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Journal Articles

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

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

Analytical Sciences, 39(9), p.1575 - 1583, 2023/09

https://doi.org/10.1007/s44211-023-00376-8

Times Cited Count：0 Percentile：0(Chemistry, Analytical)

Extraction of Rh from HCl can be performed by NTAamide(C6) (hexahexyl-nitrilotriacetamide) and other related compounds into n-dodecane. We use ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh behave as anion in hydrochloric acid and the tertiary nitrogen atom in extractant may be protonated to produce the quaternary amine in acidic condition. From the present work, the maximum distribution ratio of Rh(III) is 16. The D(Rh) values are changeable during preparation of the aqueous solutions because different Rh-Cl-H $_{2}$ O complexes are formed in HCl media and show the slow exchange rate between Cl and H $_{2}$ O. Using the UV spectrum, Rh-chloride solution having the peak of spectrum at 504 nm can be extracted effectively, where RhCl $_{4}$ (H $_{2}$ O) and RhCl(HO) exist mainly from DFT calculation. Stoichiometry of one-one complex of Rh and NTAamide is obtained from slope analysis, and 85 mM of concentrated Rh ion can be extracted.

Oral presentation

Extraction of Rh from concentrated HCl by diamide extractant having protonated amino N atom

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

no journal, ,

We obtained relatively high D(Rh) of approximate 1 by iminodioctamide (IDOA) having tertially amino N atom from concentrated HCl solution. The reason is that IDOA is protonated, behaves as cationic extractant, and extracts anionic RhCl $_6^{3-}$ through ion-pair extraction. Up to now, there is less information on Rh(III) extraction, we investigate the behavior of Rh extraction and discuss with theoretical studies.

Oral presentation

Reaction modeling of ion-pairing extraction of various meatal ions with NTAamide(C6) extractant from hydrochloric acid solution

Kinoshita, Ryoma; Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*

no journal, ,

Many metal ions are stable in hydrochloric acid solutions as anionic species; diamidic-extractants containing tertiary amino nitrogen atom, such as NTAamide (hexaalkyl-nitrilotriacetamide), are normally protonated in acidic solutions and become cationic extractants. In this study, the ion-pair extraction reactions of metal chloride anions with cationic NTAamide(C6) extractant were investigated. In addition, we attempted to predict the distribution ratio by combining the stability constants of metal chloride complexes and DFT calculations, and compared the results with experimental values.