Regularity of Thermochemical Properties of Ternary Complexes RE[（pdtc）3（phen）]  

作　　者：樊学忠 陈三平 谢钢 高胜利 史启祯 

机构地区：[1]XI'an Modern Chemical Research Institute, Xi'an, Shaanxi 710065, China [2]Department of Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an, Shaanxi 710069, China

出　　处：《Chinese Journal of Chemistry》2006年第8期1013-1019,共7页中国化学（英文版）

基　　金：Project supported by the National Natural Science Foundation of China （Nos. 20171036, 20471047）, the Natural Science Foundation of Shaanxi Province （No. 2003B 19）.

摘　　要：Treatment of hydrate rare-earth （RE=La, Pr, Nd, Sm-Lu） chloride with ammonium pyrrolidinyldithiocarboxylate （apdtc） and 1,10-phenanthroline （phen） gave rise to thirteen complexes with an empirical formula RE[（pdtc）3（phen）]. The enthalpies of solution of hydrate rare-earth （RE= Sm-Ho, Tm-Lu） chloride, apdtc and phen in ethanol were measured by an RD-496 Ш microcalorimeter at 298.15 K, along with the mixing enthalpy of ethanol solution of APDC and that of phen and the enthalpies of reaction of formation of the title complexes in ethanol. The enthalpies of reaction of formation of the title complexes in solid were available through a rationally thermochemical cycle. Using an RD-496 Ш microcalorimeter, a model was developed for calculating the specific heat capacity and the responding specific heat capacity of the complexes were determined. The thermochemical properties, including the enthalpies of solution of hydrate rare earth chloride in ethanol, the enthalpies of reaction of formation of the title complexes in ethanol, the enthalpies of reaction of formation of the title complexes in solid, the special heat capacities at room temperature, the standard molar enthalpies of combustion and the standard molar enthalpies of formation for this series of complexes versus the atomic numbers of rare earth, presented triplet effect, which is representative of certain covalent bond between RE and the ligands and the result of 4f electron not shielded fully by 5sSp.Treatment of hydrate rare-earth （RE=La, Pr, Nd, Sm-Lu） chloride with ammonium pyrrolidinyldithiocarboxylate （apdtc） and 1,10-phenanthroline （phen） gave rise to thirteen complexes with an empirical formula RE[（pdtc）3（phen）]. The enthalpies of solution of hydrate rare-earth （RE= Sm-Ho, Tm-Lu） chloride, apdtc and phen in ethanol were measured by an RD-496 Ш microcalorimeter at 298.15 K, along with the mixing enthalpy of ethanol solution of APDC and that of phen and the enthalpies of reaction of formation of the title complexes in ethanol. The enthalpies of reaction of formation of the title complexes in solid were available through a rationally thermochemical cycle. Using an RD-496 Ш microcalorimeter, a model was developed for calculating the specific heat capacity and the responding specific heat capacity of the complexes were determined. The thermochemical properties, including the enthalpies of solution of hydrate rare earth chloride in ethanol, the enthalpies of reaction of formation of the title complexes in ethanol, the enthalpies of reaction of formation of the title complexes in solid, the special heat capacities at room temperature, the standard molar enthalpies of combustion and the standard molar enthalpies of formation for this series of complexes versus the atomic numbers of rare earth, presented triplet effect, which is representative of certain covalent bond between RE and the ligands and the result of 4f electron not shielded fully by 5sSp.

关 键 词：RE[（pdtc）3（phen）] thermochemical property triplet effect REGULARITY 

分 类 号：O641.4[理学—物理化学]