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Thermodynamics and activity coefficients at infinite dilution for organic solutes in the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide

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Abstract The activity coefficients at infinite dilution, γ 13 ∞ , for 46 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, aldehyde, acetonitrile, pyridine and… Click to show full abstract

Abstract The activity coefficients at infinite dilution, γ 13 ∞ , for 46 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, aldehyde, acetonitrile, pyridine and 1-nitropropane in the ionic liquid (IL) 1-butyl-1-methylpyrrolidynium dicyanamide, [BMPYR][DCA] were determined by gas-liquid chromatography at five temperatures in range of (313.15–373.15) K at pressure, p = 101 kPa. The thermodynamic functions at infinite dilution as partial molar excess Gibbs free energy, Δ G 1 E, ∞ , enthalpy Δ H 1 E, ∞ , and entropy term T ref Δ S 1 E , ∞ and the gas-liquid partition coefficients, K L at infinite dilution were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The values of selectivity and capacity for few separation problems as n-heptane/benzene, n-heptane/thiophene, n-heptane/1-heptyne, and ethylbenzene/styrene at T = 323.15 K were calculated from γ 13 ∞ and compared to literature values for [DCA]-based ionic liquids and [BMPYR]-based ILs. In comparison with the former measured [BMPYR][TCM], or [BMPYR][SCN] ILs, the [DCA]-based IL presents high selectivities for the separation of aromatic hydrocarbons from aliphatic hydrocarbons, and especially for the extraction of thiophene, or pyridine from n-heptane with slightly lower capacity than those for [BMPYR][TCM], or [BMPYR][SCN]. New data shows that [BMPYR][DCA] IL may be proposed as an alternative solvent for the separation of aliphatic from aromatic hydrocarbons.

Keywords: bmpyr; infinite dilution; liquid; thermodynamics; dilution; coefficients infinite

Journal Title: Fluid Phase Equilibria
Year Published: 2018

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