Abbott Andrew P, Al-Barzinjy Azeez A, Abbott Paul D, Frisch Gero, Harris Robert C, Hartley Jennifer, Ryder Karl S
Chemistry Department, University of Leicester, Leicester, UK LE1 7RH.
Phys Chem Chem Phys. 2014 May 21;16(19):9047-55. doi: 10.1039/c4cp00057a.
The electrodeposition of chromium is a technologically vital process, which is principally carried out using aqueous chromic acid. In the current study, it is shown that eutectic mixtures of urea and hydrated chromium(III) chloride provide a liquid which reduces the toxicological issues associated with the current aqueous Cr(VI) electroplating solution. Using EXAFS, mass spectrometry and UV-Vis spectroscopy, it is shown that chromium is present predominantly as a cationic species. Conductivities are higher than for most comparable ionic liquids. It is shown that the electrodeposition of chromium is electrochemically reversible, with a current efficiency much higher than in aqueous electrolytes. Surface tension and density measurements indicate that hole theory is a valid model to describe transport properties in these liquids. Bulk Cr deposits are not macrocrystalline but they are generally crack-free. The deposits have a hardness of 600 ± 10 Vickers and, as such, are comparable to deposits from aqueous systems.
铬的电沉积是一个技术上至关重要的过程,主要使用铬酸水溶液进行。在当前的研究中,结果表明尿素与水合氯化铬(III)的共晶混合物提供了一种液体,该液体减少了与当前六价铬电镀水溶液相关的毒理学问题。使用扩展X射线吸收精细结构光谱(EXAFS)、质谱和紫外可见光谱表明,铬主要以阳离子形式存在。其电导率高于大多数类似的离子液体。结果表明,铬的电沉积是电化学可逆的,电流效率远高于水性电解质中的电流效率。表面张力和密度测量表明,空穴理论是描述这些液体传输性质的有效模型。块状铬沉积物不是大晶体,但通常无裂纹。这些沉积物的维氏硬度为600±10,因此与来自水性体系的沉积物相当。