Gutkowski Karin I, Fernández-Prini Roberto, Japas M Laura
Unidad de Actividad Química, Comisión Nacional de Energía Atómica, Avenida del Libertador 8250, 1429-Buenos Aires, Argentina.
J Phys Chem B. 2008 May 8;112(18):5671-9. doi: 10.1021/jp712091q.
The effect of cosolvents on the solubility equilibria near the critical end-point of binary mixtures is analyzed. The problem has received recent attention for the particular case of ionic cosolvents (Mazo, R. M. J. Phys. Chem. B 2007, 111, 7288-7290), where a pronounced salting-out effect was predicted. Here we make a thermodynamic analysis to view the problem from a different perspective. Our conclusions are that, at the critical end-point, the Setchenov constant, which reflects the effect of cosolvents on solubility equilibria, diverges following the behavior of the osmotic susceptibility and that the sign of this divergence is encoded in the critical end-line of the ternary system.
分析了助溶剂对二元混合物临界终点附近溶解度平衡的影响。对于离子助溶剂的特殊情况（马佐，R.M.《物理化学杂志B》2007年，111卷，7288 - 7290页），该问题最近受到了关注，其中预测了明显的盐析效应。在此，我们进行热力学分析，从不同角度看待该问题。我们的结论是，在临界终点，反映助溶剂对溶解度平衡影响的塞奇诺夫常数，遵循渗透磁化率的行为发散，并且这种发散的符号编码在三元系统的临界终点线上。
