Solid-Liquid and Liquid-Liquid Phase Equilibria in the Symmetrical Tetraalkylammonium Halide–Water Systems

Solid-liquid and liquid-liquid phase diagrams of the binary R4NX–water (R=n-C3H7–n-C6H13 and i-C5H11; X=F, Cl, Br, and I) systems were determined in the temperature range between −20 °C and +80 °C. These diagrams showed (1) the formation of a clathrate-like hydrate for four salts (n-C5H11)4NF, (n-C5H11)4NCl, (i-C5H11)4NBr, and (i-C5H11)4NI; (2) a phase separation into two liquid phases in the systems of (n-C5H11)4NBr, (i-C5H11)4NBr, (n-C6H13)4NCl, and (n-C6H13)4NBr; (3) that the solubility (in water at a definite temperature) of a series of the salts did not show a systematic change with respect to either the alkyl-chain length or the kind of anion; and (4) that the salt which gave the maximum solubility in water at 25 °C was (n-C5H11)4NCl for chloride, (n-C4H9)4NBr for bromide, and (C2H5)4NI for iodide, respectively. The effect of anions on the solubilities of a series of salts having the same cation was examined. It was found that the ratio mcl⁄mI at 25 °C became as high as 22800 for the tetrapentylammo...

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