扩散系数总结.doc

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1、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,

2、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，

3、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

4、 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(trifluoromethylsul

5、fonyl)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. C

6、hem. 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LiemimB

7、F4二元体系中， 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

8、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, conductivi

9、ty, 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 coefficient

10、s 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.

11、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 coe

12、fficient (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

13、.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

14、.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

15、.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 relatio

16、n 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,

17、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 fi

18、eld.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.kRe

19、ference 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 t

20、he 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

21、 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 H2Ow

22、atermolar 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 indu

23、ce 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

24、 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, Pa

25、trice 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-propylimid

26、azolium 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 sy

27、stems 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 Zi

28、stler, 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 dis

29、persion 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-e

30、thyl-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 hexafluorophospha

31、te 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

32、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 pentam

33、ethylpropylguanidinium (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 Ener

34、gies 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)611974407

35、6213.30.537.92.1an0.5(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)155416333613.30.338.71.0an

36、0.3(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 simu

37、lations 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 li

38、quidDcat/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.

39、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 a

40、nd 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

41、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

42、 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 Pian

43、et, 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 c