Abstract
In general, the vapor-pressure change due to the addition of a solute to a solvent mixture does not follow Raoult's law. We have demonstrated thermodynamically that if one adds to a binary solvent mixture solute and solvents in such a way that the vapor-phase composition remains constant, then the decrease of total pressure follows Raoult's law; a supplementary term which vanishes for very dilute solute concentration is introduced as a consequence of the nonideality of the ternary solution. Precise vapor-pressure measurements of dilute solutions of electrolytes and nonelectrolytes in a 40.000 wt. % water-tetrahydrofuran mixture are used in order to illustrate the applicability of Raoult's law under the above conditions. These may be regarded as a particular case of what has been called endostatic conditions, i.e., addition of a solute under constant solvent activity ratio.
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Tzias, P., Treiner, C. & Chemla, M. Applicability of Raoult's law in nonideal mixed solvents. J Solution Chem 6, 393–402 (1977). https://doi.org/10.1007/BF00645512
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DOI: https://doi.org/10.1007/BF00645512