Speciation and organic phase structure in nitric acid extraction with trioctylamine

Understanding chemical speciation and intermolecular interactions in multicomponent liquids is essential to understanding their phase behavior, which underpins chemical separation processes including solvent extraction. Here we report on the extraction of nitric acid from its aqueous solutions into organic solutions of trioctylamine (TOA) in toluene, investigated with spectroscopic, X-ray scattering, and computational tools to understand the molecular speciation in the organic phase and its relationship with the nanoscale structure of the organic phase. Trends in acid and water extraction clearly show two and three regimes, respectively, but the speciation of HNO3, water, and amine in these regimes is not apparent. 1H-NMR of the organic phase shows that there are at least two distinct acidic protons in the organic phase while ATR-FTIR results show that the organic phase with excess acid extraction is a mixture of trioctylammonium-nitrate ion pairs (TOAH.NO3), and undissociated HNO3 molecules. Comparison with DFT-computed IR spectra show that the chain-like configurations of TOAH.NO3.HNO3.H2O are favored over TOAH.NO3.H2O.HNO3, i.e., direct interaction between the two HNO3 molecules is more favored compared to a water-mediated interaction. SAXS of the organic phases were modeled as sums of Ornstein-Zernike (O-Z) scattering and a prepeak feature in the higher Q region, corresponding to features from density fluctuations and extractant packing, respectively. The extraction of undissociated HNO3 by the ion pairs leads to an increased X-ray scattering contrast in the organic phase without any significant change in the O-Z correlation length. These results show that the organic phase nanostructure is more sensitive to the concentration of TOAH.NO3 and is relatively unaffected by excess acid extraction. These findings will enable a molecular understanding of the mechanisms behind metal extractions from acidic media with basic extractants.