Pitzer方程应用于离子液体[C_nmim][H_2PO_4](n=3,4,5,6)溶解焓研究（英文）
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摘要
在298.15 K下,利用等温环境溶解反应热量计,测定了离子液体[C_nmim][H_2PO_4](n=3,4,5,6)(1-烷基-3-甲基咪唑磷酸盐)在水中不同浓度的摩尔溶解热(?sol Hm),根据Pitzer电解质溶液理论计算得到了标准摩尔溶解焓(?solH_m~0)和Pitzer焓参数:β_(MX)~((0)L)、β_(MX)~((1)L)和C~(ΦL),并计算了表观相对摩尔焓。通过推导讨论,得到了离子液体[C_nmim][H_2PO_4](n=3,4,5,6)同系物每摩尔亚甲基对标准摩尔溶解焓的贡献。
Ionic liquids(ILs) have become one of the most rapidly growing new research areas of ionic liquid and have attracted considerable attention from industry and the academic community since they are derived from natural ions and are heralded a new "natural ILs" or "bio-ILs". ILs can be expected to find application in all of the biological, medical, and pharmaceutical sciences. However, the fundamental physical properties of an IL are extremely important in determining if a particular IL is appropriate for a given application. Recently, there is a developing trend in the literature towards estimation of thermodynamic properties for IL's, which is to be commended because it provides valuable insight into the origins of the behaviour of ILs. Acidic ionic liquids have been applied indesulfuration process widely. Phosphoric acid IL is one kind of acidic ILs, which are also stable and economical efficiency. ILs [C_nmim][H_2PO_4](n = 3, 4, 5, 6; 1-alkyl-3-methylimidazolium phosphonate) were synthesized and characterized. An on-line solution-reaction isoperibol calorimeter was constructed. It consists of a water thermostat, a 200 mL pyrex-glass plated silver Dewar, a 4 mL glass sample cell, a calibration heater, a glass-sheathed thermistor probe, an amplifier, a circuit used as an A/D converter and a personal computer for data acquisition and processing. The performance and accuracy of the calorimetric system was tested by measuring the molar enthalpy of solution of KCl in water and THAM [tris-(hydroxymethyl) aminomethane] in 0.1 mol·dm-3 HCl(aq) at 298.15 K. The molar enthalpies of solutions of the ILs [C_nmim][H_2PO_4](n = 3, 4, 5, 6) at various molalities in water were measured by using a solution-reaction isoperibol calorimeter at 298.15 K respectively. According to the Pitzer's electrolyte solution theory, the molar standard enthalpy of the solution of [Cnmim][HO_2PO_4](n = 3, 4, 5, 6),?solH_m~0, and Pitzer's parameters,β_(MX)~((0)L)、β_(MX)~((1)L), and C~(ΦL), were calculated and deduced. The standard molar enthalpies of solution of [C_nmim][H_2PO_4](n = 3, 4, 5, 6) decreases with increasing alkyl chain length. When we make a plot with the standard molar enthalpy of solution vs carbon number in alkyl chains of the ionic liquid, a straight line was obtained with a correlation coefficient 0.99 and a slope of 1.54. The mean contribution per methylene(―CH2―) group to the standard molar enthalpies of the solution of [C_nmim][H_2PO_4](n = 3, 4, 5, 6) was then obtained, which will give reliable estimation of other IL properties.
Ionic liquids(ILs) have become one of the most rapidly growing new research areas of ionic liquid and have attracted considerable attention from industry and the academic community since they are derived from natural ions and are heralded a new "natural ILs" or "bio-ILs". ILs can be expected to find application in all of the biological, medical, and pharmaceutical sciences. However, the fundamental physical properties of an IL are extremely important in determining if a particular IL is appropriate for a given application. Recently, there is a developing trend in the literature towards estimation of thermodynamic properties for IL's, which is to be commended because it provides valuable insight into the origins of the behaviour of ILs. Acidic ionic liquids have been applied indesulfuration process widely. Phosphoric acid IL is one kind of acidic ILs, which are also stable and economical efficiency. ILs [C_nmim][H_2PO_4](n = 3, 4, 5, 6; 1-alkyl-3-methylimidazolium phosphonate) were synthesized and characterized. An on-line solution-reaction isoperibol calorimeter was constructed. It consists of a water thermostat, a 200 mL pyrex-glass plated silver Dewar, a 4 mL glass sample cell, a calibration heater, a glass-sheathed thermistor probe, an amplifier, a circuit used as an A/D converter and a personal computer for data acquisition and processing. The performance and accuracy of the calorimetric system was tested by measuring the molar enthalpy of solution of KCl in water and THAM [tris-(hydroxymethyl) aminomethane] in 0.1 mol·dm-3 HCl(aq) at 298.15 K. The molar enthalpies of solutions of the ILs [C_nmim][H_2PO_4](n = 3, 4, 5, 6) at various molalities in water were measured by using a solution-reaction isoperibol calorimeter at 298.15 K respectively. According to the Pitzer's electrolyte solution theory, the molar standard enthalpy of the solution of [Cnmim][HO_2PO_4](n = 3, 4, 5, 6),?solH_m~0, and Pitzer's parameters,β_(MX)~((0)L)、β_(MX)~((1)L), and C~(ΦL), were calculated and deduced. The standard molar enthalpies of solution of [C_nmim][H_2PO_4](n = 3, 4, 5, 6) decreases with increasing alkyl chain length. When we make a plot with the standard molar enthalpy of solution vs carbon number in alkyl chains of the ionic liquid, a straight line was obtained with a correlation coefficient 0.99 and a slope of 1.54. The mean contribution per methylene(―CH2―) group to the standard molar enthalpies of the solution of [C_nmim][H_2PO_4](n = 3, 4, 5, 6) was then obtained, which will give reliable estimation of other IL properties.
引文
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(3)Archer,D.G.;Widegren,J.A.;Kirklin,D.R.;Magee,J.W.J.Chem.Eng.2005,50,1484.doi:10.1021/je050136i
(4)Wang,J.;Pei,Y.;Zhao,Y.;Hu,Z.Green Chem.2005,7,196.doi:10.1039/B415842C
(5)Tong,J.;Qu,Y.;Jing,L.;Liu,L.;Liu,C.Acta Phys.-Chim.Sin.2018,34(2),194.[佟静,屈晔,井立强,刘璐,刘春辉.物理化学学报,2018,34(2),194.]doi:10.3866/PKU.WHXB201707262
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(7)Yang,J.Z.;Lu,X.M.;Gui,J.S.;Xu,W.G.Green Chem.2004,6,541.doi:10.1039/B412286K
(8)Guan,W.;Yang,J.Z.;Li,L.;Wang,H.;Zhang,Q.G.Fluid Phase Equilib.2006,239,161.doi:10.1016/j.fluid.2005.11.015
(9)Yang,J.Z.;Zhang,Z.H.;Fang,D.W.;Li,J.G.;Guan,W.;Tong,J.Fluid Phase Equilib.2006,247,80.doi:10.1016/j.fluid.2006.06.016
(10)Guan,W.;Wang,H.;Li,L.;Zhang,Q.G.;Yang,J.Z.Thermochim.Acta 2005,437,196.doi:10.1016/j.tca.2005.04.032
(11)Di,Y.Y.;Qu,S.S.;Liu,Y.;Wen,D.C.;Tang,H.K.;Li,L.W.Thermochim.Acta 2002,387,115.doi:10.1016/S0040-6031(01)00831-0
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(13)Fang,D.W.;Wang,H.;Yue,S.;Xiong,Y.;Yang,J.Z.;Zang,S.L.J.Phys.Chem.B 2012,116,2513.doi:10.1021/jp2111132
(14)Rychly,R.;Pekarek,V.T.J.Chem.Thermodyn.1977,9,391.doi:10.1016/0021-9614(77)90060-X
(15)Montgomery,R.L.;Melaugh,R.A.;Lau,C.C.;Meier,G.H.;Chan,H.H.;Rossini,F.D.J.Chem.Thermodyn.1977,9,915.doi:10.1016/0021-9614(77)90214-2
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(22)Tong,J.;Chen,T.F.;Zhang,D.;Wang,L.F.;Tong,J.;Yang,J.Z.Acta Phys.-Chim.Sin.2016,32,1161.[佟静,陈腾飞,张朵,王林富,佟健,杨家振.物理化学学报,2016,32,1161.]doi:10.3866/PKU.WHXB201602232
(23)Chen,F.F.;Dong,Y.;Sang,X.Y.;Zhou,Y.;Tao,D.J.Acta Phys.-Chim.Sin.2016,32,605.[陈凤凤,董艳,桑晓艳,周言,陶瑞健.物理化学学报,2016,32,605.]doi:10.3866/PKU.WHXB201512241
(24)Zheng,L.;Fan,B.H.;Bu,X.X.;Pan,Y,;Dong,J.X.;Guan,W.Acta Phys.-Chim.Sin.2015,31,2036.[郑玲,范本汉,卜晓雪,潘懿,董家新,关伟.物理化学学报,2015,31,2036.]doi:10.3866/PKU.WHXB201509111
(25)Li,C.P.;Li,Z.;Zou,B.X.;Liu,Q.S.;Liu,X.X.Acta Phys.-Chim.Sin.2013,29,2157.[李长平,李琢,邹本雪,刘青山,刘晓霞.物理化学学报,2013,29,2157.]doi:10.3866/PKU.WHXB201307293