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动力学及其伴随的热力学研究表明,在水合 DMF 中,L-色氨酸与锌(II)和钕(III)的异双金属同时络合,通过 4f-4f 吸收光谱。

Kinetics and its accompanying thermodynamics studies on simultaneous complexation of heterobimetallic neodymium (III) with zinc (II) and L-tryptophan in aquated DMF using 4f-4f absorption spectra.

机构信息

Department of Chemistry, Manipur University, Imphal 795003, Manipur, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2014 Jan 24;118:367-72. doi: 10.1016/j.saa.2013.08.084. Epub 2013 Aug 30.

Abstract

The 4f-4f absorption spectra of the simultaneous heterobimetallic complexation of trivalent neodymium ion with l-tryptophan and divalent zinc ion in aquated DMF (50%, v/v) at pH 6.0 was recorded at the time interval of 1h. From the observed absorption spectra, the values of intensity parameters such as oscillator strength (P) and Judd-Ofelt intensity (Tλ) parameters, kinetics and thermodynamics parameters were evaluated. The rate constant increases with an increase in the temperature along with the oscillator strengths and Judd-Ofelt intensity parameters. The positive values of the change in the standard enthalpy (ΔH°) and entropy (ΔS°) indicate that the complexation is endothermic. The negative values of the change in the standard free energy (ΔG°) in the range from 293.15 K to 308.15 K, indicate that the reaction occurs spontaneously and hence the formation of heterobimetallic complex in the solution is favored kinetically and thermodynamically.

摘要

在 pH 值为 6.0 的水合 DMF(50%,v/v)中,同时记录了三价钕离子与 l-色氨酸和二价锌离子的异双金属络合的 4f-4f 吸收光谱,时间间隔为 1 小时。从观察到的吸收光谱中,评估了强度参数的值,例如振子强度(P)和 Judd-Ofelt 强度(Tλ)参数、动力学和热力学参数。随着温度的升高,速率常数以及振子强度和 Judd-Ofelt 强度参数增加。标准焓(ΔH°)和熵(ΔS°)变化的正值表明络合是吸热的。在 293.15 K 至 308.15 K 的范围内,标准自由能(ΔG°)的负值表明反应是自发发生的,因此溶液中异双金属络合物的形成在动力学和热力学上是有利的。

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