Critical Properties of Ionic Liquids. Revisited - Industrial & Engineering

6890

Ind. Eng. Chem. Res. 2009, 48, 6890–6900

Critical Properties of Ionic Liquids. Revisited Jose´ O. Valderrama*,†,‡ and Roberto E. Rojas§ Department of Mechanical Engineering, Faculty of Engineering, UniVersity of La Serena, Casilla 554, La Serena, Chile, Center for Technological Information (CIT), Casilla 724, La Serena, Chile, and Department of Chemistry, Faculty of Sciences, UniVersity of La Serena, Casilla 554, La Serena, Chile

The group contribution method proposed by Valderrama and Robles in 2007 and extended by Valderrama et al. in 2008 to estimate the critical properties of ionic liquids is revised and new groups have been included. The method originally proposed has been used by several authors in applications such as high pressure phase equilibrium, density correlations, heat capacity estimations, and consistency tests for mixture data. Therefore, it is important to have a consistent and reliable method so all applications consider the same assumptions and values for the critical properties. The values previously reported by the authors are recalculated, unifying criteria for the names of the ionic liquids, for the assignment of the groups forming the molecules, and for the equivalence of groups. Also, a spreadsheet file that allows any reader to calculate the critical properties of any ionic liquid containing the 44 groups defined by the method is provided as Supporting Information. Introduction In two previous papers the authors proposed and applied a group contribution method to determine the critical properties (TC, PC, VC), the normal boiling temperature (Tb), and the acentric factor (ω) of ionic liquids.1,2 The proposed method unified the best characteristics of two of the most used simplest techniques of Lydersen3 and of Joback and Reid4 and has been named as Modified Lydersen-Joback-Reid method. As several authors have indicated, most ionic liquids start to decompose at low temperature and in many cases at temperatures approaching the normal boiling point.5 Therefore, critical properties cannot be measured. The estimated properties are useful approximations that must be interpreted as “these would be the Values of TC, PC, VC, Tb and ω, if the properties were possible to be measured.”2 Since experimental data do not exist and there is no reasonable and generally accepted theory yet available to calculate these properties for ionic liquids, the group contribution method presented by Valderrama and Robles1 that is revised in this work is considered to give reasonable estimates. In the first paper of 2007 Valderrama and Robles1 estimated the critical properties of fifty ionic liquids using a Modified Lydersen-Joback-Reid method and proposed three new groups and their values for the contributions for TC, PC, VC, and Tb. Since there are not experimental critical properties to evaluate the accuracy of the estimates, these values were tested for accuracy and consistency by determining the density of the ionic liquids, for which experimental data are available. For this, an independent equation not employed in determining the critical properties was applied. The deviations found between experimental and calculated densities are within experimental errors as shown by the authors. Soon after being published, the method of Valderrama and Robles1 and their values of the critical properties were questioned by Jones et al.6 These authors compared eight of the fifty estimated boiling temperatures with values derived from experimentally determined heats of vaporization. According to Jones et al.,6 the boiling temperatures of ionic liquids were not * To whom correspondence should be addressed. E-mail: jvalderr@ userena.cl. Tel.: 56-51-204260. Fax: 56-51-551158. † Department of Mechanical Engineering, University of La Serena. ‡ Center for Technological Information. § Department of Chemistry, University of La Serena.

well predicted by the method used by Valderrama and Robles and, by inference, the critical properties and acentric factors were also likely to be in error. To reach to this conclusion these authors extrapolated their heat of vaporization data using a constant value for the heat capacity difference CPL - CPG ) 94 J K-1 mol-1 for the eight ionic liquids and then used Trouton’s Law: [∆Hvap(at 298) - 94(Tb - 298)]/Tb ) 85, to estimate the normal boiling temperature. They did not calculate the critical properties nor the acentric factor. In another communication, Valderrama and Robles7 demonstrated that the calculations of Jones et al. were obtained using rough approximations: a constant value of -94 J K-1 mol-1 for the difference (CPG - CPL) and a constant value 85 J K-1 mol-1 for the ratio ∆Hvap(at Tb)/Tb for all ionic liquids. These values, CPG - CPL and ∆Hvap(at Tb)/Tb, vary tremendously for different types of fluids and the true values for ionic liquids are unknown. In fact, the authors demonstrated that the values of CPG - CPL vary from 15 to 287 and ∆Hvap(at Tb)/Tb goes from 20 to 181, and provided complete tables with these values for hundreds of substances. After that, Valderrama et al.2 applied the method and published critical properties for another 200 ionic liquids. The proposed Valderrama-Robles group contribution method has been used in various applications by other authors. Gardas et al.,8 calculated the critical properties and use them for estimating the density of five ionic liquids, and according to the authors the estimated values are in good agreement with their experimental results. Carvalho et al.9 and Alvarez et al.10 used the calculated critical properties to correlate high pressure phase behavior of carbon dioxide + ionic liquid mixtures. Valderrama et al.11 presented a study on thermodynamic consistency of high pressure mixtures containing ionic liquids using an equation of state model that requires the critical properties. Ge et al.12 used the method to estimate the critical temperature, the normal boiling temperature, and the acentric factor to then determine the heat capacity of several ionic liquids, using a generalized correlation. Valderrama and Zarricueta13 proposed a general model to estimate the density of ionic liquids in which the estimated critical properties are included. In further applications of the group contribution method the authors have found that some of the ionic liquids included in the list were repeated and values provided were not correct for

10.1021/ie900250g CCC: $40.75  2009 American Chemical Society Published on Web 06/09/2009

Ind. Eng. Chem. Res., Vol. 48, No. 14, 2009

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2a

Table 1. Modified Group Contribution Method

model equation the method

density model for testing

critical compressibility factor acentric factor

Tb (K) ) 198.2 + ∑n∆Tb Tc (K) ) Tb/([A + B∑n∆Tc -(∑n∆Tc)2]) Pc (bar) ) M/([C + ∑n∆Pc]2) Vc (cm3/mol) ) D + ∑n∆Vc F ) A/B + (2/7){A ln B/B}(T - Tb)/(Tc - Tb)

Zc ) PcVc/(RTc)

ω)

a

constants

[] [] []

Pc (Tb - 43)(Tc - 43) log Pb (Tc - Tb)(0.7Tc - 43) Pc Pc (Tc - 43) log + log -1 T T P P ( c b) b b

A ) 0.5703, B ) 1.0121 C ) 0.2573 D ) 6.75 A ) a + bM/Vc B ) (c/Vc + d/M)Vcδ a ) 0.3411, b ) 2.0443, c ) 0.5386, d ) 0.0393, δ ) 1.0476 R ) 84.31 (bar cm3/mol K) Pb ) 1.01325 bar

In the equations, M is in g/mol, Tb and Tc are in K, Pc is in bar and Vc is in (cm3/mol).

some few cases of the 250 ionic liquids presented in the two previous publications.1,2 These few wrong values do not change the method nor the concepts behind the proposal, but they need to be clarified for users not to be confused. Some of these problems are repeated substances, erroneous global formulas, wrong molecular mass, confusing short names, and wrong assignment of groups. It should be noted that some of these errors affect some calculations, but of the 250 ionic liquids previously considered only 13 substances are affected. Final correct values are provided in this work and new substances were added to end up with a final database including 294 ionic liquids. Also provided as Supporting Information is an excel file that will allow any reader to easily calculate the critical properties of any ionic liquid for which the groups are provided. Revised Values and Spreadsheet This work includes revised values for all ionic liquids presented by the authors in previous works.1,2 Repeated substances have been eliminated, global formulas have been revised, molecular masses have been recalculated, the IUPAC names have been included for complete names and short names, and the assignment of groups has been redone. In addition to that, values of the properties TC, PC, VC, Tb, and ω have been determined for new ionic liquids, and an excel file containing all groups and estimated properties for 294 ionic liquids is provided in the Supporting Information. Thus other ionic liquids can be included for any further study. For better clarity and to avoid confusion with previous works, Table 1 summarizes the group contribution method and Table 2 provides the values of the contributions. Also included in Table 1 is the density model used to check the set of critical properties and normal boiling temperature estimated by the group contribution method. In Table 2 the groups considered in the proposed method, the equivalences between groups, and the value of the contributions are detailed. Table 3 gives the values of the estimated properties for the 294 ionic liquids. Density estimations, used as test of the consistency of the estimated values are also provided as Supporting Information. Table 4 gives details on the structure and functioning of the spreadsheet provided as Supporting Information so the numbers presented can be checked and the properties for any other ionic liquid could be estimated. The information given in Table 4 is explained as follows. The spreadsheet provided as Supporting Information contains all the information needed to estimate the critical

Table 2. Groups Considered in the Modified Lydersen-Joback-Reid Method for Ionic Liquids3 Mi

∆Tc

∆Pc

without Rings 15.035 0.0275 14.027 0.0159 13.019 0.0002 12.011 -0.0206 14.027 0.017 13.019 0.0182 12.011 -0.0003 12.011 -0.0029 13.019 0.0078 12.011 0.0078 17.008 0.0723 16.000 0.0051 28.011 0.0247 29.019 0.0294 45.018 0.0853 44.010 0.0377 45.018 0.036 16.000 0.0273

-CH3 0.3031 -CH20.2165 >CH0.114 0.0539 >C< [>C-]dCH2 0.2493 dCH0.1866 dC< 0.0832 dCd 0.0934 tCH 0.1429 tC-COO0.1429 -OH 0.1343 -O[-O] 0.13 >CdO 0.2341 -CHO 0.3128 -COOH 0.4537 -COO0.4139 -HCOO0.4752 dO 0.2042 (any_other) -NH2 16.023 0.0364 0.1692 -NH3 17.031 0.0364 0.1692 -NH15.015 0.0119 0.0322 >N14.007 -0.0028 0.0304 dN14.007 0.0172 0.1541 -CN 26.018 0.0506 0.3697 -NO2 46.006 0.0448 0.4529 -F 18.999 0.0228 0.2912 -Cl 35.453 0.0188 0.3738 -Br 79.904 0.0124 0.5799 -I 126.905 0.0148 0.9174 -P 30.974 -0.0084 0.1776 -B 10.811 0.0352 0.0348 -S32.066 0.0006 0.6901 OdSdO 64.065 -0.0563 -0.0606 -CH2>CHdCH>C< dC< -O-OH (phenols) >CdO -NH>NdN-

[>N < ]+ [>Nd ]+

∆Vc

∆Tb

66.81 23.58 57.11 22.88 45.7 21.74 21.78 18.25 60.37 18.18 49.92 24.96 34.9 24.14 33.85 26.15 43.97 43.97 30.4 92.88 15.61 22.42 69.76 94.97 77.46 72.24 88.6 169.06 84.76 81.10 97.77 44.03 -10.50 49.1 73.23 49.1 73.23 78.96 50.17 26.7 11.74 45.54 74.60 89.32 125.66 123.62 152.54 31.47 -0.03 62.08 38.13 76.6 66.86 100.79 93.84 67.01 34.86 22.45 -24.56 184.67 117.52 112.19 147.24

with Rings 14.027 0.0116 13.019 0.0081 13.019 0.0114 12.011 -0.018 12.011 0.0051 16.000 0.0138 17.008 0.0291

0.1982 51.64 0.1773 30.56 0.1693 42.55 0.0139 17.62 0.0955 31.28 0.1371 17.41 0.0493 -17.44

27.15 21.78 26.73 21.32 31.01 31.22 76.34

28.011 0.0343 15.015 0.0244 14.007 0.0063 14.007 -0.0011

0.2751 0.0724 0.0538 0.0559

94.97 52.82 68.16 57.55

59.32 27.61 25.17 42.15

properties and to check the estimated values using the density equation. For clarity of the presentation, the columns included in the spreadsheet have been numbered from C1 to C62 and shown in file 1. Files 2 to 7 contain information about the

[P11] [tsac]

[emim] [tsac]

[TEA] [tsac]

[TMAIA] [tsac]

[TMEA] [tsac]

[TMiPA] [tsac]

[TMPA] [tsac]

[bmim] [TFES] [C12mim] [TFES] [emim] [TFES] [hpmim] [TFES] [bmim] [HFPS] [4,4,4,14-P] [HFPS] [bmim] [TPES]

[6,6,6,14-P] [TPES]

[bmim] [TTES]

[bmim] [FS]

[TMG] [Ac] [bmim] [Ac] [emim] [Ac] [emim] [BEI] [bmim] [BEI] [4MOPY] [BEI] [NH221] [BEI] [NH11(i-3)] [BEI]

[C27guan] [bti]

[dmprim] [bti] [dbim] [bti] [E1,3M4I] [bti] [dmim] [bti] [MP4] [bti] [bmpy] [bti] [C10mim] [bti] [N-epy] [bti] [hpmim] [bti] [nmim] [bti] [pmim] [bti] [MP3] [bti] [prmim] [bti]

IL-2

IL-3

IL-4

IL-5

IL-6

IL-7

IL-8 IL-9 IL-10 IL-11 IL-12 IL-13 IL-14

IL-15

IL-16

IL-17

IL-18 IL-19 IL-20 IL-21 IL-22 IL-23 IL-24 IL-25

IL-26

IL-27 IL-28 IL-29 IL-30 IL-31 IL-32 IL-33 IL-34 IL-35 IL-36 IL-37 IL-38 IL-39

ionic liquid

IL-1

No.

C10H15N3F6S2O4 C13H21N3F6S2O4 C10H15N3F6S2O4 C7H9N3F6S2O4 C11H19N2F6S2O4 C12H16N2F6S2O4 C16H27N3F6S2O4 C9H10N2F6S2O4 C13H21N3F6S2O4 C15H25N3F6S2O4 C11H17N3F6S2O4 C10H17N2F6S2O4 C9H13N3F6S2O4

C29H58N4F6S2O4

C7H17N3O2 C10H18N2O2 C8H14N2O2 C10H11N3F10S2O4 C12H15N3F10S2O4 C18H24N2F10S2O4 C9H14N2F10S2O4 C9H14N2F10S2O4

C12H16N2F8SO4

C11H16N2F6SO4

C36H69PF8SO4

C10H16N2F4SO3 C18H32N2F4SO3 C8H12N2F4SO3 C13H22N2F4SO3 C11H16N2F6SO3 C29H57PF6SO3 C12H16N2F8SO4

C9H16N2F6SO3

C9H16N2F6SO3

C8H14N2F6SO3

C9H14N2F6SO3

C11H20N2F6SO3

C9H11N3F6SO3

C9H14N2F6SO3

global formula 1,1-dimethylpyrrolidinium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide 1-ethyl-3-methylimidazolium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide tetraethylammonium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide trimethylalylammonium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide trimethylethylammonium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide trimethylisopropylammonium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide trimethylpropylammonium [2,2,2-trifluoro-n-(trifluoromethyl)sulfonyl]acetamide 1-butyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanosulfonate 1-dodecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanosulfonate 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanosulfonate 1-hepthyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanosulfonate 1-butyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate tributyl(tetradecyl)phosphonium 1,1,2,3,3,3-hexafluoropropanesulfonate 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate tetradecyl(trihexyl)phosphonium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate 1-butyl-3-methylimidazolium 2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate 1,1,3,3-tetramethylguanidine acetate 1-butyl-3-methylimidazolium acetate 1-ethyl-3-methylimidazolium acetate 1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide 1-butyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide 4-methyl-n-octylpyridinium bis(pentafluoroethylsulfonyl)imide diethylmethyl(quaternary)ammonium bis(pentafluoroethylsulfonyl)imide dimethylisopropyl(quaternary)ammonium bis(pentafluoroethylsulfonyl)imide [bis(bishexylamine)methylene]dimethylammonium bis[(trifluoromethyl)sulfonyl]imide 1,2-dimethyl-3-propylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1,3-dibutylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1,3-diethyl-4-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-2-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-3-methylpyridinium bis[(trifluoromethyl)sulfonyl]imide 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-ethylpyridinium bis[(trifluoromethyl)sulfonyl]imide 1-heptyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-nonyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-pentyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-propyl-2-methylpyrrolidinium bis([trifluoromethyl)sulfonyl]imide 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

IUPAC name

419.4 461.5 419.4 377.3 421.4 430.4 503.5 388.3 461.5 489.5 433.4 407.4 405.3

704.9

175.2 198.3 170.2 491.3 519.4 586.5 468.3 468.3

436.3

386.3

781.0

320.3 432.5 292.3 362.4 370.3 630.8 436.3

346.3

346.3

332.3

344.3

374.3

355.3

344.3

M

867.4 931.1 867.4 793.8 758.7 852.0 999.7 778.4 931.1 976.8 885.3 735.8 839.6

1262.0

518.1 624.6 578.8 853.1 898.8 979.9 743.8 743.4

788.2

770.0

1236.4

729.4 912.5 683.7 798.1 747.6 1058.5 788.2

640.3

639.9

617.4

637.0

686.1

764.4

638.9

Tb (K)

1269.7 1305.0 1269.7 1239.9 1110.0 1240.5 1345.1 1207.9 1305.0 1331.2 1281.1 1096.2 1259.3

1529.0

703.7 847.3 807.1 1231.4 1257.1 1291.4 1056.3 1060.0

1061.3

1058.3

1520.6

1030.5 1171.0 998.2 1080.8 1032.1 1281.0 1061.3

873.7

876.1

854.1

875.2

913.2

1069.9

889.7

Tc (K)

27.5 22.3 27.5 35.8 25.4 25.5 18.7 32.7 22.3 19.8 25.6 27.4 30.0

9.8

28.0 24.5 29.2 21.9 19.5 15.0 21.5 21.6

17.9

20.9

7.1

25.7 15.6 30.4 20.7 21.3 8.8 17.9

21.7

21.9

23.3

22.5

19.1

25.2

23.6

Pc (bar)

988.6 1161.5 988.6 818.8 1038.9 1038.8 1332.8 869.0 1161.5 1275.7 1047.2 981.8 933.0

2167.1

563.0 658.2 544.0 1045.4 1159.6 1436.7 1053.3 1051.6

1012.9

928.2

2446.3

827.8 1284.7 713.6 999.2 912.6 2003.3 1012.9

855.9

854.2

798.8

842.3

970.2

833.5

836.5

Vc (cm3/mol)

Table 3. Critical Properties of Ionic Liquids Calculated by Group Contribution Using the Method Summarized in Table 1 and the Group Contributions Listed in Table 2 of this Article

0.2572 0.2392 0.2572 0.2845 0.2862 0.2571 0.2225 0.2834 0.2392 0.2277 0.2521 0.2953 0.2670

0.1676

0.2698 0.2285 0.2367 0.2238 0.2158 0.2013 0.2577 0.2581

0.2056

0.2205

0.1367

0.2480 0.2059 0.2615 0.2304 0.2266 0.1662 0.2056

0.2560

0.2569

0.2622

0.2609

0.2443

0.2359

0.2670

Zc

0.3226 0.4349 0.3226 0.1752 0.2933 0.3160 0.5741 0.1671 0.4349 0.5276 0.3444 0.2498 0.2575

1.0120

0.7326 0.6681 0.5889 0.2895 0.3812 0.5858 0.3534 0.3375

0.5488

0.5085

0.5812

0.4583 0.8065 0.3743 0.5903 0.4933 0.9322 0.5488

0.5705

0.5540

0.5261

0.5479

0.6596

0.4981

0.4956

ω

6892 Ind. Eng. Chem. Res., Vol. 48, No. 14, 2009

ionic liquid

[prmpy] [bti] [N723′3′] [bti] [dmeim] [bti] [BNM2E] [bti] [N1123] [bti] [N1134] [bti] [eomim] [bti] [prmpyr] [bti] [tda] [bti] [thpa] [bti] [tha] [bti] [tpa] [bti] [toa] [bti] [S444] [bti] [N7444] [bti] [N6444] [bti] [N1444] [bti] [N8444] [bti] [N7222] [bti] [N6222] [bti] [N8222] [bti] [S222] [bti] [N1114] [bti] [N7111] [bti] [N6111] [bti] [N111C2O] [bti] [N8111] [bti] [tmpa] [bti] [S111] [bti] [Ph(CH2)mim] [bti]

[Ph(CH2)2mim] [bti]

[Ph(CH2)3mim] [bti]

[bdmim] [bti] [mbpy] [bti] [bmpyr] [bti] [bpy] [bti] [C12mim] [bti] [memim] [bti]

[C2F3mim] [bti] [4MOPY] [bti] [C23guan] [bti]

[S224] [bti] [NH221] [bti] [S221] [bti] [S225] [bti] [S223] [bti] [NH114] [bti]

No.

IL-40 IL-41 IL-42 IL-43 IL-44 IL-45 IL-46 IL-47 IL-48 IL-49 IL-50 IL-51 IL-52 IL-53 IL-54 IL-55 IL-56 IL-57 IL-58 IL-59 IL-60 IL-61 IL-62 IL-63 IL-64 IL-65 IL-66 IL-67 IL-68 IL-69

IL-70

IL-71

IL-72 IL-73 IL-74 IL-75 IL-76 IL-77

IL-78 IL-79 IL-80

IL-81 IL-82 IL-83 IL-84 IL-85 IL-86

Table 3. Continued

C10H19NF6S3O4 C7H14N2F6S2O4 C7H13NF6S3O4 C11H21NF6S3O4 C9H17NF6S3O4 C8H16N2F6S2O4

C8H8N3F9S2O4 C16H24N2F6S2O4 C25H50N4F6S2O4

C11H17N3F6S2O4 C12H16N2F6S2O4 C11H20N2F6S2O4 C11H14N2F6S2O4 C18H31N3F6S2O4 C9H13N3F6S2O4

C15H17N3F6S2O4

C14H15N3F6S2O4

C11H14N2F6S2O4 C17H34N2F6S2O4 C9H13N3F6S2O4 C10H20N2F6S2O4 C9H18N2F6S2O4 C11H22N2F6S2O4 C9H13N3F6S2O5 C10H18N2F6S2O4 C42H84N2F6S2O4 C30H60N2F6S2O4 C26H52N2F6S2O4 C22H44N2F6S2O4 C34H68N2F6S2O4 C14H27NF6S3O4 C21H42N2F6S2O4 C20H40N2F6S2O4 C15H30N2F6S2O4 C22H44N2F6S2O4 C15H30N2F6S2O4 C14H28N2F6S2O4 C16H32N2F6S2O4 C8H15NF6S3O4 C9H18N2F6S2O4 C12H24N2F6S2O4 C11H22N2F6S2O4 C7H14N2F6S2O5 C13H26N2F6S2O4 C8H16N2F6S2O4 C5H9NF6S3O4 C13H13N3F6S2O4

global formula 3-methyl-1-propylpyridinium bis[(trifluoromethyl)sulfonyl]imide di(iso)propylethylheptylammonium bis[(trifluoromethyl)sulfonyl]imide 1,2-dimethyl-3-ethylimidazolium bis[(trifluoromethyl)sulfonyl]imide dimethylethylbutylammonium bis[(trifluoromethyl)sulfonyl]imide dimethylethylpropylammonium bis[(trifluoromethyl)sulfonyl]imide dimethylpropylbutylammonium bis[(trifluoromethyl)sulfonyl]imide ethoxymethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide n-methyl-n-propylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide tetradecylammonium bis[(trifluoromethyl)sulfonyl]imide tetraheptylammonium bis[(trifluoromethyl)sulfonyl]imide tetrahexylammonium bis[(trifluoromethyl)sulfonyl]imide tetramylammonium bis[(trifluoromethyl)sulfonyl]imide tetraoctylammonium bis[(trifluoromethyl)sulfonyl]imide tributylsulfonium bis[(trifluoromethyl)sulfonyl]imide tributylheptylammonium bis[(trifluoromethyl)sulfonyl]imide tributylhexylammonium bis[(trifluoromethyl)sulfonyl]imide tributylmethylammonium bis[(trifluoromethyl)sulfonyl]imide tributyloctylammonium bis[(trifluoromethyl)sulfonyl]imide triethylheptylammonium bis[(trifluoromethyl)sulfonyl]imide triethylhexylammonium bis[(trifluoromethyl)sulfonyl]imide triethyloctylammonium bis[(trifluoromethyl)sulfonyl]imide triethylsulfonium bis[(trifluoromethyl)sulfonyl]imide trimethylbutylammonium bis[(trifluoromethyl)sulfonyl]imide trimethylheptylammonium bis[(trifluoromethyl)sulfonyl]imide trimethylhexylammonium bis[(trifluoromethyl)sulfonyl]imide trimethylmethoxymethylammonium bis[(trifluoromethyl)sulfonyl]imide trimethyloctylammonium bis[(trifluoromethyl)sulfonyl]imide trimethylpropylammonium bis[(trifluoromethyl)sulfonyl]imide trimethylsulfonium bis[(trifluoromethyl)sulfonyl]imide 1-(1-phenylalkyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-(2-phenylalkyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-(3-phenylalkyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-2,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-4-methylpyridinium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide 1-butylpyridinium bis[(trifluoromethyl)sulfonyl]imide 1-dodecyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-methyl-3-ethyl-4-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-trifluoroethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 4-methyl-n-octylpyridinium bis[(trifluoromethyl)sulfonyl]imide [bis(bispentylamine)methylene]dimethylammonium bis[(trifluoromethyl)sulfonyl]imide diethylbutylsulfonium bis[(trifluoromethyl)sulfonyl]imide diethylmethyl(quaternary)ammonium bis[(trifluoromethyl)sulfonyl]imide diethylmethylsulfonium bis[(trifluoromethyl)sulfonyl]imide diethylpentylsulfonium bis[(trifluoromethyl)sulfonyl]imide diethylpropylsulfonium bis[(trifluoromethyl)sulfonyl]imide diethylbutyl(quaternary)ammonium bis[(trifluoromethyl)sulfonyl]imide

IUPAC name

427.5 368.3 385.4 441.5 413.4 382.4

445.3 486.5 648.8

433.4 430.4 422.4 416.4 531.6 405.3

481.4

467.4

416.4 508.6 405.3 410.4 396.4 424.4 421.3 408.4 859.3 690.9 634.8 578.7 747.1 483.6 564.7 550.7 480.5 578.7 480.5 466.5 494.6 399.4 396.4 438.5 424.4 384.3 452.5 382.4 357.3 453.4

M

843.4 707.4 774.8 866.3 820.5 730.3

811.3 943.5 1170.5

890.3 852.0 759.8 824.2 1045.5 844.5

1003.5

980.6

829.1 897.6 844.5 738.3 715.4 761.2 862.0 736.9 1470.5 1195.9 1104.4 1012.9 1287.4 934.9 990.0 967.1 852.7 1012.9 852.7 829.8 875.6 797.6 715.4 784.1 761.2 692.1 807.0 692.6 729.0 957.8

Tb (K)

1214.5 1061.1 1178.3 1227.5 1202.0 1075.3

1210.5 1292.0 1432.1

1281.1 1240.5 1093.1 1229.1 1374.6 1258.9

1424.5

1414.8

1228.9 1176.6 1258.9 1054.3 1038.7 1070.1 1285.2 1078.5 1831.8 1449.6 1353.0 1267.0 1559.2 1269.2 1247.0 1227.4 1136.3 1267.0 1136.3 1119.2 1153.7 1189.9 1038.7 1086.1 1070.1 1035.7 1102.5 1023.4 1156.5 1405.9

Tc (K)

19.3 31.9 23.4 18.2 20.5 29.3

26.7 19.7 11.2

25.5 25.5 24.3 27.7 16.8 29.8

23.4

25.1

27.5 16.1 29.8 24.1 25.9 22.5 29.1 26.1 7.0 9.7 11.0 12.8 8.6 15.6 13.3 13.9 17.7 12.8 17.7 18.7 16.8 21.9 25.9 21.1 22.5 29.5 19.8 28.0 27.3 27.0

Pc (bar)

1160.9 883.8 989.5 1218.0 1103.8 940.9

925.3 1267.2 1938.7

1045.7 1038.8 1050.3 983.3 1447.0 931.5

1167.4

1110.2

981.7 1408.9 931.5 1012.6 955.5 1069.7 948.6 993.2 2840.1 2154.8 1926.4 1697.9 2383.2 1389.3 1640.8 1583.7 1298.1 1697.9 1298.1 1241.0 1355.3 1046.6 955.5 1126.8 1069.7 856.9 1183.9 898.4 875.3 1053.1

Vc (cm3/mol)

0.2221 0.3199 0.2368 0.2177 0.2268 0.3083

0.2452 0.2322 0.1828

0.2502 0.2571 0.2802 0.2666 0.2126 0.2648

0.2309

0.2367

0.2645 0.2324 0.2648 0.2779 0.2863 0.2701 0.2579 0.2889 0.1310 0.1726 0.1885 0.2060 0.1579 0.2052 0.2108 0.2156 0.2430 0.2060 0.2430 0.2492 0.2371 0.2317 0.2863 0.2627 0.2701 0.2933 0.2558 0.2953 0.2481 0.2429

Zc

0.2465 0.2805 0.1186 0.2908 0.2030 0.3229

0.2338 0.4983 1.0159

0.3669 0.3160 0.3467 0.2505 0.6662 0.2794

0.3939

0.3484

0.2723 0.6653 0.2794 0.3777 0.3334 0.4228 0.2695 0.3025 0.4734 0.9913 0.9857 0.8923 0.8960 0.4263 0.8585 0.8216 0.6068 0.8923 0.6068 0.5608 0.6523 0.1603 0.3334 0.4685 0.4228 0.2599 0.5146 0.2900 0.0384 0.3037

ω

Ind. Eng. Chem. Res., Vol. 48, No. 14, 2009 6893

ionic liquid

[S114] [bti] [S112] [bti] [NH11(i-3)] [bti]

[S115] [bti] [S113] [bti] [S124] [bti] [S125] [bti] [S123] [bti] [DEME] [bti]

[BMP] [bti] [N222(2O1)] [bti] [P222(2O1)] [bti] [N222(1O1)] [bti] [P222(1O1)] [bti]

[NH222] [bti] [N222(12)] [bti] [P222(12)] [bti] [P2228] [bti] [N2225] [bti] [P2225] [bti] [bmim] [Br] [C35guan] [Cl] [bmim] [Cl] [hmim] [Cl] [omim] [Cl] [Bemim] [Cl] [C12mim] [Cl] [emim] [Cl] [mmim] [Cl] [mim] [Cl] [ClBenmim] [Cl] [FBenmim] [Cl] [C23guan] [Cl] [dbim] [Cl] [bmim] [dca] [emim] [dca] [omim] [dca] [4MOPY] [dca] [mbpyr] [dca] [mhpyr] [dca] [mprpyr] [dca] [emim] [DEGlyMSO4] [dmim] [DMPO4] [py] [EOESO4] [edmim] [ESO4] [emim] [ESO4] [omim] [PF6] [bdmim] [PF6] [hpmim] [PF6]

No.

IL-87 IL-88 IL-89

IL-90 IL-91 IL-92 IL-93 IL-94 IL-95

IL-96 IL-97 IL-98 IL-99 IL-100

IL-101 IL-102 IL-103 IL-104 IL-105 IL-106 IL-107 IL-108 IL-109 IL-110 IL-111 IL-112 IL-113 IL-114 IL-115 IL-116 IL-117 IL-118 IL-119 IL-120 IL-121 IL-122 IL-123 IL-124 IL-125 IL-126 IL-127 IL-128 IL-129 IL-130 IL-131 IL-132 IL-133 IL-134 IL-135

Table 3. Continued

C8H16N2F6S2O4 C20H40N2F6S2O4 C20H40PNF6S2O4 C16H32PNF6S2O4 C13H26N2F6S2O4 C13H26PNF6S2O4 C8H15N2Br C35H74N3Cl C8H15N2Cl C10H19N2Cl C12H23N2Cl C11H13N2Cl C16H31N2Cl C6H11N2Cl C5H9N2Cl C4H7N2Cl C11H12N2Cl2 C11H12N2FCl C23H50N3Cl C11H21N2Cl C10H15N5 C8H11N5 C14H23N5 C16H24N4 C11H20N4 C13H24N4 C10H18N4 C11H22N2SO6 C7H15N2PO4 C9H15NSO5 C9H18N2SO4 C8H16N2SO4 C12H23N2PF6 C9H17N2PF6 C11H21N2PF6

C12H22N2F6S2O4 C11H22N2F6S2O5 C11H22PNF6S2O5 C10H20N2F6S2O5 C10H20PNF6S2O5

C9H17NF6S3O4 C7H13NF6S3O4 C9H17NF6S3O4 C10H19NF6S3O4 C8H15NF6S3O4 C10H20N2F6S2O5

C8H15NF6S3O4 C6H11NF6S3O4 C7H14N2F6S2O4

global formula dimethylbutylsulfonium bis[(trifluoromethyl)sulfonyl]imide dimethylethylsulfonium bis[(trifluoromethyl)sulfonyl]imide dimethylisopropyl(quaternary)ammonium bis[(trifluoromethyl)sulfonyl]imide dimethylpentylsulfonium bis[(trifluoromethyl)sulfonyl]imide dimethylpropylsulfonium bis[(trifluoromethyl)sulfonyl]imide methylethylbutylsulfonium bis[(trifluoromethyl)sulfonyl]imide methylethylpentylsulfonium bis[(trifluoromethyl)sulfonyl]imide methylethylpropylsulfonium bis[(trifluoromethyl)sulfonyl]imide N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis[(trifluoromethyl)sulfonyl]imide N-butyl-N-methylpiperidinium bis[(trifluoromethyl)sulfonyl]imide triethyl(2-methoxyethyl)ammonium bis[(trifluoromethyl)sulfonyl]imide triethyl(2-methoxyethyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide triethyl(2-methoxymethyl)ammonium bis[(trifluoromethyl)sulfonyl]imide triethyl(2-methoxymethyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide triethyl(quaternary)ammonium bis[(trifluoromethyl)sulfonyl]imide triethyldodecylammonium bis[(trifluoromethyl)sulfonyl]imide triethyldodecylphosphonium bis[(trifluoromethyl)sulfonyl]imide triethyloctylphosphonium bis[(trifluoromethyl)sulfonyl]imide triethylpentylammonium bis[(trifluoromethyl)sulfonyl]imide triethylpentylphosphonium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-3-methylimidazolium bromide [bis(bisoctylamine)methylene]dimethylammonium chloride 1-butyl-3-methylimidazolium chloride 1-hexyl-3-methylimidazolium chloride 1-octyl-3-methylimidazolium chloride 1-benzyl-3-methylimidazolium chloride 1-dodecyl-3-methylimidazolium chloride 1-ethyl-3-methylimidazolium chloride 1-methyl-3-methylimidazolium chloride 1-methylimidazolium chloride 1-p-chlorobenzyl-3-methylimidazolium chloride 1-p-fluorobenzyl-3-methylimidazolium chloride [bis(bispentylamine)methylene]dimethylammonium chloride 1,3-dibutylimidazolium chloride 1-butyl-3-methylimidazolium dicyanamide 1-ethyl-3-methylimidazolium dicyanamide 1-octyl-3-methylimidazolium dicyanamide 4-methyl-n-octylpyridinium dicyanamide n-methyl-n-butylpyrrolidinium dicyanamide n-methyl-n-hexylpyrrolidinium dicyanamide n-methyl-n-propylpyrrolidinium dicyanamide 1-ethyl-3-methylimidazolium diethyleneglycol monomethylethersulfate 1,3-dimethylimidazolium dimethylphosphate pyridinium ethoxyethylsulfate 1-ethyl-2,3-dimethylimidazolium ethylsulfate 1-ethyl-3-methylimidazolium ethylsulfate 1-octyl-3-methylimidazolium hexafluorophosphate 1-butyl-2,3-dimethylimidazolium hexafluorophosphate 1-heptyl-3-methylimidazolium hexafluorophosphate

IUPAC name

382.4 550.7 567.6 511.5 452.5 469.5 219.1 572.5 174.7 202.7 230.8 208.7 286.9 146.6 132.6 118.6 243.1 226.7 404.1 216.8 205.3 177.2 261.4 272.4 208.3 236.4 194.3 310.4 222.2 249.3 250.3 236.3 340.3 298.2 326.3

436.4 440.4 457.4 426.4 443.4

413.4 385.4 413.4 427.5 399.4 426.4

399.4 371.3 368.3

M

730.3 967.1 990.2 898.7 807.0 830.1 586.8 1140.7 558.0 603.8 649.6 653.4 741.1 512.3 489.4 450.5 695.8 657.6 866.1 626.7 783.0 737.2 874.5 864.1 680.3 726.1 657.4 826.2 590.0 691.4 740.5 712.7 646.1 582.4 623.2

782.7 783.6 806.7 760.7 783.9

820.5 774.8 820.5 843.4 797.6 760.7

797.6 751.9 707.0

Tb (K)

1075.3 1227.4 1260.3 1188.7 1102.5 1139.5 834.9 1411.1 789.0 829.2 869.4 921.3 951.5 748.6 728.2 677.8 969.6 913.1 1052.1 849.2 1035.8 999.0 1113.1 1094.3 887.2 929.3 866.5 1162.9 816.8 1025.9 1082.6 1067.5 810.8 746.3 787.8

1108.0 1096.3 1134.6 1080.7 1119.8

1202.0 1178.3 1202.0 1214.5 1189.9 1080.7

1189.9 1167.2 1065.7

Tc (K)

29.3 13.9 13.7 16.4 19.8 19.3 29.8 7.4 27.8 23.5 20.3 28.4 16.0 34.2 38.5 48.1 26.8 26.4 10.5 21.8 24.4 29.1 18.4 17.2 20.6 18.1 22.1 28.1 27.2 41.3 35.8 40.5 14.0 16.2 14.7

22.6 22.0 21.4 23.5 22.8

20.5 23.4 20.5 19.3 21.9 23.5

21.9 25.2 32.2

Pc (bar)

940.9 1583.7 1624.0 1395.6 1183.9 1224.2 583.3 2202.6 568.8 683.0 797.2 631.8 1025.6 454.5 397.4 333.1 682.6 652.0 1517.3 740.1 712.0 597.8 940.5 989.1 772.2 886.4 715.1 862.3 626.8 644.3 715.3 659.8 990.9 818.0 933.8

1107.4 1085.3 1125.6 1028.2 1068.5

1103.8 989.5 1103.8 1160.9 1046.6 1028.2

1046.6 932.4 882.1

Vc (cm3/mol)

0.3083 0.2156 0.2120 0.2323 0.2558 0.2499 0.2506 0.1385 0.2415 0.2328 0.2240 0.2343 0.2072 0.2495 0.2530 0.2841 0.2272 0.2271 0.1817 0.2284 0.2017 0.2095 0.1872 0.1872 0.2157 0.2078 0.2197 0.2502 0.2509 0.3116 0.2842 0.3008 0.2065 0.2141 0.2101

0.2722 0.2617 0.2553 0.2688 0.2619

0.2268 0.2368 0.2268 0.2221 0.2317 0.2688

0.2317 0.2423 0.3209

Zc

0.3229 0.8216 0.7861 0.6140 0.5146 0.4757 0.4891 0.5680 0.4914 0.5725 0.6566 0.5145 0.8212 0.4165 0.3825 0.4158 0.5521 0.5660 1.0428 0.6144 0.8419 0.7661 0.9908 0.9923 0.8555 0.9314 0.8161 0.5176 0.5973 0.4224 0.4341 0.3744 0.9385 0.8526 0.9055

0.3917 0.4370 0.3980 0.3915 0.3525

0.2030 0.1186 0.2030 0.2465 0.1603 0.3915

0.1603 0.0779 0.2648

ω


ionic liquid

[nmim] [PF6] [oprim] [PF6] [pmim] [PF6] [eommim] [PF6] [mommim] [PF6] [N-bupy] [PF6] [Ph(CH2)3mim] [PF6] [prmim] [PF6] [C2C6I] [PF6] [C2C8I] [PF6] [bmim] [HSO4] [emim] [HSO4] [mim] [HSO4] [bmim] [I] [TMG] [Lac] [bmim] [mesy] [emim] [mesy] [dmim] [MOESO4] [dmim] [MSO4] [bmim] [MSO4] [MMMPZ] [MSO4] [MTEOA] [MSO4] [bmim] [NfO] [omim] [NfO] [bmim] [C8S] [tibmp] [pTSO3] [Ch] [Sa] [bdmim] [BF4] [C10mim] [BF4] [N-epy] [BF4] [moemim] [BF4] [prmim] [BF4] [mommim] [BF4] [bpy] [BF4] [4MOPY] [BF4] [C23guan] [BF4] [DEME] [BF4] [bmim] [tca] [emim] [SCN] [N-epy] [ta] [emim] [ta] [mopmi] [TfO] [dbim] [TfO] [N8444] [TfO] [Bemim] [TfO] [mbpy] [TfO] [omim] [TfO] [4MOPY] [TfO] [dmprim] [TMEM] [bmim] [TMEM] [bmim] [BF4] [emim] [BF4]

No.

IL-136 IL-137 IL-138 IL-139 IL-140 IL-141 IL-142 IL-143 IL-144 IL-145 IL-146 IL-147 IL-148 IL-149 IL-150 IL-151 IL-152 IL-153 IL-154 IL-155 IL-156 IL-157 IL-158 IL-159 IL-160 IL-161 IL-162 IL-163 IL-164 IL-165 IL-166 IL-167 IL-168 IL-169 IL-170 IL-171 IL-172 IL-173 IL-174 IL-175 IL-176 IL-177 IL-178 IL-179 IL-180 IL-181 IL-182 IL-183 IL-184 IL-185 IL-186 IL-187

Table 3. Continued

C13H25N2PF6 C14H27N2PF6 C9H17N2PF6 C7H13N2OPF6 C6H11N2OPF6 C9H14NPF6 C13H17N2PF6 C7H13N2PF6 C11H21N2PF6 C13H25N2PF6 C8H16N2SO4 C6H13N2SO4 C4H8N2SO4 C8H15N2I C8H19N3O3 C9H18N2SO3 C7H14N2SO3 C8H16N2SO5 C6H12N2SO4 C9H18N2SO4 C7H14N2SO4 C8H21NSO7 C12H15N2F9SO3 C16H23N2F9SO3 C16H32N2SO4 C20H37PSO3 C12H19NO4 C9H17N2BF4 C14H27N2BF4 C7H10NBF4 C7H13N2OBF4 C7H13N2BF4 C6H11N2OBF4 C9H14NBF4 C14H24NBF4 C23H50N3BF4 C8H20NOBF4 C9H15N3S C7H11N3S C9H10NF3O2 C8H11N2F3O2 C12H13N2F3SO4 C12H21N2F3SO3 C21H44NF3SO3 C12H13N2F3SO3 C11H16NF3SO3 C13H23N2F3SO3 C15H24NF3SO3 C12H15N2F9S3O6 C12H15N2F9S3O6 C8H15N2BF4 C6H11N2BF4

global formula 1-nonyl-3-methylimidazolium hexafluorophosphate 1-octyl-3-propylimidazolium hexafluorophosphate 1-pentyl-3-methylimidazolium hexafluorophosphate ethoxymethyl-3-methylimidazolium hexafluorophosphate methyloxymethyl-3-methylimidazolium hexafluorophosphate n-butylpyridinium hexafluorophosphate 1-(3-phenylalkyl)-3-methylimidazolium hexafluorophosphate 1-propyl-3-methylimidazolium hexafluorophosphate 1-hexyl-3-ethylimidazolium hexafluorophosphate 1-octyl-3-methylimidazolium hexafluorophosphate 1-butyl-3-methylimidazolium hydrogensulfate 1-ethyl-3-methylimidazolium hydrogensulfate 1-methylimidazolium hydrogensulfate 1-butyl-3-methylimidazolium iodide 1,1,3,3-tetramethylguanidine lactate 1-butyl-3-methylimidazolium methanesulfonate 1-ethyl-3-methylimidazolium methanesulfonate 1,3-dimethylimidazolium methoxyethylsulfate 1,3-dimethylimidazolium methylsulfate 1-butyl-3-methylimidazolium methylsulfate 1,2,4-trimethylpyrazolium methylsulfate tris(hydroxyethyl)methylammonium methylsulfate 1-butyl-3-methylimidazolium nonafluorobutanesulfonate 1-octyl-3-methylimidazolium nonafluorobutanesulfonate 1-butyl-3-methylimidazolium octylsulfate triisobutylmethylphosphonium p-toluenesulfonate choline salicylate 1-butyl-2,3-dimethylimidazolium tetrafluoroborate 1-decyl-3-methylimidazolium tetrafluoroborate 1-ethylpyridinium tetrafluoroborate ethyloxymethyl-3-methylimidazolium tetrafluoroborate 1-propyl-3-methylimidazolium tetrafluoroborate methyloxymethyl-3-methylimidazolium tetrafluoroborate 1-butylpyridinium tetrafluoroborate 4-methyl-n-octylpyridinium tetrafluoroborate [bis(bispentylamine)methylene]dimethylammonium tetrafluoroborate N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate 1-butyl-3-methylimidazolium thiocyanate 1-ethyl-3-methylimidazolium thiocyanate 1-ethylpyridinium trifluoroacetate 1-ethyl-3-methylimidazolium trifluoroacetate 1-(4-methoxyphenyl)-3-methylimidazolium trifluoromethanesulfonate 1,3-dibutylimidazolium trifluoromethanesulfonate tributyloctylammonium trifluoromethanesulfonate 1-benzyl-3-methylimidazolium trifluoromethanesulfonate 1-butyl-4-methylpyridinium trifluoromethanesulfonate 1-octyl-3-methylimidazolium trifluoromethanesulfonate 4-methyl-n-octylpyridinium trifluoromethanesulfonate 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide 1-butyl-3-methilimidazolium tris(trifluoromethylsulfonyl)methide 1-butyl-3-methilimidazolium tetrafluoroborate 1-ethyl-3-methylimidazolium tetrafluoroborate

IUPAC name 354.3 368.3 298.2 286.2 272.1 281.2 346.3 270.2 326.3 354.3 236.3 208.2 180.2 266.1 205.3 234.3 206.3 252.3 208.2 250.3 222.3 275.3 438.3 494.4 348.5 388.6 241.3 240.1 310.2 195.0 228.0 212.0 214.0 223.0 293.2 455.5 233.1 197.3 169.3 221.2 224.2 338.3 330.4 447.7 322.3 299.3 344.4 355.4 550.4 550.4 226.0 198.0

M 669.0 691.9 577.5 554.1 531.2 516.3 695.7 531.7 623.2 669.0 782.4 736.7 674.9 613.7 632.7 713.1 667.4 735.1 666.9 735.6 694.8 865.1 762.3 853.8 895.7 894.2 762.2 523.1 632.5 411.2 494.8 472.3 471.9 456.9 576.3 803.3 393.5 763.1 717.3 535.1 573.4 830.4 776.4 858.2 803.0 697.3 799.2 788.8 1039.3 1034.4 495.2 449.5

Tb (K) 834.1 857.6 742.1 723.7 701.2 674.4 885.1 696.7 787.8 834.1 1103.8 1073.8 1012.7 871.2 816.9 1054.8 1026.0 1094.4 1040.0 1081.6 1054.2 1093.4 1028.8 1103.0 1189.8 1164.2 950.5 671.0 784.6 549.9 647.0 619.7 623.7 597.6 720.8 975.1 501.4 1047.4 1013.6 739.9 785.3 1184.7 1072.0 1066.7 1158.0 997.8 1088.7 1065.7 1568.6 1571.4 643.2 596.2

Tc (K) 13.4 12.8 16.3 18.2 19.3 17.3 15.7 18.3 14.7 13.4 43.4 57.6 91.9 28.6 27.2 37.4 48.1 38.9 52.9 36.1 45.4 35.2 17.3 14.2 20.2 16.9 23.9 18.9 14.5 23.5 21.7 21.9 23.3 20.3 15.1 9.2 17.1 19.4 22.3 24.2 24.3 28.0 23.2 12.6 29.0 26.9 21.6 20.1 23.9 24.0 20.4 23.6

Pc (bar) 1048.1 1105.2 819.6 721.0 663.9 755.6 939.7 705.4 933.8 1048.1 664.9 550.7 429.2 607.5 639.1 701.3 587.1 675.4 545.6 716.9 601.1 744.3 1004.8 1233.3 1116.7 1277.2 726.4 710.5 997.7 533.9 613.5 597.9 556.4 648.1 932.1 1603.5 693.1 780.7 666.4 586.5 593.4 827.7 922.0 1458.4 813.7 799.3 979.1 1027.8 1212.0 1213.6 655.0 540.8

Vc (cm3/mol) 0.2028 0.1991 0.2171 0.2177 0.2201 0.2325 0.2007 0.2232 0.2101 0.2028 0.3142 0.3553 0.4684 0.2402 0.2557 0.2991 0.3312 0.2887 0.3339 0.2878 0.3113 0.2885 0.2030 0.1908 0.2286 0.2236 0.2192 0.2413 0.2214 0.2747 0.2471 0.2537 0.2505 0.2652 0.2347 0.1819 0.2837 0.1738 0.1760 0.2311 0.2206 0.2353 0.2396 0.2072 0.2451 0.2587 0.2336 0.2332 0.2222 0.2233 0.2496 0.2573

Zc

0.9680 0.9937 0.8316 0.7697 0.7277 0.7381 0.8894 0.7504 0.9055 0.9680 0.7034 0.6411 0.6707 0.4835 1.1188 0.3990 0.3307 0.3855 0.3086 0.4111 0.3628 1.5198 0.5150 0.6926 0.7042 0.7445 1.4009 0.9476 1.0818 0.7495 0.8692 0.8485 0.8296 0.8307 1.0289 0.9385 0.9465 0.4781 0.3931 0.5483 0.6051 0.4481 0.5325 0.9461 0.4118 0.4153 0.5766 0.5898 0.1526 0.1322 0.8877 0.8087

ω


ionic liquid

[hmim] [BF4] [mbupy] [BF4] [omim] [BF4] [bhoedma] [Br] [ehoedma] [Br] [hhoedma] [Br] [prhoedma] [Br] [beim] [bti] [bmim] [bti] [deim] [bti] [edmim] [bti] [eDmim] [bti] [emim] [bti] [hmim] [bti] [ibmim] [bti] [mdeim] [bti] [meim] [bti] [moemim] [bti] [omim] [bti] [Ohea] [f] [bmim] [hb] [emim] [hb] [beim] [MsO] [beim] [NfO] [emim] [NfO] [bmim] [NO3] [bmim] [PF6] [emim] [PF6] [hmim] [PF6] [beim] [ta] [bmim] [ta] [deim] [ta] [beim] [TfO] [bmim] [TfO] [deim] [TfO] [C12eim] [TfO] [edmim] [TfO] [emim] [TfO] [prdmim] [bti] [C3OMEtOHMMN] [Ace] [C4OMEtOHMMN] [Ace] [C5OMEtOHMMN] [Ace] [C6OMEtOHMMN] [Ace] [C7OMEtOHMMN] [Ace] [C8OMEtOHMMN] [Ace] [C9OMEtOHMMN] [Ace] [C10OMEtOHMMN] [Ace] [C11OMEtOHMMN] [Ace] [bmim] [BMLB] [bmim] [BOB] [bpy] [BOB]

No.

IL-188 IL-189 IL-190 IL-191 IL-192 IL-193 IL-194 IL-195 IL-196 IL-197 IL-198 IL-199 IL-200 IL-201 IL-202 IL-203 IL-204 IL-205 IL-206 IL-207 IL-208 IL-209 IL-210 IL-211 IL-212 IL-213 IL-214 IL-215 IL-216 IL-217 IL-218 IL-219 IL-220 IL-221 IL-222 IL-223 IL-224 IL-225 IL-226 IL-227 IL-228 IL-229 IL-230 IL-231 IL-232 IL-233 IL-234 IL-235 IL-236 IL-237 IL-238

Table 3. Continued

C10H19N2BF4 C10H16NBF4 C12H23N2BF4 C8H20NOBr C6H16NOBr C10H24NOBr C7H18NOBr C11H17N3F6S2O4 C10H15N3F6S2O4 C9H13N3F6S2O4 C9H13N3F6S2O4 C9H13N3F6S2O4 C8H11N3F6S2O4 C12H19N3F6S2O4 C10H15N3F6S2O4 C10H15N3F6S2O4 C8H11N3F6S2O4 C9H13N3F6S2O5 C14H23N3F6S2O4 C3H9NO3 C12H15N2F7O2 C10H11N2F7O2 C10H20N2SO3 C13H17N2F9SO3 C10H11N2F9SO3 C8H15N3O3 C8H15N2PF6 C6H11N2PF6 C10H19N2PF6 C11H17N2F3O2 C10H15N2F3O2 C9H13N2F3O2 C10H17N2F3SO3 C9H15N2F3SO3 C8H13N2F3SO3 C18H33N2F3SO3 C8H13N2F3SO3 C7H11N2F3SO3 C10H15N3F6S2O4 C11H22N2SO6 C12H24N2SO6 C13H26N2SO6 C14H28N2SO6 C15H30N2SO6 C16H32N2SO6 C17H34N2SO6 C18H36N2SO6 C19H38N2SO6 C16H27N2O6B C12H15N2O8B C13H14NO8B

global formula 1-hexyl-3-methylimidazolium tetrafluoroborate 4-methyl-N-butylpyridinium tetrafluoroborate 1-octyl-3-methylimidazolium tetrafluoroborate butyl-(2-hydroxyethyl)-dimethyammonium bromide ethyl-(2-hydroxyethyl)-dimethyammonium bromide hexyl-(2-hydroxyethyl)-dimethyammonium bromide propyl-(2-hydroxyethyl)-dimethyammonium bromide 1-butyl-3-ethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1,3-diethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-ethyl-2,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-ethyl-3,5-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-isobutyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 5-methyl-1,3-diethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-methyl-3-ethylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-metoxyethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide 2-hidroxyethylammonium formate 1-butyl-3-methilimidazolium heptafluorobutanoate 1-ethyl-3-methilimidazolium heptafluorobutanoate 1-butyl-3-ethylimidazolium methylsulfonate 1-butyl-3-ethylimidazolium nonafluorobutanesulfonate 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate 1-butyl-3-methilimidazolium nitrate 1-butyl-3-methylimidazolium hexafluorophosphate 1-ethyl-3-methylimidazolium hexafluorophosphate 1-hexyl-3-methylimidazolium hexafluorophosphate 1-butyl-3-ethylimidazolium trifluoroacetate 1-butyl-3-methylimidazolium trifluoroacetate diethylimidazolium trifluoroacetate 1-butyl-3-ethylimidazolium trifluoromethanesulfonate 1-butyl-3-methylimidazolium trifluoromethanesulfonate 1,3-diethylimidazolium trifluoromethanesulfonate 1-dodecyl-3-ethylimidazolium trifluoromethanesolfonate 1-ethyl-3,5-dimethylimidazolium trifluoromethanesolfonate 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 1-propyl-2,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ethoxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate propyloxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate butoxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate pentoxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate hexyloxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate heptyloxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate octyloxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate nonyloxymethyl(2-hydroxyethyl)dimethylammonium acesulfamate (2-hydroxyethyl)dimethylundecyloxymethylammonium acesulfamate 1-butyl-3-methylimidazolium bis(2-methyllactate)borate 1-butyl-3-methylimidazolium bis(oxalate)borate n-butyl-pyridinium bis(oxalate)borate

IUPAC name 254.1 237.0 282.1 226.2 198.1 254.2 212.1 433.4 419.4 405.3 405.3 405.3 391.3 447.4 419.4 419.4 391.3 421.3 475.5 107.1 352.3 324.2 248.4 452.3 410.3 201.2 284.2 256.1 312.2 266.3 252.2 238.2 302.3 288.3 274.3 414.5 274.3 260.2 419.4 310.4 324.4 338.4 352.5 366.5 380.5 394.5 408.6 422.6 354.2 326.1 323.1

M 541.0 484.8 586.7 554.8 509.1 600.6 531.9 885.3 862.4 839.6 844.5 844.5 816.7 908.2 862.0 867.4 816.7 862.0 954.0 410.1 655.5 609.8 736.0 785.2 716.5 694.9 554.6 508.8 600.3 642.0 619.2 596.3 730.6 707.7 684.8 913.6 689.8 662.0 867.4 910.4 933.3 956.2 979.1 1001.9 1024.8 1047.7 1070.6 1093.5 905.8 819.7 781.5

Tb (K) 690.0 625.8 737.0 732.3 687.9 776.6 710.1 1281.1 1269.9 1259.3 1258.9 1258.9 1249.3 1292.8 1275.2 1269.7 1249.3 1285.2 1317.8 571.3 846.7 803.8 1069.5 1046.9 993.4 954.8 719.4 674.0 764.9 847.6 826.8 806.1 1039.5 1023.5 1007.8 1177.2 1009.2 992.3 1269.7 1186.6 1204.7 1223.2 1242.2 1261.7 1281.7 1302.2 1323.4 1345.1 1146.2 1031.5 988.3

Tc (K) 17.9 18.9 16.0 25.2 30.2 21.6 27.5 25.6 27.6 30.0 29.8 29.8 32.7 23.9 27.9 27.5 32.7 29.1 21.0 49.6 15.6 17.4 33.6 16.4 19.4 27.3 17.3 19.5 15.5 19.6 20.9 22.5 27.0 29.5 32.4 16.1 32.1 35.8 27.5 28.5 26.2 24.3 22.6 21.1 19.8 18.6 17.6 16.7 17.7 22.3 22.3

Pc (bar) 769.2 703.7 883.4 626.4 512.2 740.7 569.3 1047.2 990.1 933.0 931.5 931.5 875.9 1104.4 988.4 988.6 875.9 948.6 1218.6 298.2 877.1 762.8 758.4 1061.9 890.6 645.9 762.5 648.3 876.7 764.7 707.6 650.5 807.8 750.7 693.6 1264.7 692.0 636.4 988.6 863.1 920.2 977.3 1034.4 1091.5 1148.6 1205.7 1262.8 1319.9 1041.9 868.2 861.3

Vc (cm3/mol) 0.2406 0.2556 0.2310 0.2596 0.2705 0.2483 0.2652 0.2521 0.2592 0.2670 0.2648 0.2648 0.2753 0.2454 0.2598 0.2572 0.2753 0.2579 0.2333 0.3116 0.1949 0.1991 0.2864 0.2000 0.2088 0.2224 0.2203 0.2258 0.2137 0.2124 0.2154 0.2182 0.2527 0.2600 0.2679 0.2079 0.2646 0.2765 0.2572 0.2492 0.2409 0.2333 0.2262 0.2196 0.2135 0.2077 0.2022 0.1969 0.1935 0.2261 0.2342

Zc

0.9625 0.8924 1.0287 0.8840 0.8079 0.9601 0.8456 0.3444 0.3004 0.2575 0.2794 0.2794 0.2157 0.3893 0.2846 0.3226 0.2157 0.2695 0.4811 0.8477 0.7598 0.6755 0.4366 0.5605 0.4239 0.6436 0.7917 0.7083 0.8697 0.7312 0.6891 0.6469 0.4463 0.4046 0.3643 0.7935 0.3869 0.3255 0.3226 1.0565 1.0930 1.1284 1.1620 1.1932 1.2212 1.2456 1.2656 1.2807 1.0185 1.2455 1.1914

ω


[moenm2e] [BOB] [bmim] [BScB] [C3(mim)2] [bti]

[C6(mim)2] [bti]

[C9(mim)2] [bti]

[C12(mim)2] [bti]

[C9(bim)2] [bti] [C9(m2im)2] [bti]

[C12(benzim)2] [bti]

[C9(mpy)2] [bti] [moenm2e] [bti]

[(be)2dmg] [bti]

[C10OOEtC2OMMMN] [bti]











[C9(mim)2] [Br] [C12(mim)2] [Br] [C9(bim)2] [Br] [pmim] [Br] [C5O2mim] [Cl] [(di-h)2dmg] [Cl] [(di-o)2dmg] [Cl] [BM2I] [dca] [C2OHmim] [PF6] [C3Omim] [PF6] [C5O2mim] [PF6]

IL-242

IL-243

IL-244

IL-245 IL-246

IL-247

IL-248 IL-249

IL-250

IL-251

IL-252

IL-253

IL-254

IL-255

IL-256

IL-257

IL-258

IL-259

IL-260

IL-261

IL-262 IL-263 IL-264 IL-265 IL-266 IL-267 IL-268 IL-269 IL-270 IL-271 IL-272

ionic liquid

IL-239 IL-240 IL-241

No.

Table 3. Continued

C17H30N4Br2 C20H36N4Br2 C23H42N4Br2 C9H17N2Br C9H17N2O2Cl C27H58N3Cl C35H74N3Cl C14H19N7 C6H11N2OPF6 C7H13N2OPF6 C9H17N2O2PF6

C28H54N2F6S2O7

C27H52N2F6S2O7

C26H50N2F6S2O7

C25H48N2F6S2O7

C24H46N2F6S2O7

C23H44N2F6S2O7

C22H42N2F6S2O7

C21H40N2F6S2O7

C20H38N2F6S2O7

C19H36N2F6S2O7

C18H34N2F6S2O7

C17H34N4F6S2O4

C25H34N4F12S4O8 C9H18N2F6S2O4

C36H44N6F12S4O8

C27H42N6F12S4O8 C23H36N6F12S4O8

C24H36N6F12S4O8

C21H30N6F12S4O8

C18H24N6F12S4O8

C11H18NO9B C22H23N2O6B C15H18N6F12S4O8

global formula N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(oxalate)borate 1-butyl-3-methylimidazolium bis(salicylate)borate 1,3-di(3-methylimidazolium)propane di-bis[(trifluoromethyl)sulfonyl]imide 1,6-di(3-methylimidazolium)hexane di-bis[(trifluoromethyl)sulfonyl]imide 1,9-di(3-methylimidazolium)nonane di-bis[(trifluoromethyl)sulfonyl]imide 1,12-di(3-methylimidazolium)dodecane di-bis[(trifluoromethyl)sulfonyl]imide 1,9-di(3-butylimidazolium)nonane di-bis[(trifluoromethyl)sulfonyl]imide 1,9-di(2,3-dimethylimidazolium)nonane di-bis[(trifluoromethyl)sulfonyl]imide 1,12-di(3-benzylimidazolium)dodecane di-bis[(trifluoromethyl)sulfonyl]imide 1,9-di(methylpyridinium)nonane di-bis[(trifluoromethyl)sulfonyl]imide N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis[(trifluoromethyl)sulfonyl]imide N,N′-dibutyl-N,N′-diethyl-N″,N″-dimethylguanidinium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)ethyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)propyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)butyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)pentyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)hexyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)heptyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)octyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)nonyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)decyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)undecyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide (2-decanoyloxyethyl)dodecyloxymethyldimethylammonium bis[(trifluoromethyl)sulfonyl]imide 1,9-di(3-methylimidazolium)nonane dibromide 1,12-di(3-methylimidazolium)dodecane dibromide 1,9-di(3-butylimidazolium)nonane dibromide 1-pentyl-3-methylimidazolium bromide 1-[2-(methoxyethoxy)-ethyl]-3-methylimidazolium chloride N,N,N′,N′-tetrahexyl-N″,N″-dimethylguanidinium chloride N,N,N′,N′-tetraoctyl-N″,N″-dimethylguanidinium chloride 1-(n-butyl)-1,3′-dimethyl-2,2′-biimidazolium dicyanamide 1-(2-hidroxyethyl)-3-methylimidazolium hexafluorophosphate 1-propoxymethyl-3-methylimidazolium hexafluorophosphate 1-[2-(methoxyethoxy)-ethyl]-3-methylimidazolium hexafluorophosphate

IUPAC name

450.3 492.3 534.4 233.2 220.7 460.2 572.5 285.4 272.1 286.2 330.2

708.9

694.8

680.8

666.8

652.8

638.7

624.7

610.7

596.7

582.6

568.6

536.6

874.8 412.4

1045.0

934.9 878.8

892.8

850.8

808.7

319.1 422.3 766.6

M

996.8 1065.4 1134.1 609.6 625.8 957.6 1140.7 1021.0 601.0 554.1 622.3

1267.1

1244.2

1221.3

1198.5

1175.6

1152.7

1129.8

1106.9

1084.1

1061.2

1038.3

987.5

1518.8 737.9

1944.7

1685.4 1603.9

1616.8

1548.2

1479.5

695.2 1112.8 1410.9

Tb (K)

1270.4 1328.7 1392.3 854.2 863.6 1158.9 1411.1 1306.0 766.9 723.7 795.3

1537.9

1513.5

1489.9

1467.1

1445.0

1423.7

1403.0

1382.9

1363.5

1344.7

1326.4

1271.0

1970.3 1065.4

2395.1

2116.5 2069.1

2079.4

2052.8

2037.2

868.1 1383.0 2033.6

Tc (K)

16.6 14.4 12.6 27.2 24.8 9.2 7.4 21.1 20.2 18.2 16.1

10.3

10.6

11.0

11.4

11.8

12.2

12.7

13.2

13.8

14.4

15.1

15.6

13.2 25.2

10.6

11.9 13.6

13.2

14.8

16.9

20.2 17.7 19.5

Pc (bar)

1197.5 1368.8 1540.2 640.4 657.1 1745.7 2202.6 951.3 669.0 721.0 850.8

2084.4

2027.3

1970.2

1913.1

1856.0

1798.9

1741.8

1684.7

1627.6

1570.5

1513.3

1481.8

2131.1 971.1

2651.2

2353.9 2122.3

2182.6

2011.2

1839.9

849.1 1196.6 1668.6

Vc (cm3/mol)

0.1883 0.1779 0.1680 0.2454 0.2273 0.1665 0.1385 0.1852 0.2120 0.2177 0.2069

0.1675

0.1711

0.1747

0.1784

0.1822

0.1861

0.1900

0.1941

0.1983

0.2026

0.2070

0.2184

0.1715 0.2764

0.1409

0.1588 0.1680

0.1666

0.1747

0.1831

0.2382 0.1838 0.1920

Zc

0.9068 1.0089 1.0752 0.5292 0.5707 0.9692 0.5680 1.0362 1.0367 0.7697 0.8676

1.0302

1.0332

1.0299

1.0205

1.0054

0.9850

0.9597

0.9301

0.8967

0.8599

0.8204

0.7803

0.6110 0.3467

0.8928

0.7974 0.6720

0.6748

0.5354

0.3899

1.2619 1.2047 0.2458

ω


0.1451 0.1361 0.1164 0.1235 0.2408 0.2471 0.2331 0.1702 0.1580 0.2225 0.1640 0.1318 0.2240 0.2065 0.2677 0.2310 0.2374 0.1565 0.1564 0.1462 0.1708 0.2359 1727.3 1898.6 2196.0 2396.4 561.5 613.5 743.3 1512.3 1683.6 1146.7 1832.0 2288.9 797.2 990.9 819.8 883.4 1159.9 2002.2 2423.5 2091.7 796.4 976.6 8.5 7.9 7.4 6.4 24.7 21.7 18.8 10.1 9.1 12.2 8.2 6.7 20.3 14.0 32.7 16.0 22.2 7.9 8.5 7.6 21.1 23.9 1219.8 1318.6 1671.1 1482.8 691.9 647.0 720.2 1074.4 1170.9 755.9 1100.3 1403.7 869.4 810.8 1204.8 737.0 1305.5 1222.8 1586.7 1315.9 1185.1 1192.7 1001.1 1069.7 1329.0 1137.2 541.6 494.8 562.9 882.4 951.0 620.3 894.8 1077.9 649.6 646.1 836.3 586.7 936.1 1006.2 1310.6 1072.7 915.1 871.9 1,12-di(3-methylimidazolium)dodecane bis(hexafluorophosphate) 1,9-di(3-butylimidazolium)nonane bis(hexafluorophosphate) 1,12-di(3-benzylimidazolium)dodecane bis(hexafluorophosphate) N,N,N′,N′-tetraoctyl-N″,N″-dimethylguanidinium hexafluorophosphate 1-(2-hidroxyethyl)-3-methylimidazolium tetrafluoroborate 1-propoxymethyl-3-methylimidazolium tetrafluoroborate 1-[2-(methoxyethoxy)-ethyl]-3-methylimidazolium tetrafluoroborate 1,12-di(3-methylimidazolium)dodecane bis(tetrafluoroborate) 1,9-di(3-butylimidazolium)nonane bis(tetrafluoroborate) N,N′-dibutyl-N,N′-diethyl-N″,N″-dimethylguanidinium tetrafluoroborate N,N,N′,N′-tetrahexyl-N″,N″-dimethylguanidinium tetrafluoroborate N,N,N′,N′-tetraoctyl-N″,N″-dimethylguanidinium tetrafluoroborate 1-methyl-3-octylimidazolium chloride 1-methyl-3-octylimidazolium hexafluorophosphate 1-ethyl-3-methylimidazolium tosylate 1-methyl-3-octylimidazolium tetrafluoroborate 1-hexyl-2,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide trihexyltetradecylphosphonium chloride trihexyltetradecylphosphonium bis[(trifluoromethyl)sulfonyl]imide tetradecyl(trihexyl)phosphonium acetate 1-butyl-3-methylimidazolium tricyanomethane 1-butyl-3-methylimidazolium diethyleneglycol monomethylethersulfate C20H36N4P2F12 C23H42N4P2F12 C32H44N4P2F12 C35H74N3PF6 C6H11N2OBF4 C7H13N2OBF4 C9H17N2O2BF4 C20H36N4B2F8 C23H42N4B2F8 C15H34N3BF4 C27H58N3BF4 C35H74N3BF4 C12H23N2Cl C12H23N2PF6 C13H18N2SO3 C13H18N2BF4 C13H21N3F6S2O4 C32H68PCl C34H68NF6PS2O4 C34H71O2P C12H15N5 C13H26N2SO6

622.5 664.5 774.7 682.0 214.0 228.0 272.1 506.1 548.2 343.3 511.6 623.8 230.8 340.3 282.4 282.1 461.5 519.3 764.0 542.9 229.3 338.4

Zc Vc (cm3/mol) Pc (bar) Tc (K) Tb (K) IUPAC name global formula

M

0.8285 0.6496 0.4407 0.1285 1.1643 0.8692 0.9644 0.9804 0.7841 1.1454 0.7076 0.1696 0.6566 0.9385 0.4670 1.0287 0.4578 0.7947 0.8915 0.6705 0.9266 0.6039


ω

6898

values of the contributions to estimate the properties. These numbers must not be changed. Columns from C1 to C4 contain information to identify the ionic liquid. File C5 contains the molecular mass of the substance and files from C6 to C49 include the numbers of groups of each type forming the molecule. Columns 50 and 51 contain values of density and the corresponding temperature than can be included to check the accuracy of the critical properties. These columns (50 and 51) are optional, although it is recommended to fill with the value 1.0 for the density and 298 for the temperature so the following columns where the density and the density deviations are calculated are not undefined. If this is the case, deviations have no meaning. From columns C52 to C57 (yellow) the calculated values of Vc (cm3/mol), Tb (K), Tc (K), Pc (bar), Zc, and ω are listed. Columns C58 and C59 (light green) gives the molecular mass M determined using the number of groups introduced by the user in columns C6 to C49. This is done to check that the groups and the number of groups forming that molecule that were introduced in columns C6 to C49 are correct. If they are correct the difference between the calculated M (column C58) and the value determined by the global formula and introduced by the user in column C5 should be zero (column C59). Care must be taken when selecting the groups forming the molecule, to clearly distinguish between ring contributions (in red color in columns C39 to C49) and nonring contributions (in blue color in columns C6 to C38). In columns C60 and C61 (light blue), density estimations are provided. Column C60 shows the density of the ionic liquid, estimated using the generalized equation recently proposed by Valderrama and Zarricueta,13 shown in Table 1. Column C61 shows the deviation between the calculated density Fcalc and the literature value Flit introduced in column C50. The temperature used in this calculation is that introduced in column C51. Finally, column C62 shows the reference from the literature from where the experimental density (column C50) was obtained. The full reference is listed in the second sheet of the Excel file. As previously explained by the authors,1,2 the calculation of the density is done as a global test of the consistency of the estimated critical properties. If fact the 294 ionic liquids considered in this study are those for which density values are available in the literature, so that the test could be performed. Errors are within deviations found between experimental data reported by different authors for some ionic liquids. Overall deviations and some other statistical values are similar as those found in previous papers by the authors, the fact that reinforces the statement given above that the changes introduced in this paper do not affect the overall estimation of the proposed method1,2 by correctness must prevail.

ionic liquid

[C12(mim)2] [PF6] [C9(bim)2] [PF6] [C12(benzim)2] [PF6] [(di-o)2dmg] [PF6] [C2OHmim] [BF4] [C3Omim] [BF4] [C5O2mim] [BF4] [C12(mim)2] [BF4] [C9(bim)2] [BF4] [(be)2dmg] [BF4] [(di-h)2dmg] [BF4] [(di-o)2dmg] [BF4] [moim] [Cl] [moim] [PF6] [emim] [tos] [moim] [BF4] [hdmim] [bti] [6,6,6,14-P] [Cl] [6,6,6,14-P] [bti] [6,6,6,14-P] [Ac] [bmim] [tcc] [bmim] [DEGlyMSO4]

No.

IL-273 IL-274 IL-275 IL-276 IL-277 IL-278 IL-279 IL-280 IL-281 IL-282 IL-283 IL-284 IL-285 IL-286 IL-287 IL-288 IL-289 IL-290 IL-291 IL-292 IL-293 IL-294

Table 3. Continued

Conclusions A consistent group contribution method proposed by the authors in previous communications has been revised and some inaccuracies have been corrected. The method as stated in this paper could be used for any reasonable estimation of critical properties of ionic liquids. In the future, new groups could be added, but the basis given with the 44 defined groups should be enough to involve hundreds or thousands of ionic liquids. The values provided plus the results previously presented by the authors3 represent the most complete database on estimated critical properties, normal boiling


6899

Table 4. Sample of the Spreadsheet Provided as Supporting Information to Determine the Critical Properties of Ionic Liquids C1

C2

no. IL-1

C3

ionic liquid [P11] [tsac]

C14

C4

global formula C9H14N2F6SO3

C15

C16

C17

IUPAC name 1,1-dimethylpyrrolidinium [2,2,2-trifluoro-n-(trifluoro methyl) sulfonyl]acetamide

C18

d(-)CH d(-)C- -OH -O- >CdO 13.019 12.011 17.008 15.999 28.011 0.0078 0.0078 0.0723 0.0051 0.0247 0.1429 0.1429 0.1343 0.13 0.2341 43.97 43.97 30.4 15.61 69.76 92.88 22.42 94.97 d(-)CH d(-)C- -OH -O- >CdO 0 0 0 0 1

C19

C5

C6

C7

C8

C9

C10

C11

C12

C13

Mi ) ∆Tc ) ∆Pc ) ∆Vc) ∆Tb ) M 344.3

-CH3 15.035 0.0275 0.3031 66.81 23.58 -CH3 2

-CH214.027 0.0159 0.2165 57.11 22.88 -CH24

>CH13.019 0.0002 0.114 45.7 21.74 >CH0

>C< 12.011 -0.0206 0.0539 21.78 18.25 >C< 2

dCH2 14.027 0.017 0.2493 60.37 18.18 dCH2 0

dCH13.019 0.0182 0.1866 49.92 24.96 dCH0

dC< 12.011 -0.0003 0.0832 34.9 24.14 dC< 0

dCd 12.011 -0.0029 0.0934 33.85 26.15 dCd 0

C27

C28

C24

C25

-CHO -COOH -COO- -HCOO- dO (any_other) 29.019 45.018 44.010 45.018 15.999 0.0294 0.0853 0.0377 0.036 0.0273 0.3128 0.4537 0.4139 0.4752 0.2042 77.46 88.6 84.76 97.77 44.03 72.24 169.06 81.10 -10.50 -CHO -COOH -COO- HCOOdO (other) 0 0 0 0 0

C20

C21

C22

C23

-NH2 16.023 0.0364 0.1692 49.1 73.23 -H2 0

-NH3 17.031 0.0364 0.1692 49.1 73.23 -NH3 0

C26

-NH>NdN15.015 14.007 14.007 0.0119 -0.0028 0.0172 0.0322 0.0304 0.1541 78.96 26.7 45.54 50.17 11.74 74.60 -NH>NdN0 2 0

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

-CN 26.018 0.0506 0.3697 89.32 125.66 -CN 0

-NO2 46.006 0.0448 0.4529 123.62 152.54 -NO2 0

-F 18.999 0.0228 0.2912 31.47 -0.03 -F 6

-Cl 35.453 0.0188 0.3738 62.08 38.13 -Cl 0

-Br 79.904 0.0124 0.5799 76.6 66.86 -Br 0

-I 126.905 0.0148 0.9174 100.79 93.84 -I 0

-P 30.974 -0.0084 0.1776 67.01 34.86 -P 0

· -B 10.811 0.0352 0.0348 22.45 -24.56 -B 0

· -S32.066 0.0006 0.6901 184.67 117.52 -S0

OdSdO 64.065 -0.0563 -0.0606 112.19 147.24 -SO2 1

-CH214.027 0.0116 0.1982 51.64 27.15 -CH20

>CH13.019 0.0081 0.1773 30.56 21.78 >CH0

dCH13.019 0.0114 0.1693 42.55 26.73 dCH0

>C< 12.011 -0.018 0.0139 17.62 21.32 >C< 0

dC< 12.011 0.0051 0.0955 31.28 31.01 dC< 0

-O15.999 0.0138 0.1371 17.41 31.22 -O0

C45

C46

C47

C48

C49

-OH (phenols) 17.008 0.0291 0.0493 -17.44 76.34 -OH 0

>CdO 28.011 0.0343 0.2751 59.32 94.97 >CdO 0

-NH15.015 0.0244 0.0724 27.61 52.82 -NH0

>N14.007 0.0063 0.0538 25.17 68.16 >N0

dN14.007 -0.0011 0.0559 42.15 57.55 dN0

C58

C59

checking molecular mass. M(cal) should be equal to the value M entered as data (column C5)

M(calc) 344.3

∆M 0.0

C50

C51

expt density, to check critical properties (optional) F (lit) 1.4300

T (K) 298.15

C60

C52

C53

temperature, and acentric factor of ionic liquids available in the open literature. Acknowledgment The authors thank the support of the Direction of Research of the University of La Serena, of the Center for Technological Information of La Serena-Chile, and of the National Council for Scientific and Technological Research (CONICYT), through the research grant FONDECYT 1070025. Supporting Information Available: The spreadsheet described in Table 4, that can be used for further calculations, is provided. This material is available free of charge via the Internet at http://pubs.acs.org.

C55

C56

C57

calculated properties; the equations used in the calculation are given in the other sheet: “eqns. & refs.” used”

Vc (cm3/mol) 836.5

Tb (K) 638.9

Tc (K) 889.7

C61

calculated density and deviation %∆F from expt density, given as data (column C50)

F(calc) 1.3845

C54

Pc (bar) 23.61

Zc 0.2670

ω 0.4956

C62 references for expt density (C50-C51). Full reference in the other sheet:“eqns. & refs. used”

%∆F -3.2

ref 1

CPG - CPL ) Heat capacity difference M ) molecular mass Mcal ) calculated molecular mass no. ) number of ionic liquids n ) number of times that a group appears in a molecule (number frequency, in Table 1) Pb ) normal boiling pressure (1.01325 bar) Pc ) critical pressure R ) ideal gas constant (83.144 bar cm3/mol K) T ) temperature Tb ) normal boiling temperature Tc ) critical temperature Vc ) critical volume Zc ) critical compressibility factor

Notation

AbbreViations

A, B, C, D ) coefficients in the Modified Lydersen-Joback-Reid method

IL ) ionic liquid log ) base 10 logarithm

6900


Greek Letters FL ) liquid density Fcalc ) liquid density calculated with the proposed method Flit ) liquid density from the literature %∆F ) percent relative deviation between calculated and literature values for the liquid density ∆Hvap ) heat of vaporization ∆M ) difference in molecular mass: M-M(cal) ∆Tb ) contribution to the normal boiling temperature the Modified Lydersen-Joback-Reid method ∆Tc, ∆Pc, ∆Vc ) contribution to the critical properties in the Modified Lydersen-Joback-Reid method Ω ) temperature function in density equation (Table 1) ω ) acentric factor

Literature Cited (1) Valderrama, J. O.; Robles, P. A. Critical Properties, Normal Boiling Temperatures, and Acentric Factors of Fifty Ionic Liquids. Ind. Eng. Chem. Res. 2007, 46, 1338–1344. (2) Valderrama, J. O.; Sanga, W. W.; Lazzs´, J. A. Critical Properties, Normal Boiling Temperatures, and Acentric Factors of Another 200 Ionic Liquids. Ind. Eng. Chem. Res. 2008, 47, 1318–1330. (3) Lydersen, A. L. Estimation of Critical Properties of Organic Compounds; Univ. of Wisconsin, Coll. Eng., Engineering Experimental Station: Madison, WI, 1955; Report 3. (4) Joback, K. K.; Reid, R. Estimation of Pure Component Properties from Group Contribution. Chem. Eng. Commun. 1987, 57, 233–247.

(5) Rebelo, L. P.; Canongia, J. N.; Esperanca, J. M.; Filipe, E. On the Critical Temperature, Normal Boiling Point, and Vapor Pressure of Ionic Liquids. J. Phys. Chem. B 2005, 109 (13), 6040–6043. (6) Jones, R. G.; Licence, P.; Lovelock, K. R. J.; Villar-Garcia, I. J. Comment on Critical Properties, Normal Boiling Temperatures, and Acentric Factors of Fifty Ionic Liquids. Ind. Eng. Chem. Res. 2007, 46, 6061–6062. (7) Valderrama, J. O.; Robles, P. A. Reply to Comment on Critical Properties, Normal Boiling Temperature, and Acentric Factor of Fifty Ionic Liquids. Ind. Eng. Chem. Res. 2007, 46 (18), 6063–6064. (8) Gardas, R. L.; Freire, M. G.; Carvalho, P. J.; Marrucho, I. M.; Fonseca, I. M. A.; Ferreira, A. G. M.; Coutinho, J. A. P. PFT Measurements of Imidazolium-Based Ionic Liquids. J. Chem. Eng. Data 2007, 52 (5), 1881–1888. (9) Carvalho, P. J. et al. High pressure phase behavior of carbon dioxide in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids. Jo. Supercrit. Fluids, in press. doi:10.1016/j.supflu.2008.10.012. (10) Alvarez, V. H.; Larico, R.; Ianos, Y.; Aznar, M. Parameter Estimation For VLE Calculation by Global Minimization: The Genetic Algorithm. Braz. J. Chem. Eng. 2008, 25 (2), 409–418. (11) Valderrama, J. O.; Reategui, a.; Sanga, W. W. Thermodynamic Consistency Test of Vapor-Liquid Equilibrium Data for Mixtures Containing Ionic Liquids. Ind. Eng. Chem. Res. 2008, 47 (21), 8416–8422. (12) Ge, R.; Hardacre, C.; Jacquemin, J.; Nancarrow, P.; Rooney, D. W. Heat Capacities of Ionic Liquids as a Function of Temperature at 0.1 MPa. Measurement and Prediction. J. Chem. Eng. Data 2008, 53, 2148–2153. (13) Valderrama, J. O.; Zarricueta, K. A. A Simple and Generalized Model for Predicting the Density of Ionic Liquids. Fluid Phase Equilib. 2009, 275, 145–151.

ReceiVed for reView February 16, 2009 ReVised manuscript receiVed April 19, 2009 Accepted May 5, 2009 IE900250G

Critical Properties of Ionic Liquids. Revisited - Industrial & Engineering

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