金属深共融溶剂的物化性质研究
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摘要
合成了四种成分不同的新型三组分金属深共融溶剂:四丁基氯化铵:聚乙二醇-400:三氯化铁(TBAC:PEG:Fe Cl3)、四丁基氯化铵:聚乙二醇-400:氯化锌(TBAC:PEG:Zn Cl2)、四丁基氯化铵:聚乙二醇-400:氯化镍(TBAC:PEG:Ni Cl2)、四丁基氯化铵:聚乙二醇-400:氯化铜(TBAC:PEG:Cu Cl2)。四丁基氯化铵、聚乙二醇-400和金属盐的摩尔比为4:1:0.05。在293.15 338.15 K温度范围内,以5K为一间隔,测量了深共融溶剂的密度、电导率、动力粘度及折光率,结果表明温度对其物理性质影响很大。通过经验方程得到了深共融溶剂的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数。从电导率和密度计算出了深共融溶剂的摩尔电导率。利用Vogel-Fulcher-Tamman(VFT)和Arrhenius方程,将测量的动力粘度和电导率对温度进行拟合,得到了动力粘度和电导率随温度变化的方程。通过Walden规则,建立了粘度与摩尔电导率之间的联系。此研究对金属深共融溶剂的应用具有重要的指导意义。
Four metal deep eutectic solvents(MDESs), namely TBAC:PEG:Fe Cl3、TBAC:PEG:Zn Cl2、TBAC:PEG: Ni Cl2、TBAC:PEG:Cu Cl2 were synthesized in which the molar ratio of TBAC, PEG and metal salt was 4: 1: 0.05. The density, electrical conductivity, dynamic viscosity and refractive index of the four MDESs were measured within temperature range from 293.15 K to 338.15 K at an interval of 5 K. The results showed that the temperature had a great influence on the physical properties of MDESs. The thermal expansion coefficient, molecular volume, standard molar entropy and lattice energy were calculated by empirical equation. The molar conductivity was determined from the data of density and conductivity. The temperature dependence of electrical conductivities and dynamic viscosities for the DESs were fitted by Vogel–Fulcher–Tamman(VFT) and Arrhenius equation. The relationship of the molar conductivity and viscosity was established by the Walden rule. The present study will provide a guide for further applications of MDESs.
Four metal deep eutectic solvents(MDESs), namely TBAC:PEG:Fe Cl3、TBAC:PEG:Zn Cl2、TBAC:PEG: Ni Cl2、TBAC:PEG:Cu Cl2 were synthesized in which the molar ratio of TBAC, PEG and metal salt was 4: 1: 0.05. The density, electrical conductivity, dynamic viscosity and refractive index of the four MDESs were measured within temperature range from 293.15 K to 338.15 K at an interval of 5 K. The results showed that the temperature had a great influence on the physical properties of MDESs. The thermal expansion coefficient, molecular volume, standard molar entropy and lattice energy were calculated by empirical equation. The molar conductivity was determined from the data of density and conductivity. The temperature dependence of electrical conductivities and dynamic viscosities for the DESs were fitted by Vogel–Fulcher–Tamman(VFT) and Arrhenius equation. The relationship of the molar conductivity and viscosity was established by the Walden rule. The present study will provide a guide for further applications of MDESs.
引文
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[12]Schreiner C,Zugmann S,Hartl R,et al.Fractional Walden rule for ionic liquids:examples from recent measurements and a critique of the so-called ideal KCl line for the Walden plot[J].Journal of Chemical&Engineering Data,2010,55(5):1784-1788.
[2]Paiva A,Craveiro R,Aroso I,et al.Natural deep eutectic solvents-solvents for the 21st century[J].Acs Sustainable Chemistry&Engineering,2014,2(5):1063-1071.
[3]王爱玲,郑学良,赵壮志,等.深共融溶剂在有机合成中的应用[J].化学进展,2014,26(5):784-795.
[4]Mohammed H C,Farouq S M,Inas M A,et al.Prospects of applying ionic liquids and deep eutectic solvents for renewable energy storage by means of redox flow batteries[J].Renewable&Sustainable Energy Reviews,2014,30(2):254-270.
[5]侯玉翠,么聪菲,吴卫泽.低共熔溶剂:一种应用在混合物分离过程中的绿色溶剂[J].物理化学学报,2018,34(8):873-885.
[6]Li C P,Zhang J J,Li Z,et al.Extraction desulfurization of fuels with‘metal ions’based deep eutectic solvents(MDESs)[J].Green Chemistry,2016,18(13):3789-3795.
[7]Liu Q S,Li P P,Welz-Biermann U,et al.Density,dynamic viscosity,and electrical conductivity of pyridinium-based hydrophobic ionic liquids[J].The Journal of Chemical Thermodynamics,2013,66(66):88-94.
[8]Tong J,Hong M,Chen Y,et al.The surface tension,density and refractive index of amino acid ionic liquids:[C3mim][Gly]and[C4mim][Gly][J].The Journal of Chemical Thermodynamics,2012,54:352-357.
[9]Jacquemin J,Husson P,Padua A A H,et al.Density and viscosity of several pure and water-saturated ionic liquids[J].Green Chemistry,2006,8(2):172-180.
[10]Glasser L.Lattice and phase transition thermodynamics of ionic liquids[J].Thermochimica acta,2004,421(1-2):87-93.
[11]Vila J,Gines P,Pico J M,et al.Temperature dependence of the electrical conductivity in EMIM-based ionic liquids:evidence of Vogel–Tamman–Fulcher behavior[J].Fluid Phase Equilibria,2006,242(2):141-146.
[12]Schreiner C,Zugmann S,Hartl R,et al.Fractional Walden rule for ionic liquids:examples from recent measurements and a critique of the so-called ideal KCl line for the Walden plot[J].Journal of Chemical&Engineering Data,2010,55(5):1784-1788.