calculate altitude-composition profiles for condensing clouds of liquid ammonia-water solution on Jupiter.

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