贵金属
貴金屬
귀금속
PRECIOUS METALS
2004年
1期
11-18
,共8页
顾永万%董守安%罗一江%王仕兴%段德良
顧永萬%董守安%囉一江%王仕興%段德良
고영만%동수안%라일강%왕사흥%단덕량
物理化学%铑(III)氯水配合物%动力学%热力学
物理化學%銠(III)氯水配閤物%動力學%熱力學
물이화학%로(III)록수배합물%동역학%열역학
Physicochemistry%Chloroaquorhodium(III) complexes%Kinetics%Thermodynamics
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]cis-[RhCl4(H2O)2]-[RhCl5(H2O)]2-[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.
作者詳細研究瞭各銠(III)氯水配閤物在水溶液中隨時間、溫度變化而變化的規律,穫得的結果錶明,Cl-濃度是影響銠(III)在各種態中分佈的主要因數,但是,對于陰離子種態,其放置的時間和溫度也是不可忽略的.對于下麵這箇短的平衡反應鏈:fac-[RhCl3(H2O)3]cis-[RhCl4(H2O)2]-[RhCl5(H2O)]2-[RhCl6]3-作者繫統的研究瞭在不同溫度下其各種態的分佈,結果髮現fac-[RhCl3(H2O)3]的含量隨溫度的升高而增加,而cis-[RhCl4(H2O)2]-、[RhCl5(H2O)]2-和[RhCl6]3-卻隨溫度的升高而降低.氯代和水閤作為銠(III)氯水配閤物在溶液中的競爭反應,在放置開始,氯代佔優勢,但隨時間的延長,水閤逐漸趨于優勢.
작자상세연구료각로(III)록수배합물재수용액중수시간、온도변화이변화적규률,획득적결과표명,Cl-농도시영향로(III)재각충태중분포적주요인수,단시,대우음리자충태,기방치적시간화온도야시불가홀략적.대우하면저개단적평형반응련:fac-[RhCl3(H2O)3]cis-[RhCl4(H2O)2]-[RhCl5(H2O)]2-[RhCl6]3-작자계통적연구료재불동온도하기각충태적분포,결과발현fac-[RhCl3(H2O)3]적함량수온도적승고이증가,이cis-[RhCl4(H2O)2]-、[RhCl5(H2O)]2-화[RhCl6]3-각수온도적승고이강저.록대화수합작위로(III)록수배합물재용액중적경쟁반응,재방치개시,록대점우세,단수시간적연장,수합축점추우우세.
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]cis-[RhCl4(H2O)2] --[RhCl5(H2O)]2- [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.