4.5 Article

Molar enthalpy of mixing and refractive indices of choline chloride-based deep eutectic solvents with water

Journal

JOURNAL OF CHEMICAL THERMODYNAMICS
Volume 105, Issue -, Pages 30-36

Publisher

ACADEMIC PRESS LTD- ELSEVIER SCIENCE LTD
DOI: 10.1016/j.jct.2016.10.002

Keywords

Deep eutectic solvents; Aqueous solutions; Molar enthalpies of mixing; Refractive indices; NRTL model

Funding

  1. Chinese MOST 973 project [2013CB733501]
  2. National Natural Foundation of China [21136004, 21476106]
  3. priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)

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The molar enthalpies of mixing were measured for binary systems of choline chloride-based deep eutectic solvents (glycerol, ethylene glycol and malonic acid) with water at 298.15 K and 308.15 K, and atmospheric pressure with an isothermal calorimeter. Refractive indices were also measured at 303.15 K and atmospheric pressure. The binary mixtures of {chcl/glycerol (1:2) + water, chcl/ethylene glycol (1:2) + water} showed exothermic behaviour over the entire range of composition, while the binary mixture of {chclimalonic acid (1:1) + water} showed endothermic behaviour at first and then changed to be exothermic with the increasing content of chcl/malonic acid (1:1). Experimental refractive indices were fitted with the Redlich-Kister equation, and experimental molar enthalpies of mixing were correlated with the Redlich-Kister equation and the non-random two-liquid (NRTL) model. The NRTL model with the fitted parameters was used to predict the vapour pressures of these three mixtures. For mixtures of {chcl/glycerol (1:2) + water} and {chcl/ethylene glycol (1:2) + water}, the predicted vapour pressures agreed well with the experimental results from the literature. While for mixture of {chclimalonic acid (1:1) + water}, the predicted vapour pressures showed deviation at the high concentration of chcl/malonic acid (1:1), and this was probably because of the complex molecular interaction between chcl/malonic acid (1:1) and water. (C) 2016 Elsevier Ltd.

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