Excess Enthalpies of Mixing of Piperidinium Ionic Liquids with Short-Chain Alcohols: Measurements and PC-SAFT Modeling

Abstract

This work is a continuation of our systematic study on thermodynamic properties of 1-n-alkyl-1-methylpiperdinium bis[(trifluoromethyl)sulfonyl]imides homologous series of ionic liquids ([CnC1Pip][NTf2]). Excess enthalpies of mixing (H(E)) of four binary systems containing two ionic liquids, namely [C4C1Pip][NTf2] and [C6C1Pip][NTf2], and two short-chain alcohols, namely ethanol and 1-propanol, were measured by isothermal titration calorimetry. Alcohol-to-ionic liquid and ionic liquid-to-alcohol titration experiments were carried out at temperature T = 298.15 K and atmospheric pressure. The experimental data were modeled in terms of perturbed-chain statistical associating fluid theory (PC-SAFT). Wolbach-Sandler combining rules were adopted in order to account for ionic liquid-alcohol cross-association. The model was applied in a conventional manner (i.e., without any binary corrections) as well as in a novel predictive mode developed previously by our group [Paduszyński, K.; Domańska, U. J. Phys. Chem. B 2012, 116, 5002-5018; Domańska et al. J. Phys. Chem. B 2012, 116, 8191-8200]. The latter approach employs temperature-dependent binary correction fitted to experimental limiting activity coefficient of alcohol in ionic liquid.

Solid–liquid phase equilibria in binary mixtures of functionalized ionic liquids with sugar alcohols: New experimental data and modelling

“…Among all the version of SAFT proposed in literature over the last decade, the perturbed-chain SAFT (PC-SAFT) proposed by Gross and Sadowski [33,34] is surely the most popular and successful one. A vast amount of attention has been recently devoted to model ILs and systems formed by them by using PC-SAFT [22,[35][36][37][38].…”

“…Most of PC-SAFT pure-fluid parameters used in modelling presented in this contribution were taken from our previous papers [16,37] and thus we will not discuss them in detail herein. Only in the case of meso-erythritol, the parameters were determined in this work.…”

Excess molar enthalpies of binary and ternary liquid mixtures

“…Such information is useful for good design of industrial processes and to test the predictive capability of theoretical models/theories of liquid mixtures [3][4][5]. For the development of model/theories and also to obtain a better understanding for the use of ionic liquids as alternative to conventional organic solvents in chemical and separation processes, measurements of thermodynamic properties of liquid mixtures containing ionic liquids are required [4,6].…”

“…Such information is useful for good design of industrial processes and to test the predictive capability of theoretical models/theories of liquid mixtures [3][4][5]. For the development of model/theories and also to obtain a better understanding for the use of ionic liquids as alternative to conventional organic solvents in chemical and separation processes, measurements of thermodynamic properties of liquid mixtures containing ionic liquids are required [4,6]. In earlier publication [7][8][9][10][11], excess molar volumes and excess isentropic compressibilities for binary and ternary mixtures containing 1-ethyl-3-methylimidazolium tetrafluoroborate as one of the component have been reported.…”

“…The excess molar enthalpies data have been used to test the applicability of Graph and Prigogine-Flory-Patterson theories. 4 ] (Fluka, 0.98 GC) was used without further purification. The water content in ionic liquid was regularly checked using Karl Fischer titration [15] and found to be less than 328 ppm.…”