The pervasive impact of critical fluctuations in liquid–liquid extraction organic phases

Servis, Michael J.; Nayak, Srikanth; Seifert, Soenke

doi:10.1063/5.0074995

Title: The pervasive impact of critical fluctuations in liquid–liquid extraction organic phases

Journal Article · 27 December 2021 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0074995 · OSTI ID:1878617

^[1]; Nayak, Srikanth ^[1]; Seifert, Soenke ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)

Liquid-liquid extraction is an essential chemical separation technique where polar solutes are extracted from an aqueous phase into a nonpolar organic solvent by amphiphilic extractant molecules. A fundamental limitation to the efficiency of this important technology is third phase formation, wherein the organic phase splits upon sufficient loading of polar solutes. The nanoscale drivers of phase splitting are challenging to understand in the complex hierarchically structured organic phases. In this study, we demonstrate that the organic phase structure and phase behavior are fundamentally connected in a way than can be understood with critical phenomena theory. For a series of binary mixtures of trialkyl phosphate extractants with linear alkane diluents, we combine small angle x-ray scattering and molecular dynamics simulations to demonstrate how the organic phase mesostructure over a wide range of compositions is dominated by critical concentration fluctuations associated with the critical point of the third phase formation phase transition. These findings reconcile many longstanding inconsistencies in the literature where small angle scattering features, also consistent with such critical fluctuations, were interpreted as reverse micellar-like particles. Altogether, this study shows how the organic phase mesostructure and phase behavior are intrinsically linked, deepening our understanding of both and providing a new framework for using molecular structure and thermodynamic variables to control mesostructure and phase behavior in liquid-liquid extraction.

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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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1878617

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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