THEORY OF UPPER AND LOWER CRITICAL SOLUTION TEMPERATURES
THEORY OF UPPER AND LOWER CRITICAL SOLUTION TEMPERATURES
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DOI：
10.1039/df9531500188
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发表时间：
1953-01-01
期刊：
影响因子：
--
通讯作者：
FOCK, W
中科院分区：
文献类型：
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作者：
BARKER, JA;FOCK, W
研究了分子间相互作用依赖于相对取向的一些模型的相分离行为。一个模型以尼古丁+水系统的方式显示了上临界溶液温度和下临界溶液温度。另一个例子显示了在部分混溶固体中观察到的化合物形成的行为。第三种代表两种羟基化合物的混合物，只显示出上临界溶解温度，某些液体对，尼古丁+水是经典的例子，在上临界溶解温度（CST）以上和下CST以下是完全混溶的，在这些温度之间分离成两相。没有理论解释这一现象可比的解释上CST提供的理论的正规解决方案。Ono 1指出，自由体积随组成的变化可能会导致较低的CST，尽管他的结论受到Rowlinson的质疑。2 Hirschfelder、史蒂文森和Eyring 3认为，较低的CST是由于氢键等相互作用干扰了分子的自由旋转，Rushbrooke 4表明这种作用可能导致较低的CST。然而，以前没有计算表明存在的上限和下限CST的一个明确的模型。这种计算在这里描述。
The phase separation behaviour of a number of models in which the molecular interactions depend on relative orientation is investigated. One model shows upper and lower critical solution temperatures in the manner of the nicotine+ water system. Another shows the kind of behaviour observed with partially miscible solids in which compound formation occurs. A third, representing a mixture of two hydroxy-compounds, shows only an upper critical solution temperature.Certain pairs of liquids, nicotine+ water being the classical example, are completely miscible above an upper critical solution temperature (CST) and below a lower CST, separating into two phases between these temperatures. There is no theoretical explanation of this phenomenon comparable with the explanation of the upper CST offered by the theory of regular solutions. Ono 1 has shown that the variation of free volume with composition may give rise to a lower CST, though his conclusions have been questioned by Rowlinson. 2 Hirschfelder, Stevenson and Eyring 3 suggested that the lower CST was due to an interaction such as hydrogen bonding which interfered with the free rotation of the molecules, and Rushbrooke4 showed that such an effect could give rise to a lower CST. However, no calculations have previously been made showing the existence of both upper and lower CST for a definite model. Such calculations are described here.