TaCl_5-NaCl二元系气态配合物生成热力学

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588~663 K和0.06~0.12 MPa范围内,反应6 h的条件下,对气态配合物NauTavClu+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ΔHm=(-25.2±1.5)kJ.mol-1和ΔSm=(-58.4±2.0)J.mo...

Formation Thermodynamics of the Vapour Complexes in the TaCl5-NaCl Binary System

Taking advantage of the theory of chemical vapour transfer reaction, the formation thermodynamics of vapour complex NauTavClu+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 high-temperature 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., ΔHm^⊖ = (-25.2 ± 1.5) kJ·mol^-1 and ΔSm^⊖ (-58.4 ± 2.0) J·mol^-1·K^-1, respectively.