The structure of some molecular complexes in the liquid phase.
The structure of some molecular complexes in the liquid phase.
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DOI：
10.1039/tf9373300200
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发表时间：
1937-01-01
影响因子：
--
通讯作者：
Glasstone, S
中科院分区：
文献类型：
--
作者：
Glasstone, S
202液相中的一些分子复合物，根据总极化和三种组分A、B和AB的极化知识确定，假设总极化是混合物中单独组分极化的加性函数。在进行计算时，必须使用与测量总极化的介质具有相同介电常数的介质相应的各个极化值：这是通过适当的内插或外推来完成的，为此目的，相对于介电常数的函数绘制极化曲线。通常，质量作用”常数”在整个浓度范围内保持显著恒定，特别是当极端介电常数相差不大时。然而，对于某些体系，如丙酮和氯仿，在介电常数随浓度变化而迅速变化的区域，质量作用表达式并不完全恒定，但结果足够清楚，可以推导出近似的质量作用常数。所获得的一些结果总结在表I中：在每种情况下，计算都基于复合物由等分子量的两种组分组成的假设。在某些情况下，也作了其他的计算，例如一个丙酮分子比两个氯仿分子，三个喹啉分子比一个氯仿分子，但质量作用函数显示出非常明显的漂移，例如在后一种情况下，从13，000到0.06。表中的第一列给出了组分，下一列显示了两种组分的等分子混合物中存在的络合物的摩尔分数，然后是相应的质量作用常数，最后一列给出了从给定系统的所有混合物中获得的常数的平均值，明显不同的结果被忽略。
202 SOME MOLECULAR COMPLEXES IN THE LIQUID PHASE determined from the total polarisation and a knowledge of the polarisations of the three constituents A, B and AB, assuming the total polarisation to be an additive function of the polarisations of the separate constituents of the mixture. In applying the calculation it is necessary to use values for the individual polarisations appropriate to a medium of the same dielectric constant as that of which the total polarisation was measured: this was done by suitable interpolation or extrapolation, the polarisations being plotted for the purpose against the function of the dielectric constantIn general, the mass-action" constant" remained remarkably constant over the whole range of concentration, especially when the extreme dielectric constants were not greatly different. With some systems, however, eg acetone and chloroform, in the region wherein the dielectric constant was changing rapidly with varying concentration, the mass-action expression was not altogether constant, but the results were sufficiently clear for an approximate mass-action constant to be deduced. Some of the results obtained are summarised in Table I.: the calculations are based in every case on the assumption that the complex consists of equimolecular amounts of the two constituents. Alternative calculations were made in certain cases, eg for one molecule of acetone to two of chloroform, and for three molecules of quinoline to one of chloroform, but the mass-action function showed very marked drifts, eg in the latter case from 13,000 to 0.06. The first column in the table gives the components, the next shows the molar fraction of complex present in an equimolecular mixture of the two components, then follows the corresponding mass-action constant, and in the last column is given the average value for the constant obtained from all the mixtures of a given system, the obviously divergent results being ignored.