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水合氯化镧与二乙氨基荒酸二乙铵配合行为的热化学
引用本文:高胜利,陈三平,焦宝娟,任宜霞,胡荣祖,赵凤起,史启祯.水合氯化镧与二乙氨基荒酸二乙铵配合行为的热化学[J].化学学报,2003,61(12):2020-2024.
作者姓名:高胜利  陈三平  焦宝娟  任宜霞  胡荣祖  赵凤起  史启祯
作者单位:1. 西北大学化学系,陕西省物理无机化学重点实验室,西安,710069
2. 西北大学化学系,陕西省物理无机化学重点实验室,西安,710069;西安近代化学研究所,西安,710065
3. 西安近代化学研究所,西安,710065
基金项目:国家自然科学基金 (No.2 0 1 71 0 36),陕西省自然科学基金 (No .2 0 0 2B0 3),陕西省教育厅专项基金 (No .0 1JK2 2 9)资助项目
摘    要:在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化镧与二乙氨基荒酸 二乙铵(D-DDC)的配合物,确定其组成为Et_2NH_2La(S_2CNEt_2)_4]。用微量热 法测定了298.15 K下水合氯化镧和D-DDC在无水乙醇中的溶解焓和不同温度下二乙 氨基荒酸镧液相生成反应的焓变。在实验和计算基础上,得到了液相生成反应的热 力学参数(活化焓、活化熵和活化自由能)、速率常数和动力学参数(表现活化能 、频率因子和反应基数),通过合理的热化学循环,求得了标题固相反应的焓变。

关 键 词:氯化镧  二乙氨基荒酸二乙铵  乙醇  热力学性质  活化能
修稿时间:2003年4月22日

Thermochemistry on Coordination Behavior of Lanthanum Chloride Hydrate with Diethylammonium Diethyldithiocarbamate
GAO,Sheng-Li,a CHEN,San-Ping a JIAO,Bao-Juan a REN,Yi-Xia a HU,Rong-Zu a,b ZHAO,Feng-Qi b SHI,Qi-Zhen a.Thermochemistry on Coordination Behavior of Lanthanum Chloride Hydrate with Diethylammonium Diethyldithiocarbamate[J].Acta Chimica Sinica,2003,61(12):2020-2024.
Authors:GAO  Sheng-Li  a CHEN  San-Ping a JIAO  Bao-Juan a REN  Yi-Xia a HU  Rong-Zu a  b ZHAO  Feng-Qi b SHI  Qi-Zhen a
Institution:Chemistry Department of Northwest University, Shaanxi Key Laboratory of Physico-Inorganic Chemistry;Xi'an Modern Chemistry Research Institute
Abstract:The complex of lanthanum chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized in dry N 2 atmosphere and absolute alcohol. The composition of the complex Et 2NH 2La(S 2-CNEt 2) 4] was determined by chemical and elemental analyses. The enthalpies of solution of lanthanum chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpy change of liquid-phase reaction of formation for Et 2NH 2La(S 2CNEt 2) 4] at different temperatures were determined by a microcalorimeter. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained. The enthalpy change of solid-phase title reaction was obtained by rational thermochemical cycle.
Keywords:lanthanum chloride hydrate  diethylammonium diethyldithiocarbamate (D-DDC)  microcalorimetric method  thermochemistry
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