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本文测定了KClO_4在甲醇-苯,甲醇-甲苯,甲醇-四氯化碳及甲醇-环己烷四个混合溶剂中的溶解度。使用A.D＇Aprano[4]和C.W.Davies[2],报告的KClO_4及KNO_3在甲醇中的缔合常数,计算得“自由离子”浓度。盐的介质效应活度系数f_(MX)以S_o/Sm或S_(o+)、D_(m±)的表示值趋近相等,与非电解质的摩尔分数X_(Ne的关系符合经验公式:1gf_(MX)=kX_(Ne),这里S+o和S_m分别是盐在甲醇和混合溶剂中的溶解度;脚注(±)标识“自由离子”;k为常数。电解质的溶剂化数公式:n_++n_-=-21gf_(MX)/1gφ_ρ,对KClO_4在这些混合溶剂中的情况并不适用,这里n_++n_-是正、负离子溶剂化数之和;φ_p是甲醇在混合溶剂中的体积分数。这个结果表明ClO_4~-的溶剂化层不是完全由甲醇分子所形成,非电解质也影响着ClO_4~-在这些溶剂中的溶剂化层。 KNO_3的实验数据,溶解度公式和溶剂化数公式是引自李芝芬、黄子卿、刘瑞麟以前的论文。
In this paper, the solubility of KClO_4 in four mixed solvents of methanol-benzene, methanol-toluene, methanol-carbon tetrachloride and methanol-cyclohexane was measured. Using the association constants of KClO 4 and KNO 3 in methanol reported by A. D’Anprano [4] and C. W. Davies [2], the “free ion” concentration was calculated. The medium effect activity coefficient f_ (MX) of salt approaches equal to S_o / Sm or S_ (o +) and D_ (m ±), and its relationship with the non-electrolyte mole fraction X_ (Ne is in accordance with the empirical formula: 1gf_ MX) = kX_ (Ne), where S + o and S_m are the solubility of the salt in methanol and mixed solvent, respectively. The footnote (±) identifies “free ion” and k is constant. The solvating number of the electrolyte is: n_ ++ n _- = - 21gf_ (MX) / 1gφ_ρ is not suitable for KClO_4 in these mixed solvents, where n_ ++ n_- is the sum of the solvation numbers of positive and negative ions; φ_p is the volume fraction of methanol in the mixed solvent. This result shows that the solvation of ClO 4 - is not completely formed by methanol molecules, and the non-electrolyte also affects the solvation of ClO 4 - in these solvents. The experimental data, solubility and solvation numbers of KNO 3 are derived from Li Zhi Fen, Huang Ziqing, Liu Ruilin previous papers.