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TaCl_5-NaCl二元系气态配合物生成热力学

Formation Thermodynamics of the Vapour Complexes in the TaCl_5-NaCl Binary System
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摘要 以密闭的Pyrex玻璃瓶为反应器,利用化学气相传输反应原理,通过高温相平衡淬冷实验方法,在588~663K和0.06~0.12MPa范围内,反应6h的条件下,对气态配合物NauTavCl(u+5v)的生成热力学进行了研究.结果显示,TaCl5-NaCl二元系的ln(pNaTaCl6/P)-ln(pTaCl5/p)和lnKp-1/T都呈线性关系,五氯化钽和氯化钠生成的气态配合物NaTaCl6是惟一反应产物.反应的热力学平衡常数由实验结果计算.反应的焓变和熵变由不同温度的稳定常数经最小二乘法求得,分别是△Hm=(-25.2±1.5)kJ·mol^-1和△Sm=(-58.4±2.0)J·mol^-1·K^-1. Taking advantage of the theory of chemical vapour transfer reaction, the formation thermodynamics of vapour complex NauTavCl(u+5v) was experimentally investigated in closed Pyrex ampoules as reactors at 588~663 K under 0.06~0.12 MPa for about 6 h by way of hightemperature phase equilibrium quenching. The results showed that the ln(pNaTaCl6/P) vs. ln(pTaCl5/p) plot and lnKp vs. 1/T plot are both in linear relation and the vapour complex NaTaCl6 is the sole reaction product from tantalum chloride and sodium chloride. The thermodynamic equilibrium constants of the reaction are all determined from experimental result. Based on the stability constant obtained at different temperatures from experiments, the changes in enthalpy and entropy in reaction are given by least square method, i. e, , △Hm=(-25.2±1.5)kJ·mol^-1 and △Sm=(-58.4±2.0)J·mol^-1·K^-1. respectively.
机构地区 东北大学理学院
出处 《东北大学学报(自然科学版)》 EI CAS CSCD 北大核心 2007年第10期1517-1520,共4页 Journal of Northeastern University(Natural Science)
基金 国家自然科学基金资助项目(50274027)
关键词 TaCl6 TaCl5 NACL 气态配合物 相平衡淬冷法 NaTaCl6 TaCl5 NaCl vapour complex phase equilibrium quenching process
作者简介 李军丽(1978-),女,辽宁新民人,东北大学博士研究生; 王之昌(1940-),男,江苏昆山人,东北大学教授,博士生导师.
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参考文献12

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