LiX(X=Cl,Br,I)在乙醇、异丙醇及三氟乙醇中的电导率实验研究
|
摘要
为了研发逆电渗析法闭式热–电转换系统匹配工作溶液,选取强电解质LiCl、LiBr和LiI为溶质,低气化潜热的乙醇、异丙醇及三氟乙醇为溶剂,利用所建立的电导率测试装置进行实验研究。通过数据拟合(修正高斯振幅方程法)和溶液热力学、电化学理论分析,获得溶质、溶剂、温度以及添加剂对溶液电导率的影响规律及作用机理。结果表明:当溶质相同时,LiX–乙醇体系电导率最大,LiX–异丙醇体系最小;而当溶剂相同时,LiI–溶剂体系电导率最大,LiCl-溶剂体系最小。实验还发现提升溶液温度或加入强极性添加剂(H_2O、二甲基乙酰胺)均可强化溶液电导性,而添加N-甲基吡咯烷酮和二氯甲烷对体系电导率影响非常微弱。
In order to develop suitable working fluids for a closed type heat-power conversion system with reverse electrodialysis method, three strong electrolytes(LiCl, LiBr and LiI) were selected as the solutes and three solvents with low latent heat of vaporization(ethanol, isopropanol and 2,2,2–trifluoroethanol) were used as solvents to study the conductivities of solutions by using a conductivity measurement apparatus. Effects of solute, solvent, temperature, and additives on solution conductivity were studied by experimental data correlation(modified GuassAmp equation) and solution thermodynamical/electrochemical analysis. The results show that the Li X–ethanol and Li X–isopropanol systems have the maximal and minimum conductivities,respectively. The Li I–solvent system possesses the maximal conductivity and the Li Cl–solvent system has the minimum conductivity when using the same solvent. Conductivities were also found to be improved by increasing the solution temperature or adding additives with strong polarity(H_2O, N,N-dimethylacetamide). However, there is no obvious effect when adding either dichloromethane or N,N,-dimethylpropionamide into the solutions.
In order to develop suitable working fluids for a closed type heat-power conversion system with reverse electrodialysis method, three strong electrolytes(LiCl, LiBr and LiI) were selected as the solutes and three solvents with low latent heat of vaporization(ethanol, isopropanol and 2,2,2–trifluoroethanol) were used as solvents to study the conductivities of solutions by using a conductivity measurement apparatus. Effects of solute, solvent, temperature, and additives on solution conductivity were studied by experimental data correlation(modified GuassAmp equation) and solution thermodynamical/electrochemical analysis. The results show that the Li X–ethanol and Li X–isopropanol systems have the maximal and minimum conductivities,respectively. The Li I–solvent system possesses the maximal conductivity and the Li Cl–solvent system has the minimum conductivity when using the same solvent. Conductivities were also found to be improved by increasing the solution temperature or adding additives with strong polarity(H_2O, N,N-dimethylacetamide). However, there is no obvious effect when adding either dichloromethane or N,N,-dimethylpropionamide into the solutions.
引文
[1]姚志敏,薛冰,盛遵荣,等.开式高温吸附热泵生成蒸汽系统的耐久性能研究[J].高校化学工程学报,2016,30(4):791-799.YAO Z M,XU B,SHENG Z R,et al.Cyclic durability of a high temperature open adsorption heat pump for steam generation[J].Journal of Chemical Engineering of Chinese Universities,2016,30(4):791-799.
[2]CIPOLLINA A,MICALE G.Sustainable energy from salinity gradients[M].Duxford:Woodhead Publishing,2016.
[3]徐士鸣,吴曦,吴德兵.一种新型低品位热能发电方法及装置:CN,105 261 808 A[P].2017-07-11.XU S M,WU X,WU D B.A novel low-grade heat energy generation method and device:CN,105 261 808 A[P].2017-07-11.
[4]吴曦,徐士鸣,吴德兵,等.逆电渗析法热-电转换系统循环工质匹配准则[J].化工学报,2016,67(S2):326-332.WU X,XU S M,WU D B,et al.Methodology of assessing working mediums availability for a novel heat-power conversion system with reverse electrodialysis technology[J].CIESC Journal,2016,67(S2):326-332.
[5]姜波,王利生,李弥异.NaBr,NaCl和KBr在几种有机溶剂中活度系数的测定[J].化学工业与工程,2011,28(3):25-32.JIANG B,WANG L S,LI M Y.Activity coefficient measurement of NaBr,NaCl and KBr in selected organic solvents[J].Chemical Industry and Engineering,2011,28(3):25-32.
[6]郭磊,刘亚文,刘春丽,等.NaCl、NaBr、NaI在DMA水溶液中的电导率[J].全面腐蚀控制,2013,27(12):63-66.GUO L,LIU Y W,LIU C L,et al.Study of the conductivity of NaCl,NaBr and NaI in DMA aqueous solution[J].Total Corrosion Control,2013,27(12):63-66.
[7]MAEDA K,MAENO K,FUKUI K,et al.Electrical conductivity of aqueous ethanol solutions containing ammonium salts under high pressure at 298 K[J].Journal of Chemical and Engineering Data,2013,58(2):264-270.
[8]王卫东.LiCl在异丙醇中热力学性质的研究[J].盐湖研究,2007(3):28-32.WANG W D.Study on thermodynamic properties of LiCl in 2-propanol solvent[J].Journal of Salt Lake Research,2007(3):28-32.
[9]REHMAN H,ANSARI M S.Density,Viscosity,and electrical conductivity measurements on the ternary system H2O+C2H5OH+LiCl over the entire ranges of solvent composition and LiCl solubility from(-5 to+50)℃[J].Joural of Chemical and Engineering Data,2008,53(9):2072-2088.
[10]WU X,XU S M,WU D B,et al.Electric conductivity and electric convertibility of potassium acetate in water,ethanol,2,2,2-trifluoroethanol,2-propanol and their binary blends[J].Chinese Journal of Chemical Engineering.2018,26(12):2581-2591.
[11]HAMANN C H,HAMNETT A,VIELSTICH W.Electrochemistry[M].Weinheim:Wiley-VCH,2007.
[12]李以圭,陆九芳.电解质溶液理论[M].北京:清华大学出版社,2005.LI Y G,LU J F.The theory of electrolyte solutions[M].Beijing:Tsinghua University Press,2005.
[13]刘丹,毛丽莉,王海增.六水氯化镁在醇类溶剂中溶解度的测定与关联[J].高校化学工程学报,2018,32(1):24-29.LIU D,MAO L L,WANG H Z.Determination and correlation of magnesium chloride hexahydrate solubility in alcohol solvents[J].Journal of Chemical Engineering of Chinese Universities,2018,32(1):24-29.
[14]靳朝辉,张凤宝,张国亮.电导法确定离子交换树脂中反离子的解离度[J].高校化学工程学报,2004,18(6):671-675.JIN Z H,ZHANG F B,ZHANG G L.Determining the dissociation degree of counter ions in ion-exchange resin by conductivity measurement[J].Journal of Chemical Engineering of Chinese Universities,2004,18(6):671-675.
[15]CHMIELEWSKA A,ZURADA M,KLIMASZEWSKI K,et al.Dielectric properties of methanol mixtures with ethanol,isomers of propanol,and butanol[J].Journal of Chemical and Engineering Data,2009,54(3),801-806.
[16]KRUMGALE B S.Ion-sovent interaction and ionic association in ethanol solutions[J].Journal of Solution Chemistry,1982,11(4):283-292.
[17]STOCKTON G W,MARTIN J S.Proton nuclear magnetic resonance study of diamagnetic cation association with hydroxylic substates.Interpretation of ionic molal shifts in methanol and water[J].Journal of the American Chemical Society,1972,94(20):6921-6930.
[18]凌锦龙,余成芸,姜垚,等.甲酰胺+乙醇/丙醇/异丙醇/乙酸乙酯二元混合物的体积及黏度性质[J].高校化学工程学报,2017,31(6):1267-1275.LING J L,YU C Y,JIANG Y,et al.Volumetric and viscous properties for binary mixtures of formamide and ethanol/propanol/isopropanol/ethyl acetate[J].Journal of Chemical Engineering of Chinese Universities,2017,31(6):1267-1275.
[19]黄子卿.电解质溶液理论导论[M].北京:科学出版社,1983.HUANG Z Q.Introduction to the theory of electrolyte solution[M].Beijing:Science China Press,1983.
[20]HAYNES W M.CRC Handbook of Chemistry and Physics 2014-2015[M].Florida:CRC Press,2014.
[21]刘成伦,徐龙君,鲜学福.水溶液中盐的浓度与其电导率的关系研究[J].中国环境监测,1999,15(4):21-24.LIU C L,XU L J,XIAN X F.Study on the relationship between concentration of salt solution and its conductivity[J].Environmental Monitoring in China,1999,15(4):21-24.
[2]CIPOLLINA A,MICALE G.Sustainable energy from salinity gradients[M].Duxford:Woodhead Publishing,2016.
[3]徐士鸣,吴曦,吴德兵.一种新型低品位热能发电方法及装置:CN,105 261 808 A[P].2017-07-11.XU S M,WU X,WU D B.A novel low-grade heat energy generation method and device:CN,105 261 808 A[P].2017-07-11.
[4]吴曦,徐士鸣,吴德兵,等.逆电渗析法热-电转换系统循环工质匹配准则[J].化工学报,2016,67(S2):326-332.WU X,XU S M,WU D B,et al.Methodology of assessing working mediums availability for a novel heat-power conversion system with reverse electrodialysis technology[J].CIESC Journal,2016,67(S2):326-332.
[5]姜波,王利生,李弥异.NaBr,NaCl和KBr在几种有机溶剂中活度系数的测定[J].化学工业与工程,2011,28(3):25-32.JIANG B,WANG L S,LI M Y.Activity coefficient measurement of NaBr,NaCl and KBr in selected organic solvents[J].Chemical Industry and Engineering,2011,28(3):25-32.
[6]郭磊,刘亚文,刘春丽,等.NaCl、NaBr、NaI在DMA水溶液中的电导率[J].全面腐蚀控制,2013,27(12):63-66.GUO L,LIU Y W,LIU C L,et al.Study of the conductivity of NaCl,NaBr and NaI in DMA aqueous solution[J].Total Corrosion Control,2013,27(12):63-66.
[7]MAEDA K,MAENO K,FUKUI K,et al.Electrical conductivity of aqueous ethanol solutions containing ammonium salts under high pressure at 298 K[J].Journal of Chemical and Engineering Data,2013,58(2):264-270.
[8]王卫东.LiCl在异丙醇中热力学性质的研究[J].盐湖研究,2007(3):28-32.WANG W D.Study on thermodynamic properties of LiCl in 2-propanol solvent[J].Journal of Salt Lake Research,2007(3):28-32.
[9]REHMAN H,ANSARI M S.Density,Viscosity,and electrical conductivity measurements on the ternary system H2O+C2H5OH+LiCl over the entire ranges of solvent composition and LiCl solubility from(-5 to+50)℃[J].Joural of Chemical and Engineering Data,2008,53(9):2072-2088.
[10]WU X,XU S M,WU D B,et al.Electric conductivity and electric convertibility of potassium acetate in water,ethanol,2,2,2-trifluoroethanol,2-propanol and their binary blends[J].Chinese Journal of Chemical Engineering.2018,26(12):2581-2591.
[11]HAMANN C H,HAMNETT A,VIELSTICH W.Electrochemistry[M].Weinheim:Wiley-VCH,2007.
[12]李以圭,陆九芳.电解质溶液理论[M].北京:清华大学出版社,2005.LI Y G,LU J F.The theory of electrolyte solutions[M].Beijing:Tsinghua University Press,2005.
[13]刘丹,毛丽莉,王海增.六水氯化镁在醇类溶剂中溶解度的测定与关联[J].高校化学工程学报,2018,32(1):24-29.LIU D,MAO L L,WANG H Z.Determination and correlation of magnesium chloride hexahydrate solubility in alcohol solvents[J].Journal of Chemical Engineering of Chinese Universities,2018,32(1):24-29.
[14]靳朝辉,张凤宝,张国亮.电导法确定离子交换树脂中反离子的解离度[J].高校化学工程学报,2004,18(6):671-675.JIN Z H,ZHANG F B,ZHANG G L.Determining the dissociation degree of counter ions in ion-exchange resin by conductivity measurement[J].Journal of Chemical Engineering of Chinese Universities,2004,18(6):671-675.
[15]CHMIELEWSKA A,ZURADA M,KLIMASZEWSKI K,et al.Dielectric properties of methanol mixtures with ethanol,isomers of propanol,and butanol[J].Journal of Chemical and Engineering Data,2009,54(3),801-806.
[16]KRUMGALE B S.Ion-sovent interaction and ionic association in ethanol solutions[J].Journal of Solution Chemistry,1982,11(4):283-292.
[17]STOCKTON G W,MARTIN J S.Proton nuclear magnetic resonance study of diamagnetic cation association with hydroxylic substates.Interpretation of ionic molal shifts in methanol and water[J].Journal of the American Chemical Society,1972,94(20):6921-6930.
[18]凌锦龙,余成芸,姜垚,等.甲酰胺+乙醇/丙醇/异丙醇/乙酸乙酯二元混合物的体积及黏度性质[J].高校化学工程学报,2017,31(6):1267-1275.LING J L,YU C Y,JIANG Y,et al.Volumetric and viscous properties for binary mixtures of formamide and ethanol/propanol/isopropanol/ethyl acetate[J].Journal of Chemical Engineering of Chinese Universities,2017,31(6):1267-1275.
[19]黄子卿.电解质溶液理论导论[M].北京:科学出版社,1983.HUANG Z Q.Introduction to the theory of electrolyte solution[M].Beijing:Science China Press,1983.
[20]HAYNES W M.CRC Handbook of Chemistry and Physics 2014-2015[M].Florida:CRC Press,2014.
[21]刘成伦,徐龙君,鲜学福.水溶液中盐的浓度与其电导率的关系研究[J].中国环境监测,1999,15(4):21-24.LIU C L,XU L J,XIAN X F.Study on the relationship between concentration of salt solution and its conductivity[J].Environmental Monitoring in China,1999,15(4):21-24.