| 用微量热法测定稀土含硫有机配合物的比热容 |
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| 引用本文： | 帅琪,高胜利,陈三平,刘明艳,胡荣祖,史启祯.用微量热法测定稀土含硫有机配合物的比热容[J].化学学报,2005,63(21):1962-1966. |
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| 作者姓名： | 帅琪 高胜利 陈三平 刘明艳 胡荣祖 史启祯 |
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| 作者单位： | 西北大学化学系陕西省物理无机化学重点实验室 西安710069
(帅琪，高胜利，陈三平)，绵阳中物热分析仪器有限公司 绵阳621900
(刘明艳)，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
(胡荣祖)，西北大学化学系陕西省物理无机化学重点实验室 西安710069(史启祯) |
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| 基金项目： | 国家自然科学基金（No.20471047）和陕西省自然科学基金（No.2003819）资助项目. |
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| 摘 要： | 推导了用改进的RD496-III型微热量计测定固态物质比热容的计算式. 用Joule 效应确定了仪器在298.15 K时的量热常数和相对标准偏差分别为(63.901±0.030) μV?mW－1和0.08%, 用Peltier效应测定总不平衡热. 在该仪器上测定的两种标准物质(基准苯甲酸和α-Al2O3)比热容的计算值与文献值相差在0.4%以内. 用本法测定了13种固态配合物RE(PDC)3(phen) (RE＝La, Pr, Nd, Sm～Lu; PDC＝ )的比热容值, 总偏差在1.0%, 与稀土原子序数ZRE作图呈现“三分组现象”, 说明配合物中RE3＋与配体间的化学键有一定程度的共价性, 显示了稀土离子4f电子云的扩大效应.
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| 关 键 词： | 微量热法 不平衡热 稀土氯化物 吡咯烷-N-二硫代甲酸铵 邻二氮菲 固态配合物 比热容 |
| 收稿时间： | 2005-01-12 |
| 修稿时间： | 2005-01-122005-07-12 |
Determination of Specific Heat Capacity of Rare Earth Organic-sulfur Complexes by Microcalorimetry |
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| SHUAI,Qia GAO,Sheng-Li,a CHEN,San-Pinga LIU,Ming-Yanb HU,Rong-Zua,c SHI,Qi-Zhena.Determination of Specific Heat Capacity of Rare Earth Organic-sulfur Complexes by Microcalorimetry[J].Acta Chimica Sinica,2005,63(21):1962-1966. |
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| Authors: | SHUAI Qia GAO Sheng-Li a CHEN San-Pinga LIU Ming-Yanb HU Rong-Zua c SHI Qi-Zhena |
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| Institution: | (Shaanxi Key Laboratory of Physico-inorganic Chemistry, Department of Chemistry, Northwest University, Xi'an 710069)( Mianyang Chinese Physics Thermal Analysis Instrument Co., Ltd, Mianyang 621900)(Research Institute of Xi'an Modern Chemistry, Xi'an 710065) |
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| Abstract: | A calculation formula for determining the specific heat capacity of solid with an improved RD496-III microcalorimeter was derived. The calorimetric constant and the relative standard deviation determined by use of Joule effect were (63.901±0.030) μV?mW－1 and 0.08% at 298.15 K, respectively, and the total disequilibrium heat has been measured by Peltier effect. The specific heat capacities of two standard samples (benchmark benzene carboxylic acid and α-Al2O3) were obtained with this microcalorimeter, and differences between their calculated values and their literature ones were less than 0.4%. Accordingly, the specific heat capacities of thirteen solid complexes RE(PDC)3(phen) (RE＝La, Pr, Nd, Sm～Lu; PDC＝ ) were also gained by the same method with their total deviations within 1.0%. These values were plotted against the atomic number of rare earth, which presents tripartite effect. It suggests existence of a certain amount of covalent character in the bond of RE3＋and ligands, according to Nephelauxetic effect of 4f electrons of rare earth ions. |
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| Keywords: | microcalorimetry disequilibrium heat rare earth chloride ammonium pyrrolidinyl-N-dithio-carboxylate o-phenanthroline solid complex specific heat capacity |
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