扩散系数总结 参考内容

1.离子液体在其他溶剂中的扩散系数7. 五种1-乙基-3-甲基咪唑型离子液体在水溶液中无限稀释，温度范围303.2-323.2K下的扩散系数 Taylor dispersion method9. 甲醇/BMIMPF6体系中，25下不同BMIMPF6浓度的相互扩散系数42. C4C1imBF4, C4C1imN(OTf)2， C4C1imPF6 三种离子液体在甲醇，CH2Cl2中的扩散系数2.其他物质在离子液体中的扩散系数2.1 具有氧化还原活性的分子在离子液体中的扩散系数5. 水在离子液体BMIMTFSI 中的反常扩散6. 三碘化物在混合离子液体中的扩散系数 MPII,EMIC,EMIDCA,EMIBF4,EMINTf214. CO,DPA,DPCP在不同离子液体中的扩散系数17.CO2在离子液体中的扩散系数41.气体在BMIMPF6中的扩散系数和离子液体的自扩散系数20. 气体在五种鏻型离子液体中的扩散系数21. 25下三碘化物在两种离子液体混合物中的扩散系数43 1,1,1,2-tetrafluoroethane (R-134a)在七种离子液体中的扩散系数3.离子液体的自扩散系数3.1 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4) 和LiBF4混合 Li BF4六种不同浓度下 离子的自扩散系数3. EMIBF4，EMITFSI，BPBF4，BPTFSI中阳离子和阴离子的自扩散系数4. 咪唑型离子液体分子动力学模拟 自扩散8. BMIMPF6 （自制和购买两种）在不同温度下的自扩散系数10. 胍基型离子液体的自扩散研究模型11. bmimPF6的分子动力学研究12. N-methyl-N-propyl-pyrrolidinium bis-(trifluoromethanesulfonyl)imide (PYR13TFSI)和LiTFSI混合体系中不同温度和组成下离子的自扩散系数13. (1 x)(BMITFSI), xLiTFSI x0.415. 质子传递的离子液体的自扩散系数16. DEME-TFSA 和 DEME-TFSA-Li 的自扩散系数18 用pulsed field gradient NMR测离子液体和离子液体混合物的传递性质41.气体在BMIMPF6中的扩散系数和离子液体的自扩散系数25. 离子液体不同侧链长度对扩散的影响1. 离子液体在其他溶剂中的扩散系数2. 其他物质在离子液体中的扩散系数2.1 具有氧化还原活性的分子在离子液体中的扩散系数离子液体1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)amide BMIMTFSIbutyltriethylammonium bis(trifluoromethylsulfonyl)amide) Et3BuNTFSIN-methyl-N-butylpyrrolidinium bis(trifluoromethyl)sulfonyl-amide PyrTFSI被测的氧化还原对Dodzi Zigah, Jalal Ghilane, Corinne Lagrost, and Philippe Hapiot .Variations of diffusion coefficients of redox active molecules in room temperature ionic liquids upon electron transfer. J. Phys. Chem. B, 2008, 112 (47), 14952-149583. 离子液体的自扩散系数3.1 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4) 和LiBF4混合 Li BF4六种不同浓度下 离子的自扩散系数Fig.1 Arrhenius plots of the self-diffusion coefficients for (a) Li, (b) BF4, and (c) emim.在emimBF4中，尽管emim分子大小比BF4大，但是 emim扩散比BF4稍微快一点，说明 BF4不是以单个离子扩散的。在LiemimBF4二元体系中， emim扩散最快，然后是BF4，Li最慢。最小的离子尺寸扩散最慢。Hayamizu K, Aihara Y, Nakagawa H, Nukuda T, Price WS. Ionic conduction and ion diffusion in binary room-temperature ionic liquids composed of emimBF4 and LiBF4. JOURNAL OF PHYSICAL CHEMISTRY B,108(2004):19527-195323. EMIBF4，EMITFSI，BPBF4，BPTFSI中阳离子和阴离子的自扩散系数1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4)1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI)1-butylpyridinium tetrafluoroborate (BPBF4)1-butylpyridinium bis(trifluoromethylsulfonyl)imide (BPTFSI)N.A.Stolwijk ,Sh.Obeidi. Combined analysis of self-diffusion, conductivity, and viscosity data on room temperature ionic liquids. Electrochimica Acta,54(2009),1645-16535. 咪唑型离子液体分子动力学模拟 自扩散1- alkyl-3-methylimidazolium amim(+) (alkyl=methyl, ethyl, propyl, and butyl) family with PF6-, NO3-, and Cl- counterions模拟结果Table II. Simulated cation and anion diffusion coefficients Di (in 1011m2 s1) and cationic transference numbers of ionic liquids at different temperatures from MSD plots. The melting points for ionic liquids from literature are also reported.IL (amimX)T(K)D+Dt+Tmp(K)dmimCl4232.701.850.593398admimNO33833.942.950.572357admimPF63763.832.040.652362bemimCl3772.431.530.614360aemimNO33795.033.860.566312aemimPF63703.662.050.641333apmimCl3841.551.380.529333apmimNO33774.123.430.546pmimPF63733.361.850.645313abmimCl3800.680.640.515340abmimNO33792.592.290.531bmimPF63742.702.010.573279aaFrom Refs. 4,66.bFrom Dzyuba and Bartsch, Ref. 67.Table III. The diffusion coefficient (in 1011m2 s1) for the cations and anions from the slope of MSD plots (with values in parentheses) and integration of the VACFs (with the standard deviations in parentheses) and the cationic transference number t+ for 12 ionic liquids at T=400K.IL (amimX)MSDVACFD+ ()D ()t+D+Dt+dmimCl1.46 (0.56)0.96 (0.45)0.602.9(0.7)2.7(0.7)0.52dmimNO34.72 (0.78)3.91 (0.75)0.557.2(0.6)6.0(0.8)0.54dmimPF63.69 (0.67)2.31 (0.60)0.626.6(1.1)4.4(1.1)0.60emimCl3.78 (0.74)2.59 (0.62)0.595.7(1.1)5.6(1.3)0.50emimNO36.74 (0.82)5.61 (0.78)0.559.3(1.2)8.4(1.3)0.53emimPF65.74 (0.75)3.04 (0.61)0.657.8(1.4)4.8(1.6)0.62pmimCl2.61 (0.74)2.20 (0.68)0.544.9(0.8)5.5(0.9)0.47pmimNO34.97 (0.74)4.47 (0.70)0.538.2(0.7)8.3(0.9)0.50pmimPF64.71 (0.74)2.79 (0.63)0.635.0(1.0)4.3(1.0)0.54bmimCl0.72 (0.39)0.75 (0.37)0.492.5(1.0)3.2(1.2)0.44bmimNO34.70 (0.78)4.47 (0.78)0.515.4(1.1)4.9(1.2)0.53bmimPF64.56 (0.77)3.15 (0.68)0.595.8(1.0)4.8(1.0)0.55First citation in article Table IV. Cation and anion diffusion coefficients Di (in 1011m2 s1) for various ionic liquids from the present simulations at 400 K and the recent literature. In all references, the simulated diffusion coefficients are calculated from the Einstein relation except for Refs. 40,41 which used integration of the VACF(t).RTILD+DOur workSimulationsExpt.Our workSimulationsExpt.dmimCl1.461.09,a 11,b 43c0.960.88,a 8,b 38cdmimPF63.692.6,a 4.7,d 12b2.311.3,a 3.2,d 6bemimCl3.7817.0,a 34,e 3.6f2.599.4,a 19.9,e 1.4femimNO36.743.1,g 9.6,h 5.1,i14.9j5.611.65,g 5.8,h 4.8,i15.5jemimPF65.742.3,i 5.6,k 0.13a3.041.05,i 3.54,k 0.13abmimCl0.7222.3,a 1.4l0.7511.4,a 3.1lbmimNO34.705.3,m 23.8n4.474.5,m 27.5nbmimPF64.565.6,a 14.1,o 24.4,p 3.5q20.91r3.152.8,a 6.2,o 20.5,p 2.9q17.86raReference 37.bReference 18, united atom force field.cReference 18, explicit atom force field.dReference 30.eReference 41, force field of Urahata and Ribeiro, Ref. 35.fReference 40, 404 K, force field of Shim et al., Ref. 42.gReference 41, force field of Shim et al., Ref. 42.hReference 32.iReference 34, using a nonpolarizable force field.jReference 34, using a polarizable force field.kReference 45, force field of Hanke et al., Ref. 18.lReference 58.mReference 59, 363 K.nReference 59, 423 K.oReference 68.pReference 64, refined force field of Bhargava and Balasubramanian, Ref. 64.qReference 64, force field of Canongia Lopes et al., Ref. 20.rReference 27(a), experimental values from the VFT equation.扩散系数的变化趋势：对于相同阴离子，emim+pmim+bmim+ ，对于相同阳离子，NO3PF6Cl。dmim+ 因为结构对称并且在液相中排列得好（its symmetric structure and good packing in the liquid phase），扩散系数相对小。决定自扩散大小的主要因素是离子液体阴离子的几何形状，其他因素包括离子大小和阴离子电荷移位。M. H. Kowsari,Saman Alavi,Mahmud Ashrafizaadeh,and Bijan Najafi. Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient. J. Chem. Phys. 129 (2008) 5. 水在离子液体BMIMTFSI 中的反常扩散BMIMTFSI + water 体系中 BMIM, TFSI, 和 H2O的自扩散系数butyl-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide (BMIMTFSI)Table 1: Self-Diffusion Coefficients of BMIM, TFSI, and H2Owatermolar fractionDcationm2/s(1H)Danionm2/s(19F)Dwaterm2/s(1H) 0.03(=W0) 2.310-11 2.010-11 3.510-11 0.12 2.610-11 2.310-11 13.410-11 0.22 2.710-11 2.510-11 20.610-11 0.3 2.910-11 2.610-11 26.810-11The variation of the self-diffusion coefficients versus water amount indicates that water does not induce a significant increase of the ion pair dissociation but disturbs the RTIL cohesion. Moreover, whereas very similar evolutions are observed for anion and cation (increase of 30%), in the same range of water molar fraction the increase of Dwater is 25 times greater. It indicates that miscibility of water is not complete at the microscale and that the BMIMTFSI + water system shows a partial segregation between BMIMTFSI + some water molecules phase and water + some BMIMTFSI ions phase. o Top of Page o Introduction o Experimental Methods o Results and Discussion o ConclusionAnne-Laure Rollet, Patrice Porion, Michel Vaultier, Isabelle Billard, Michael Deschamps, Catherine Bessada, and Laurence Jouvensal. Anomalous Diffusion of Water in BMIMTFSI Room-Temperature Ionic Liquid. J. Phys. Chem. B, 2007, 111 (41), 11888118916. 三碘化物在混合离子液体中的扩散系数 MPII,EMIC,EMIDCA,EMIBF4,EMINTf21-Methyl-3-propylimidazolium iodide (MPII)1-Ethyl-3-methylimidazolium chloride (EMIC)1-Ethyl-3-methylimidazolium dicyanamide (EMIDCA)1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4)1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMINTf2)The determined triiodide diffusion coefficients for the three systems with 0.05 mol L_1 iodine and varying MPII concentration in an IL based electrolyte are in a range from 1.2210-7 cm2 s-1 for MPII up to 8.3010-7 cm2 s_1 for 91 mol% EMIDCA, 3.6110_7 cm2 s_1 for 90mol% EMIBF4 and 4.0710_7cm2 s_1 for 90mol% EMINTf2.Phillipp Wachter, Christian Schreiner, Markus Zistler, Dirk Gerhard, Peter Wasserscheid, Heiner J. Gores. A microelectrode study of triiodide diffusion coefficients in mixtures of room temperature ionic liquids, useful for dye-sensitised solar cells. Microchim Acta (2008) 160: 1251337. 五种1-乙基-3-甲基咪唑型离子液体在水溶液中无限稀释，温度范围303.2-323.2K下的扩散系数 Taylor dispersion method EmimC2N3 (dicyanamide),EmimBF4 (tetrafluoroborate), EmimC2H5SO4 (ethylsulfate), EmimCF3SO3 (trifluoromethanesulfonate), EmimMDEGSO4 (2-(2-methoxyethoxy) ethylsulfate)Chun-LiWong, Allan N. Soriano, Meng-Hui Li. Diffusion coefficients and molar conductivities in aqueous solutions of 1-ethyl-3-methylimidazolium-based ionic liquids. Fluid Phase Equilibria 271 (2008) 43528. BMIMPF6 （自制和购买两种）在不同温度下的自扩散系数合成和购买的离子液体两个样品的自扩散系数有很大差异，说明很少量的杂质可以在很大程度上影响离子液体中的传递现象。Tatsuya Umecky, Mitsuhiro Kanakubo, Yutaka Ikushima. Self-diffusion coefficients of 1-butyl-3-methylimidazolium hexafluorophosphate with pulsed-field gradient spin-echo NMR technique. Fluid Phase Equilibria 228229 (2005) 3293339. 甲醇/BMIMPF6体系中，25下不同BMIMPF6浓度的相互扩散系数实验结果说明即使很少量的离子液体也能很大地干扰混合物的物质传递特性。J.Richter, A.Lerchter, N.Grober. Digital image holography for diffusion measurements in melten salts and ionic liquids-method and first results. Journal of Molecular Liquids 103104 (2003) 35937010. 胍基型离子液体的自扩散研究模型离子液体类型：The GILs simulated in this work were constituted by pairing guanidinium-based cations with nitrate (-N) and perchlorate anions (-C). Four cations were used for simulated GILs: two acyclic cations, namely pentamethylpropylguanidinium (AP) and pentamethylbutylguanidinium (AB), as well as two cyclic cations, tetramethylguanidinium (CM) and trimethylbutylguanidinium (CB).Table 2. Self-Diffusion Coefficients of Cations and Anions at Different Temperatures, Pre-Exponential Factors, and Diffusive Activation Energies aGILD300KD400KD450KD500KD550KD600Kln DEaAP-Ncat1.3(2.9)9824552984614.30.332.61.3an2.0(2.9)145384759126213.90.332.41.4AB-Ncat1.1(3.6)9828160591613.9 0.633.92.5an1.7(4.3)150461906148313.40.634.22.5AP-Ccat0.5(1.8)5716334862414.00.335.91.2an0.5(2.3)7320247586213.4 0.237.30.9AB-Ccat0.4(1.6)6119744076213.30.537.92.1an0.5(1.2)7523655291113.20.537.82.3CM-Ncat0.4(0.5)176821237413.10.638.72.5an0.4(0.7)176619639513.10.338.61.3CM-Ncat0.174612325112.51.043.24.0an0.184312929712.10.644.52.3CB-Ncat0.6(1.2)218319841413.60.436.51.6an0.9(1.4)278019438914.2 0.333.81.0CM-Ccat0.3(1.3)155416333613.30.338.71.0an0.3(1.6)164820436713.00.939.63.4CB-Ccat0.3(1.5)177018839713.30.338.71.0an0.4(1.5)177517537313.50.637.52.2a Self-diffusion coefficients are given in 1012 m2/s and activation energies in kJ/mol.b Diffusion coefficient extrapolated using Arrhenius equation (eq ). The value derived directly from MD simulations at 300 K is given in parenthesis.c Data based on FFgas, i.e. on the charge distribution of isolated ions.Table 5. Ratio of Self-Diffusion Coefficients of Cations and Paired Anions, and Ratio of Number of Anion Hydrogen Acceptor Atoms and Cation Hydrogen Atoms of Various Ionic Liquidsionic liquidDcat/DanbmimTf2N1.310.67bmimBF41.000.26bmimCF3CO21.160.33bmimPF61.250.40bmimCF3SO31.380.40bmimC2F5SO2)2N1.450.91(n-C4H9)(CH3)3NTf2N1.210.56bpyTf2N1.270.71bmproTf2N1.220.63mmimTf2N1.761.11emimTf2N1.680.91C6mimTf2N1.160.53C8mimTf2N1.000.43hmpyTf2N0.990.50ompyTf2N0.940.42hdmpyTf2N0.940.45AP-N0.680.14AB-N0.650.13AP-C0.780.18AB-C0.820.17CM-N1.020.25CB-N1.040.16CM-C1.130.31CB-C0.930.21a Taken from measurements of Tokuda et al. at 300 K.(40)b Taken from measurements of Cadena et al. at 300 K.(41)c Derived from the simulations of GILs at 450 K presented in this work.Marco Klhn, Abirami Seduraman and Ping Wu. A Model for Self-Diffusion of Guanidinium-Based Ionic Liquids: A Molecular Simulation Study. J. Phys. Chem. B, 2008, 112 (44), 138491386111. bmimPF6的分子动力学研究在不同温度下模拟得到的自扩散系数：Timothy I. Morrow and Edward J. Maginn. Molecular Dynamics Study of the Ionic Liquid 1-n-Butyl-3-methylimidazolium Hexafluorophosphate. J. Phys. Chem. B, 2002, 106 (49), 128071281312. N-methyl-N-propyl-pyrrolidinium bis-(trifluoromethanesulfonyl)imide (PYR13TFSI)和LiTFSI混合体系中不同温度和组成下离子的自扩散系数Isabella Nicotera, Cesare Oliviero, Wesley A. Henderson, Giovanni B. Appetecchi, and Stefano Passerini. NMR Investigation of Ionic LiquidLiX Mixtures:Pyrrolidinium Cations and TFSI- Anions. J. Phys. Chem. B, 2005, 109 (48), 22814-2281913. (1 x)(BMITFSI), xLiTFSI x0.41-butyl-3-methylimidazolium cation (BMI+) and bis(trifluoromethane-sulfonyl)imide anion (TFSI)Sandrine Duluard,Joseph Grondin,Jean-Luc Bruneel, Isabelle Pianet, Axelle Gre lard,Guy Campet,Marie-He le ne Delville1 and Jean-Claude Lasse gues.Lithium solvation and diffusion in the1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide ionic liquid. J. Raman Spectrosc. 2008; 39: 62763214. CO,DPA,DPCP在不同离子液体中的扩散系数Y. Nishiyama, M. Fukuda, M. Terazima, and Y. Kimura. Study of the translational diffusion of the benzophenone ketyl radical in comparison with stable molecules in room temperature ionic liquids by transient grating spectroscopy. THE JOURNAL OF CHEMICAL PHYSICS 128, 164514 _2008_15. 质子传递的离子液体的自扩散系数AA: CH3COOH; TFA:CF3COOH; MS: CH3SO3H; Trif: CF3SO3H; TFSi: HN(SO2-CF3)2 TEA: (CH3CH2)3NPatrick Judeinstein,Cristina Iojoiu,Jean-Yves Sanchez,and Bernard Ancian. Proton Conducting Ionic Liquid Organization as Probed by NMR: Self-DiffusionCoefficients and Heteronuclear Correlations. J. Phys. Chem. B 2008, 112, 3680-368316. DEME-TFSA 和 DEME-TFSA-Li 的自扩散系数N,Ndiethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl) amide (DEME-TFSA) Kikuko Hayamizu, Seiji Tsuzuki, Shiro Seki, Yasutaka Ohno, Hajime Miyashiro, and Yo Kobayashi. Quaternary Ammonium Room-Temperature Ionic Liquid Including an OxygenAtom in Side Chain/Lithium Salt Binary Electrolytes: Ionic Conductivity and 1H, 7Li, and 19F NMR Studies on Diffusion Coefficients and Local Motions. J. Phys. Chem. B, 2008, 112 (4), 1189-119717.CO2在离子液体中的扩散系数Ying Hou, and Ruth E. Baltus. Experimental Measurement of the Solubility and Diffusivity of CO2 in Room-Temperature Ionic Liquids Using a Transient Thin-Liquid-Film Method. Ind. Eng. Chem. Res., 2007, 46 (24), 8166-817518 用pulsed field gradient NMR测离子液体和离子液体混合物的传递性质N-methyl-N-propylpyrrolidinium dicyanamide (C3mpyrdca), N-methyl-N-propylpyrrolidnium bis(trifluoromethylsulfonyl)amide (C3mpyrNTf2), N-methyl-N-butylpyrrolidnium bis(trifluoromethylsulfonyl)amides (C4mpyrNTf2), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide (C2mimNTf2)trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide P6,6,6,14NTf2Pulsed Field Gradient Spin Echo (PGSE) Pulse MethodPulsed Field Gradient Stimulated Echo (PGSTE) Pulse MethodC3mpyrNTf2和C4mpyrNTf2混合物取不同的比例。19 Jyri-Pekka Mikkola, Johan Wrn, Pasi Virtanen, and Tapio Salmi. Effect of Internal Diffusion in Supported Ionic Liquid Catalysts: Interaction with Kinetics.Ind. Eng. Chem. Res., 2007, 46 (12), 3932-394041.气体在BMIMPF6中的扩散系数和离子液体的自扩散系数当C3mpyr+是混合物中主要组分时，C3mpyr+阳离子扩散得更慢。因为 C4mpyr+的流体动力学半径比C3mpyr+大。Gary Annat, Douglas R. MacFarlane, and Maria Forsyth.Transport Properties in Ionic Liquids and Ionic Liquid Mixtures: The Challenges of NMR Pulsed Field Gradient Diffusion Measurements.J. Phys. Chem. B, 2007, 111 (30), 9018-902420. 气体在五种鏻型离子液体中的扩散系数30下CO2，乙烯，丙烯，1.3-二丁烯，丁烯在五种离子液体中的扩散系数气体在P(14)444+DBS-型离子液体中扩散系数的值是在其他离子液体中的一半，这与P(14)444+DBS-的黏度大（3000cP）有关。离子液体黏度相同的情况下，气体扩散系数在鏻型离子液体中比在咪唑型离子液体中明显大很多。这与鏻阳离子上脂肪族链数量和长度有关。因为这些侧链可以伸展，比整个阳离子活动更快，可以允许溶质在鏻型离子液体中从一个空隙到另外一个空隙快速扩散。Lee Ferguson, and Paul Scovazzo.Solubility, Diffusivity, and Permeability of Gases in Phosphonium-Based Room Temperature Ionic Liquids: Data and Correlations.Ind. Eng. Chem. Res., 2007, 46 (4), 1369-137426. 25下三碘化物在两种离子液体混合物中的扩散系数离子液体混合物：1-methyl-3-propylimidazolium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate比较了四种方法：impedance spectroscopy and polarization measurements at thin layer cel