Görgényi Miklós, Dewulf Jo, Van Langenhove Herman, Héberger Károly
Department of Physical Chemistry, University of Szeged, H-6721 Szeged, Rerrich Béla tér 1, Hungary.
Chemosphere. 2006 Oct;65(5):802-10. doi: 10.1016/j.chemosphere.2006.03.029. Epub 2006 May 18.
The salting-out effects of 27 lithium, sodium, potassium, ammonium and magnesium salts and HCl on chloroform, benzene, chlorobenzene and anisole were characterized in aqueous solutions at 303 K by measuring the Henry's law constants. The concentration of the salt solutions was 0.5 mol dm(-3), i.e., similar to the salinity of sea water. The solubility change was described in terms of the Setschenow constant, K(S)(salt,solute). The highest salting-out effects were observed for the solutions of salts involving doubly charged anions, and the smallest for NO(-)(3). The individual ionic Setschenow constants, K(S)(cation,solute) and K(S)(anion,solute), were determined by multilinear regression, using the assumption of additivity for the ions. Cl(-) was selected as the reference ion for calculation of the K(S)(ion,solute) values of the other ions. The estimations resulted systematically in significant positive K(S)(cation,solute) values, ranging from 0.13+/-0.026 (NH(+)(4)) to 0.28+/-0.032 (Mg(2+)), which were hardly affected by the accompanying anion in solution, and only slightly affected by the non-electrolytes present. NO(-)(3) resulted in a slight salting-in effect: K(S)(NO(-)(3),solute)=-0.083+/-0.019; the other anions displayed salting-out effect for all of the non-electrolytes studied, with K(S)(anion,solute) ranging between 0.090+/-0.008 (HCO(-)(3)) and 0.21+/-0.035 (CO(2-)(3)).
在303 K的水溶液中,通过测量亨利定律常数,表征了27种锂盐、钠盐、钾盐、铵盐、镁盐和盐酸对氯仿、苯、氯苯和苯甲醚的盐析效应。盐溶液的浓度为0.5 mol dm(-3),即类似于海水的盐度。溶解度变化用Setschenow常数K(S)(盐,溶质)来描述。观察到涉及双电荷阴离子的盐溶液盐析效应最高,而NO(-)(3)的盐析效应最小。利用离子加和性假设,通过多元线性回归确定了单个离子的Setschenow常数K(S)(阳离子,溶质)和K(S)(阴离子,溶质)。选择Cl(-)作为参考离子来计算其他离子的K(S)(离子,溶质)值。估算结果系统地得出显著的正K(S)(阳离子,溶质)值,范围从0.13±0.026(NH(+)(4))到0.28±0.032(Mg(2+)),该值几乎不受溶液中伴随阴离子的影响,仅受存在的非电解质轻微影响。NO(-)(3)导致轻微的盐溶效应:K(S)(NO(-)(3),溶质)= -0.083±0.019;其他阴离子对所有研究的非电解质均表现出盐析效应,K(S)(阴离子,溶质)范围在0.090±0.008(HCO(-)(3))到0.21±0.035(CO(2-)(3))之间。