Speciation and Organic Phase Structure in Nitric Acid Extraction with Trioctylamine

Nayak, Srikanth; Servis, Michael J.; Combs, Derrick; Szeliga, Krystian; Seifert, Soenke

doi:10.1021/acs.jpcb.3c08268

Title: Speciation and Organic Phase Structure in Nitric Acid Extraction with Trioctylamine

Journal Article · 19 March 2024 · Journal of Physical Chemistry. B

DOI: https://doi.org/10.1021/acs.jpcb.3c08268 · OSTI ID:2497722

^[1];

^[1]; Combs, Derrick ^[1]; Szeliga, Krystian ^[1]; Seifert, Soenke ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)

Understanding chemical speciation and intermolecular interactions in multicomponent liquids is essential to understanding their phase and chemical equilibria, which underpin 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 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, indicating different stoichiometric relationships, but 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 (TOAHNO₃), and undissociated HNO₃ molecules. Comparison with DFT-computed IR spectra show that the chain-like configurations of TOAHNO₃HNO₃H₂O are favored over TOAHNO₃H₂OHNO₃, i.e., direct interaction between the nitrate and 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 that corresponds to extractant packing. 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 correlation length. These results show that the organic phase nanostructure is more sensitive to the concentration of TOAHNO₃ and is relatively unaffected by excess acid extraction. Finally, these findings will enable a molecular understanding of the mechanisms behind metal extraction from acidic media with basic extractants.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2497722

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 13 Vol. 128; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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