Ion-pairing extraction and their reaction modeling of anionic M-Cl species with cationic NTAamide(C6) extractant and comparison with density functional theory calculations

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

Hydrometallurgy, 222, p.106159_1 - 106159_12, 2023/10

https://doi.org/10.1016/j.hydromet.2023.106159

Solvent extraction is conducted using a total of 20 metals revealing high stability constants with Cl and hexahexyl-nitrilotriacetamide (NTAamide(C6)) extractant. The metals used here may behave as anions at high Cl concentrations, and NTAamide(C6), which contains a tertiary N atom, is protonated under acidic conditions. Most of the metal ions in this study display higher distribution ratios (D(M)) from HCl than those from HNO, and exhibit 1:1 stoichiometries with NTAamide. Following the experimental results, the association constants and distribution coefficients of the group 12 elements are calculated via ion-pair extraction modeling using density functional theory calculations, and the simulations of D yield calculated values with the same trend as that of the measured values.