Abstract
By use of a diamond anvil cell, we show that at high pressures aqueous solutions of tetra-n-butylammonium bromide form a closed liquid–liquid immiscibility loop with a critical concentration of about 2.0 mol-kg−1. We report data for a near-critical isopleth, which describes the pressure dependence of the upper and lower consolute points. At about 700 MPa and 373 K both consolute points coincide to form a hypercritical point, which characterizes the minimum pressure to achieve immiscibility. We show that this immiscibility can be rationalized in terms of Pitzer's ion-interaction theory. We determine the ion-interaction parameters of Pitzer's theory up to 423 K at normal pressure. Inclusion of volumetric data gives the correct trend toward a high-pressure immiscibility. We discuss the results in terms of the interplay between ionic and hydrophobic forces in this system.
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Weingärtner, H., Klante, D. & Schneider, G.M. High-Pressure Liquid-Liquid Immiscibility in Aqueous Solutions of Tetra-n-butylammonium Bromide Studied by a Diamond Anvil Cell Technique. Journal of Solution Chemistry 28, 435–446 (1999). https://doi.org/10.1023/A:1022612029577
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DOI: https://doi.org/10.1023/A:1022612029577