电动势法测定Cu(Ⅰ)与乙炔生成配合物的热力学函数

DETERMINATION OF THE THERMODYNAMIC PARAMETERS FOR COMPLEXATIONREACTION OF Cu( I ) WITH ACETYLENE BY EMFMETHOD

乙炔与Cu(I)生成配合物的热力学函数文献报道鲜见,且不同作者的测定结果差异较大。本文用改进的电动势法。对在氯丁橡胶、聚氯乙烯,乙醛等工业过程有重大意义的Cu(I)与乙炔配合物进行测定,得到更合理的结果。

The thermodynamic parameters K, △H° , △C° and △S° values of complexation reaction for Cu( I ) with acetylene in CuCl-NH4Cl-HCl-H2O system have been determined by emf method with some improvement on experimental technique. The results obtained are as follows: For Cu·C2H2+ complex compound, the formation constants K values are 2.39%105, 1.70×105, 1.35×103, 1.00×103, at 25℃, 35℃,45℃, 55℃, respectively. That for Cu+·C2H- complex are 27.8, 33.8, 48.4, 64.2, respectively. These data are of interest in homogeneous liquid phase catalytic conversion of acetylene to various products, such as acetaldehyde, monovinylacetylene, vinyl chloride, etc.