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Yang, Fan, et al. Chemical Engineering Science 282 (2023): 119314.
Tributylmethylammonium acetate ([N4441][Ac]) represents a structurally versatile acetate-based ionic liquid with promising applicability in azeotrope separation. Recent vapor-liquid equilibrium (VLE) studies demonstrate its effectiveness in disrupting the methyl ethyl ketone (MEK)-methanol (MeOH) azeotropic system, enabling selective enhancement of MEK relative volatility when incorporated at appropriate mole fractions.
Although [N4441][Ac] exhibits comparatively weaker separation efficiency than tetraethylammonium acetate and 1-hexyl-2,3-dimethylimidazolium acetate, it still successfully eliminates the azeotropic point through strong, preferential interactions with MeOH. Microscopic analyses-including COSMO-RS, interaction energy calculations, and FT-IR spectroscopy-reveal that the acetate anion forms dominant hydrogen-bonding interactions with MeOH, shifting equilibrium toward MeOH-IL association and allowing MEK to vaporize as the light component.
Thermodynamically consistent VLE measurements confirm that incorporation of [N4441][Ac] modifies liquid-phase nonideality sufficiently for azeotrope breaking, and NRTL-based correlations show excellent agreement with experimental data. The mechanistic interpretation is reinforced by IGMH and AIM topological analyses, which emphasize the critical role of localized hydrogen-bond networks between MeOH and the acetate anion.
Overall, tributylmethylammonium acetate provides a viable extraction and separation medium for MEK-MeOH systems. Its capacity to selectively bind MeOH enables controlled azeotrope elimination, offering a tunable and theoretically predictable approach to difficult separations in fine chemical processing and solvent purification applications.
