authors |
Schaeffer, N; Perez-Sanchez, G; Passos, H; Gomes, JRB; Papaiconomou, N; Coutinho, JAP |
nationality |
International |
journal |
PHYSICAL CHEMISTRY CHEMICAL PHYSICS |
keywords |
COARSE-GRAINED MODEL; IONIC-LIQUID; WATER; SURFACTANTS; COACERVATION; TRANSITION; EXTRACTION; MIXTURES; MICELLES; BEHAVIOR |
abstract |
The temperature responsive solubility of ionic liquids with bulky' polar regions, such as tributyltetradecyl phosphonium chloride ([P-44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P-44414]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 [P-44414]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 [P-44414]Cl results in a decrease in the electrostatic repulsion between the cationic moieties, leading the [P-44414](+) 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 [P-44414]Cl aggregation. |
publisher |
ROYAL SOC CHEMISTRY |
issn |
1463-9076 |
isbn |
1463-9084 |
year published |
2019 |
volume |
21 |
issue |
14 |
beginning page |
7462 |
ending page |
7473 |
digital object identifier (doi) |
10.1039/c8cp07750a |
web of science category |
Chemistry, Physical; Physics, Atomic, Molecular & Chemical |
subject category |
Chemistry; Physics |
unique article identifier |
WOS:000464580600021
|