Journal of Molecular Liquids 193 (2014) 262–266

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Review

A review on the transport properties of ionic liquids

Xiaojing Wang a, Yanling Chi b, Tiancheng Mu c,⁎
a
School of Science, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
b
Materials Science and Engineering College, Northeast Forestry University, Harbin 415000, China
c
Department of Chemistry, Renmin University of China, Beijing 100872, China

a r t i c l e i n f o a b s t r a c t

Article history: Transport properties include the thermal conductivity for heat transfer, the viscosity for the momentum transfer,
Received 5 November 2013 and the diffusion coefficient for mass transfer. The transport properties are very important for chemical engineer-
Received in revised form 27 December 2013 ing design. The ionic liquids are liquids with good conductivity thus may have promising applications in battery
Accepted 7 March 2014
industry. However, the high viscosity hinders the applications of them. In this paper, we firstly reviewed the
Available online 20 March 2014
values of transport properties of pure ionic liquids, then these properties of the mixtures of ionic liquids with
Keywords:
other compounds were discussed, and lastly we reviewed the correlation researches on the transport properties
Transport property of systems including ionic liquids and the molecular dynamics simulation investigations on these systems.
Ionic liquid © 2014 Elsevier B.V. All rights reserved.
Correlation
Molecular dynamics simulation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
2. Transport properties of pure ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
3. Transport properties of the mixtures including ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4. Correlations and molecular dynamics simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.1. Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2. Molecular dynamics simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
4.3. Comparison of the predictive methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266

1. Introduction
Ionic liquids (ILs) have attracted much attention in the scientific
community recently due to their novel and highly customizable
properties [1,2]. They have been used in various fields such as extraction
and separation [3,4], catalyst, materials fabrication [5,6], analytical tech-
nology, and energy [7]. The transport properties include the diffusion
rate coefficients such as the thermal conductivity (for heat transfer)
[8–11], the viscosity (for momentum transfer), and diffusion coefficient
(for mass transfer) [12–15]. Thus, the transport properties play crucial
roles in chemical and engineering processes. The relatively high viscosity
of ILs poses serious limitations to the use of ILs. Considered the high
⁎ Corresponding author. Tel.: +86 10 62514925; fax: +86 10 62516444.
E-mail address: tcmu@chem.ruc.edu.cn (T. Mu).
viscosity of most ILs, the transport properties of ILs are more important.
Since the ILs are composed of cations and anions, the electric conductiv-
ity of ILs is widely concerned [16–19]. According to the previous reports,
the transport properties of ILs are mainly determined by hydrogen
bonding, van der Waals forces, molecular weight and mobility [16,20].
There have been several reviews published on the transport properties,
and different models (correlation, group contribution [21], quantitative
structure property relationship (QSPR) [22], computer-aided molecular
design [23], etc.) for the prediction of the transport properties of ILs
were compared.
Hence, in this mini-review, we mainly discuss the viscosities of ILs.
Both the experimental data and prediction methods were discussed.
The transport properties of pure ILs, the mixtures of ILs with molecular
solvents, or the mixtures of two or more ILs were discussed. The defini-
tion and nomenclature of mixtures of ILs were given in a previous report

http://dx.doi.org/10.1016/j.molliq.2014.03.011
0167-7322/© 2014 Elsevier B.V. All rights reserved.
 X. Wang et al. / Journal of Molecular Liquids 193 (2014) 262–266 263

[24]; in that report, they also gave a comprehensive review of the Table 2
properties of mixtures of ionic liquids. For prediction methods, Das VFT parameters of ionic conductivity data for [BMIM]-based [27], [CnMIM] [Tf2N] [28] and
[Tf2N]-based [26] ILs.
and Roy have given a comprehensive review on the QSPR models [22].
Therefore we will only discuss the correlation methods based on IL σ0/10−1 S cm−1 B/102 K T0/K
group contribution concept because it is simple and easy to use, and [BMIM][BETI] 7.1 ± 0.5 7.96 ± 0.22 169 ± 2
molecular dynamics because it is molecular based. [BMIM][Tf2N] 4.3 ± 0.2 5.65 ± 0.14 178 ± 2
[BMIM][OTF] 9.8 ± 0.8 7.93 ± 0.26 162 ± 3
[BMIM][PF6] 14.7 ± 1.0 8.55 ± 0.20 174 ± 2
2. Transport properties of pure ionic liquids
[BMIM][TFA] 9.2 ± 0.4 7.19 ± 0.13 172 ± 1
[BMIM][BF4] 13.8 ± 0.6 7.41 ± 0.13 174 ± 1
The transport properties of ILs are determined by the nature of its [MMIM][Tf2N] 6.6 ± 0.4 5.62 ± 0.18 168 ± 3
cation and anion and conditions such as temperature and pressure. [EMIM][Tf2N] 5.8 ± 0.2 5.54 ± 0.13 165 ± 2
Tokuda et al. investigated the influence of cation, anion, the alkyl [HMIM][Tf2N] 6.1 ± 0.3 7.31 ± 0.13 168 ± 1
[OMIM][Tf2N] 6.1 ± 0.2 8.11 ± 0.12 166 ± 1
chain length of cation, and temperature on the transport properties of
[BPy][Tf2N] 5.5 ± 0.5 6.33 ± 0.24 175 ± 3
IL [25–28]. [BMPyrr][Tf2N] 5.6 ± 0.2 6.75 ± 0.14 171 ± 1
The transport properties (diffusion coefficient, viscosity, ionic [(n-C4H9)(CH3)3N][Tf2N] 6.1 ± 0.1 6.89 ± 0.04 177 ± 0
conductivity) of ILs: (1) with a variety of fluorinated anions combined
with [BMIM] [27]; (2) with different cationic structures [BMIM], [BPy],
[BMPyrr], and [(n-C4H9)(CH3)3N] combined with an anion, [Tf2N] To the ILs with different type of cations, the magnitude of cationic
[26]; (3) with imidazolium based cation but different alkyl chain length and anionic diffusion coefficients for the ILs follows the order:
([CnMIM][Tf2N], n = 1, 2, 4, 6, and 8) [28]; were measured and correlat- [BMIM][Tf2N] N [BPy][Tf2N] N [BMPyrr][Tf2N] N [(n-C4H9)(CH3)3N]
ed with Vogel–Fulcher–Tamman (VFT) equation (Eqs. (1)–(3)), [Tf2N]; which coincides with the reverse order to the viscosity data. The
the viscosity and ionic conductivity results are presented in Tables 1 ratio of the experimental to that of the calculated molar conductivity
and 2, respectively. data from the ionic diffusivity using the Nernst–Einstein equation
follows the order: [BMPyrr] [Tf2N] N [(n-C4H9)(CH3)3N] [Tf2N] N [BPy]
h . i
D ¼ D0 exp −B1 T−T 0;1 ð1Þ [Tf2N] N[BMIM][Tf2N] at 30 °C, which also provides quantitative infor-
mation on the active ions contribution to ionic conduction [26].
The investigation of the ILs with imidazolium based cation but
h . i different alkyl chain length led to the following conclusions. The
η ¼ η0 exp B2 T−T 0;2 ð2Þ summation of the cationic and anionic diffusion coefficients follows
the order: [EMIM][Tf2N] N [MMIM][Tf2N] N [BMIM][Tf2N] N [HMIM]
[Tf2N] N [OMIM][Tf2N]. The ratio of the calculated and experimental
h . i data of molar conductivity decreases with increasing number of carbon
σ ¼ σ 0 exp −B3 T−T 0;3 ð3Þ atoms in the alkyl chain [28]. The effect of position and length of alkyl
substituent in pyridinium based ILs has been studied too. It was found
that the position of the methyl substituent had significant influence of
The anionic effect on the self-diffusion coefficients of the cation and
on the transport properties. Walden plots indicate that these ILs
anion, viscosity, and ionic conductivity of ILs [BMIM] with a variety of
have high ionicity, closer to the “ideal” KCl line, suggesting less ion
fluorinated anions at 30 °C lead to the following conclusions: (1) The
association compared to their 1-butyl-3,5-dimethylpyridinium homo-
VFT equation is suitable to describe the temperature dependencies of
logues [29]. The temperature dependence of transport properties of
the transport properties such as self-diffusion coefficient, viscosity,
ammonium-based ILs N-alkyl-triethylammonium [Tf2N] with different
ionic conductivity, and molar conductivity; (2) the self-diffusion coeffi-
alkyl chain length on the cation (from 293.15 to 363.15) K [30] and
cients exhibit higher values for the cation compared with the anion,
dynamic viscosity for three phosphonium-based ionic liquids: tributyl
even if its radius is larger than that of the anionic radii. The cationic
methyl phosphonium methylsulfate (P4441C1SO4), tributyl ethyl
and anionic diffusion coefficients for the ILs follow the order: [BMIM]
phosphonium diethylphosphate (P4442(C2)2PO4) and tributyl octyl
[Tf2N] N [BMIM][TFA] N [BMIM][OTF] N [BMIM][BF4] N [BMIM][BETI] N
phosphonium chloride (P4448Cl) (from 293.15 to 343.15 K) can be
[BMIM][PF6]. The order of the diffusion coefficients greatly contrasts to
described by VFT equations.
the viscosity data; (3) the ratio of the experimental molar conductivity
The high-pressure (up to 126 MPa) viscosity of [EMIM], [HMIM],
to that of the calculated data follows the order: [BMIM][PF6] N [BMIM]
and [DMIM] with [Tf 2N], and [HMIM] with [Tf 2N], [PF6 ], and [BF4]
[BF4] N [BMIM][BETI] N [BMIM][Tf2N] N [BMIM][OTF] N [BMIM][TFA]
was measured. The increase of the alkyl-chain length induced the
[27].
viscosity increase at elevated pressures. [HMIM][PF6 ] and [BMIM]
[PF6] demonstrated a nonlinear pressure dependence even at rela-
Table 1
VFT parameters of viscosity data for [BMIM]-based [27], [C n MIM][Tf 2 N] [28] and
tively moderate pressures (to 30 MPa) [31]. Harris et al. carried out
[Tf 2N]-based [26] ILs. a series of research on the temperature and pressure dependence
of viscosity of ILs [32–37]. The transport properties of pyridinium
IL η0/10−1 mPa s B/102 K T0/K
based ILs [29], pyrrolidinium based ILs [38], phosphonium-based
[BMIM][BETI] 1.7 ± 0.2 7.63 ± 0.38 180 ± 3 ILs [39,40] could be well described with the VFT equation.
[BMIM][Tf2N] 2.5 ± 0.2 6.25 ± 0.22 180 ± 2
[BMIM][OTF] 3.7 ± 0.6 5.70 ± 0.37 193 ± 4
[BMIM][PF6] 3.6 ± 0.5 6.39 ± 0.25 201 ± 2 3. Transport properties of the mixtures including ionic liquids
[BMIM][TFA] 1.1 ± 0.2 7.88 ± 0.53 177 ± 4
[BMIM][BF4] 2.1 ± 0.1 6.97 ± 0.69 185 ± 6 A considerable amount of work on the transport properties of pure IL
[MMIM][Tf2N] 2.9 ± 0.6 5.87 ± 0.57 178 ± 7
has been published. At the same time, the properties of both mixtures of
[EMIM][Tf2N] 4.0 ± 1.3 5.09 ± 0.81 182 ± 10
[HMIM][Tf2N] 1.6 ± 0.2 7.57 ± 0.39 173 ± 3
IL with molecular solvent and the mixtures of two or more ILs are
[OMIM][Tf2N] 1.5 ± 0.2 8.02 ± 0.30 173 ± 2 important because the mixtures might enormously enlarge the applica-
[BPy][Tf2N] 2.1 ± 0.4 6.71 ± 0.52 179 ± 5 tions of the ILs.
[BMPyrr][Tf2N] 2.9 ± 0.4 6.51 ± 0.31 181 ± 3 Seddon et al. discovered that the viscosity of ionic liquid mixtures
[(n-C4H9)(CH3)3N][Tf2N] 4.5 ± 0.6 5.34 ± 0.27 199 ± 3
with impurities or additives was dependent mainly on the mole fraction
264 X. Wang et al. / Journal of Molecular Liquids 193 (2014) 262–266
of added molecular solvents and only to a lesser extent upon their
identity. The addition of molecular solvents decreases the viscosity
and density, while the addition of chloride impurities, arising from the
preparation of the ILs, increases viscosity dramatically [41]. Most of
the ILs are hygroscopic in air [42–44], the viscosities of ILs are strongly
dependent on the amount of dissolved water [45]. Recently, Khupse
and Kumar reviewed the effect of molecular solvents, including water
on the viscosity of ILs [46]. They summed the experimental data with
the empirical equations. Rheological properties of a homologous series
of ammonium-based [Tf2N] ILs were measured for both pure and
water-saturated ionic liquids [30]. It appears that the presence of
water dramatically decreases the viscosity of ILs by up to three times
[30]. There are also other researches on the viscosity and surface tension
of ILs plus water with composition [47–49].
Navis et al. investigated the viscosities of IL binary mixtures with a
common ion ([C6mim] + [C2mim]) [BF4], ([C6mim] + [C4mim]) [BF4],
[C4mim] ([BF4] + [MeSO4]) and [C4mim] ([PF6] + [BF4]) within the
temperature range (298.15–308.15) K [50]. The viscosity of a binary
mixture does not obey Eq. (4), which means that the interactions of
these systems are complicated [51].
η ¼ xη1 þ ð1−xÞlog 10 η 2 ð4Þ
It should be noted here that the transport properties reported by
different authors sometimes show significant discrepancy, this may be
caused by the impurities, especially water. Therefore special care should
be taken to compare the transport properties of ILs from different
sources.
The temperature dependence of viscosity for mixtures containing
[BMIM][SCN] and 1-alcohol (methanol, ethanol, and 1-propanol) in a
temperature range (298.15 to 348.15) K and ambient pressure of
these systems can be described by the VFT equation [52]. Similar to
the pure ionic liquid systems, the viscosity of [BMIM][SCN] + 1-
alcohol binary system decreases with the temperature. As the increase
of alcohol mole fraction, the system viscosity decreases dramatically
[53].
The experimental investigation on viscosity, density, and conductiv-
ity of mixture of PEG (Mw = 200, 300, 400) and PEI (Mw = 423) with ILs
[BMIM][BF4] and [BMIM][PF6] indicates that the viscosity and conduc-
tivity of the ionic liquid/solvent mixture decrease significantly as the
concentration of PEG increases [54]. Liu et al. investigated the VLE and
viscosity of CO2/[BMIM][PF6]/methanol ternary mixture at pressures
up to 12.5 MPa. It demonstrated that the viscosity of the IL-rich phase
decreases significantly with increasing pressure of CO2, and indicated
that compressed CO2 may be used to reduce the viscosity of ILs in
many applications [55].
The transport properties of ILs containing metal ions and H2O are
important to evaluate the suitability of ILs for applications in batteries.
The 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] contain-
ing 30 mol% Zn(DCA)2 electrolyte displayed higher conductivities
(15 mS.cm− 1 at 25 °C) than the same IL containing 30 mol% ZnCl2
(12 mS.cm− 1 at 25 °C). The different solvation environments of the
Zn2+ in the two IL/zinc salt mixtures results in a significant improve-
ment in transport properties of [EMIM][DCA] containing Zn(DCA)2
over ZnCl2 [56]. Forsyth et al. investigated on the effect of organic addi-
tives [57], anion mixing [58] on the transport properties of ILs/Li[Tf2N]
mixtures [59]. To investigate the effect of anion mixing on the lithium
ion speciation, conductivity and PFG-NMR diffusion measurements of
binary IL system N-methyl-N-propylpyrrolidinium, and either [Tf2N])
or bis(fluorosulfonyl)imide [FSI] as the anion as well as the Li-[Tf2N]-
containing ternary system were investigated. The addition of the
lithium salt to the IL system resulted in a decrease in conductivity. The
conductivity and ion diffusion have linear behavior as a function of the
anion ratio for a fixed lithium salt composition. The addition of the FSI
to the [Tf2N] IL results in a considerable increase in lithium ion diffusiv-
ity without additional complex ion behavior [58]. Organic solvent
additives (toluene and THF) effect on IL/Li[Tf2N] over a wide tempera-
ture range indicated that both additives enhanced the conductivity
most at low temperatures. Both the anion and lithium self-diffusivity
are enhanced in the same order by the additives while that of the
pyrrolidinium cation is marginally enhanced [57]. Besides that, the
ionic conductivity of mixtures of N-alkyl-N-methylpyrrolidinium
[Tf2N] ILs with Li[Tf2N] was investigated [59]. The ionic conductivity
variability correlates well with the phase behavior [59].
4. Correlations and molecular dynamics simulations
4.1. Correlations
Since experimental data of transport properties of ILs are scarce and
often contradictory, the development of correlation and predictive
models are quiet necessary. For transport properties, most of the
proposed predictive methods are QSPR and group contribution
methods. Coutinho and his coworkers did a lot of researches on this
topic. Recently, they had given a review on the predictive methods for
the estimation of thermophysical properties of ILs [2]. In the review,
they introduced some correlation works, which were complicated. The
complex of the models will decrease both the applicant and the theoret-
ically base, which should not be encouraged. In this paper, we only
introduce the simple correlation methods and molecular dynamics
simulations.
An Orrick–Erbar-type approach [60] was employed to estimate the
viscosity of ILs by Gardas and Coutinho [20]. A group contribution
technique was employed to estimate the A and B parameters in Eq. (5):
η B
ln ¼Aþ ð5Þ
ρM T
Where η and ρ are the viscosity and density, respectively. M is the
molecular weight and T is the absolute temperature. For around 500
data points of 29 ILs studied, in ranges of temperature, 293–393 K and
viscosity, 4–21,000 cP, a MPD of 7.7% with a maximum deviation small-
er than 28% was observed. The Orrick–Erbar method requires density
data for the prediction of viscosity, in case the density is unavailable,
the authors suggested using Eq. (3) to estimate it. Gardas and Coutinho
proposed a further new correlation [61] based on the VTF equation
(Eq. (6)) to estimate the viscosity, electrical conductivity, thermal
conductivity, refractive index, isobaric expansivity, and isothermal
compressibility, of various families of ILs. The new model is also a
group contribution method based on experimental data.
Bη
ln η ¼ Aη þ   ð6Þ
T−T 0η
where η is viscosity, T is temperature in K, and Aη, Bη, and T0η are adjust-
able parameters. T0η is similar for all the ILs. Aη and Bη can be obtained
by a group contribution method according to:
X
k X
k
Aη ¼ ni ai;η Bη ¼ ni bi;η ð7Þ
i¼1 i¼1
where ni is the number of groups of type i, k is the total number of
different groups in the IL. Similar models were proposed to estimate
other transport properties; the estimated data are consistent with the
experimental data. The correlation of viscosities of [BMIM][DCA] and
[BMIM][C(CN)3], for mole fractions up to 0.6, at atmospheric pressure
was consistent to the experimental viscosity data [62]. The electrical
conductivity of ILs can also be predicted by the above group methods,
the correlation coefficient between the experimental data (around
 X. Wang et al. / Journal of Molecular Liquids 193 (2014) 262–266
300 data points of 15 ILs) and this group contribution predicted that the
method reaches 0.9985 [62].
Ghatee [63,64] proposed a linear equation (Eq. (8)) to fit the viscosity
of the ILs. The results are quite in agreement with the experiments, with
a maximum deviation of 3.00%.
 ϕ
1 transport properties of the pure ILs [74,75] and their mixtures with
¼ a þ bT
η conventional solvents.
where a and b are substance dependent constants and ϕ is a character-
istic exponent. Here we should point out again that the values of
transport properties are significantly influenced by the small amounts
of impurities, which may result in the inaccuracy of the experimental
data, therefore influence the group contribution parameters regressed
from experimental data.
The viscosity of mixtures with ILs are very sensitive to the structure
of constitute. Thus, although there are models to correlation of transport
properties of mixtures including ILs, most of them are based on the
knowledge of viscosity of pure ILs. Usually these models can be only
used to ideal systems. Redlich–Kister polynomial was used to fit the
viscosity and molar refraction, the excess molar volume, and deviation
in isentropic compressibility of [BMIM][PF6] in tetrahydrofuran,
dimethylsulfoxide, methanol, and acetonitrile [65]. A model with one
parameter was proposed to calculate viscosities of binary mixtures
from pure component physical properties to overcome the difficulty
that the numbers of parameters for Redlich–Kister polynomial
equations are large [66,67]. Geng et al. proposed a model based on an
equation of state for estimating the viscosity of [BMIM][PF6] and DMF
binary mixtures by coupling with the excess Gibbs free energy model
of viscosity. The model gives a deviation of 8.29% for the viscosity [68].
Carvalho extended the one-constant Grunberg and Nissan equation [69]
to describe viscosity of [BMIM][DCA] + water and [BMIM][C(CN)3] +
water [62]. Equation derived data are consistent with the experimental
data.
X 1X n X m
ln ηm ¼ xi ln ηi þ xx G
2 i¼1 j¼1 i j ij
The x is the liquid mole fraction of the component, and Gij is a
temperature dependent interaction parameter [70].
The viscosities of the IL binary mixtures with a common ion ([C6mim] +
[C2mim])[BF4], ([C6mim] + [C4mim])[BF4], [C4mim]([BF4] + [MeSO4])
and [C4mim]([PF6] + [BF4]) can be predicted by the following expression
Δg E
log 10 ðηV Þ ¼ x log10 ðη1 V 1 Þ þ ð1−xÞlog 10 ðη2 V 2 Þ þ
RT
where V is the molar volume and Δg E denotes the excess molar Gibbs en-
ergy of activation for flow [50]. If a mixture does not deviate significantly
from the ideal mixture model, Δg E = 0, then the viscosity for a mixture
can be obtained from its molar volumes and from pure product molar
volumes and viscosities, which is the “ideal” Katti and Chaudhri mixing
law [71,72].
log 10 ðηÞ ¼ x log10 ðη1 Þ þ ð1−xÞlog10 ðη2 Þ
It is obvious that the key point for developing predictive methods
based on group contribution is to have enough reliable experimental
data. Then comprehensive investigations should be carried out on the
relationship between the structure and properties of ILs. Besides that,
a criteria should be established to evaluate the reliability of the experi-
mental data of transport properties to avoid the use of the inaccuracy
data in the regression of the group contribution parameters, just like
what was used in selecting the activity coefficient data from DDB [73].
Hence, special care should be given to the inconsistent data because
265
sometimes it is caused by the inaccuracy of experimental data, while
the predicated data is more reliable.
4.2. Molecular dynamics simulations
To elucidate the physical aspects behind transport properties of ILs,
molecular dynamics (MD) simulations were also used to study the
ð8Þ
Borodin et al. reported that the transport properties such as ion self-
diffusion coefficients, conductivity, and viscosity of ILs obtained by MD
simulations were in good agreement with experimental measurements.
The systems that they investigated include [MPPy][Tf2N] [76], [EMIM]
[Tf2N] [77,78], and 30 ILs containing [CnMIM] cations and [BF4],
[CF3BF3], [CH3BF3], [OTF], [PF6], [DCA], [C(CN)3], [B(CN)4], [Tf2N], [FSI]
and nitrate anions [77]. Other MD simulation research gave similar
results [79].
The investigation on the transport coefficients of ILs of [P4444] cation
with six amino acid [AA] anions indicates that the self-diffusion coeffi-
cients of the [P4444] cations are smaller than those of amino acid anions.
The diffusion coefficient and electrical conductivity of these [P4444][AA]
ILs decrease because of the polar functional groups on the side chain of
[AA] anion [74]. The dependence of the properties of the ILs on simula-
tion parameters, e.g., system-size effects or the choice of the interaction
potential, is analyzed in detail [80]. Chaban et al. proposed a new, non-
polarizable force field model to ILs as well as condensed matter systems
in which the ionic interaction requires an account of polarization effects
[75]. The influence of the temperature and the cation's alkyl chain
length of [CnMIM][Tf2N] (n = 4, 8, 12) ILs on the transport properties
was thoroughly investigated by MD simulations from 298.15 to 498.15
K [81]. Density functional theory is incorporated in the charge distribu-
tion to calculate the partial charges. Results show that the calculation of
transport properties is very complicated, especially at low temperatures
[81]. MD simulations on the transport properties of [BMIM][Tf2N],
[BMIM][Tf2N], [BMMIM][Tf2N], [BMPyr][Tf2N], [N4111][Tf2N], and
[N4111][COOHTf2N] show that several of these ILs are quite favorable
to act as high temperature heat transfer fluids. The MD simulation re-
ð9Þ
sults of transport properties qualitatively agree with the experimental
data. The simulated thermal conductivity of the [Tf2N]-based ionic liq-
uids has good correlation with their density and molecular weight
[82]. The performance of MD simulations on the transport properties
of [PYR] [Tf2N] mixed with [Li][Tf2N] salt has been conducted by using
a polarizable force field. Mixture simulations with lithium salt mole
fractions between 0% and 33% at 363 and 423 K yield the simulation
results on ion self-diffusion coefficients and ionic conductivities are
in very good agreement with available experimental data. The ionic
ð10Þ conductivity of the electrolytes decreases with increasing salt
concentration [83].
4.3. Comparison of the predictive methods
The prediction methods for transport properties are either based on
the experimental data (such as correlations or group contribution
methods) or based on the a priori methods (such as molecular dynamics
simulations). The advantage of a priori methods is the less or no
ð11Þ dependent on the experimental data, especially for new compounds
or molecules that have new groups. However, the predicted results
based only on molecular structure instead of experimental data are
usually less accurate than that based on experimental data. And since
the transport properties are seriously affected by small amount of impu-
rities, a comprehensive comparison on the performance of different
methods should be carried out to give chemists and engineering estima-
tion on the error of the predicted data, just as we have done on the
comparison of the performance of COSMO-RS and UNIFAC (Do) for
the prediction of the activity coefficient at infinite dilution and vapor
liquid equilibrium [84–87]. Such comparison should be carried out
266 X. Wang et al. / Journal of Molecular Liquids 193 (2014) 262–266

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