An insight into third-phase formation in the extraction of thorium nitrate by tris(2-methylbutyl) phosphate and tri-<i>n</i>-alkyl phosphates

Sarkar, Sudip Kumar; Suresh, A.; Sivaraman, N.; Aswal, Vinod K.

doi:10.1080/01496395.2018.1521832

Cited by 19 publications

(2 citation statements)

References 39 publications

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“…45 The resulting three-phase system is incompatible with processing equipment, resulting in a limit to the per-contact loading capacity of the organic phase. While organic phase structure has long been linked to its phase behavior, 20,39,43,[46][47][48][49][50][51][52][53][54][55][56][57][58] we recently proposed that organic phase structure over a wide range of binary extractant/diluent mixtures is consistent with critical fluctuations originating from the critical point associated with the third phase formation phase transition. 59,60 That is, organic phase structuring is consistent with what would be expected from the concentration fluctuations induced by the critical point associated with the liquid-liquid phase transition.…”

Section: Introductionmentioning

confidence: 99%

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Bonnett

Sheyfer

Wimalasiri

et al. 2023

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Bonnett

Sheyfer

Wimalasiri

et al. 2023

Phys. Chem. Chem. Phys.

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“…While organic phase structure has long been linked to its phase behavior, 20,39,43,[46][47][48][49][50][51][52][53][54][55][56][57][58] we recently proposed that organic phase structure over a wide range of binary extractant/diluent mixtures is consistent with critical fluctuations originating from the critical point associated with the third phase formation phase transition. 59,60 This could explain certain limitations to common microemulsion descriptions of LLE systems, such as the presence of structure in the organic phase even in the absence of extracted polar solutes needed to induce the formation of water-in-oil aggregates.…”

Section: Introductionmentioning

confidence: 99%

Critical Fluctuations in Liquid-Liquid Extraction Organic Phases Controlled by Extractant and Diluent Molecular Structure

Bonnett

Sheyfer

Wimalasiri

et al. 2023

Preprint

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Extractant aggregation in liquid-liquid extraction organic phases impacts extraction energetics and is related to the deleterious efficiency-limiting liquid-liquid phase transition known as third phase formation. Using small angle x-ray scattering, we find that structural heterogeneities across a wide range of compositions in binary mixtures of malonamide extractants and alkane diluents are well described by Ornstein-Zernike scattering. This suggests that structure in these simplified organic phases originates from the critical point associated with the liquid-liquid phase transition. To confirm this, we measure the temperature dependence of the organic phase structure, finding critical exponents consistent with the 3D Ising model. Molecular dynamics simulations were also consistent with this mechanism for extractant aggregation. Due to the absence of water or any other polar solutes required to form reverse-micellar-like nanostructures, these fluctuations are inherent to the binary extractant/diluent mixture. Our previous work found pseudobinary critical fluctuations near the critical point for more complex organic phases with extracted polar solutes, including water, acid and metal ions. Taken together, these results suggest this mechanism for explaining organic phase aggregation may dominate over a wide range of conditions encountered in practical liquid-liquid extraction organic phases. We also show how the molecular structure of the extractant and diluent modulate these critical concentration fluctuations by shifting the critical temperature: critical fluctuations are suppressed by increasing extractant alkyl tail lengths or decreasing diluent alkyl chain lengths. This is consistent with how extractant and diluent molecular structure are known to impact metal and acid loading capacity in many-component LLE organic phases, suggesting phase behavior of practical systems may be effectively studied in simplified organic phases. Overall, the explicit connection between molecular structure, aggregation and phase behavior demonstrated here will enable the design of more efficient separations processes.

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Studies on the aggregation behaviour of radiolytically degraded tetra(2-ethyhexyl)diglycolamide in n-dodecane medium during the extraction of trivalent metal ions

Swami

Venkatesan

Selvan

2020

J Radioanal Nucl Chem

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An insight into third-phase formation in the extraction of thorium nitrate by tris(2-methylbutyl) phosphate and tri-n-alkyl phosphates

Cited by 19 publications

References 39 publications

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Critical Fluctuations in Liquid-Liquid Extraction Organic Phases Controlled by Extractant and Diluent Molecular Structure

Studies on the aggregation behaviour of radiolytically degraded tetra(2-ethyhexyl)diglycolamide in n-dodecane medium during the extraction of trivalent metal ions

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