三元配合物RE [(Pdtc)3(phen)]热化学性质的规律性

Treatment of hydrate rare-earth(RE=La,Pr,Nd,Sm-Lu)chloride with ammonium pyrrolidinyldithiocarboxy-late(apdtc)and 1,10-phenanthroline(phen)gave rise to thirteen complexes with an empirical formulaRE(pdtc)_3(phen)].The enthalpies of solution of hydrate rare-earth(RE= Sm-Ho,Tm-Lu)chloride,apdtc and phenin ethanol were measured by an RD-496 Ⅲ microcalorimeter at 298.15 K,along with the mixing enthalpy of etha-nol 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 thermo-chemical cycle.Using an RD-496 Ⅲ microcalorimeter,a model was developed for calculating the specific heat ca-pacity 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 formationof the title complexes in ethanol,the enthalpies of reaction of formation of the title complexes in solid,the specialheat capacities at room temperature,the standard molar enthalpies of combustion and the standard molar enthalpiesof formation for this series of complexes versus the atomic numbers of rare earth,presented triplet effect,which isrepresentative of certain covalent bond between RE and the ligands and the result of 4f electron not shielded fullyby 5s5p.

Regularity of Thermochemical Properties of Ternary Complexes RE[(pdtc)_3(phen)]