1338 Ind. Eng. Chem. Res.

2007, 46, 1338-1344

Critical Properties, Normal Boiling Temperatures, and Acentric Factors of Fifty

Ionic Liquids
J. O. Valderrama*,†,‡ and P. A. Robles‡
Faculty of Engineering, Department of Mechanical Engineering, UniVersity of La Serena, Casilla 554, La
Serena, Chile, and Center for Technological Information (CIT), Casilla 724, La Serena, Chile

The critical properties, the normal boiling temperatures, and the acentric factors of ionic liquids have been
determined using an extended group contribution method based on the well-known concepts of Lydersen and
of Joback and Reid. The critical properties of ionic liquids cannot be experimentally determined in many
cases since most of these compounds start to decompose as the temperature approaches the normal boiling
point. However, for the development of thermodynamic models either for pure components or for mixtures
containing ionic liquids, the critical properties and other physical parameters are required. The so-called group
contribution methods have been commonly used to estimate the critical properties of many substances for
which these properties are not available, but no attempt has been made to estimate the critical properties of
ionic liquids, as presented in this study. The method does not require any additional data besides the knowledge
of the structure of the molecule and its molecular weight. Since experimental critical properties of ionic
liquids are not available, the accuracy of the method is checked by calculating the liquid densities of the
ionic liquids considered in the study. The results show that the values determined for the critical properties,
for the normal boiling temperatures, and for the acentric factors are accurate enough for engineering calculations,
for generalized correlations, and for equation of state methods, among other applications.

Introduction For the development of new processes using ionic liquids or

to continue some of the current studies, the knowledge of
Ionic liquids have attracted special attention from the scientific
physical, physicochemical, and transport properties is essential.
community in recent years, and hundreds of studies involving
In particular, the knowledge of the phase equilibrium behavior
different aspects of properties and applications of ionic liquids
is required. During the past five years different research groups
have been presented in the literature. Ionic liquids are organic
have started to measure the required pure-component properties
salts with some special characteristics that make them suitable
and mixture data. Part of the data has been already published.18,19
for many applications. Ionic liquids have low melting temper-
Studies on physical and chemical properties of ionic liquids,
atures, are liquid at room temperature, have thermal stability
property measurement methodology, high-quality data on refer-
up to high temperatures, possess high solubility for both polar
ence systems, standards for reporting thermodynamic data, and
and nonpolar organic and inorganic substances, exhibit interest-
the creation of a comprehensive database have been promoted
ing solvation and coordination properties that depend on the
by IUPAC and other institutions.20 Another effort has been made
nature of the cation and/or anion, and have very low vapor
by the Dortmund Data Bank that presently contains pure-
pressures.1,2 This special characteristic of almost null vapor
component data and mixture data for more than 160 ionic
pressure has transformed ionic liquids into good alternatives as
liquids.21
the green solvents of future potential and of high commercial
For a better understanding of several of these applications,
interest.
the thermodynamic behavior of mixtures containing ionic liquids
Ionic liquids are typically composed of a large organic cation
must be known. Also, the development of acceptable thermo-
and an inorganic polyatomic anion. There is virtually no limit
dynamic models requires reliable experimental phase equilib-
to the number of possible ionic liquids since there are a large
rium data and some basic thermophysical data. However,
number of cations and anions that can be combined. Among
strategies to determine the critical properties of ionic liquids
the many applications of ionic liquids that have been reported
have not received much attention in the literature. One reason
in the literature are the following: as media for clean liquid-
for this slow development is that critical properties of ionic
liquid extraction processes;3 as solvents for electrochemical
liquids cannot be determined since many of these compounds
applications;4-6 as recyclable alternatives to aprotic solvents or
start to decompose as the temperature approaches the normal
catalysts for organic and organometallic synthesis,7 for catalytic
boiling point (salts that include the nitrate anion are a good
cracking of polyethylene,8 and for radical polymerization;9,10
example). Therefore, there are not enough data available to test
and as media for analytical and physical chemistry.11 Some ionic
any predicting or correlating method.2 To the best of our
liquids possess liquid crystal or lubricant properties,12,13 and
knowledge, hypothetical critical properties of ionic liquids are
others can be used as biocatalysts with great advantages
unknown until today.
compared to conventional organic solvents.14,15 Detailed infor-
mation about the synthesis and application of ionic liquids is Recently, Rebelo and co-workers2 presented a method to
available in the literature.16,17 estimate the critical temperatures of some ionic liquids based
on the temperature dependence of their surface tensions and
* To whom correspondence should be addressed. Tel.: 56-51-204260.
liquid densities. These authors used the empirical equations
Fax: 56-51-551158: E-mail: [email protected]. proposed by Eotvos and by Guggenheim. They validated their
† University of La Serena. proposal by estimating critical and normal boiling temperatures
‡ CIT. of 90 compounds with known Tc and/or Tb values. Then, they
10.1021/ie0603058 CCC: $37.00 © 2007 American Chemical Society
Published on Web 01/25/2007
 Ind. Eng. Chem. Res., Vol. 46, No. 4, 2007 1339

provided estimations of normal boiling temperatures and critical 1

temperatures for 15 ionic liquids. The authors suggest that the Pc ) (5)
method allows the prediction of those properties with accuracy
better than 10%.
[CJ + DJN - ∑ni∆PJ] 2

In this paper, the critical properties (Tc, Pc, Vc), the normal
boiling temperatures, and the acentric factors of 50 ionic liquids
V c ) EJ + ∑ni∆VJ (6)
are determined. The global accuracy and consistency of the
In these equations ni is the number of times that a group appears
estimated values are done by calculating liquid densities of the
in the molecule, N is the number of atoms in the molecule, Tb
ionic liquids and bubble pressures of mixtures containing carbon
is the normal boiling temperature, ∆TJ is the contribution to
dioxide and ionic liquids.
the critical temperature, ∆PJ is the contribution to the critical
pressure, ∆VJ is the contribution to the critical volume, and AJ,
Group Contribution Methods for Critical Properties
BJ, CJ, DJ, and EJ are constants. The values of these constants
The development of thermodynamic models for both pure are AJ ) 0.584, BJ ) 0.965, CJ ) 0.113, DJ ) 0.0032, and EJ
components and mixtures requires the knowledge of the critical ) 17.5.
properties and other physical parameters. As stated above, these Constantinou et al.27 proposed a complex estimation tech-
properties cannot be measured for ionic liquids but are still nique, which is based on conjugate forms (alternative formal
needed in modeling and correlating experimental data on ionic arrangements of valence electrons). This technique provides
liquid properties and mixtures containing ionic liquids. The so- reasonable estimations of several properties of pure compounds
called group contribution methods have been commonly used and allows capturing the differences among isomers. However,
to estimate the critical properties of many substances for which the generation of conjugate forms is a nontrivial issue and
these properties are not available. No attempts have been made requires a symbolic computing environment. Another somewhat
to apply these methods to estimate the critical temperatures, complex method has been proposed by Constantinou and Gani.28
pressures, and volumes of these ionic liquids. The method considers the molecular structure of the molecule
Among the several proposals presented in the literature, the and estimates a given property at two levels. The primary level
approach developed by Lydersen22 is perhaps the most widely uses contributions from simple groups that allow describing a
used group contribution method to estimate critical properties. wide variety of organic compounds, while the higher level
Similar proposals were presented by Ambrose23 and Klincewicz involves polyfunctional and structural groups that provide more
and Reid.24 Later, Joback and Reid25 developed a method that information about molecular fragments whose description
is frequently mentioned in the literature and used in several through first-order groups is not possible. Joback29 has shown
applications. In all these methods, the property of a compound that the method of Constantinou and Gani28 gives errors a little
is calculated by summing up the contributions of certain defined higher than the Lydersen method.
groups of atoms, considering at the same time the number
Marrero and Pardillo30 proposed another technique that
frequency of each group occurring in the molecule. Although
considers the contributions of interactions between bonding
all these methods have been questioned in the literature,26 they
groups instead of the contributions of simple groups, a method
have the advantage of quick estimates without requiring
that allows distinguishing among isomers. Another interesting
sophisticated computational calculations.
method based on neural networks that does not need any
Lydersen22 defined 43 structural groups and proposed the
following model equations for the critical properties: additional information, besides the molecular structure, can be
found on the Internet,31 although no details about the method
are provided.
Tb
Tc ) (1) Alvarez and Valderrama32 combined the best results of

∑ni∆TL - (∑ni∆TL)
Lydersen’s method with the best results of the Joback-Reid
AL + 2
method to propose a “modified Lydersen-Joback-Reid”
method that proved to give good results for molecules of high
M molecular weight. The method considers the equations of
Pc ) (2) Lydersen for the critical pressure and critical volume and the
[CL + ∑ni∆PL] 2
equations of Joback-Reid for the normal boiling temperature
and the critical temperature. The authors modified the parameters
V c ) EL + ∑ni∆VL (3) involved in the different equations for the critical properties.
The equation for the normal boiling point was kept as in the
original method. The modified Lydersen-Joback-Reid method
In these equations ni is the number of times that a group appears is summarized in the following four equations:
in the molecule, Tb is the normal boiling temperature, ∆TL is
the contribution to the critical temperature, ∆PL is the contribu-
tion to the critical pressure, ∆VL is the contribution to the critical Tb ) 198.2 + ∑n∆TbM (7)
volume, M is the molecular mass, and AL, CL, and EL are
constants. The values of these constants are AL ) 0.567, CL ) Tb
0.34, and EL ) 40. Tc ) (8)
Joback and Reid25 defined 41 structural groups and proposed
the following model equations for the critical properties:
A M + BM ∑n∆TM - (∑n∆TM) 2

Tb M
Tc ) (4) Pc ) (9)
AJ + B J∑ni∆TJ - (∑ni∆TJ)2 [CM + ∑n∆PM] 2
1340 Ind. Eng. Chem. Res., Vol. 46, No. 4, 2007

Vc ) EM + ∑n∆VM (10) Table 1. Groups Considered for the Modified

Lydersen-Joback-Reid Method
groups ∆TbM ∆TM ∆PM ∆VM
The parameters that appear in eqs 7-10 were calculated as AM
) 0.5703, BM ) 1.0121, CM ) 0.2573, and EM ) 6.75. Without Rings
-CH3 23.58 0.0275 0.3031 66.81
To the best of our knowledge the most recent group
-CH2- 22.88 0.0159 0.2165 57.11
contribution method proposed in the literature to estimate the >CH- 21.74 0.0002 0.1140 45.70
critical properties is that of Skander and Chitour.33 The authors >C< 18.18 -0.0206 0.0539 21.78
considered the estimation of critical properties, heats of )CH2 24.96 0.0170 0.2493 60.37
vaporization, refractive index parameters, and molar volumes )CH- 18.25 0.0182 0.1866 49.92
)C< 24.14 -0.0003 0.0832 34.90
of hydrocarbons and petroleum fractions. In another develop- )C) 26.15 -0.0029 0.0934 33.85
ment, Kolská34 presented a group contribution method to ≡CH 0.0078 0.1429 43.97
estimate the enthalpies and entropies of vaporization of pure ≡C- 0.0078 0.1429 43.97
organic compounds. Stefanis et al.35 have extended the method -OH (alcohol) 92.88 0.0723 0.1343 30.40
-O- 22.42 0.0051 0.1300 15.61
of Constantinou and Gani28 and applied it to the calculation of >CdO 94.97 0.0247 0.2341 69.76
the octanol-water partition coefficient, the flash point, and the -CHO 72.24 0.0294 0.3128 77.46
solubility parameters at 25 °C. -COOH 169.06 0.0853 0.4537 88.60
-COO- 81.10 0.0377 0.4139 84.76
HCOO- 0.0360 0.4752 97.77
Extension of the Methods to Ionic Liquids )O (others) -10.50 0.0273 0.2042 44.03
Of the methods explained above, the modified Lydersen- -NH2 73.23 0.0364 0.1692 49.10
>NH 50.17 0.0119 0.0322 78.96
Joback-Reid, developed by one of the authors, has been used >N- 11.74 -0.0028 0.0304 26.70
to extend its applicability to predict the critical properties of -N) 74.60 0.0172 0.1541 45.54
ionic liquids. The extension of the method has been done in a -CN 125.66 0.0506 0.3697 89.32
simple way. Three new groups were included: -B, -SO2, -P. -NO2 152.54 0.0448 0.4529 123.62
-F -0.03 0.0228 0.2912 31.47
Their contributions to Tb, Tc, Pc, and Vc were determined in a -Cl 38.13 0.0188 0.3738 62.08
way similar to that explained by Alvarez and Valderrama.32 The -Br 66.86 0.0124 0.5799 76.60
values of these groups are summarized in Table 1. The table -I 93.84 0.0148 0.9174 100.79
also shows the values of all groups for this method. Once the With Rings
values of the three new groups (-B, -SO2, -P) have been -CH2- 27.15 0.0116 0.1982 51.64
determined, the critical properties, the acentric factors, and the >CH- 21.78 0.0081 0.1773 30.56
)CH- 26.73 0.0114 0.1693 42.55
normal boiling temperatures of 50 ionic liquids have been
>C< 21.32 -0.0180 0.0139 17.62
determined. )C< 31.01 0.0051 0.0955 31.28
As a test of the “consistency” of the predicted properties, -O- 31.22 0.0138 0.1371 17.41
the liquid densities of the ionic liquids have been estimated using -OH (phenol) 76.34 0.0291 0.0493 -17.44
a generalized correlation proposed by one of the authors.36 The >CdO 94.97 0.0343 0.2751 59.32
>NH 52.82 0.0244 0.0724 27.61
generalized correlation is based on the equation of Spencer and >N- 0.0063 0.0538 25.17
Danner37 and needs only the normal boiling temperature, the -N) 57.55 -0.0011 0.0559 42.15
molecular weight, and the critical properties: New Groups

[ ]
-B -24.56 0.0352 0.0348 22.45
MPc 0.3445PcVc1.0135 Ω -P 34.86 -0.0084 0.1776 67.01
FL ) (11) -SO2 147.24 -0.0563 -0.0606 112.19
RTc RTc

[ ]
C ) 43 (with T in Kelvin), a value corresponding to water, the
1 + (1 - TR)2/7 reference fluid. The equation is
Ω)-
1 + (1 - TbR)2/7 B
log Ps ) A - (13)
T - 43
In these equations, FL is the liquid density in grams per cubic
centimeter, R is the ideal gas constant, TR is the reduced Replacing the above equations, the acentric factor is calculated
temperature (TR ) T/Tc), and TbR is the reduced temperature at as
the normal boiling point (TbR ) Tb/Tc).
The acentric factors of the ionic liquids, also needed for
equation of state applications, were determined using the ω)
(Tb - 43)(Tc - 43)
(Tc - Tb)(0.7Tc - 43)
log []
Pc
Pb
-
(Tc - 43)
(Tc - Tb)
log []
Pc
Pb
+

[]
definition of this property:
Pc

()
log - 1 (14)
Ps Pb
ω ) -log - 1.0 (12)
Pc (T/Tc))0.7
The calculated critical properties, the normal boiling tem-
peratures (Tb for Pb ) 1 atm), and the acentric factors are
The value of the saturation pressure Ps at T/Tc ) 0.7 was presented in Table 2. The molecular weight is also included in
estimated using the values of temperature and pressure at the Table 3, a value that is needed in density calculations (eq 11).
critical point (Pc, Tc), using the values at the normal boiling
point (Pb, Tb), and considering the relation of Rudkin38 for the
Results and Discussion
vapor pressure. In this approach the author considered water as
the reference fluid and used the Antoine equation to relate the The estimated critical properties are listed in Table 2 for 50
vapor pressure Ps and the temperature T. Rudkin used the value ionic liquids. Table 3 presents the estimated densities of the
Table 2. Critical Properties of Ionic Liquids, Calculated by Group Contribution
no. ionic liquid global formula IUPAC name Tb (K) Tc (K) Pc (bar) Vc (cm3/mol) ω Tb/Tc
1 [bmim][BF4] C8H15N2BF4 1-butyl-3-methylimidazolium tetrafluoroborate 484.6 632.3 20.4 672.0 0.8489 0.766
2 [emim][BF4] C6H11N2BF4 1-ethyl-3-methylimidazolium tetrafluoroborate 438.9 585.3 23.6 557.8 0.7685 0.750
3 [hmim][BF4] C10H19N2BF4 1-hexyl-3-methylimidazolium tetrafluoroborate 530.4 679.1 17.9 786.2 0.9258 0.781
4 [mbupy][BF4] C10H16NBF4 4-methyl-n-butylpyridinium tetrafluoroborate 484.8 625.8 18.9 703.7 0.8923 0.775
5 [N-bupy][BF4] C9H14NBF4 N-butylpyridinium tetrafluoroborate 456.9 597.6 20.3 648.1 0.8307 0.765
6 [omim][BF4] C12H23N2BF4 1-n-octyl-3-methylimidazolium tetrafluoroborate 576.1 726.1 16.0 900.4 0.9954 0.793
7 [bhoedma][Br] C8H20NBrO butyl-(2-hydroxyethyl)-dimethylammonium bromide 554.8 732.3 25.2 626.4 0.8841 0.758
8 [ehoedma][Br] C6H16NBrO ethyl-(2-hydroxyethyl)-dimethylammonium bromide 509.1 687.9 30.2 512.2 0.8078 0.740
9 [hhoedma][Br] C10H24NBrO hexyl-(2-hydroxyethyl)-dimethylammonium bromide 600.6 776.6 21.7 740.7 0.9601 0.773
10 [hoedmpa][Br] C7H18NBrO (2-hydroxyethyl)-dimethylpropylammonium bromide 531.9 710.1 27.5 569.3 0.8455 0.749
11 [beim][bti] C11H17N3F6S2O4 1-butyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide 874.7 1275.9 25.6 1064.2 0.3093 0.686
12 [bmim][bti] C1oH15N3F6S2O4 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 851.8 1265.0 27.6 1007.1 0.2656 0.673
13 [bmpyr][bti] C10H17N2F6S2O4 1-butyl-1-methylpirrolidinium bis(trifluoromethylsulfonyl)imide 741.6 1110.1 27.9 960.1 0.2383 0.668
14 [deim][bti] C9H13N3F6S2O4 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide 829.0 1254.7 29.9 950.0 0.2231 0.661
15 [dmeim][bti] C9H16N3F6S2O4 dimethyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide 833.9 1254.1 29.7 948.4 0.2447 0.665
16 [dmim][bti] C7H9N3F6S2O4 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide 783.2 1235.7 35.8 835.8 0.1418 0.634
17 [edmim][bti] C9H13N3F6S2O4 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide 833.9 1254.1 29.7 948.4 0.2447 0.665
18 [eDmim][bti] C9H13N3F6S2O4 1-ethyl-3,5-dimethylimidazolium bis(trifluoromethylsulfonyl)imide 833.9 1254.1 29.7 948.4 0.2447 0.665
19 [emim][bti] C8H11N3F6S2O4 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 806.1 1244.9 32.6 892.9 0.1818 0.647
20 [hmim][bti] C12H19N3F6S2O4 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 897.6 1287.3 23.9 1121.3 0.3539 0.697
21 [ibmim][bti] C1oH15N3F6S2O4 1-isobutyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 851.4 1270.4 27.8 1005.4 0.2501 0.670
22 [mdeim][bti] C1oH15N3F6S2O4 5-methyl-1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide 856.8 1264.7 27.4 1005.5 0.2875 0.678
23 [meim][bti] C8H14N3F6S2O4 1-methyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide 806.1 1244.9 32.6 892.9 0.1818 0.647
24 [moemim][bti] C9H13N3F6S2O4 1-metoxyethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 851.4 1280.6 27.9 965.6 0.2208 0.665
25 [omim][bti] C14H23N3F6S2O4 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 943.4 1311.9 21.0 1235.6 0.4453 0.719
26 [tfemim][bti] C8H8N3F9S2O4 1-trifluoroethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 800.7 1205.3 26.6 942.3 0.2004 0.664
27 [omim][Cl] C12H23N2Cl 1-octyl-3-methylimidazolium chloride 638.9 860.1 20.3 814.2 0.6190 0.743
28 [emim][EtSO4] C8H16N2SO4 1-ethyl-3-methylimidazolium ethyl sulfate 702.1 1061.1 40.4 676.8 0.3368 0.662
29 [OHea][f] C3H9NO3 2-hydroxyethylammonium formate 491.2 683.2 54.0 285.2 0.8979 0.719
30 [bmim][hb] C12H15N2F7O2 1-butyl-3-methylimidazolium heptafluorobutanoate 644.9 836.7 15.6 894.0 0.7249 0.771
31 [emim][hb] C10H11N2F7O2 1-ethyl-3-methylimidazolium heptafluorobutanoate 599.2 793.9 17.4 779.8 0.6393 0.755
32 [beim][MsO] C10H20N2SO3 1-butyl-3-ethylimidazolium methylsulfonate 725.4 1062.7 33.5 775.4 0.3986 0.683
33 [emim][MsO] C7H14N2SO3 1-ethyl-3-methylimidazolium methylsulfonate 656.8 1019.5 48.0 604.0 0.2930 0.644
34 [beim][NfO] C13H17N2F9SO3 1-butyl-3-ethylimidazolium nonafluorobutanesulfonate 774.6 1038.5 16.4 1078.9 0.5256 0.746
35 [emim][NfO] C12H15N2F9SO3 1-butyl-3-methylimidazolium nonafluorobutanesulfonate 752.4 1012.1 16.7 1031.5 0.5159 0.743
36 [bmim][NO3] C8H15N3O2 1-n-butyl-3-methylimidazolium nitrate 684.3 946.3 27.3 662.9 0.6039 0.723
37 [bmim][PF6] C8H15N2PF6 1-n-butyl-3-methylimidazolium hexafluorophosphate 544.0 708.9 17.3 779.5 0.7553 0.767
38 [emim][PF6] C6H11N2PF6 1-ethyl-3-methylimidazolium hexafluorophosphate 498.2 663.5 19.5 665.3 0.6708 0.751
39 [hmim][PF6] C10H19N2PF6 1-hexyl-3-methylimidazolium hexafluorophosphate 589.7 754.3 15.5 893.7 0.8352 0.782
40 [omim][PF6] C12H23N2PF6 1-n-octyl-3-methylimidazolium hexafluorophosphate 635.5 800.1 14.0 1007.9 0.9069 0.794
41 [beim][ta] C11H17N2F3O2 1-butyl-3-ethylimidazolium trifluoroacetate 631.4 838.0 19.6 781.7 0.6936 0.754
42 [bmim][ta] C10H15N2F3O2 1-butyl-3-methylimidazolium trifluoroacetate 608.6 817.2 20.9 724.6 0.6509 0.745
43 [deim][ta] C9H13N2F3O2 1,3-diethylimidazolium trifluoroacetate 585.7 796.5 22.4 667.5 0.6085 0.735
44 [emim][ta] C8H15N2F3O2 1-ethyl-3-methylimidazolium trifluoroacetate 562.8 775.7 24.2 610.4 0.5664 0.725
45 [beim][TfO] C10H17N2F3SO3 1-butyl-3-ethylimidazolium trifluoromethanesulfonate 720.0 1032.1 27.0 824.8 0.4091 0.698
46 [bmim][TfO] C9H15N2F3SO3 1-butyl-3-methylimidazolium trifluoromethanesulfonate 697.1 1016.3 29.4 767.6 0.3677 0.686
47 [deim][TfO] C8H13N2F3SO3 1,3-diethylimidazolium trifluoromethanesulfonate 674.2 1000.7 32.3 710.5 0.3276 0.674
48 [doeim][TfO] C18H31N2F3SO3 1-dodecyl-3-ethylimidazolium trifluoromethanesulfonate 903.0 1168.6 16.0 1281.6 0.7552 0.773
49 [edmim][TfO] C8H13N2F3SO3 1-ethyl-3,5-dimethylimidazolium trifluoromethanesulfonate 679.2 1001.9 32.0 709.0 0.3499 0.678
Ind. Eng. Chem. Res., Vol. 46, No. 4, 2007 1341

50 [emim][TfO] C7H11N2F3SO3 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 651.4 985.2 35.8 653.4 0.2891 0.661
1342 Ind. Eng. Chem. Res., Vol. 46, No. 4, 2007

Table 3. Densities Calculated with the Generalized Correlation (Equation 11) and Comparison with Literature Valuesa
no. formula M T Flit Fcalc %∆Fcalc
1 [bmim][BF4] 226.0 298.15 1.208041 1.1398 -5.6
2 [emim][BF4] 198.0 295.15 1.240041 1.1541 -6.9
3 [hmim][BF4] 254.0 298.15 1.148442 1.1415 -0.6
4 [mbupy][BF4] 237.0 298.15 1.184243 1.1514 -2.8
5 [N-bupy][BF4] 223.0 313.15 1.203019 1.1229 -6.7
6 [omim][BF4] 282.1 313.15 1.080019 1.1362 5.2
7 [bhoedma][Br] 226.2 298.15 1.067044 1.2602 18.1
8 [ehoedma][Br] 198.1 298.15 1.101844 1.3002 18.0
9 [hhoedma][Br] 254.3 298.15 1.041244 1.2425 19.3
10 [hoedmpa][Br] 212.1 298.15 1.082744 1.2762 17.9
11 [beim][bti] 433.3 295.15 1.404041 1.4284 1.7
12 [bmim][bti] 419.2 295.15 1.429041 1.4381 0.6
13 [bmpyr][bti] 407.3 313.15 1.386045 1.4125 1.9
14 [deim][bti] 405.2 295.15 1.452041 1.4515 -0.03
15 [dmeim][bti] 405.2 298.15 1.480246 1.4593 -1.4
16 [dmim][bti] 377.2 298.15 1.559041 1.4910 -4.4
17 [edmim][bti] 405.2 295.15 1.495041 1.4609 -2.3
18 [eDmim][bti] 405.2 295.15 1.470041 1.4609 -0.6
19 [emim][bti] 391.2 295.15 1.520041 1.4689 -3.4
20 [hmim][bti] 447.3 313.15 1.356045 1.4118 4.1
21 [ibmim][bti] 419.2 295.15 1.428041 1.4365 0.6
22 [mdeim][bti] 419.2 295.15 1.432041 1.4473 1.1
23 [meim][bti] 391.2 298.15 1.525246 1.4673 -3.8
24 [moemim][bti] 405.2 295.15 1.496041 1.4482 -3.2
25 [omim][bti] 475.4 313.15 1.311045 1.4049 7.2
26 [tfemim][bti] 445.2 295.15 1.656041 1.6212 -2.1
27 [omim][Cl] 230.8 298.15 1.007047 1.0158 0.9
28 [emim][EtSO4] 236.3 313.15 1.225019 1.1476 -6.3
29 [OHea][f] 107.1 298.15 1.204048 1.2420 3.2
30 [bmim][hb] 352.3 295.15 1.133041 1.4850 11.4
31 [emim][hb] 324.2 295.15 1.450041 1.5130 4.3
32 [beim][MsO] 248.3 298.15 1.140041 1.0830 -5.0
33 [emim][MsO] 206.2 298.15 1.240041 1.0990 -11.3
34 [beim][NfO] 452.3 295.15 1.427041 1.5796 10.7
35 [emim][NfO] 438.3 295.15 1.443041 1.5905 8.0
36 [bmim][NO3] 201.2 313.15 1.149019 1.0758 -6.4
37 [bmim][PF6] 284.2 313.15 1.346019 1.2760 -5.2
38 [emim][PF6] 256.2 298.15 1.4133b 1.3122 7.2
39 [hmim][PF6] 312.2 298.15 1.278142 1.2871 0.7
40 [omim][PF6] 340.3 313.15 1.211019 1.2744 5.2
41 [beim][ta] 266.3 295.15 1.183041 1.2422 5.0
42 [bmim][ta] 252.2 295.15 1.209041 1.2474 3.2
43 [deim][ta] 238.2 295.15 1.250041 1.2568 0.5
44 [emim][ta] 224.2 295.15 1.285041 1.2710 -1.1
45 [beim][TfO] 302.2 295.15 1.270041 1.2690 -0.1
46 [bmim][TfO] 288.2 298.15 1.298050 1.2795 -1.4
47 [deim][TfO] 274.2 295.15 1.330041 1.2963 -2.5
48 [doeim][TfO] 412.5 295.15 1.100041 1.2698 15.4
49 [edmim][TfO] 274.2 295.15 1.334041 1.3061 -2.1
50 [emim][TfO] 260.2 298.15 1.390041 1.3168 -5.3
a The reference corresponds to the source from where the literature value was obtained. b Extrapolated value.
substances determined using the generalized correlation given the 29 substances with molecular weight higher than 200 (as
by eq 11. As explained above, this calculation of density is done the majority of the ionic liquids considered in this study), the
as a global test of the consistency of the estimated critical average ratio Tb/Tc is 0.71. The conclusion one can obtain from
properties presented in Table 3. In fact, the 50 ionic liquids these values is that considering the ratio Tb/Tc ) 0.6 for ionic
considered in this study are those for which density values are liquids is not sustained by the tendency of hundreds of other
available in the literature, so that the test could be performed. substances. The results presented in Table 2 give values of Tb/
As explained in the Introduction, Rebelo and co-workers2 Tc in the range 0.64-0.79, the average being 0.72.
presented some values for the critical temperature of selected As observed in Table 3, the predicted densities, using
ionic liquids using the empirical equations proposed by Eotvos exclusively the calculated critical properties and the calculated
and by Guggenheim. However, the calculation method deserves normal boiling temperatures, are within acceptable margins of
at least some comments. They determined first the normal errors for the purpose of the checking. The maximum deviation
boiling temperature using the methods of Eotvos and of is 19.3% for [hhoedma][Br], the average deviation is 1.6%, and
Guggenheim. Then they assumed that the ratio Tb/Tc was equal the average absolute deviation is 5.2%.
to 0.6 and estimated the critical temperatures as Tc ) 0.6Tb. It should be finally mentioned that the generalized correlation
Riddick at al.39 gives the average value of this ratio for groups used to estimate the densities of ionic liquids (eq 11), was
of compounds and shows that for all of them the ratio is higher derived totally independent of the group contribution method
than 0.6: it is 0.686 for alcohols, 0.676 for acids, 0.677 for used to estimate the critical properties of ionic liquids (eqs
esters, 0.658 for amines, and 0.621 for halides. If one takes all 7-10) and has been successfully applied to estimate the densities
the substances for which Tb and Tc are available in the database of complex substances.36,40 Therefore, density calculation is a
of Poling et al.,26 the average ratio Tb/Tc is 0.71; if one takes reliable independent test to show that the values of the critical
 Ind. Eng. Chem. Res., Vol. 46, No. 4, 2007 1343

properties of ionic liquids are acceptable and can be used in ∆TM, ∆PM, ∆VM ) contribution to the critical properties in the
other applications where these properties are needed. modified Lydersen-Joback-Reid method (eqs 7-10)

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