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用质子化的NTA酰胺(C6)及类似化合物从盐酸中萃取Rh(III)并通过紫外光谱和密度泛函理论计算理解萃取平衡

Extraction of Rh(III) from hydrochloric acid by protonated NTAamide(C6) and analogous compounds and understanding of extraction equilibria by using UV spectroscopy and DFT calculations.

作者信息

Sasaki Yuji, Kaneko Masashi, Ban Yasutoshi, Kinoshita Ryoma, Matsumiya Masahiko, Shinoku Kota, Shiroishi Hidenobu

机构信息

Nuclear Science and Engineer Center, Japan Atomic Energy Agency, 2-4 Shirakata, Tokai, Ibaraki, 319-1195, Japan.

Department of Chemistry, Chemical Engineering and Life Science, Yokohama National University, 79-2 Tokiwadai, Hodogaya-Ku, Yokohama, 240-8501, Japan.

出版信息

Anal Sci. 2023 Sep;39(9):1575-1583. doi: 10.1007/s44211-023-00376-8. Epub 2023 Jun 8.

Abstract

Extraction of Rh from hydrochloric acid is conducted using NTAamide(C6) (N,N,N´,N´,N´´,N´´-hexahexyl-nitrilotriacetamide) and other related compounds. We use the ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh ions exist as Rh(Cl)(HO) (n ≤ 5) and the tertiary nitrogen atom in an extractant are protonated to produce a quaternary amine in acidic condition. The D(Rh) values are changeable because the Rh-Cl-HO complex forms from + 3 to - 2 valency. Rh-chloride ion with a peak of spectrum at 504 nm can be extracted effectively, where RhCl(HO) and RhCl(HO) exist from Density functional theory calculation and UV spectrum. The maximum distribution ratio (D) of Rh(III) is 16, and 85 mM Rh can be extracted from 1 M HCl dissolving 96 mM, due to less third phase formation. Approximate 80% of Rh can be stripped by the water-soluble reagents having the activities of neutralization and solvation. The figure for the Graphical Index saved in the JPEG, PNG or TIFF format at 300 dpi should be pasted with the size adjusted to the frame below (5 cm long and 8 cm wide).

摘要

使用NTA酰胺(C6)(N,N,N′,N′,N″,N″-六己基次氮基三乙酰胺)及其他相关化合物从盐酸中萃取铑。我们采用离子对萃取法来萃取铑的氯化物阴离子物种和质子化萃取剂。铑离子以Rh(Cl)(HO) (n ≤ 5)形式存在,在酸性条件下,萃取剂中的叔氮原子被质子化形成季铵。由于Rh-Cl-HO络合物的化合价从 +3变为 -2,D(Rh)值是可变的。在504 nm处有光谱峰的铑氯化物离子可被有效萃取,密度泛函理论计算和紫外光谱表明此时存在RhCl(HO) 和RhCl(HO) 。铑(III)的最大分配比(D)为16,由于三相形成较少,可从溶解96 mM的1 M HCl中萃取85 mM铑。约80%的铑可用具有中和和溶剂化活性的水溶性试剂反萃取。以300 dpi保存为JPEG、PNG或TIFF格式的图形索引图应粘贴,尺寸调整为下方框架大小(长5 cm,宽8 cm)。

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