resumo
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.
palavras-chave
COARSE-GRAINED MODEL; IONIC-LIQUID; WATER; SURFACTANTS; COACERVATION; TRANSITION; EXTRACTION; MIXTURES; MICELLES; BEHAVIOR
categoria
Chemistry; Physics
autores
Schaeffer, N; Perez-Sanchez, G; Passos, H; Gomes, JRB; Papaiconomou, N; Coutinho, JAP
nossos autores
Germán Pérez-Sánchez
Investigador Júnior
Helena Isabel Sousa Passos
Investigador Júnior
José R. B. Gomes
Investigador Principal
Nicolas Schaeffer
Investigador AuxiliarGrupos
G4 - Materiais Renováveis e Economia Circular
G6 - Materiais Virtuais e Inteligência Artificial
agradecimentos
This work was part of BATRE-ARES project (ERA-MIN/0001/2015) funded by ADEME and FCT. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019, financed by national funds through the FCT/MCTES. GPS acknowledges the research contract under the project CENTRO-01-0145-FEDER-000005: SusPhotoSolutions: Solucoes Fotovoltaicas Sustentaveis.