铑(Ⅲ)氯水配合物在水溶液中的热力学和动力学平衡行为研究(英文)

Study on the Thermodynamic and Kinetic Equilibrium Behaviors of Chloroaquorhodium(III) Complexes

作者详细研究了各铑(III)氯水配合物在水溶液中随时间、温度变化而变化的规律,获得的结果表明,Cl-浓度是影响铑(III)在各种态中分布的主要因数,但是,对于阴离子种态,其放置的时间和温度也是不可忽略的。对于下面这个短的平衡反应链: fac-[RhCl3(H2O)3]K34cis-[RhCl4(H2O)2]-K45[RhCl5(H2O)]2- 56[RhCl6]3- 作者系统的研究了在不同温度下其各种态的分布,结果发现fac-[RhCl3(H2O)3]的含量随温度的升高而增加,而cis-[RhCl4(H2O)2]-、[RhCl5(H2O)]2-和[RhCl6]3-却随温度的升高而降低。氯代和水合作为铑(III)氯水配合物在溶液中的竞争反应,在放置开始,氯代占优势,但随时间的延长,水合逐渐趋于优势。

The varied law of chloroaquorhodium (III)complex species in acidic solution with aged time and temperature was studied. The results indicated that a short true equilibrium series for the following unstable anionic species exists in the solution fac-[RhCl3(H2O)3]KC34cis-[RhCl4(H2O)2] -KC45-[RhCl5(H2O)]2-K 56 [RhCl6]3- After the solution containing K2[Rh(H2O)Cl5] was placed for a long time, fac-[Rh(H2O)3Cl3] complex became a dominant species because of the aquation. The mixture of above species equilibrated under different temperatures was separated and determined, the content of fac-[Rh(H2O)3Cl3] increased with temperature rising, on the contrary, that of [RhCl6]3-winsignificant. The experiments showed also that aquation and chloride anation of chloroaquorhodium(III) complexes were the competitive reaction in dilute HCl solution, the chloride anation was predominant at the beginning, then, aquation was predominant.