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Issue 14, 2019
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Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems

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Abstract

The temperature responsive solubility of ionic liquids with ‘bulky’ polar regions, such as tributyltetradecyl phosphonium chloride ([P44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P44414]Cl/H2O was characterised in the range 273 K to 373 K and was found to significantly deviate from the corresponding aqueous biphasic system with NaCl. A new transferable coarse grained MARTINI model for [P44414]Cl was developed, validated and applied to provide a molecular understanding of the experimental results. It is shown that the presence of large aliphatic moieties around the central phosphorus atoms of [P44414]Cl results in a decrease in the electrostatic repulsion between the cationic moieties, leading the [P44414]+ cation to present a behaviour conventionally associated with non-ionic surfactants. This difference in behaviour between HCl and NaCl was shown to result from the greater interaction of the hydronium cation with the micelle surface, thereby enhancing the [P44414]Cl aggregation.

Graphical abstract: Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems

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Publication details

The article was received on 19 Dec 2018, accepted on 11 Mar 2019 and first published on 12 Mar 2019


Article type: Paper
DOI: 10.1039/C8CP07750A
Phys. Chem. Chem. Phys., 2019,21, 7462-7473

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    Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems

    N. Schaeffer, G. Pérez-Sánchez, H. Passos, J. R. B. Gomes, N. Papaiconomou and J. A. P. Coutinho, Phys. Chem. Chem. Phys., 2019, 21, 7462
    DOI: 10.1039/C8CP07750A

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