| 稀土配合物[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3的标准生成焓及热分解动力学研究 |
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| 引用本文： | 但悠梦,胡卫兵,余华光,董家新,刘义,屈松生. 稀土配合物[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3的标准生成焓及热分解动力学研究[J]. 化学学报, 2006, 64(1): 70-78 |
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| 作者姓名： | 但悠梦 胡卫兵 余华光 董家新 刘义 屈松生 |
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| 作者单位： | 湖北民族学院化学与环境工程学院，湖北民族学院化学与环境工程学院，武汉大学化学与分子科学学院，武汉大学化学与分子科学学院，武汉大学化学与分子科学学院，武汉大学化学与分子科学学院 恩施445000，武汉大学化学与分子科学学院，武汉430072，恩施445000，武汉430072，武汉430072，武汉430072，武汉430072 |
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| 基金项目： | 教育部高校优秀青年教师教学科研奖励计划(2001)，湖北省教育厅重点(No.D200529003)资助项目. |
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| 摘 要： | 合成了高氯酸镨和咪唑(C3H4N2), DL-α-丙氨酸(C3H7NO2)混配配合物晶体. 经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3. 使用具有恒温环境的溶解-反应量热计, 以2.0 mol•L－1 HCl为量热溶剂, 在T＝(298.150±0.001) K时测定出化学反应PrCl3•6H2O(s)＋2C3H7NO2(s)＋C3H4N2(s)＋3NaClO4(s)＝[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)＋3NaCl(s)＋5H2O(1)的标准摩尔反应焓为ΔrHmө＝(39.26±0.11) kJ•mol－1. 根据盖斯定律, 计算出配合物的标准摩尔生成焓为ΔfHmө{[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s), 298.150 K}＝(－2424.2±3.3) kJ•mol－1. 采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学, 运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析, 求得分解反应的表观活化能E＝108.9 kJ•mol－1, 动力学方程式为dα/dt＝2(5.90×108/3)(1－α)[－ln(1－α)]－1exp(－108.9×103/RT).
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| 关 键 词： | 稀土配合物 溶解-反应量热 标准生成焓 TG-DTG技术 热分解动力学 |
| 收稿时间： | 2004-10-26 |
| 修稿时间： | 2004-10-262005-06-17 |
Standard Molar Enthalpy of Formation and Thermal Decomposition Kinetic Study of Rare Earth Complex [Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3 |
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| DAN You-Meng,HU Wei-Bing,YU Hua-Guang,DONG Jia-Xin,LIU Yi,QU Song-Sheng. Standard Molar Enthalpy of Formation and Thermal Decomposition Kinetic Study of Rare Earth Complex [Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3[J]. Acta Chimica Sinica, 2006, 64(1): 70-78 |
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| Authors: | DAN You-Meng HU Wei-Bing YU Hua-Guang DONG Jia-Xin LIU Yi QU Song-Sheng |
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| Affiliation: | (School of Chemistry and Environmental Engineering, Hubei Institute for Nationalities, Enshi 445000)( College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072) |
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| Abstract: | The crystal of a mixed ligand complex of praseodymium perchlorate with imidazole (C3H4N2) and DL-α-alanine (C3H7NO2) was synthesized and characterized. The empirical formula of the crystal was determined to be [Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3 by FT-IR spectrum, chemical analysis and elemental analysis. The enthalpy of reaction of PrCl3•6H2O(s)＋2C3H7NO2(s)＋C3H4N2(s)＋3NaClO4(s)＝[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)＋3NaCl(s)＋5H2O(l) in 2.0 mol•L－1 HCl solvents was determined to beΔrHmө＝(39.26±0.11) kJ•mol－1 by a solution-reaction isoperibol calorimeter at T＝(298.150±0.001) K. According to Hess’s Law, the standard molar enthalpy of formation of the title complex was derived, ΔfHmө{[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s), 298.150 K}＝(－2424.2±3.3) kJ•mol－1. The non-isothermal thermal decomposition kinetics of the complex in flow atmosphere of high purity nitrogen (99.99%) was studied by TG-DTG techniques. The non-isothermal kinetics parameters were analyzed by means of differential (Achar-Brindley-shap and Kissinger method) and integral (Satava-Sastak and Coats-Redfern methods) methods, respectively. The apparent activation energy of the thermal decomposition reaction was obtained to give: E＝108.9 kJ•mol－1, and the kinetic equation may be expressed as: dα/dt＝2(5.90×108/3)(1－α)[－ln(1－α)]－1exp(－108.9×103/RT). |
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| Keywords: | complex of rare earth solution-reaction calorimetry standard enthalpy of formation TG-DTGtechnique thermal decomposition kinetics |
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