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镍离子与硼酸或（聚）硼酸盐的络合作用。

Complexation of Nickel Ions by Boric Acid or (Poly)borates.

作者信息

Graff Anais, Barrez Etienne, Baranek Philippe, Bachet Martin, Bénézeth Pascale

机构信息

EDF R&D - Department of Material and Mechanic of Component, EDF Lab Les Renardières, Avenue des Renardières - Ecuelles, 77818 Moret-Sur-Loing Cedex, France.

EDF R&D - Department of Material and Mechanic of Component, EDF Lab Les Renardières, Avenue des Renardières - Ecuelles, 77818 Moret-Sur-Loing Cedex, France ; PPSM, ENS Cachan, CNRS, Université Paris - Saclay, 94235 Cachan, France.

出版信息

J Solution Chem. 2017;46(1):25-43. doi: 10.1007/s10953-016-0555-x. Epub 2016 Dec 17.

DOI:10.1007/s10953-016-0555-x
PMID:28163341
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5241352/
Abstract

An experiment based on electrochemical reactions and pH monitoring was performed in which nickel ions were gradually formed by oxidation of a nickel metal electrode in a solution of boric acid. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel-boron complexation. A triborate nickel complex was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70 °C. The calculated enthalpy and entropy at 25 °C for the formation of the complex from boric acid and Ni ions are respectively equal to (65.6 ± 3.1) kJ·mol and (0.5 ± 11.1) J·K·mol. The results of this study suggest that complexation of nickel ions by borates can significantly enhance the solubility of nickel metal and nickel oxide depending on the concentration of boric acid and pH. First principles calculations were investigated and tend to show that the complex is thermodynamically stable and the nickel cation in solution should interact more strongly with the [Formula: see text] than with boric acid.

摘要

进行了一项基于电化学反应和pH监测的实验，其中镍金属电极在硼酸溶液中氧化逐渐形成镍离子。基于实验结果和水相形态建模，pH的变化表明存在显著的镍-硼络合作用。当存在多硼酸盐时，在高硼酸浓度下推测形成了一种三硼酸镍络合物，并在25、50和70°C下测定了平衡常数。在25°C下，由硼酸和镍离子形成络合物的计算焓和熵分别等于(65.6±3.1)kJ·mol和(0.5±11.1)J·K·mol。本研究结果表明，硼酸盐对镍离子的络合作用可根据硼酸浓度和pH显著提高镍金属和氧化镍的溶解度。研究了第一性原理计算，结果倾向于表明该络合物在热力学上是稳定的，溶液中的镍阳离子与[化学式：见原文]的相互作用应比与硼酸的相互作用更强。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/01246810d75b/10953_2016_555_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/73656fef0a5f/10953_2016_555_Fig1_HTML.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/0651a8764a9a/10953_2016_555_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/9901fac55b7f/10953_2016_555_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/736eec31fb97/10953_2016_555_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/01246810d75b/10953_2016_555_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/73656fef0a5f/10953_2016_555_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/ca2980237007/10953_2016_555_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/eb58a87c5756/10953_2016_555_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/0651a8764a9a/10953_2016_555_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/9901fac55b7f/10953_2016_555_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/736eec31fb97/10953_2016_555_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bb50/5241352/01246810d75b/10953_2016_555_Fig7_HTML.jpg

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