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尿素与锰（II）、镍（II）和锌（II）离子在N，N-二甲基甲酰胺中形成配合物的热力学

Thermodynamics of formation of urea complexes with manganese(II), nickel(II) and zinc(II) ions in N,N-dimethylformamide.

作者信息

Ozutsumi K, Taguchi Y, Kawashima T

机构信息

Laboratory of Analytical Chemistry, Department of Chemistry, University of Tsukuba, Tsukuba, Japan.

出版信息

Talanta. 1995 Apr;42(4):535-41. doi: 10.1016/0039-9140(95)01437-g.

DOI:10.1016/0039-9140(95)01437-g
PMID:18966261
Abstract

The complexation of urea (ur) with manganese(II), nickel(II) and zinc(II) ions has been studied by titration calorimetry in N,N-dimethylformamide (DMF) containing 0.4M (C(2)H(5))(4) NBF(4) as a constant ionic medium at 25 degrees C. The calorimetric data were well explained in terms of the formation of Mn(ur), Mn(ur)(2) and Mn(ur)(4) for manganese(II), Ni(ur) for nickel(II) and Zn(ur) and Zn(ur)(2) for zinc(II), and their formation constants, reaction enthalpies and entropies were determined. The complexation of the nickel(II)-urea system in DMF has also been studied by means of spectrophotometric titration and electronic spectra of individual nickel(II) complexes were determined. On the basis of the stepwise thermodynamic quantities and the individual electronic spectra of the complexes, it is revealed that the Mn(ur), Mn(ur)(2), Ni(ur), Zn(ur) and Zn(ur)(2) complexes have a six-coordinate octahedral structure, while the Mn(ur)(4) complex has a four-coordinate tetrahedral structure.

摘要

在25℃下，以0.4M四乙基氯化铵四氟硼酸盐（(C₂H₅)₄NBF₄）作为恒定离子介质的N,N -二甲基甲酰胺（DMF）中，通过滴定量热法研究了尿素（ur）与锰（II）、镍（II）和锌（II）离子的络合作用。根据锰（II）形成的[Mn(ur)]²⁺、[Mn(ur)₂]²⁺和[Mn(ur)₄]²⁺，镍（II）形成的[Ni(ur)]²⁺，以及锌（II）形成的[Zn(ur)]²⁺和[Zn(ur)₂]²⁺，很好地解释了量热数据，并测定了它们的形成常数、反应焓和熵。还通过分光光度滴定法研究了DMF中镍（II） - 尿素体系的络合作用，并测定了各个镍（II）配合物的电子光谱。根据络合物的逐步热力学量和各个电子光谱，发现[Mn(ur)]²⁺、[Mn(ur)₂]²⁺、[Ni(ur)]²⁺、[Zn(ur)]²⁺和[Zn(ur)₂]²⁺配合物具有六配位八面体结构，而[Mn(ur)₄]²⁺配合物具有四配位四面体结构。

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