Martins Mónia A R, Neves Catarina M S S, Kurnia Kiki A, Carvalho Pedro J, Rocha Marisa A A, Santos Luís M N B F, Pinho Simão P, Freire Mara G
CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal; Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands.
Fluid Phase Equilib. 2016 Jan 15;407:188-196. doi: 10.1016/j.fluid.2015.05.023.
In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [C C im][NTf] (with = 1-8 and 10) and asymmetric [C Cim][NTf] (with = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.
为了评估阳离子的烷基侧链长度和对称性对水饱和离子液体(ILs)热物理性质的影响,在大气压下以及(298.15至363.15)K温度范围内,对含有两个系列双(三氟甲基磺酰)亚胺基化合物的体系测量了密度和粘度随温度的变化:对称的[CₙCₘim][NTf₂](n = 1 - 8和10)和不对称的[CₙCₘim][NTf₂](n = 2 - 5、7、9和11)离子液体。对于水饱和离子液体,密度随烷基侧链长度的增加而降低,而粘度随脂肪族链的大小增加。基于水饱和离子液体的密度进一步合理估算了每种离子液体中的饱和水溶解度,进一步证实了对于所研究的离子液体,离子液体与水的体积混合性质遵循近理想行为。水饱和对称离子液体的密度和粘度通常低于其不对称对应物。从实验数据中,还估算了等压热膨胀系数和能垒。发现水饱和离子液体和纯离子液体之间能垒值的差异与每种离子液体中的水含量密切相关,这支持了在水存在下离子液体粘度的降低与能垒的降低直接相关。