Heats of Mixing of Electrolytes of the 1-1 Charge Type
Heats of Mixing of Electrolytes of the 1-1 Charge Type
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DOI：
10.1021/j100890a015
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发表时间：
1965-06
期刊：
影响因子：
--
通讯作者：
Y. C. Wu;M. Smith;T. F. Young
中科院分区：
文献类型：
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作者：
Y. C. Wu;M. Smith;T. F. Young
在 25 ℃ 测量了 8 对 1-1 电解质的 1 m 水溶液的混合热，该溶液不具有该对共有的离子。混合摩尔热的绝对值的平均值稍大于分组的相同电解质对的混合热的绝对值的平均值，每对中都有一个公共离子。交叉混合热和共离子混合热之间的热化学关系（交叉平方法则）已通过应用于四个系统进行了测试。该规则与数据非常吻合。已经指出了稀释热和交叉混合热之间的纯热力学关系，因此是精确的关系，并说明了其应用。使用相对稀的溶液进行工作不符合特定离子相互作用的布朗斯台德原理。图 1 中正方形的角标出了四种电解质的水溶液。如果将 0.5 摩尔的 LiCl 与 0.5 摩尔的 LiBr 混合（各自在 25 ℃ 的 1 m 溶液中），则吸收的热量为 0.81 卡/摩尔电解质，如正方形左侧所示。 2 0.5 摩尔 NaCl 和 0.5 摩尔 NaBr 混合导致吸收 0.79 卡/摩尔。 LiCl 和 NaCl 各 0.5 摩尔的混合伴随着 21.15 卡/摩尔的吸收，如正方形上侧所示； LiBr和NaBr各0.5摩尔的混合伴随着20.67卡/摩尔的吸收。
Heats of mixing of eight pairs of 1 m aqueous solutionsof 1-1 electrolytes not having an ion common to the pair have been measured at 25. The average of the absolute values of the molal heats of mixing is somewhat larger than the average of the absolute values of the heats of mixing of pairs of the same electrolytes so grouped that there is a common ion within each pair. The thermochemical relation between the heats of cross mixing and the heats of common-ion mixing (the cross-square rule) has been tested by application to four systems. The rule fits the data remarkably well. The purely thermodynamic, and hence exact, relation between heats of dilution and heats of cross mixing has been pointed out and its application illustrated. Work with relatively dilute solutions is not in accord with the Br0nsted principle of specific ionic interaction.Aqueous solutions of four electrolytes are indicated at the corners of the square in Figure 1. If 0.5 mole of LiCl is mixed with 0.5 mole of LiBr (each in a 1 m solu-tion at 25), the heat absorbed is 0.81 cal./mole of elec-trolyte as indicated on the left side of the square. 2 The mixing of 0.5 moleof NaCl and 0.5 mole of NaBr causes the absorption of 0.79 cal./mole. The mixing of 0.5 mole each of LiCl and NaCl is accompanied by the absorption of 21.15 cal./mole as indicated on the upper side of the square; the mixing of 0.5 mole each of LiBr and NaBr is accompanied by the absorption of 20.67 cal./mole.