Surface tensions of ionic liquids: Non-regular trend along the number of cyano groups


Ionic liquids (ILs) with cyano-functionalized anions are a set of fluids that are still poorly characterized despite their remarkably low viscosities and potential applications. Aiming at providing a comprehensive study on the influence of the number of -CN groups through the surface tension and surface organization of ILs, the surface tensions of imidazolium-based ILs with cyano-functionalized anions were determined at atmospheric pressure and in the (298.15-343.15) K temperature range. The ILs investigated are based on 1-alkyl-3-methylimidazolium cations (alkyl = ethyl, butyl and hexyl) combined with the [SCN](-), [N(CN)(2)](-), [C(CN)(3)](-) and [B(CN)(4)](-) anions. Although the well-known trend regarding the surface tension decrease with the increase of the size of the aliphatic moiety at the cation was observed, the order obtained for the anions is more intricate. For a common cation and at a given temperature, the surface tension decreases according to: [N(CN)(2)](-) > [SCN](-) > [C(CN)(3)](-) > [B(CN)(4)](-). Therefore, the surface tension of this homologous series does not decrease with the increase of the number of -CN groups at the anion as has been previously shown by studies performed with a more limited matrix of ILs. A maximum in the surface tension and critical temperature was observed for [N(CN)2]-based ILs. Furthermore, a minimum in the surface entropy, indicative of a highly structured surface, was found for the same class of ILs. All these evidences seem to be a result of stronger hydrogen-bonding interactions occurring in [N(CN)(2)]-based ILs, when compared with the remaining CN-based counterparts, and as sustained by cation-anion interaction energies derived from the Conductor Like Screening Model for Real Solvents (COSMO-RS). (C) 2015 Elsevier B.V. All rights reserved.




Thermodynamics; Chemistry; Engineering


Almeida, HFD; Carvalho, PJ; Kurnia, KA; Lopes-da-Silva, JA; Coutinho, JAP; Freire, MG

nossos autores


The authors acknowledge Merck for kindly supplying some ionic liquid samples used in this work. This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID /CTM /50011/2013), financed by national funds through the FCT/MEC and co-financed by FEDER under the PT2020 Partnership Agreement. H.F.D.A. and P.J.C. also acknowledge FCT for their PhD and post-doctoral grants SFRH/BD/88369/2012 and SFRH/BPD/82264/2011, respectively.The research leading to results reported in this work has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement no 337753.

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