Aqueous Solubility of Polychlorinated Biphenyls Related to Molecular Structure
Aqueous Solubility of Polychlorinated Biphenyls Related to Molecular Structure
复制标题
多氯联苯的水溶性与分子结构的关系
DOI：
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发表时间：
1988
期刊：
影响因子：
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通讯作者：
O. Hutzinger
中科院分区：
文献类型：
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作者：
A. Opperhuizen;F. Gobas;J. Van der Steen;O. Hutzinger
多氯联苯的水溶解度表现出水活度系数的对数与总表面积（TSA）或总分子体积（TMV）之间的线性关系。水活度系数由实验溶解度数据和文献值计算得出。如果假设过冷液体和固体化学物质之间的差热容 (..delta..C/sub p/) 等于聚变熵 (..delta..S/sub f/)，而不是 ..delta..C/sub p/ = O，则相关性会显着改善。此外，还发现2,2',4,4'-四氯联苯和2,2',4,4'5,5'-六氯联苯的溶解伴随着正的焓变和熵变，其中在室温下熵占主导地位。对于前一种化合物，表明融合熵约为J K/sup -1/ mol/sup -1/，这与瓦尔登规则一致。对于 2,2',4,4',5,5'-六氯联苯，Hildebrand 图提供了恒定的斜率。这支持了微分热容 (..delta..C/sub p/) 等于聚变熵的假设。
Aqueous solubilities of polychlorinated biphenyls show a linear relationship between logarithms of aqueous activity coefficients and total surface areas (TSA) or total molecular volumes (TMV). The aqueous activity coefficients were calculated from experimental solubility data and values taken from the literature. The correlations improved substantially if a differential heat capacity between supercooled liquid and solid chemical (..delta..C/sub p/) equal to the entropy of fusion (..delta..S/sub f/), instead of ..delta..C/sub p/ = O, was assumed. In addition, it was found that dissolution of 2,2',4,4'-tetra- and 2,2',4,4'5,5'-hexachlorobiphenyl was accompanied by positive enthalpy and entropy changes, the entropy being dominant at room temperature. For the former compound, it was shown that the entropy of fusion is approximately to J K/sup -1/ mol/sup -1/, which is in agreement with the Walden rule. For 2,2',4,4',5,5'-hexachlorobiphenyl, it was shown that a Hildebrand plot provides a constant slope. This supported the assumption that differential heat capacity (..delta..C/sub p/) equals the entropy of fusion.