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 method
9. 甲醇/[BMIM][PF6]体系中,25℃下不同[BMIM][PF6]浓度的相互扩散系数
42. [C4C1im]BF4, [C4C1im][N(OTf)2], [C4C1im]PF6 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[BMIM][TFSI] 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,EMINTf2
14. 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[BMIM][PF6]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 ([emim][BF4]) 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. [BMIM][PF6] (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. [bmim][PF6]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 x<0.4
15. 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[BMIM][PF6]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 [BMIM][TFSI]
butyltriethylammonium bis(trifluoromethylsulfonyl)amide) [Et3BuN][TFSI]
N-methyl-N-butylpyrrolidinium bis{(trifluoromethyl)sulfonyl}-amide [Pyr][TFSI]
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), 14952-14958
3. 离子液体的自扩散系数
3.1 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]) 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[emim][BF4]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[Li][emim][BF4]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 [emim][BF4] and LiBF4. JOURNAL OF PHYSICAL CHEMISTRY B,108(2004):19527-19532
3. 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),1645-1653
5. 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 10−11 m2 s−1) 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 ([amim][X])
T
(K)
D+
D−
t+
Tmp
(K)
[dmim][Cl]
423
2.70
1.85
0.593
398a
[dmim][NO3]
383
3.94
2.95
0.572
357a
[dmim][PF6]
376
3.83
2.04
0.652
362b
[emim][Cl]
377
2.43
1.53
0.614
360a
[emim][NO3]
379
5.03
3.86
0.566
312a
[emim][PF6]
370
3.66
2.05
0.641
333a
[pmim][Cl]
384
1.55
1.38
0.529
333a
[pmim][NO3]
377
4.12
3.43
0.546
[pmim][PF6]
373
3.36
1.85
0.645
313a
[bmim][Cl]
380
0.68
0.64
0.515
340a
[bmim][NO3]
379
2.59
2.29
0.531
[bmim][PF6]
374
2.70
2.01
0.573
279a
aFrom Refs. 4,66.
bFrom Dzyuba and Bartsch, Ref. 67.
Table III. The diffusion coefficient (in 10−11 m2 s−1) 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=400 K.
IL ([amim][X])
MSD
VACF
D+ ()
D− ()
t+
D+
D−
t+
[dmim][Cl]
1.46 (0.56)
0.96 (0.45)
0.60
2.9(0.7)
2.7(0.7)
0.52
[dmim][NO3]
4.72 (0.78)
3.91 (0.75)
0.55
7.2(0.6)
6.0(0.8)
0.54
[dmim][PF6]
3.69 (0.67)
2.31 (0.60)
0.62
6.6(1.1)
4.4(1.1)
0.60
[emim][Cl]
3.78 (0.74)
2.59 (0.62)
0.59
5.7(1.1)
5.6(1.3)
0.50
[emim][NO3]
6.74 (0.82)
5.61 (0.78)
0.55
9.3(1.2)
8.4(1.3)
0.53
[emim][PF6]
5.74 (0.75)
3.04 (0.61)
0.65
7.8(1.4)
4.8(1.6)
0.62
[pmim][Cl]
2.61 (0.74)
2.20 (0.68)
0.54
4.9(0.8)
5.5(0.9)
0.47
[pmim][NO3]
4.97 (0.74)
4.47 (0.70)
0.53
8.2(0.7)
8.3(0.9)
0.50
[pmim][PF6]
4.71 (0.74)
2.79 (0.63)
0.63
5.0(1.0)
4.3(1.0)
0.54
[bmim][Cl]
0.72 (0.39)
0.75 (0.37)
0.49
2.5(1.0)
3.2(1.2)
0.44
[bmim][NO3]
4.70 (0.78)
4.47 (0.78)
0.51
5.4(1.1)
4.9(1.2)
0.53
[bmim][PF6]
4.56 (0.77)
3.15 (0.68)
0.59
5.8(1.0)
4.8(1.0)
0.55
First citation in article
Table IV. Cation and anion diffusion coefficients Di (in 10−11 m2 s−1) 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).
RTIL
D+
D−
Our work
Simulations
Expt.
Our work
Simulations
Expt.
[dmim][Cl]
1.46
1.09,a 11,b 43c
0.96
0.88,a 8,b 38c
[dmim][PF6]
3.69
2.6,a 4.7,d 12b
2.31
1.3,a 3.2,d 6b
[emim][Cl]
3.78
17.0,a 34,e 3.6f
2.59
9.4,a 19.9,e 1.4f
[emim][NO3]
6.74
3.1,g 9.6,h 5.1,i
14.9j
5.61
1.65,g 5.8,h 4.8,i
15.5j
[emim][PF6]
5.74
2.3,i 5.6,k 0.13a
3.04
1.05,i 3.54,k 0.13a
[bmim][Cl]
0.72
22.3,a 1.4l
0.75
11.4,a 3.1l
[bmim][NO3]
4.70
5.3,m 23.8n
4.47
4.5,m 27.5n
[bmim][PF6]
4.56
5.6,a 14.1,o 24.4,p 3.5q
20.91r
3.15
2.8,a 6.2,o 20.5,p 2.9q
17.86r
aReference 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,[NO3]−>[PF6]−>[Cl]−。[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[BMIM][TFSI] 中的反常扩散
[BMIM][TFSI] + water 体系中 BMIM, TFSI, 和 H2O的自扩散系数
butyl-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide ([BMIM][TFSI])
Table 1: Self-Diffusion Coefficients of BMIM, TFSI, and H2O
water molar fraction
Dcation m2/s (1H)
Danion m2/s (19F)
Dwater m2/s (1H)
0.03 (=W0)
2.3 × 10-11
2.0 × 10-11
3.5 × 10-11
0.12
2.6 × 10-11
2.3 × 10-11
13.4 × 10-11
0.22
2.7 × 10-11
2.5 × 10-11
20.6 × 10-11
0.3
2.9 × 10-11
2.6 × 10-11
26.8 × 10-11
The 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 [BMIM][TFSI] + water system shows a partial segregation between [BMIM][TFSI] + some water molecules phase and water + some [BMIM][TFSI] ions phase.
o Top of Page
o Introduction
o Experimental Methods
o Results and Discussion
o Conclusion
Anne-Laure Rollet, Patrice Porion, Michel Vaultier, Isabelle Billard, Michael Deschamps, Catherine Bessada, and Laurence Jouvensal. Anomalous Diffusion of Water in [BMIM][TFSI] Room-Temperature Ionic Liquid. J. Phys. Chem. B, 2007, 111 (41), 11888–11891
6. 三碘化物在混合离子液体中的扩散系数 MPII,EMIC,EMIDCA,EMIBF4,EMINTf2
1-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 1.22×10-7 cm2· s-1 for MPII up to 8.30×10-7 cm2· s_1 for 91 mol% EMIDCA, 3.61×10_7 cm2· s_1 for 90mol% EMIBF4 and 4.07×10_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: 125–133
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 method
[Emim][C2N3 (dicyanamide)],[Emim][BF4 (tetrafluoroborate)],
[Emim][C2H5SO4 (ethylsulfate)], [Emim][CF3SO3 (trifluoromethanesulfonate)],
[Emim][MDEGSO4 (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) 43–52
8. [BMIM][PF6] (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 228–229 (2005) 329–333
9. 甲醇/[BMIM][PF6]体系中,25℃下不同[BMIM][PF6]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 103–104 (2003) 359–370
10. 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 a
GIL
D300K
D400K
D450K
D500K
D550K
D600K
ln D∞
Ea
AP-N
cat
1.3(2.9)
98
245
529
846
−14.3±0.3
32.6±1.3
an
2.0(2.9)
145
384
759
1262
−13.9±0.3
32.4±1.4
AB-N
cat
1.1(3.6)
98
281
605
916
−13.9 ±0.6
33.9±2.5
an
1.7(4.3)
150
461
906
1483
−13.4±0.6
34.2±2.5
AP-C
cat
0.5(1.8)
57
163
348
624
−14.0±0.3
35.9±1.2
an
0.5(2.3)
73
202
475
862
−13.4 ±0.2
37.3±0.9
AB-C
cat
0.4(1.6)
61
197
440
762
−13.3±0.5
37.9±2.1
an
0.5(1.2)
75
236
552
911
−13.2±0.5
37.8±2.3
CM-N
cat
0.4(0.5)
17
68
212
374
−13.1±0.6
38.7±2.5
an
0.4(0.7)
17
66
196
395
−13.1±0.3
38.6±1.3
CM-N
cat
0.1
7
46
123
251
−12.5±1.0
43.2±4.0
an
0.1
8
43
129
297
−12.1±0.6
44.5±2.3
CB-N
cat
0.6(1.2)
21
83
198
414
−13.6±0.4
36.5±1.6
an
0.9(1.4)
27
80
194
389
−14.2 ±0.3
33.8±1.0
CM-C
cat
0.3(1.3)
15
54
163
336
−13.3±0.3
38.7±1.0
an
0.3(1.6)
16
48
204
367
−13.0±0.9
39.6±3.4
CB-C
cat
0.3(1.5)
17
70
188
397
−13.3±0.3
38.7±1.0
an
0.4(1.5)
17
75
175
373
−13.5±0.6
37.5±2.2
a Self-diffusion coefficients are given in 10−12 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 Liquids
ionic liquid
Dcat/Dan
σ
[bmim][Tf2N]
1.31
0.67
[bmim][BF4]
1.00
0.26
[bmim][CF3CO2]
1.16
0.33
[bmim][PF6]
1.25
0.40
[bmim][CF3SO3]
1.38
0.40
[bmim][C2F5SO2)2N]
1.45
0.91
[(n-C4H9)[(CH3)3N][Tf2N]
1.21
0.56
[bpy][Tf2N]
1.27
0.71
[bmpro][Tf2N]
1.22
0.63
[mmim][Tf2N]
1.76
1.11
[emim][Tf2N]
1.68
0.91
[C6mim][Tf2N]
1.16
0.53
[C8mim][Tf2N]
1.00
0.43
[hmpy][Tf2N]
0.99
0.50
[ompy][Tf2N]
0.94
0.42
[hdmpy][Tf2N]
0.94
0.45
AP-N
0.68
0.14
AB-N
0.65
0.13
AP-C
0.78
0.18
AB-C
0.82
0.17
CM-N
1.02
0.25
CB-N
1.04
0.16
CM-C
1.13
0.31
CB-C
0.93
0.21
a 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), 13849–13861
11. [bmim][PF6]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), 12807–12813
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
Isabella Nicotera, Cesare Oliviero, Wesley A. Henderson, Giovanni B. Appetecchi, and Stefano Passerini. NMR Investigation of Ionic Liquid−LiX Mixtures:Pyrrolidinium Cations and TFSI- Anions. J. Phys. Chem. B, 2005, 109 (48), 22814-22819
13. (1− x)(BMITFSI), xLiTFSI x<0.4
1-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: 627–632
14. 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)3N
Patrick Judeinstein,Cristina Iojoiu,Jean-Yves Sanchez,and Bernard Ancian. Proton Conducting Ionic Liquid Organization as Probed by NMR: Self-Diffusion
Coefficients and Heteronuclear Correlations. J. Phys. Chem. B 2008, 112, 3680-3683
16. 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 Oxygen
Atom 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), 1189-1197
17.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), 8166-8175
18 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 ([C3mpyr][dca]),
N-methyl-N-propylpyrrolidnium bis(trifluoromethylsulfonyl)amide ([C3mpyr][NTf2]),
N-methyl-N-butylpyrrolidnium bis(trifluoromethylsulfonyl)amides ([C4mpyr][NTf2]), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide ([C2mim][NTf2])
trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide [P6,6,6,14][NTf2]
Pulsed Field Gradient Spin Echo (PGSE) Pulse Method
Pulsed Field Gradient Stimulated Echo (PGSTE) Pulse Method
[C3mpyr][NTf2]和[C4mpyr][NTf2]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), 3932-3940
41.气体在[BMIM][PF6]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), 9018-9024
20. 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), 1369-1374
26. 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
:
impedance spectroscopy and polarization measurements at thin layer cells
cyclic voltammetry and chronoamperometry at microelectrodes of different radii.
M. Zistler , P. Wachter , P. Wasserscheid , D. Gerhard ,A. Hinsch , R. Sastrawan , H.J. Gores.Comparison of electrochemical methods for triiodide diffusion coefficient measurements and observation of non-Stokesian diffusion behaviour in binary mixtures of two ionic liquids. Electrochimica Acta 52 (2006) 161–169
27. 离子液体不同侧链长度对扩散的影响
The tail groups of the cations with a sufficient side-chain length are found to aggregate, forming spatially heterogeneous domains, due to the competition between the electrostatic interactions
between the charged head groups and the anions and the collective short-range interactions between the neutral tail groups. With a sufficiently long alkyl chain at a low enough temperature, the tail domains remain relatively stable, despite the diffusion of individual ions in the liquid phase.
Yanting Wang, and Gregory A. Voth. Tail Aggregation and Domain Diffusion in Ionic Liquids. J. Phys. Chem. B, 2006, 110 (37), 18601-18608
42. [C4C1im]BF4, [C4C1im][N(OTf)2], [C4C1im]PF6 三种离子液体在甲醇,CH2Cl2中的扩散系数
Devendrababu Nama , P.G. Anil Kumar, Paul S. Pregosin ,Tilmann J. Geldbach, Paul J. Dyson. 1H, 19F-HOESY and PGSE diffusion studies on ionic liquids:The effect of co-solvent on structure. Inorganica Chimica Acta 359 (2006) 1907–1911
43 1,1,1,2-tetrafluoroethane (R-134a)在七种离子液体中的扩散系数
[bmim][PF6],[emim][BEI],[bmim][HFPS],[bmim][TPES],[bmim][TTES],[6,6,6,14-P][TPES],[4,4,4,14-P][TPES]
28.
Mark B. Shiflett, Mark A. Harmer, Christopher P. Junk and A. Yokozeki. Solubility and diffusivity of 1,1,1,2-tetrafluoroethane in room-temperature ionic liquids. Fluid Phase Equilibria 242 (2006) 220–232
25. 二氟甲烷在19种离子液体中的扩散
[bmim][PF6], [bmim][BF4],
1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide [dmpim][TMeM] or [dmpim][Tf3C],
1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide [emim][BEI],
1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)-imide [dmpim][BMeI] or [dmpim][Tf2N],
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [emim][BMeI] or [emim][Tf2N], 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl) imide [pmpy][BMeI] or [pmpy][Tf2N],
1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, [bmpy][BMeI] or [bmpy][Tf2N], 1-butyl-3-methylimidazolium acetate [bmim][Ac],
1-butyl-3-methylimidazolium thiocyanate [bmim][SCN],
1-butyl-3-methylimidazolium methyl sulfate [bmim][MeSO4]
1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [emim][TFES], 1-butyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [bmim][TFES], 1-heptyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [hmim][TFES],
1-dodecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [dmim][TFES], 1-butyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate [bmim][HFPS], 1-butyl-3-methylimidazolium 2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate [bmim][FS],
1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate [bmim][TPES],
1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate [bmim][TTES]
Mark B. Shiflett, Mark A. Harmer, Christopher P. Junk, and A. Yokozeki.Solubility and Diffusivity of Difluoromethane in Room-Temperature Ionic Liquids.J. Chem. Eng. Data, 2006, 51 (2), 483-495
26. 二茂铁在两种离子液体混合物中的扩散系数及与温度的关系
Clment Comminges, Rachid Barhdadi, Michel Laurent, and Michel Troupel.Determination of Viscosity, Ionic Conductivity, and Diffusion Coefficients in Some Binary Systems: Ionic Liquids + Molecular Solvents.J. Chem. Eng. Data, 2006, 51 (2), 680-685
27. hydrofluocarbons在离子液体中的扩散系数
trifluoromethane, difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane, and 1,1-difluoroethane在 l-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])和1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4])中的扩散系数
Shiflett MB, Yokozeki A. Solubility and diffusivity of hydrofluorocarbons in room-temperature ionic liquids. AICHE JOURNAL , 52(3),2006 ,1205-1219
28. 气体在离子液体[EMIM][Tf2N]中的扩散系数
Dean Camper, Collin Becker, Carl Koval, and Richard Noble .Diffusion and Solubility Measurements in Room Temperature Ionic Liquids.Ind. Eng. Chem. Res., 2006, 45 (1), 445-450
29.气体( carbon dioxide, ethylene, propylene, 1-butene, and 1,3-butadiene)在咪唑型和鏻型离子液体中的扩散
气体在离子液体中的扩散系数比在其他有机溶剂中的小,主要是因为离子液体的黏度太大。溶剂尺寸和温度有关。
David Morgan, Lee Ferguson, and Paul Scovazzo.Diffusivities of Gases in room-Temperature Ionic Liquids:Data and Correlations Obtained Using a Lag-Time echnique.Ind. Eng. Chem. Res., 2005, 44 (13), 4815-4823
30. Fe3+在BPBF4中的扩散系数
Yang JZ, Jin Y, Wei P. Measurement of diffusion coefficient of Fe3+ in ionic liquid BPBF4 by chronoampermetry. CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE ,26(6),2005
31.二氧化碳在[bmim][PF6]和[bmim][BF4]中的扩散
Mark B. Shiflett, and A. Yokozeki .Solubilities and Diffusivities of Carbon Dioxide in Ionic Liquids: [bmim][PF6] and [bmim][BF4]. Ind. Eng. Chem. Res., 2005, 44 (12), 4453-4464
32. N,N,N’,N’-tetramethyl-para-phenylenediamine在离子液体和acetonitrile中的扩散系数比较
Evans RG, Klymenko OV, Price PD, Davies SG, Hardacre C, Compton RG. A comparative electrochemical study of diffusion in room temperature ionic liquid solvents versus acetonitrile. CHEMPHYSCHEM,6(3),2005,526-533
33. 离子液体中的扩散系数与黏度的关系(模拟)
Richard Brookes, Alun Davies, Gyanprakash Ketwaroo, and Paul A. Madden.Diffusion Coefficients in Ionic Liquids: Relationship to the Viscosity†J. Phys. Chem. B, 2005, 109 (14), 6485-6490
34. [emim][BF4] 和 LiBF4构成的二元离子液体中离子的自扩散系数
Kikuko Hayamizu, Yuichi Aihara, Hiroe Nakagawa, Toshiyuki Nukuda, and William S. Price. Ionic Conduction and Ion Diffusion in Binary Room-Temperature Ionic Liquids Composed of [emim][BF4] and LiBF4.J. Phys. Chem. B, 2004, 108 (50), 19527-19532
35. 与浓度有关的扩散
Claudine A. Brooks, Andrew P. Doherty. Concentration-dependent diffusion in room temperature ionic liquids: a microelectrode study. Electrochemistry Communications 6 (2004) 867–871
36. FCS测定荧光探针分子在[bmim][PF6] 中的扩散
James H. Werner, Sheila N. Baker and Gary A. Baker. Fluorescence correlation spectroscopic studies of diffusion within the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. Analyst, 2003, 128, 786 - 789, DOI: 10.1039/b300734k
37.碱-银-硝酸根熔融盐 和 [bmim][pf6]/甲醇混合物的相互扩散系数
方法:Digital image holography
J. Richter, A. Leuchter and N. Großer.Digital image holography for diffusion measurements in molten salts and ionic liquids - method and first results .Journal of Molecular Liquids 103–104 (2003) 359–370
38. 离子液体的自扩散系数
1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4)
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI)
1-butylpyridinium tetrafluoroborate (BPBF4)
1-butylpyridinium bis(trifluoromethylsulfonyl)imide (BPTFSI)
Akihiro Noda, Kikuko Hayamizu, and Masayoshi Watanabe. Pulsed-Gradient Spin-Echo 1H and 19F NMR Ionic Diffusion Coefficient, Viscosity, and Ionic Conductivity of Non-Chloroaluminate Room-Temperature Ionic Liquids. J. Phys. Chem. B 2001, 105, 4603-4610
39.三种有代
性的氧化还原系统在离子液体中的扩散系数
the oxidation of neutral N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD)
the reduction of cationic methyl viologen (MV2+) and reduction of anionic hexacyanoferrate(III), Fe(CN)63—
[BMIM][BF4], [BMIM][PF6],
[MDIM][BF4](1-methyl-3-[2,6-(S)-dimethylocten-2-yl]imidazolium tetrafluoroborate)
Uwe Schröder, Jay D. Wadhawan, Richard G. Compton, Frank Marken, Paulo A. Z. Suarez, Crestina S. Consorti, Roberto F. de Souza and Jaïrton Dupont. Water-induced accelerated ion diffusion: voltammetric studies in 1-methyl-3-[2,6-(S)-dimethylocten-2-yl] imidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate ionic liquids. New J. Chem., 2000, 24, 1009 - 1015, DOI: 10.1039/b007172m
40. 二茂铁在离子液体中的扩散系数
1,2-dimethyl, 3-(1-propyl) imidazolium tetrafluoroburate (DMPIBF4) or 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and hexafluoropropylene-vinylidene fluoride copolymer
Kosmulski M, Osteryoung RA, Ciszkowska M. Diffusion coefficients of ferrocene in composite materials containing ambient temperature ionic liquids. JOURNAL OF THE ELECTROCHEMICAL SOCIETY ,147(4),2000,1454-1458
41.
4. 离子液体的性质与扩散的关系
4.1
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), 3932-3940
4.2 离子液体中的扩散系数与黏度的关系(模拟)
Richard Brookes, Alun Davies, Gyanprakash Ketwaroo, and Paul A. Madden.Diffusion Coefficients in Ionic Liquids: Relationship to the Viscosity†J. Phys. Chem. B, 2005, 109 (14), 6485-6490
4.3 与浓度有关的扩散
Claudine A. Brooks, Andrew P. Doherty. Concentration-dependent diffusion in room temperature ionic liquids: a microelectrode study. Electrochemistry Communications 6 (2004) 867–871