Fluid Phase Equilibria 294 (2010) 157179

Contents lists available at ScienceDirect

Fluid Phase Equilibria

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

Studies on the density, heat capacity, surface tension and innite dilution
diffusion with the ionic liquids [C4 mim][NTf2 ], [C4 mim][dca], [C2 mim][EtOSO3 ]
and [Aliquat][dca]
Carlos A. Nieto de Castro a,c, , Elisa Langa a , Ana L. Morais a , Manuel L. Matos Lopes a,c ,
Maria J.V. Lourenco a,c , Fernando J.V. Santos a,c , M. Soledade C.S. Santos b,c , Jos N. Canongia Lopes d ,
Helena I.M. Veiga d , Mafalda Macatro d , Jos M.S.S. Esperanca d , Carolina S. Marques e ,
Lus P.N. Rebelo d , Carlos A.M. Afonso e
a
Centro de Cincias Moleculares e Materiais, Faculdade de Cincias, Faculdade de Cincias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
b
Centro de Qumica e Bioqumica, Faculdade de Cincias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
c
Departamento de Qumica e Bioqumica, Faculdade de Cincias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
d
Instituto de Tecnologia Qumica e Biolgica, ITQB2, Universidade Nova Lisboa, Av. Repblica, Apartado 127, 2780-901 Oeiras, Portugal
e
CQFM - Centro de Qumica-Fsica Molecular and IN - Institute of Nanosciences and Nanotechnology, Instituto Superior Tcnico, 1049-001 Lisboa, Portugal

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

Article history: Ionic liquids are a class of uids that requires the attentions of experimentalist and theoreticians.
Received 7 December 2009 In a new project on synthesis and characterization of new and not-so-new ionic liquids, the study
Received in revised form 3 March 2010 of several thermophysical properties of these liquids was started, namely binary diffusion, electri-
Accepted 6 March 2010
cal conductivity, heat capacity, surface tension, viscosity and thermal conductivity. Among others we
Available online 12 March 2010
will study 1-n-butyl-3-methyl-imidazolium bis(triuoromethanesulfonyl)imide, ([C4 mim][NTf2 ]), 1-n-
butyl-3-methyl-imidazolium dicyanamide, ([C4 mim][dca]), 1-ethyl-3-methyl-imidazolium ethylsulfate,
Keywords:
([C2 mim][EtOSO3 ]) and methyltrialkylammonium dicyanamide [Aliquat 336-derived][dca], and in the
Ionic liquids
Density
case of diffusion, their mixtures with water.
Diffusion It is the purpose of this paper to report data on the density, using vibrating tube densimetry, innite
Heat capacity dilution diffusion coefcients, using the Taylor dispersion method, heat capacity, using DSC equip-
Heat storage capacity ment and surface tension, using the Wilhelmy plate method. Density measurements were performed
Heat transfer uids at atmospheric pressure between 293 and 363 K and several isotherms, depending on the stability of
Surface tension the compound, up to 60 MPa, with an uncertainty of 0.4%. Measurements were performed at 298.03 K
Thermal expansion coefcient for the innite dilution measurements, with an uncertainty of 1.33.5%, for temperatures between 300
Isothermal compressibility
and 370 K for heat capacity, with an uncertainty better than 1.5%, and between 292 and 395 K for surface
tension, with an uncertainty of 1.51.8%.
A brief analysis of the potential of the uids studied as engineering heat transfer uids, namely its heat
storage capacity was also performed.
2010 Elsevier B.V. All rights reserved.

1. Introduction solvent properties as well as their heat transfer/heat storage

Ionic liquids have proven to be safe and sustainable alternatives
for many applications in industry and chemical manufactur-
ing. Their success arises mainly from their thermophysical and
phase-equilibria properties, and the versatility of their synthe-
sis, manageable to be tailored for a given application. Their
Corresponding author at: Departamento de Qumica e Bioqumica, Faculdade de
Cincias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.
Tel.: +351 217 500 918; fax: +351 217 500 088.
E-mail address: cacastro@fc.ul.pt (C.A. Nieto de Castro).
and surface properties, makes this class of uids possible to
use in a high plethora of applications [1,2]. Thermophysical
properties data, that we can trust, not only because the sam-
ples are well puried and characterized, but also because the
uncertainty of the data is well discussed, are needed for sev-
eral applications and for the design of chemical plants. They
can be obtained from experimental measurements, predictive or
estimation techniques, and although there were some interest-
ing developments in this last area, by using group contribution
methods, the calculation of the thermophysical properties of
ionic liquids with more or less theoretical based schemes is
currently very difcult, but useful for some properties [3]. Exper-

0378-3812/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2010.03.010
158 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179
iment, although not yet perfect, is still our main source of
information.
Recently we have presented two reports where the situation
of the values of the thermophysical properties of ionic liquids
[4] and their application as heat transfer uids has been ana-
lyzed [5,6], taking into account the measuring methods used, the
uncertainty of the measurements and possible application. Addi-
tionally an IUPAC project on the thermophysical properties of one
chosen uid, produced a complete analysis on the determination
of properties from the same batch of synthesized liquid, 1-
hexyl-3-methylimidazolium bis(triuoromethanesulfonyl)imide,
[C6 mim][NTf2 ], making a critical evaluation and proposing refer-
ence values for heat capacities, density, vapor pressure, viscosity,
electrolytic conductivity, speed of sound and relative permittiv-
ity [7,8]. When comparing data previously obtained by different
authors and different methods, namely for viscosity, discrepancies
at room temperature could easily reach 30% for [C6 mim][NTf2 ][8].
However, these reports show that, good agreement between mea-
surements made in different laboratories can be achieved, if careful
control of water (and purity) before and during the measurements,
is maintained. Therefore, any careful measurement of physic-
chemical properties of ionic liquids, must follow a strategy of
control of purity of the samples before, and after the measurements,
as well as a careful choice of experimental methods and procedures
[4].
Among the considerable options available to design a new ionic
liquid or use an existing and commercially available, the actual
project team based the selection of the ionic liquids on the follow-
ing criterions, inspired by the guidelines and rational behind the
previous IUPAC project [7,8]:
(i) Being representative of different ionic liquids generations
namely the ones based on the combination of imidazolium,
ammonium, phosphonium and guanidinium cations and stable
imide and alkylsulfonate (including chiral one) anions.
(ii) Presenting a broader range of potential applications in dif-
ferent areas such as reaction media, catalyst immobilization,
nanotechnology, electrochemistry, solar cells and separation
processes based on liquids phase extraction, membranes and
supercritical uids.
(iii) Being chemically and thermally stable to support the puri-
cation conditions, in special the ones under high temperature
and high vacuum distillation, with low hygroscopicity.
(iv) Having a large range of viscosities, from medium (30 mPa s) to
high (400 mPa s).
The liquids selected span from 1-n-butyl-3-methyl-
imidazolium bis(triuoromethanesulfonyl)imide [C4 mim][Ntf2],
an archetypal stable ionic liquid, 1-ethyl-3-methyl-imidazolium
ethylsulfate, [C2 mim][EtOSO3 ], a cheap, thus very popular, and fully
commercially available IL (ECOENG 212), a new IL, the methyl-
trialkylammonium dicianamide, [Aliquat 336 -derived][dca],
derived from a very popular, cheap IL [Aliquat 336]Cl and, nally,
an ionic liquid that bridges the gap between different ionic liq-
uid generations, 1-n-butyl-3-methyl-imidazolium dicyanamide,
[C4 mim][dca]. For the sake of internal coherence of the data
obtained, the same ionic liquid sample was used in all experi-
mental determinations. Aliquat 336 is frequently referred in the
literature as a 2:1 mixture of methyl trioctyl- and methyl tride-
cylammonium chloride. However, as we will describe in the next
section, that mixture is, in fact, a well characterized combination
of ve quaternary ammonium ion components, that, for the sake
of simplicity and general usage, we will continue in this paper to
refer as [Aliquat][dca].
We report in this paper data on the density () of [C4 mim][NTf2 ],
[C4 mim][dca], [C2 mim][EtOSO3 ] and [Aliquat 336-derived][dca]
using vibrating tube densimetry, on the innite dilution dif-
fusion coefcients (D0 ) of [C2 mim][EtOSO3 ] in water, of water
in [C4 mim][NTf2 ] and [C4 mim][dca], using the Taylor disper-
sion method, heat capacity (CP ) of [C4 mim][NTf2 ], [C4 mim][dca],
[C2 mim][EtOSO3 ] and [Aliquat][dca], using our DSC equipment and
surface tension () of [C2 mim][EtOSO3 ], using the Wilhelmy plate
method. Data on viscosity, electrical conductivity, thermal conduc-
tivity and electrical permittivity are currently being measured and
will be reported in a near future.
Density measurements were performed between the nom-
inal pressures of 0.1 and 60 MPa in the temperature interval
293363 K and several isotherms were studied, depending on
the stability of the compound, up to 60 MPa, with an uncer-
tainty of 0.4%. Measurements were performed at 298.15 K for the
innite dilution measurements, with an uncertainty of 1.33.5%,
for temperatures between 300 and 370 K for heat capacity, with
an estimated uncertainty better than 1.5%, and between 292
and 332 K for surface tension, with an uncertainty better than
1.8%. The reported expanded uncertainty of measurement is
stated as the standard uncertainty of measurement multiplied by
the corresponding coverage factor for a probability of approx-
imately 95% (EAL Publication EAL-R2, http://www.european-
accreditation.org/content/publications/pub.htm).
2. Materials and methods
2.1. Materials
The ionic liquids studied were synthesized at the organic
chemistry laboratories of the Centro de Qumica-Fsica Molecular
(IST, UTL) following general reported procedures for 1-n-butyl-
3-methyl-imidazolium chloride, [C4 mim][Cl] precursor [9],
[C4 mim][NTf2 ] [10], [C4 mim][dca] [11], [C2 mim][EtOSO3 ][12] and
[Aliquat][dca] [13]. Their structures are shown in Fig. 1. All the
reagents used were high purity, and were acquired from Sigma-
Aldrich, Fluka or Acros-Organics. Their purication followed
accepted methods described in the literature [14] and after the
synthesis all the ionic liquids were allowed to stay several days in
high vacuum (P = 1 mbar) to remove any excess organic solvents.
The ionic liquids were characterized using NMR spectroscopy
(Bruker Avance 400 e 300 Ultrashield), elemental analysis (Leco,
model Trunspec), mass spectrometry with electrospray ionization
source (ESI) (Finningan LCQ Duo ion trap mass spectrometer), the
chloride ion content determined by ion chromatography and the
water content by coulometric Karl-Fisher titration (Metrohm 831
KF Coulometer). One of the compounds, [Aliquat][dca] deserves
particular comments. The designation Aliquat refers not to a pure
cation, methyltrioctylyammonium dicianamide, but to a complex
mixture of cations, where three of the alkyl chains have different
number of carbon atoms. Following the work that inspired the
synthesis performed in this work [15], the precursor used is
Aliquat 336 , referred to as 2:1 mixture of methyl trioctyl- and
methyl tridecylammonium cations, with an average molecular
weight of 396.55 g mol1 . The characterization of this compound
Fig. 1. Synthesized ionic liquids. As reported in this paper, [Aliquat 336 -
derived][dca], here abbreviated as [Aliquat][dca], is a ve-component mixture of
methytrilalkyl ammonium cations, where, R can be n-hexyl (1), n-octyl (0-3) and
n-decyl (0-3).
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 159

by mass spectrometry, was performed at the Departamento
de Qumica e Bioqumica (FCUL), and the results are reported
in the Supplementary Information (SI). However, the MS data
have shown that our sample contains a ve-component mixture
of methyl(n-hexyl)di(n-octyl)ammonium (0.8%), methyltri(n-
octyl)ammonium (29.8%), methyldi(n-octyl)decylammonium
(43.6%), methyl(n-octyl)di(n-decyl)ammonium (21.9%), and
methyltri(n-decyl)ammonium (3.8%), a result that agrees qualita-
tively with previous publications, in 1981 (GC) and 1998 (ESMS)
[16,17]. This corresponds to an average molecular weight of the
cation of 396.04 g mol1 , a value which is very close to the value
reported in reference [15]. Nonetheless it expresses a markedly
different chemical and thermodynamic reality. Although in the
literature the designation aliquat appears for different cations, we
prefer to designate our compound as [Aliquat 336 -derived][dca]
or [Aliquat][dca] as a short name.
Table 1 reports on the characterization of the ionic liquids. The
resulting yields are very satisfactory (7090%) and their purity as
far as the chloride ion is concerned is quite good; however, water
content is greater than one would wish for the physical property
measurements [1823]. Therefore, and prior to the measurements,
the ionic liquids were further dried in high vacuum (typically 1 Pa),
at moderate temperatures (typically 320 K), after which the water
content was substantially reduced (Table 1); in no case the water
content amounts to more than 120 ppm, a proper value for mea-
surement purposes. This drying procedure is paramount as it has
been proven that the presence of residual water may have a marked
effect in the values of the ionic liquid properties. Finally, the ele-
mental analysis agrees very well with the theoretical expected
values.
2.2. Methods
2.2.1. Density measurement
The density measurements were performed with a vibrating
tube densimeter model DMA 5000. In the case of high-pressure
density data the experimental measurements were obtained
using a high-pressure cell also from Anton Paar model DMA HP at
pressures up to 60 MPa. The DMA 5000 only allows operation up to
363.15 K, while the use of the high-pressure cell extends that range
up to 473.15 K. The calibration of the DMA 5000 was done using the
density data for dry air and water and the calibration was tested
with standard uids. The substances used were pentane, benzene,
water and dichloromethane (bi-distilled Millipore water; all others
HPLC grade from Aldrich, with purity better than 99.9%, except
pentane, with purity better than 99%). The reason to choose these
substances was the need to cover an extended density range (from
0.6 to 1.4 kg dm3 ). The calibration data for these substances were
taken from the Anton Paar manual, and are based on previously
published works, respectively [2427]. More than 500 data points
were measured and the standard deviation of the t (density as
a function of pressure, temperature and period) was 0.03%. The

Table 1
Ionic liquids characterization.

Ionic liquid NMR analysis Elemental analysis Cl content (%) H2 O content

(w/w) (ppm)
Exp. Calc.

[C2 mim][EtOSO3 ] 1
H NMR (400 MHz, CDCl3 ) : 1.03 (t, J = 7.2 Hz, NCH2 CH3 , 3H); C8 H16 N2 O4 S C8 H16 N2 O4 S BFD 26641.23
(M = 236.29 g mol1 ) 1.33 (t, J = 7.2 Hz, OCH2 CH3 , 3H); 3.79 (s, NCH3 , 3H); 3.84 (q, C 40.55 C 40.66 AFD <100
J = 7.2 Hz, OCH2 CH3 , 2H); 4.10 (q, J = 7.5 Hz, NCH2 CH3 , 2H); 7.39 H 6.97 H 6.83
(s, C(4, 5)H, 2H); 9.21 (s, C(2)H, 1 H). N 11.89 N 11.86
13
C NMR (100 MHz, CDCl3 ) : 14.11 (NCH2 CH3 ); 14.41 S 13.58 S 13.57
(OCH2 CH3 ); 35.01 (NCH3 ); 43.80 (NCH2 CH3 ); 61.89
(OCH2 CH3 ); 121.31 (C(5)H); 122.80 (C(4)H); 135.42 (C(2)H).
[C4 mim][NTf2 ] 1
H NMR (400 MHz, CDCl3 ) : 0.87 (t, J = 7.4 Hz, C10 H15 F6 N3 O4 S2 C10 H15 F6 N3 O4 S2 0 BFD 638.42
(M = 419.37 g mol1 ) CH3 CH2 CH2 CH2 N, 3H); 1.28 (sex, J = 7.6 Hz, CH3 CH2 CH2 CH2 N, C 28.57 C 28.64 .02 AFD <120
2H); 1.77 (quint, J = 7.6 Hz, CH3 CH2 CH2 CH2 N, 2H); 3.85 (s, H 3.25 H 3.61
NCH3 , 3H); 4.09 (t, J = 7.4 Hz, CH3 CH2 CH2 CH2 N, 2H); 7.28 (d, N 10.25 N 10.02
J = 1.6 Hz, NCHCHN, 1 H); 7.29 (d, J = 1.6 Hz, NCHCHN, 1 H); 8.57 S 14.84 S 15.29
(s, NCHN, 1 H).
13
C NMR (100 MHz, CDCl3 ) : 13.09 (CH3 CH2 CH2 CH2 N); 19.25
(CH3 CH2 CH2 CH2 N); 31.88(CH3 CH2 CH2 CH2 N); 36.14 (NCH3 );
49.85 (CH3 CH2 CH2 CH2 N); 118.26 (q, CF3 ); 122.50 (NCHCHN);
123.79 (NCHCHN); 135.74 (NCHN).
[C4 mim][dca] 1
H NMR (400 MHz, CDCl3 ) : 0.86 (t, J = 7.2 Hz, C10 H15 N5 C10 H15 N5 0 BFD 8441.26
(M = 205.26 g mol1 ) CH3 CH2 CH2 CH2 N, 3H); 1.27 (sex, J = 7.6 Hz, CH3 CH2 CH2 CH2 N, C 58.76 C 58.51 .36 AFD <110
2H); 1.78 (quint, J = 7.6 Hz, CH3 CH2 CH2 CH2 N, 2H); 3.89 (s, H 8.10 H 7.37
NCH3, 3H); 4.12 (t, J = 7.4 Hz, CH3 CH2 CH2 CH2 N, 2H); 7.37 (m, N 32.47 N 34.12
NCHCHN, 2H); 9.04 (s, NCHN, 1 H).
13
C NMR (100 MHz, CDCl3) : 12.06 (CH3 CH2 CH2 CH2 N); 17.99
(CH3 CH2 CH2 CH2 N); 30.53 (CH3 CH2 CH2 CH2 N); 34.98 (NCH3);
48.37 (CH3 CH2 CH2 CH2 N); 118.27 (N(CN)2 ); 121.34 (NCHCHN);
122.46 (NCHCHN); 134.87 (NCHN).
[Aliquat][dca]* 1
H NMR (400 MHz, CDCl3 ) : 0.80 (t, J = 4.6 Hz, CH3, 9H); C27 H54 N4 C27 H54 N4 0 BFD 1972.22
(M = 462.21 g mol1 ) 1.201.30 (m, (CH2 )n CH3 , 34H); 1.62 (s br, NCH2 CH2 , 6H); 3.01 C 74.10 C 74.53 .03 AFD <120
(s, NCH3 , 3H); 3.19 (m, NCH2 , 6H). H 12.01 H 12.42
13
C NMR (100 MHz, CDCl3 ) : 13.50 ((CH2 )n CH3 ); 21.71 (CH2 ); N 11.84 N 12.88
22.07 (CH2 ); 22.16 (CH2 ); 25.69 (CH2 ); 28.40 (CH2 ); 28.46
(CH2 ); 28.67 (CH2 ); 28.76 (CH2 ); 28.83 (CH2 ); 31.04 (CH2 );
31.26 (CH2 ); 47.86 (NCH3 ); 61.36 (NCH2 (CH2 )n ); 119.35
(N(CN)2 ).

BFD: water content after organic solvent cleaning and before drying in vacuum at moderate temperatures; AFD: water content after drying in vacuum at moderate
temperatures.
*
[Aliquat 336-derived][dca]; see Section 2.1. The calculated chemical formula correspond to the 2.1 mixture, as the 5 component mixture gives a very similar molecular
weight.
160 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

maximum deviation was 0.08%. The calibration was checked with brought about only by molecular diffusion. The coupling of the ow
toluene (HPLC grade from Aldrich, with purity better than 99.9%) induced dispersion with molecular diffusion results in a signicant
by measuring 10 data points within the calibrated p, T range dispersion in a short time. The method was rstly conceived by G.I.
(pressure up to 60 MPa, temperature between 283 and 473 K), with Taylor, in 1953, and its theory, that makes possible its classication
deviations lower than 0.02% when comparing with the data of as an absolute and primary method, was presented by Alizadeh et
[28]. The Peltier units responsible for controlling the temperature al. [31]. In its experimental realization a uid mixture of compo-
allow a temperature stability better than 2 mK for periods over nents A and B, ows in laminar ow through a straight, innitely
10 min. The repeatability in the temperature measurement in long, isothermal tube, of uniform circular cross section, of radius
both densimeters is better than 0.01 K, while the repeatability in a0 , with impermeable walls. The molar concentrations of species
the pressure measurement for the high-pressure densimeter is A and B in the owing solution are denoted by cAf and cBf and the
better than 0.7 bar (0.1% of the full scale). Under these operating mean velocity of the liquid mixture by u0 . At time t = 0, a sample of
conditions, we found that the repeatability of the density mea- the liquid mixture of slightly different composition, given by cAi and
surements at atmospheric pressure was better than 0.005 kg m3 , cBi , with a density identical at the owing stream (to avoid buoy-
while when using the high-pressure cell the repeatability was ancy forces) is introduced at z = 0, in the form of a pulse. The joint
better than 0.06 kg m3 . However, and taking into account the action of convective ow and molecular diffusion results, at a time t
uncertainties related to calibration of the apparatus and the down the tube in a dispersion of the pulse. The governing differen-
purity of the ionic liquid samples, the expanded uncertainty was tial equation for the perturbation of the pulse molar concentration
estimated to be 0.4% for the ionic liquids used in this work (see cA is [31]:
Section 3).   r 2  (c )
The reported atmospheric pressure density data were corrected 1 (cA ) 2u0 A
= 2 (cA ) 12 (1)
for the effect of viscosity using the internal calibration of the den- DAB t DAB a0 z
simeter, while for the high-pressure density data no correction was
perform due to the lack of high-pressure viscosity data for these The initial conditions for its solution are:
substances. During the measurements the liquid was transferred 
to a syringe and injected into the densimeter. To prevent any air = 0, z =
/ 0
cA (r, , 0, 0) = (z)(cAi cAf ); (z) (2)
bubble, the vibrating tube was rst lled with some of the con- = 1, z = 0
tents of the syringe, and a rst density measurement was taken
(after the temperature set point was reached). Another measure- and the boundary conditions are:
ment followed after the liquid of the vibrating tube was replaced
with the one that remained in the syringe. The agreement between (cA )
= 0 at r = a0 for all t
both values is a measure of the effectiveness of the method and the z (3)
absence of air bubbles. cA 0 as z =

where DAB is the interdiffusion or mutual diffusion coefcient of A

2.2.2. Heat capacity measurement
in B. This equation can not be solved directly to obtain cA (z, t),
The heat capacity measurements were obtained with a dif-
but it can be solved for the spatial moments of the concentration
ferential scanning calorimeter DSC-111, Setaram, France, which
distribution, at a particular time. In fact, the enhanced dispersion of
was calibrated in enthalpy (Joule effect) and temperature (CRMs,
the pulse results in a broadening of the distribution. If we monitor
LGC, UK). Details of these calibration procedures can be found in
the cross section averaged concentration distribution at an axial
previous publications [6,29,30]. The uncertainty in the enthalpy
position z = L as a function of time, provided that
measurements was found to be of the order of 1%, while the temper-
ature measurements agree within 0.1 K with the standard values. DAB t DAB
The heat capacity was obtained using closed stainless steel cru- > 700 and u0 > 700 (4)
a20 a0
cibles, by continuous method-standard zone, with a scanning rate
of 2 K min1 (Setaram SETSOFT 2000, Version 3.0). The mass of the
Then, with an error smaller than 0.01%, the rst and the second
samples was conrmed after each run to conrm possible weight
central moment (variance) of the temporal distribution are given
losses. The measurement technique uses a double experiment per-
by [31]:
forming two nearly identical runs, one with the two cells without
sample and the other with the sample in one of the cells. In this L
way any differences between the two crucibles are eliminated from tid = (1 + 2)
u0
the nal signal to be used in the calculation of the heat capac-  L 2
2 =
id (8 2 + 2)
ity, at atmospheric pressure. The uncertainty of the heat capacity (5)
u0
determinations is better than 1.5% at a 95% condence level.
u0 a20
=
2.2.3. Innite dilution diffusion coefcients measurements 48DAB L
The diffusion process in liquids is by far one of the most difcult
If the rst and the second central moment (variance) of the tem-
transport phenomena, and can be simply dened as the process
poral distribution are determined at a cross section of the tube at
whereby an initially non-uniform distribution of species in a mix-
a distance L from the injection point, the interdiffusion coefcient
ture proceeds towards a uniform distribution. Details about the
can be obtained from:
discussion of this problem, regarding the difculties about the
methods, the different diffusion coefcients that exist, and the com- 2 /t 2 )] 1/2
a20 [1 + 4(id id
+3
parability of the results, can be found in reference [4]. DAB = (6)
The present measurements were obtained with the Taylor dis- 24tid [1 + 4( 2 /t 2 )]1/2 + 2( 2 /t 2 ) 1
id id id id
persion technique, and we will describe it briey here. The Taylor
dispersion technique uses, in essence, the velocity prole of the Any experimental realization of the ideal method clearly
ow of a liquid in a cylindrical tube, to enhance the dispersion of a involves departures from it, and all of them have been considered
pulse of a mixture in another one of slightly different composition, by Alizadeh et al. [31]. In particular it was found that the ideal
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179
moments have to be corrected by:

tid = texp + ti

i
2 = 2 +
id exp  i2
i
2 denote the experimentally measured moments
where texp and exp
2
and ti and  i are the different corrections to the ideal model.
They involve the nite volume of the detector, the nite volume
of the injected sample, the tube connection to the detection cell,
the secondary ow effects induced by the diffusion tube, the non-
uniformity and the non-circularity of the tube cross section, as well
as the concentration dependence of the interdiffusion coefcient,
assumed constant in the ideal model. A suitable design can make
most of these corrections negligible, the remaining ones not con-
tributing to more than 0.5% of the moments of the experimental
curve.
The reference state of the measured diffusion coefcient is
dened by the temperature and pressure of the measurement, and
a composition cAref given by:
cAref = cA1 + cA
where the correction cA depends on the number of moles of the
species A present in the injection sample in excess of those in the
owing stream.
The Taylor dispersion technique, although of slight higher
uncertainty, has two great advantages over the other methods
[4]. It is very rapid and can be used, without loss of accu-
racy, in wide ranges of temperature and pressure. Furthermore,
it has been applied already to diffusion of water in alkylimi-
dazolium tetrauoroborates and hexauorophosphates [32] and
1-alkyl-3-methylimidazolium ionic liquids in water, methanol and
acetonitrile [33]. Matos Lopes and Nieto de Castro developed an
instrument of this type, where the detection is made by using
a differential liquid refractometer, normally used in HPLC, for
measurements in binary mixtures of alkanes, at atmospheric pres-
sure and temperatures between 290 and 350 K, with an accuracy
reported to be better than 1% [34,35], later applied to the H2 O/D2 O
system [36], diffusion in micelar solutions [37] and binary mixtures
near consolute critical points [38]. The application of this system
to diffusion of ionic liquids at innite dilution is straightforward,
but the inverse, innite dilution of a solvent, such as water in a
ionic liquid, raises several problems because of the high viscosity
of some of these mixtures, and the validity of the relations imposed
by Eq. (4). This requires changes in the geometrical congurations,
namely the diffusion tube radius, if we want to apply it to diffusion
in mixtures with viscosities greater than 60 mPa s. For the moment
we present in this paper only results for the innite dilution diffu-
sion coefcients of water in [C4 mim][NTf2 ] and [C4 mim][dca], and
of [C2 mim][EtOSO3 ] in water.
The actual instrument used in these measurements, with a
few improvements, has already been described elsewhere [38,39]
(Fig. 2). The direct ow of the mixtures into the diffusion tube
is obtained with a Harvard Apparatus, model PHP2000, syringe
infusion pump. The solution of slightly different concentration is
injected through a Rheodyne, model7010, six-port injection valve.
The diffusion tube 13m long and with inner diameter of 0.4 mm,
made of 316 stainless steel, is wound with a circular radius of
16 mm, within a square shaped stainless steel circular container
lled with molten lead to ensure good thermal contact. The entire
block was suspended from a marble table to avoid vibrational dis-
persion effects. This block together with the injection valve and a
pre-heat exchanger coil is immersed in an oil thermostated bath.
The temperature is regulated with a PID controller. A Waters 2410
differential refractometer was used as detector, its analogical sig-
161
(7)
Fig. 2. Scheme of the experimental diffusion apparatus.
(8)
nal digitized with a Keithley 2000 multimeter and registered in a
microcomputer. The data points relative to the temporal concen-
tration prole of each measurement were subsequently tted to
a Gaussian distribution yielding t and  2 . The temperature of the
detector cell was controlled separately within 0.1 K. The tempera-
ture of the diffusion tube ensemble was measured with a resolution
of 2.5 mK, with platinum probes with a resistance of 100 . Tem-
perature stability within a run of few hours is 4 mK, and the
reproducibility between runs, in different occasions, is 8 mK.
To ensure that the instrument operated in accordance with the
supporting theory, experiments were carried out at various ow
rates. Results demonstrated optimal experimental conditions for
ow rates conducing to diffusion times ranging around 314 ks.
Mole fraction differences between injected solutions (xA + xA ) and
carrier solutions (xA ) were in the order of 0.0050.010. To ensure
that the measured diffusion coefcients were independent of the
initial concentration difference and of the inuence of any buoy-
ancy effects, solutions of different compositions were injected into
each carrier and different ow rates were used for each set of
measurements. No such effects were detected. A number of 410
replicate measurements for the diffusion coefcient were deter-
mined for each system, at innite dilution. The uncertainty is found
to be in the order of 1% expanded uncertainty ranging from 1.3 to
3.5%.
2.2.4. Surface tension measurements
The surface tension of [C2 mim][EtOSO3 ] was measured with
a K100MK2 tensiometer from Kruss GmbH, based on force mea-
surements, with a precision balance (10 g resolution) and using
a platinum Wilhelmy plate. The measurements were carried at
atmospheric pressure for temperatures between 292 and 323 K.
The sample was kept in a custom made micro PTFE sample ves-
sel (
=1 ml) and thermostated in a double-jacketed stainless steel
thermostatic sleeve by means of a circulating water bath, using an
HAAKE DC30/K10 circulator controlled within 0.1 K. The sample
temperature was monitored with an independent external Pt 100
thermometer, inserted next to the sample vessel, measurements
being performed after equilibrium periods larger than 1hr and
with temperature uctuations below 0.02 K. The tensiometer was
calibrated with standard masses, provided by the manufacturer,
and also checked at 298.15 K with reference liquids (n-heptane,
n-decane and toluene). Before each measurement, at each tempera-
ture, the calibration was further checked, with MilliQ grade 1 water.
162 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Table 2
Experimental density data,  (kg m3 ), and calculated isobaric thermal expansion coefcient, p (k K1 ), at atmospheric pressure for [C4 mim][Ntf2 ] obtained with the
atmospheric pressure densimeter.

T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 )

293.15 1441.34 0.6696 318.15 1417.41 0.6674 343.15 1394.01 0.6652

294.15 1440.37 0.6695 319.15 1416.47 0.6673 344.15 1393.09 0.6651
295.15 1439.40 0.6694 320.15 1415.53 0.6672 345.15 1392.16 0.6651
296.15 1438.43 0.6693 321.15 1414.58 0.6671 346.15 1391.23 0.6650
297.15 1437.46 0.6692 322.15 1413.64 0.6671 347.15 1390.31 0.6649
298.15 1436.50 0.6692 323.15 1412.70 0.6670 348.15 1389.38 0.6648
299.15 1435.53 0.6691 324.15 1411.76 0.6669 349.15 1388.46 0.6647
300.15 1434.57 0.6690 325.15 1410.82 0.6668 350.15 1387.54 0.6646
301.15 1433.61 0.6689 326.15 1409.88 0.6667 351.15 1386.61 0.6645
302.15 1432.64 0.6688 327.15 1408.94 0.6666 352.15 1385.69 0.6644
303.15 1431.69 0.6687 328.15 1408.00 0.6665 353.15 1384.77 0.6644
304.15 1430.73 0.6686 329.15 1407.06 0.6665 354.15 1383.85 0.6643
305.15 1429.77 0.6685 330.15 1406.12 0.6664 355.15 1382.93 0.6642
306.15 1428.82 0.6685 331.15 1405.19 0.6663 356.15 1382.01 0.6641
307.15 1427.86 0.6684 332.15 1404.25 0.6662 357.15 1381.09 0.6640
308.15 1426.90 0.6683 333.15 1403.32 0.6661 358.15 1380.17 0.6639
309.15 1425.95 0.6682 334.15 1402.39 0.6660 359.15 1379.25 0.6638
310.15 1425.00 0.6681 335.15 1401.45 0.6659 360.15 1378.34 0.6638
311.15 1424.05 0.6680 336.15 1400.52 0.6658 361.15 1377.42 0.6637
312.15 1423.10 0.6679 337.15 1399.59 0.6658 362.15 1376.50 0.6636
313.15 1422.15 0.6678 338.15 1398.66 0.6657 363.15 1375.58 0.6635
314.15 1421.20 0.6678 339.15 1397.73 0.6656
315.15 1420.25 0.6677 340.15 1396.80 0.6655
316.15 1419.30 0.6676 341.15 1395.87 0.6654
317.15 1418.36 0.6675 342.15 1394.94 0.6653

The PTFE vessel was carefully cleaned with water and detergent and
nally extensively ushed with MilliQ grade 1 water, being dried
before use. The curved roughened Wilhelmy platinum plate was
rinsed with ethanol and water and nally ame cleaned in a Bunsen
burner to eliminate any contaminants before every measurement.
The IL was transferred to the sample cell under a dry nitrogen ux,
the liquid surface being ushed with dry nitrogen before each mea-
surement, all IL measurements being performed under dry nitrogen
atmosphere. For each temperature at least three independent sets
of 20 immersion detachment cycles were measured, which allowed
the determination of an average surface tension value over at least
30 surface tension values. This procedure allowed to estimate the
uncertainty of the experimental measurements as better than 1.8%
(k = 2.04 for n = 30 at 95%).
3. Results and discussion
3.1. Density
The experimental density values at atmospheric pressure and
the corresponding thermal expansion coefcients, p , of the
[C4 mim][NTf2 ], [C4 mim][dca], [C2 mim][EtSO4 ], and [Aliquat][dca]
ionic liquids are presented in Tables 25, respectively. Taking as
reference for the T data analysis a linear dependence of ln 

Table 3
Experimental density data,  (kg m3 ), and calculated isobaric thermal expansion coefcient, p (k K1 ), at atmospheric pressure for [C4 mim][dca] obtained with the
atmospheric pressure densimeter.

T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 )

293.15 1063.73 0.6013 318.15 1047.94 0.5938 343.15 1032.61 0.5862

294.15 1063.09 0.6010 319.15 1047.32 0.5935 344.15 1032.00 0.5859
295.15 1062.45 0.6007 320.15 1046.70 0.5932 345.15 1031.40 0.5856
296.15 1061.81 0.6004 321.15 1046.08 0.5929 346.15 1030.79 0.5853
297.15 1061.17 0.6001 322.15 1045.46 0.5926 347.15 1030.19 0.5850
298.15 1060.53 0.5998 323.15 1044.84 0.5923 348.15 1029.59 0.5847
299.15 1059.89 0.5995 324.15 1044.22 0.5919 349.15 1028.98 0.5844
300.15 1059.26 0.5992 325.15 1043.61 0.5916 350.15 1028.38 0.5841
301.15 1058.62 0.5989 326.15 1042.99 0.5913 351.15 1027.78 0.5838
302.15 1057.99 0.5986 327.15 1042.37 0.5910 352.15 1027.18 0.5835
303.15 1057.35 0.5983 328.15 1041.76 0.5907 353.15 1026.58 0.5832
304.15 1056.72 0.5980 329.15 1041.14 0.5904 354.15 1025.98 0.5829
305.15 1056.09 0.5977 330.15 1040.53 0.5901 355.15 1025.38 0.5826
306.15 1055.45 0.5974 331.15 1039.92 0.5898 356.15 1024.79 0.5823
307.15 1054.82 0.5971 332.15 1039.30 0.5895 357.15 1024.19 0.5820
308.15 1054.19 0.5968 333.15 1038.69 0.5892 358.15 1023.59 0.5817
309.15 1053.56 0.5965 334.15 1038.08 0.5889 359.15 1022.99 0.5814
310.15 1052.93 0.5962 335.15 1037.47 0.5886 360.15 1022.40 0.5811
311.15 1052.31 0.5959 336.15 1036.86 0.5883 361.15 1021.80 0.5808
312.15 1051.68 0.5956 337.15 1036.25 0.5880 362.15 1021.21 0.5805
313.15 1051.05 0.5953 338.15 1035.64 0.5877 363.15 1020.61 0.5802
314.15 1050.43 0.5950 339.15 1035.03 0.5874
315.15 1049.80 0.5947 340.15 1034.42 0.5871
316.15 1049.18 0.5944 341.15 1033.82 0.5868
317.15 1048.56 0.5941 342.15 1033.21 0.5865
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 163

Table 4
Experimental density data,  (kg m3 ), and calculated isobaric thermal expansion coefcient, p (k K1 ), at atmospheric pressure for [C2 mim][EtSO4 ] obtained with the
atmospheric pressure densimeter.

T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 )

293.15 1241.37 0.5581 318.15 1224.23 0.5507 343.15 1207.63 0.5433

294.15 1240.67 0.5578 319.15 1223.56 0.5504 344.15 1206.97 0.5430
295.15 1239.97 0.5575 320.15 1222.89 0.5501 345.15 1206.32 0.5427
296.15 1239.28 0.5572 321.15 1222.21 0.5498 346.15 1205.66 0.5424
297.15 1238.58 0.5569 322.15 1221.54 0.5495 347.15 1205.01 0.5421
298.15 1237.88 0.5566 323.15 1220.88 0.5492 348.15 1204.36 0.5418
299.15 1237.19 0.5563 324.15 1220.21 0.5489 349.15 1203.70 0.5416
300.15 1236.50 0.5560 325.15 1219.54 0.5486 350.15 1203.05 0.5413
301.15 1235.81 0.5557 326.15 1218.87 0.5483 351.15 1202.40 0.5410
302.15 1235.12 0.5554 327.15 1218.21 0.5480 352.15 1201.75 0.5407
303.15 1234.43 0.5551 328.15 1217.54 0.5477 353.15 1201.09 0.5404
304.15 1233.74 0.5548 329.15 1216.88 0.5474 354.15 1200.44 0.5401
305.15 1233.05 0.5545 330.15 1216.21 0.5472 355.15 1199.79 0.5398
306.15 1232.37 0.5542 331.15 1215.55 0.5469 356.15 1199.14 0.5395
307.15 1231.69 0.5539 332.15 1214.89 0.5466 357.15 1198.49 0.5392
308.15 1231.00 0.5536 333.15 1214.23 0.5463 358.15 1197.84 0.5389
309.15 1230.32 0.5533 334.15 1213.56 0.5460 359.15 1197.20 0.5386
310.15 1229.64 0.5530 335.15 1212.90 0.5457 360.15 1196.55 0.5383
311.15 1228.96 0.5527 336.15 1212.24 0.5454 361.15 1195.90 0.5380
312.15 1228.28 0.5525 337.15 1211.58 0.5451 362.15 1195.26 0.5377
313.15 1227.61 0.5522 338.15 1210.92 0.5448 363.15 1194.61 0.5374
314.15 1226.93 0.5519 339.15 1210.26 0.5445
315.15 1226.25 0.5516 340.15 1209.60 0.5442
316.15 1225.58 0.5513 341.15 1208.95 0.5439
317.15 1224.90 0.5510 342.15 1208.29 0.5436

Table 5
Experimental density data,  (kg m3 ), and calculated isobaric thermal expansion coefcient, p (k K1 ), at atmospheric pressure for [Aliquat][dca]* obtained with the
atmospheric pressure densimeter.

T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 ) T (K)  (kg m3 ) p (k K1 )

293.15 895.86 0.6431 318.15 881.64 0.6396 343.15 867.68 0.6361

294.15 895.29 0.6430 319.15 881.07 0.6395 344.15 867.13 0.6359
295.15 894.72 0.6428 320.15 880.51 0.6393 345.15 866.58 0.6358
296.15 894.15 0.6427 321.15 879.94 0.6392 346.15 866.03 0.6357
297.15 893.58 0.6425 322.15 879.38 0.6390 347.15 865.48 0.6355
298.15 893.00 0.6424 323.15 878.82 0.6389 348.15 864.93 0.6354
299.15 892.43 0.6423 324.15 878.26 0.6388 349.15 864.38 0.6352
300.15 891.86 0.6421 325.15 877.69 0.6386 350.15 863.83 0.6351
301.15 891.29 0.6420 326.15 877.13 0.6385 351.15 863.28 0.6350
302.15 890.72 0.6418 327.15 876.57 0.6383 352.15 862.74 0.6348
303.15 890.15 0.6417 328.15 876.01 0.6382 353.15 862.19 0.6347
304.15 889.58 0.6416 329.15 875.45 0.6380 354.15 861.64 0.6345
305.15 889.01 0.6414 330.15 874.89 0.6379 355.15 861.10 0.6344
306.15 888.44 0.6413 331.15 874.34 0.6378 356.15 860.55 0.6342
307.15 887.87 0.6411 332.15 873.78 0.6376 357.15 860.01 0.6341
308.15 887.30 0.6410 333.15 873.22 0.6375 358.15 859.46 0.6340
309.15 886.73 0.6409 334.15 872.66 0.6373 359.15 858.92 0.6338
310.15 886.17 0.6407 335.15 872.11 0.6372 360.15 858.37 0.6337
311.15 885.60 0.6406 336.15 871.55 0.6371 361.15 857.83 0.6335
312.15 885.03 0.6404 337.15 870.99 0.6369 362.15 857.29 0.6334
313.15 884.46 0.6403 338.15 870.44 0.6368 363.15 856.74 0.6333
314.15 883.90 0.6402 339.15 869.89 0.6366
315.15 883.33 0.6400 340.15 869.34 0.6365
316.15 882.77 0.6399 341.15 868.78 0.6364
317.15 882.20 0.6397 342.15 868.23 0.6362
*
[Aliquat 336 -derived][dca]; see Section 2.1.

Table 6
Fitting parameters and corresponding mean square deviations for the quadratic polynomial equation, Eq. (9), used to t the atmospheric pressure density data for the studied
ionic liquids.

Ionic liquid A  A (kg m3 ) B  B (104 kg m3 K1 ) C  C (108 kg m3 K2 )  (kg m3 )

[C4 mim][Ntf2 ] 7.4733 0.0002 6.9514 0.0137 4.3577 0.2083 6.59 106
[C4 mim][dca] 7.1587 0.0002 6.8939 0.0120 15.030 0.1830 5.79 106
[C2 mim][EtSO4 ] 7.3002 0.0004 6.4443 0.0261 14.732 0.3982 1.26 105
[Aliquat][dca]* 6.9924 0.0003 6.8435 0.0153 7.0340 0.2336 7.39 106
*
[Aliquat 336 -derived][dca]; see Section 2.1.
164 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

with temperature, an approach based upon the fact that gener- Table 7
Experimental density data,  (kg m3 ), calculated isobaric thermal expansion coef-
ally and in rst approximation ionic liquids present a temperature
cient, p (k K1 ), and isothermal compressibility, T (GPa1 ), for [C4 mim][Ntf2 ]
independent p [40], our data of the logarithm of density versus obtained from the high-pressure densimeter.
temperature were tted with a second order polynomial equation
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )
(Eq. (9)), with the coefcients from Table 6. The thermal expansion
coefcient is the symmetric value of the derivative of ln  in respect 293.15 K
to temperature. 0.10 1441.8 0.663 0.514
0.25 1441.9 0.663 0.514
ln(/kg m3 ) = A + B(T /K) + C(T /K)2 (9) 0.50 1442.1 0.663 0.513
1.00 1442.4 0.662 0.512
The pT data for the same systems are presented in 2.00 1443.2 0.661 0.510
Tables 710, along with the corresponding thermal expansion and 4.99 1445.4 0.654 0.502
10.00 1449.0 0.646 0.491
isothermal compressibility coefcients p and T . Based on our 15.00 1452.5 0.639 0.480
previous experience (comparison of different calculation methods) 20.00 1456.0 0.632 0.469
and the ttings of the density data we estimate an error of 4% in p 25.01 1459.3 0.625 0.459
and 2% in T . The experimental and calculated values are depicted 30.00 1462.6 0.619 0.449
35.00 1465.8 0.613 0.440
in graphical form in Figs. 36. In this case, due to the unusually
40.00 1469.1 0.607 0.431
broad temperature range, the data of the logarithm of density ver- 45.00 1472.2 0.602 0.423
sus temperature was tted with a third order polynomial equation 50.00 1475.3 0.597 0.415
(Eq. (10)) with the coefcients from Table 11. 55.00 1478.3 0.592 0.407
59.97 1481.3 0.587 0.400
ln(/kg m3 ) = A + B(T /K) + C(T /K)2 + D(T /K)3 (10)
303.15 K
The data of density versus pressure was tted with a Tait equa- 0.10 1432.3 0.660 0.532
0.25 1432.4 0.660 0.531
tion (Eq. (11)), with the coefcients from Table 12. The isothermal 0.50 1432.6 0.660 0.531
compressibility was obtained by deriving density in order to pres- 1.00 1432.9 0.659 0.529
sure. 2.00 1433.7 0.657 0.526

1
 B + p/MPa  5.00 1436.0 0.651 0.519
1/(/kg m3 ) = + A ln (11) 10.00 1439.7 0.643 0.506
C B + 0.1 MPa 15.00 1443.3 0.636 0.494
20.00 1446.8 0.628 0.483
The density under atmospheric pressure and around room tem- 25.00 1450.2 0.621 0.472
perature is a property that is available nowadays for many ionic 30.00 1453.6 0.614 0.461
liquids [41]. Moreover, the expected overall uncertainty of such 34.99 1456.9 0.608 0.452
data are expected to be lower than 0.5% if one is using a reliable 40.00 1460.2 0.602 0.442
45.01 1463.4 0.597 0.433
experimental setup (for example, a vibrating tube densimeter with
50.00 1466.5 0.592 0.424
adequate thermostat devices) and samples of controlled purity [21]. 54.99 1469.6 0.587 0.416
The present set of data falls in that category (cf. Section 2). 60.01 1472.7 0.581 0.408
Systematic studies where a property like density is measured 313.15 K
along a homologous series of ionic liquids [42,43] or a set of dif- 0.10 1422.8 0.659 0.551
ferent thermodynamic properties are studied for a selected group 0.25 1422.9 0.659 0.550
of ionic liquids (this work) are much more uncommon, especially 0.50 1423.1 0.658 0.549
1.00 1423.5 0.657 0.548
if one takes into account the extended temperature (293473 K)
2.00 1424.3 0.655 0.545
and pressure (0.160 MPa) ranges used in the volumetric mea- 5.00 1426.6 0.650 0.536
surements. The high-precision measurement of density over those 10.00 1430.4 0.641 0.523
extended ranges allowed us to discover new trends in the cor- 15.01 1434.1 0.633 0.510
responding derivative properties p and T and allowed us to 20.01 1437.7 0.625 0.497
25.00 1441.2 0.617 0.485
conclude that, in spite of their volumetric good-behavior, differ- 30.00 1444.7 0.611 0.474
ent ionic liquids exhibit different rates of expansion/compression 34.99 1448.0 0.604 0.464
as temperature and pressure are progressively distanced from 40.00 1451.4 0.598 0.454
ambient conditions. 45.01 1454.6 0.592 0.444
50.01 1457.9 0.587 0.435
The notion that for ionic liquids the logarithm of the density at
55.00 1461.0 0.582 0.426
constant pressure is a quasi-linear function of temperature can be, 60.00 1464.1 0.576 0.417
to reasonable approximation, extended to the present systems. This
323.15 K
means that if ln () = A T + B than p is simply constant and takes the
0.10 1413.5 0.659 0.571
value of A. For the studied ionic liquids at atmospheric pressure 0.25 1413.6 0.658 0.571
and temperatures below 100 C the linear relation with its constant 0.50 1413.8 0.658 0.570
slope holds true within 1%. 1.01 1414.2 0.657 0.568
2.00 1415.0 0.655 0.565
However, the present volumetric data set, Figs. 3a6a, probably
4.99 1417.4 0.649 0.556
one of the most extensive in terms of temperature range, pressure 10.01 1421.3 0.639 0.541
range and ionic liquid diversity, enables one to explore even subtler 14.99 1425.1 0.631 0.526
details of its thermal and pressure rates of variation. The isothermal 20.01 1428.8 0.622 0.513
compressibility coefcients, Figs. 3b6b, exhibit rather expected 24.99 1432.4 0.615 0.500
30.01 1435.9 0.608 0.488
and monotonous trends for all systems, with T increasing along an
35.01 1439.4 0.601 0.476
isotherm with decreasing pressure, and increasing along an isobar 40.00 1442.8 0.594 0.465
with increasing temperature. 45.00 1446.1 0.658 0.571
On the other hand, and if for each isobar the ln() versus T data 50.00 1449.4 0.658 0.570
55.00 1452.6 0.657 0.568
are tted to cubic equations, then the values of p show in many
60.00 1455.8 0.655 0.565
cases non-monotonous behavior, Figs. 3c6c and 3d6d. This may
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 165

Table 7 (Continued ) Table 7 (Continued )

p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )

333.15 K 0.50 1367.7 0.674 0.692

0.10 1404.2 0.660 0.592 1.01 1368.2 0.673 0.689
0.25 1404.3 0.659 0.591 2.00 1369.1 0.670 0.685
0.50 1404.5 0.659 0.591 4.99 1371.9 0.662 0.670
1.01 1404.9 0.658 0.589 10.00 1376.5 0.648 0.647
2.00 1405.8 0.655 0.585 14.99 1380.8 0.636 0.626
4.99 1408.2 0.649 0.575 20.00 1385.1 0.625 0.607
10.00 1412.3 0.639 0.559 24.99 1389.2 0.615 0.588
14.99 1416.2 0.630 0.544 30.01 1393.3 0.605 0.571
20.01 1420.0 0.621 0.529 34.97 1397.1 0.595 0.555
25.00 1423.6 0.613 0.515 40.00 1401.0 0.586 0.539
30.01 1427.3 0.605 0.503 45.00 1404.7 0.578 0.525
34.99 1430.8 0.598 0.490 50.00 1408.4 0.570 0.511
40.01 1434.3 0.591 0.477 54.99 1411.9 0.563 0.498
45.00 1437.6 0.585 0.468 60.01 1415.5 0.555 0.486
50.00 1441.0 0.579 0.457
393.15 K
54.99 1444.3 0.573 0.447
0.10 1348.8 0.755 0.690
60.00 1447.5 0.567 0.437
0.25 1348.9 0.754 0.690
343.15 K 0.50 1349.2 0.753 0.689
0.10 1395.0 0.662 0.615 1.00 1349.7 0.750 0.687
0.25 1395.1 0.661 0.614 2.00 1350.7 0.744 0.684
0.50 1395.3 0.661 0.613 4.99 1353.7 0.727 0.675
1.00 1395.7 0.660 0.611 10.00 1358.6 0.701 0.659
2.00 1396.6 0.657 0.608 15.00 1363.2 0.676 0.645
4.99 1399.1 0.651 0.596 20.01 1367.8 0.653 0.632
10.01 1403.3 0.640 0.579 25.00 1372.1 0.632 0.620
14.91 1407.2 0.630 0.563 30.01 1376.4 0.612 0.609
20.00 1411.2 0.620 0.547 35.00 1380.5 0.594 0.598
24.99 1414.9 0.612 0.532 40.00 1384.6 0.576 0.588
30.01 1418.7 0.604 0.518 45.00 1388.5 0.560 0.579
34.99 1422.3 0.597 0.505 50.00 1392.4 0.545 0.569
39.99 1425.8 0.589 0.492 55.02 1396.2 0.530 0.561
45.00 1429.3 0.582 0.480 60.00 1399.9 0.517 0.552
50.00 1432.7 0.576 0.469
413.15 K
55.00 1436.1 0.570 0.459
0.10 1330.0 0.710 0.827
60.00 1439.4 0.563 0.448
0.25 1330.2 0.710 0.826
353.15 K 0.50 1330.5 0.708 0.824
0.10 1385.8 0.665 0.640 1.00 1331.0 0.707 0.821
0.25 1385.9 0.665 0.639 2.00 1332.1 0.703 0.814
0.50 1386.1 0.664 0.638 4.99 1335.3 0.692 0.794
1.00 1386.5 0.663 0.636 10.00 1340.6 0.675 0.763
2.00 1387.4 0.660 0.632 14.99 1345.6 0.659 0.734
5.00 1390.1 0.653 0.620 20.01 1350.5 0.644 0.707
10.00 1394.3 0.642 0.600 25.00 1355.1 0.630 0.683
14.99 1398.4 0.631 0.582 30.00 1359.7 0.617 0.660
20.01 1402.5 0.621 0.565 34.99 1364.0 0.604 0.639
24.99 1406.3 0.612 0.550 40.00 1368.4 0.592 0.619
30.01 1410.2 0.603 0.535 45.00 1372.5 0.581 0.600
34.99 1413.8 0.595 0.520 50.00 1376.6 0.571 0.583
40.00 1417.5 0.588 0.507 55.00 1380.6 0.561 0.566
45.00 1421.0 0.580 0.494 60.00 1384.5 0.551 0.551
50.00 1424.6 0.573 0.482
433.15 K
54.99 1427.9 0.567 0.471
0.10 1311.0 0.735 0.910
60.01 1431.3 0.560 0.460
0.25 1311.1 0.734 0.909
363.15 K 0.50 1311.4 0.733 0.907
0.10 1376.6 0.670 0.666 1.00 1312.0 0.731 0.902
0.25 1376.7 0.669 0.665 2.00 1313.2 0.726 0.894
0.50 1376.9 0.668 0.664 4.99 1316.7 0.714 0.870
1.01 1377.4 0.667 0.661 10.00 1322.4 0.694 0.834
4.99 1381.0 0.657 0.644 15.00 1327.8 0.676 0.800
10.01 1385.4 0.644 0.623 20.01 1333.0 0.659 0.769
14.99 1389.6 0.633 0.604 25.01 1338.0 0.642 0.740
20.01 1393.8 0.622 0.585 30.01 1342.9 0.627 0.714
25.00 1397.8 0.613 0.568 34.99 1347.5 0.613 0.690
30.01 1401.7 0.604 0.552 40.00 1352.1 0.600 0.667
34.99 1405.5 0.595 0.537 45.00 1356.6 0.587 0.646
40.00 1409.2 0.587 0.523 50.00 1360.9 0.575 0.626
45.01 1412.8 0.579 0.509 55.00 1365.1 0.563 0.607
50.00 1416.4 0.571 0.496 60.00 1369.3 0.552 0.590
54.99 1419.9 0.564 0.484
453.15 K
60.00 1423.4 0.557 0.473
0.10 1291.4 0.764 1.003
373.15 K 0.25 1291.7 0.764 1.002
0.10 1367.3 0.675 0.694 0.50 1292.0 0.762 1.000
0.25 1367.4 0.675 0.693 1.00 1292.6 0.760 0.995
166 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Table 7 (Continued ) Table 8 (Continued )

p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )

1.95 1294.0 0.755 0.986 313.15 K

4.99 1297.7 0.740 0.957 0.10 1051.5 0.602 0.390
10.00 1303.9 0.717 0.915 0.25 1051.5 0.602 0.390
15.00 1309.7 0.697 0.876 0.50 1051.6 0.602 0.389
20.00 1315.3 0.677 0.840 1.00 1051.8 0.601 0.388
25.00 1320.7 0.659 0.807 2.00 1052.3 0.600 0.387
30.01 1325.9 0.641 0.777 4.99 1053.4 0.596 0.382
35.00 1330.9 0.625 0.749 10.00 1055.5 0.591 0.374
40.00 1335.9 0.609 0.724 14.99 1057.4 0.585 0.366
45.01 1340.6 0.595 0.700 20.01 1059.4 0.579 0.359
50.00 1345.3 0.581 0.677 25.00 1061.2 0.574 0.352
54.99 1349.8 0.567 0.656 30.00 1063.1 0.568 0.345
60.00 1354.3 0.555 0.637 35.00 1064.9 0.564 0.339
40.01 1066.7 0.559 0.333
473.15 K
45.00 1068.4 0.554 0.327
0.10 1271.4 0.799 1.113
50.00 1070.2 0.550 0.321
0.25 1271.7 0.798 1.111
55.01 1071.9 0.546 0.316
0.50 1272.0 0.796 1.108
60.00 1073.6 0.541 0.310
0.99 1272.7 0.793 1.102
2.00 1274.2 0.787 1.091 323.15 K
4.99 1278.2 0.771 1.058 0.10 1045.2 0.597 0.403
10.00 1285.0 0.745 1.008 0.25 1045.3 0.597 0.403
15.00 1291.2 0.722 0.963 0.50 1045.4 0.597 0.403
20.01 1297.4 0.700 0.922 1.00 1045.6 0.596 0.402
24.99 1303.2 0.678 0.885 2.01 1046.0 0.595 0.400
30.01 1308.9 0.659 0.850 4.99 1047.3 0.591 0.395
34.99 1314.2 0.640 0.818 10.01 1049.3 0.585 0.386
40.01 1319.6 0.622 0.789 14.99 1051.3 0.580 0.378
45.00 1324.7 0.605 0.762 20.01 1053.3 0.573 0.370
50.00 1329.7 0.590 0.737 25.00 1055.2 0.569 0.363
55.00 1334.5 0.574 0.713 30.01 1057.1 0.563 0.356
60.00 1339.3 0.559 0.691 34.99 1058.9 0.559 0.349
40.00 1060.8 0.553 0.342
45.00 1062.6 0.549 0.336
Table 8 50.00 1064.4 0.544 0.330
Experimental density data,  (kg m3 ), calculated isobaric thermal expansion coef- 55.00 1066.1 0.540 0.324
cient, p (k K1 ), and isothermal compressibility, T (GPa1 ), for [C4 mim][dca] 60.00 1067.8 0.536 0.318
obtained from the high-pressure densimeter.
333.15 K
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) 0.10 1039.0 0.593 0.416
293.15 K 0.25 1039.1 0.592 0.416
0.10 1064.4 0.614 0.366 0.50 1039.2 0.592 0.415
0.25 1064.4 0.615 0.366 1.00 1039.4 0.591 0.414
0.50 1064.5 0.614 0.365 2.00 1039.9 0.590 0.412
1.00 1064.7 0.613 0.364 4.99 1041.1 0.587 0.407
2.00 1065.1 0.612 0.363 10.00 1043.2 0.581 0.398
4.99 1066.2 0.607 0.358 15.00 1045.2 0.574 0.389
10.01 1068.2 0.603 0.351 20.00 1047.3 0.569 0.381
15.00 1070.0 0.599 0.344 25.00 1049.2 0.564 0.373
20.00 1071.9 0.591 0.338 30.00 1051.3 0.558 0.366
25.00 1073.6 0.586 0.332 34.99 1053.1 0.554 0.359
30.00 1075.4 0.579 0.326 40.00 1055.0 0.548 0.352
35.00 1077.1 0.575 0.320 45.01 1056.8 0.544 0.345
40.00 1078.9 0.571 0.314 50.00 1058.6 0.539 0.339
45.00 1080.5 0.566 0.309 55.00 1060.4 0.535 0.333
50.00 1082.2 0.561 0.303 60.00 1062.2 0.531 0.327
55.00 1083.8 0.558 0.298 343.15 K
60.00 1085.4 0.553 0.294 0.10 1032.9 0.589 0.428
303.15 K 0.25 1033.0 0.589 0.428
0.10 1057.9 0.608 0.377 0.50 1033.1 0.589 0.427
0.25 1057.9 0.608 0.377 1.00 1033.3 0.588 0.426
0.50 1058.0 0.607 0.377 2.00 1033.7 0.587 0.424
1.00 1058.2 0.607 0.376 4.99 1035.0 0.583 0.418
2.00 1058.6 0.605 0.374 10.01 1037.2 0.576 0.409
4.99 1059.8 0.601 0.370 15.00 1039.2 0.570 0.400
10.00 1061.8 0.596 0.362 20.01 1041.4 0.565 0.392
14.99 1063.6 0.592 0.355 25.00 1043.3 0.560 0.384
20.01 1065.5 0.584 0.348 30.00 1045.4 0.554 0.376
25.00 1067.4 0.580 0.342 35.01 1047.3 0.549 0.369
30.00 1069.2 0.573 0.336 40.00 1049.3 0.544 0.362
34.99 1070.9 0.570 0.329 45.00 1051.1 0.539 0.355
40.00 1072.7 0.565 0.324 50.00 1053.0 0.535 0.348
45.00 1074.4 0.560 0.318 55.00 1054.7 0.530 0.342
50.00 1076.1 0.555 0.313 60.00 1056.6 0.526 0.336
55.00 1077.8 0.551 0.307 353.15 K
60.00 1079.4 0.547 0.302 0.10 1026.8 0.586 0.442
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 167

Table 8 (Continued ) Table 9

Experimental density data,  (kg m3 ), calculated isobaric thermal expansion coef-
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) cient, p (k K1 ), and isothermal compressibility, T (GPa1 ), for [C2 mim][EtSO4 ]
0.25 1026.9 0.586 0.441 obtained from the high-pressure densimeter.
0.50 1027.0 0.585 0.441
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )
1.00 1027.2 0.585 0.440
2.00 1027.7 0.584 0.438 293.15 K
5.00 1029.0 0.580 0.432 0.10 1241.3 0.565 0.329
10.00 1031.3 0.573 0.422 0.25 1241.4 0.565 0.329
15.00 1033.4 0.566 0.412 0.50 1241.4 0.564 0.329
20.00 1035.5 0.561 0.403 1.00 1241.7 0.564 0.328
25.00 1037.5 0.556 0.395 1.99 1242.1 0.563 0.327
30.01 1039.6 0.550 0.387 4.99 1243.3 0.560 0.323
35.00 1041.6 0.545 0.379 10.01 1245.3 0.556 0.318
40.00 1043.6 0.540 0.371 14.99 1247.2 0.552 0.313
45.00 1045.4 0.535 0.364 20.00 1249.2 0.548 0.307
50.00 1047.4 0.531 0.357 24.99 1251.1 0.544 0.302
55.00 1049.2 0.526 0.351 30.01 1253.0 0.541 0.298
60.00 1051.0 0.522 0.344 35.00 1254.8 0.537 0.293
40.00 1256.6 0.533 0.288
363.15 K
45.00 1258.4 0.529 0.284
0.10 1020.8 0.584 0.457
50.00 1260.2 0.526 0.280
0.25 1020.9 0.583 0.456
55.00 1262.0 0.524 0.276
0.50 1021.0 0.583 0.456
60.00 1263.7 0.519 0.272
1.00 1021.3 0.582 0.455
2.00 1021.7 0.581 0.452 303.15 K
4.99 1023.1 0.577 0.446 0.10 1234.3 0.559 0.339
10.00 1025.4 0.570 0.435 0.25 1234.4 0.559 0.338
14.99 1027.6 0.563 0.425 0.50 1234.5 0.558 0.338
20.01 1029.8 0.558 0.415 1.00 1234.7 0.558 0.337
25.01 1031.8 0.552 0.406 2.01 1235.1 0.557 0.336
30.00 1033.9 0.547 0.397 4.99 1236.3 0.554 0.332
35.00 1035.9 0.541 0.389 10.01 1238.4 0.550 0.326
40.00 1038.0 0.536 0.381 14.99 1240.4 0.546 0.321
45.00 1039.9 0.531 0.373 20.00 1242.4 0.542 0.315
50.00 1041.8 0.527 0.366 24.99 1244.3 0.538 0.310
55.00 1043.7 0.522 0.358 30.01 1246.3 0.534 0.305
60.00 1045.6 0.518 0.352 35.01 1248.1 0.531 0.300
40.00 1250.0 0.526 0.295
373.15 K
45.00 1251.8 0.523 0.290
0.10 1014.9 0.582 0.470
50.00 1253.6 0.520 0.286
0.25 1015.0 0.582 0.469
55.00 1255.4 0.517 0.281
0.50 1015.1 0.581 0.469
60.00 1257.1 0.513 0.277
1.00 1015.4 0.580 0.468
2.00 1015.8 0.580 0.465 313.15 K
4.99 1017.2 0.575 0.458 0.10 1227.5 0.554 0.348
10.00 1019.5 0.568 0.447 0.25 1227.5 0.554 0.348
15.00 1021.8 0.561 0.437 0.50 1227.6 0.553 0.347
20.00 1024.0 0.556 0.427 2.00 1228.3 0.552 0.345
25.00 1026.2 0.549 0.417 4.99 1229.5 0.549 0.342
30.00 1028.3 0.544 0.408 10.01 1231.7 0.545 0.335
35.00 1030.3 0.538 0.399 14.99 1233.7 0.540 0.329
40.00 1032.4 0.533 0.391 20.00 1235.7 0.536 0.323
45.00 1034.4 0.527 0.383 25.00 1237.6 0.532 0.318
50.00 1036.4 0.523 0.376 30.01 1239.6 0.529 0.312
55.00 1038.3 0.518 0.368 35.00 1241.5 0.525 0.307
60.00 1040.2 0.515 0.361 40.00 1243.4 0.521 0.302
44.99 1245.3 0.517 0.297
393.15 K
50.00 1247.1 0.514 0.292
0.10 1003.2 0.582 0.502
54.99 1248.9 0.511 0.288
0.25 1003.3 0.581 0.502
60.00 1250.7 0.507 0.283
0.50 1003.4 0.580 0.501
1.00 1003.7 0.579 0.499 323.15 K
2.00 1004.1 0.579 0.497 0.10 1220.7 0.550 0.358
4.99 1005.6 0.573 0.489 0.25 1220.8 0.550 0.357
10.01 1008.1 0.565 0.476 0.50 1220.9 0.550 0.357
15.00 1010.4 0.559 0.464 1.01 1221.1 0.550 0.356
20.01 1012.8 0.553 0.453 2.01 1221.6 0.549 0.355
25.00 1015.0 0.544 0.442 4.99 1222.9 0.546 0.351
30.00 1017.2 0.540 0.431 10.01 1225.0 0.541 0.344
35.00 1019.4 0.532 0.421 14.99 1227.1 0.536 0.338
40.00 1021.6 0.529 0.412 20.01 1229.1 0.531 0.332
45.00 1023.6 0.521 0.403 25.00 1231.1 0.527 0.326
50.00 1025.7 0.517 0.395 30.01 1233.1 0.524 0.320
55.00 1027.7 0.512 0.386 35.00 1235.1 0.520 0.315
60.00 1029.6 0.509 0.379 40.00 1237.0 0.516 0.309
45.00 1238.9 0.512 0.304
50.00 1240.8 0.509 0.299
55.00 1242.6 0.505 0.295
60.00 1244.5 0.502 0.290
168 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Table 9 (Continued ) Table 9 (Continued )

p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )

333.15 K 373.15 K
0.10 1214.1 0.548 0.367 0.10 1187.8 0.548 0.417
0.25 1214.1 0.548 0.367 0.25 1187.9 0.547 0.417
0.50 1214.2 0.547 0.367 0.50 1188.0 0.547 0.416
1.00 1214.4 0.547 0.366 1.01 1188.2 0.546 0.415
2.01 1214.9 0.546 0.364 2.00 1188.7 0.545 0.413
5.00 1216.2 0.543 0.360 4.99 1190.2 0.541 0.408
10.01 1218.4 0.538 0.353 10.01 1192.6 0.534 0.399
14.99 1220.5 0.533 0.347 14.99 1194.9 0.528 0.390
20.00 1222.7 0.528 0.341 20.01 1197.3 0.522 0.381
24.99 1224.7 0.524 0.335 25.00 1199.5 0.517 0.373
30.00 1226.7 0.519 0.329 30.01 1201.7 0.511 0.366
34.99 1228.7 0.515 0.323 34.99 1203.9 0.506 0.359
40.00 1230.7 0.511 0.318 40.00 1206.1 0.502 0.352
45.02 1232.6 0.508 0.312 45.00 1208.1 0.497 0.345
50.00 1234.5 0.504 0.307 50.00 1210.2 0.492 0.338
54.99 1236.4 0.500 0.302 54.99 1212.3 0.488 0.332
60.00 1238.3 0.497 0.298 60.00 1214.3 0.484 0.326

343.15 K 393.15 K
0.10 1207.4 0.546 0.380 0.10 1174.8 0.554 0.446
0.25 1207.5 0.546 0.379 0.25 1174.9 0.553 0.445
0.50 1207.6 0.545 0.379 0.50 1175.0 0.553 0.445
1.01 1207.8 0.545 0.378 1.01 1175.3 0.552 0.444
1.99 1208.3 0.544 0.377 2.00 1175.8 0.551 0.441
4.99 1209.6 0.541 0.372 4.99 1177.3 0.546 0.435
10.01 1211.9 0.535 0.364 10.00 1179.9 0.539 0.425
14.99 1214.1 0.530 0.357 15.00 1182.3 0.532 0.415
20.01 1216.3 0.525 0.350 20.01 1184.8 0.525 0.405
24.99 1218.3 0.521 0.343 24.99 1187.1 0.519 0.396
30.00 1220.4 0.516 0.337 30.01 1189.5 0.512 0.388
35.01 1222.4 0.512 0.331 34.99 1191.7 0.507 0.380
40.00 1224.5 0.508 0.325 40.00 1194.0 0.501 0.372
45.00 1226.4 0.504 0.319 45.01 1196.2 0.496 0.364
50.00 1228.4 0.500 0.314 50.00 1198.4 0.490 0.357
54.99 1230.3 0.496 0.308 55.00 1200.5 0.486 0.350
60.00 1232.2 0.493 0.303 60.00 1202.6 0.481 0.344

353.15 K 413.15 K
0.10 1200.9 0.546 0.392 0.10 1161.7 0.564 0.480
0.25 1200.9 0.545 0.392 0.25 1161.8 0.564 0.480
0.50 1201.0 0.545 0.391 0.50 1162.0 0.563 0.479
1.01 1201.3 0.545 0.390 1.01 1162.2 0.562 0.478
2.00 1201.8 0.543 0.389 2.00 1162.8 0.561 0.475
4.99 1203.1 0.540 0.383 4.99 1164.4 0.555 0.468
10.01 1205.5 0.534 0.375 10.00 1167.2 0.547 0.456
15.00 1207.6 0.529 0.368 14.99 1169.7 0.539 0.444
20.00 1209.9 0.523 0.360 20.01 1172.4 0.531 0.434
24.99 1212.0 0.519 0.353 24.99 1174.8 0.525 0.424
30.01 1214.2 0.514 0.346 30.00 1177.4 0.517 0.414
34.99 1216.2 0.509 0.339 34.99 1179.7 0.511 0.405
40.00 1218.3 0.505 0.333 40.00 1182.1 0.504 0.396
45.00 1220.2 0.501 0.327 45.00 1184.4 0.497 0.387
50.00 1222.3 0.497 0.321 50.00 1186.7 0.491 0.379
54.99 1224.2 0.493 0.316 54.99 1188.9 0.486 0.372
60.00 1226.1 0.489 0.310 60.00 1191.1 0.480 0.364

363.15 K 433.15 K
0.10 1194.3 0.546 0.403 0.10 1148.6 0.579 0.518
0.25 1194.4 0.546 0.402 0.25 1148.7 0.579 0.517
0.50 1194.5 0.545 0.402 0.50 1148.8 0.578 0.517
1.00 1194.7 0.545 0.401 1.01 1149.1 0.575 0.515
2.00 1195.2 0.543 0.399 2.00 1149.7 0.575 0.512
4.99 1196.6 0.540 0.394 4.99 1151.4 0.569 0.504
10.01 1199.0 0.534 0.386 10.01 1154.4 0.559 0.491
14.99 1201.3 0.528 0.378 14.99 1157.1 0.550 0.478
19.99 1203.6 0.522 0.370 20.01 1159.9 0.541 0.466
25.00 1205.7 0.518 0.363 24.99 1162.5 0.534 0.455
30.00 1207.9 0.512 0.356 30.01 1165.2 0.525 0.444
34.99 1210.0 0.508 0.350 34.99 1167.6 0.517 0.434
40.00 1212.2 0.503 0.343 40.00 1170.2 0.510 0.424
45.00 1214.2 0.499 0.337 45.01 1172.6 0.501 0.414
50.00 1216.2 0.494 0.331 50.00 1175.1 0.495 0.406
55.00 1218.2 0.490 0.325 54.99 1177.4 0.490 0.397
60.00 1220.2 0.486 0.320 60.00 1179.7 0.482 0.389
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 169

Table 10 Table 10 (Continued )

Experimental density data,  (kg m3 ), calculated isobaric thermal expansion coef-
cient, p (k K1 ), and isothermal compressibility, T (GPa1 ), for [Aliquat][dca]* p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )
obtained from the high-pressure densimeter. 333.15 K
0.10 872.0 0.650 0.635
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 )
0.25 872.1 0.650 0.634
293.15 K 0.50 872.3 0.649 0.633
0.10 895.2 0.666 0.536 1.00 872.5 0.648 0.631
0.25 895.3 0.666 0.536 2.00 873.1 0.645 0.626
0.50 895.5 0.666 0.535 4.99 874.6 0.637 0.613
1.00 895.7 0.668 0.533 10.01 877.4 0.626 0.592
2.01 896.2 0.662 0.530 14.99 879.9 0.615 0.572
4.99 897.6 0.658 0.519 20.01 882.4 0.604 0.554
10.01 899.9 0.643 0.503 25.00 884.7 0.593 0.537
15.01 902.1 0.635 0.488 30.01 887.2 0.585 0.521
20.01 904.3 0.621 0.474 35.00 889.4 0.576 0.506
24.99 906.4 0.616 0.460 40.00 891.6 0.568 0.491
30.00 908.5 0.605 0.448 45.00 893.7 0.560 0.478
35.00 910.4 0.595 0.436 50.00 895.9 0.552 0.465
40.01 912.5 0.587 0.424 54.99 897.9 0.545 0.453
44.99 914.3 0.579 0.414 60.00 900.0 0.538 0.442
50.00 916.2 0.571 0.403
343.15 K
54.99 918.0 0.562 0.394
0.10 866.4 0.647 0.662
60.00 919.8 0.554 0.385
0.25 866.5 0.647 0.661
303.15 K 0.45 866.6 0.646 0.660
0.10 889.4 0.661 0.560 1.00 866.9 0.644 0.657
0.25 889.4 0.661 0.559 2.00 867.5 0.642 0.652
0.50 889.6 0.661 0.558 5.00 869.1 0.634 0.638
1.01 889.8 0.661 0.556 10.01 872.0 0.623 0.615
2.01 890.3 0.657 0.553 15.00 874.5 0.611 0.594
4.99 891.7 0.652 0.542 20.00 877.1 0.600 0.574
10.01 894.2 0.638 0.525 25.00 879.5 0.589 0.555
15.00 896.5 0.629 0.509 30.00 882.0 0.581 0.538
20.01 898.7 0.617 0.494 34.99 884.2 0.572 0.522
25.00 900.9 0.609 0.480 40.00 886.6 0.564 0.507
30.01 903.1 0.600 0.467 45.00 888.8 0.555 0.493
35.00 905.1 0.590 0.454 50.00 891.0 0.547 0.479
40.01 907.2 0.582 0.443 55.00 893.0 0.541 0.467
45.00 909.1 0.574 0.431 60.00 895.2 0.534 0.455
50.01 911.1 0.566 0.421
353.15 K
54.99 913.0 0.558 0.411
0.10 860.8 0.645 0.692
60.00 914.8 0.550 0.401
0.25 860.9 0.645 0.691
313.15 K 0.50 861.0 0.644 0.690
0.10 883.5 0.657 0.586 1.00 861.3 0.642 0.687
0.25 883.6 0.657 0.586 2.00 861.9 0.640 0.681
0.45 883.7 0.656 0.585 5.00 863.6 0.631 0.665
1.00 883.9 0.656 0.583 10.00 866.5 0.620 0.640
2.00 884.5 0.653 0.579 15.00 869.2 0.607 0.617
4.99 885.9 0.647 0.567 20.00 871.9 0.597 0.595
10.00 888.6 0.634 0.548 24.99 874.3 0.585 0.575
15.00 890.8 0.624 0.531 30.01 876.9 0.577 0.557
20.00 893.3 0.612 0.515 34.99 879.2 0.568 0.539
24.99 895.4 0.604 0.499 40.00 881.6 0.559 0.523
30.01 897.7 0.594 0.485 45.00 883.9 0.551 0.507
35.00 899.8 0.585 0.471 50.00 886.1 0.543 0.493
40.00 902.0 0.577 0.459 55.00 888.3 0.537 0.479
45.00 903.9 0.569 0.446 60.00 890.4 0.530 0.467
50.00 906.0 0.561 0.435
363.15 K
54.99 907.9 0.554 0.424
0.10 855.3 0.644 0.719
60.00 909.8 0.546 0.414
0.25 855.4 0.643 0.718
323.15 K 0.50 855.5 0.643 0.717
0.10 877.7 0.653 0.611 1.00 855.8 0.640 0.714
0.25 877.8 0.653 0.610 2.00 856.4 0.638 0.708
0.50 877.9 0.652 0.609 4.99 858.2 0.629 0.691
1.01 878.2 0.651 0.607 10.01 861.2 0.617 0.664
2.00 878.8 0.649 0.603 14.99 863.9 0.604 0.640
4.99 880.3 0.642 0.590 20.01 866.7 0.594 0.617
10.00 882.9 0.630 0.570 25.00 869.3 0.582 0.596
15.00 885.3 0.619 0.551 30.00 871.9 0.573 0.576
20.00 887.8 0.608 0.534 34.99 874.3 0.564 0.558
24.99 890.0 0.598 0.518 40.00 876.8 0.555 0.541
30.01 892.4 0.590 0.503 45.01 879.0 0.547 0.525
34.99 894.5 0.581 0.488 50.00 881.4 0.539 0.510
40.00 896.8 0.572 0.475 55.00 883.5 0.532 0.495
45.00 898.8 0.564 0.462 60.00 885.7 0.525 0.482
50.00 900.9 0.556 0.450
54.99 902.9 0.550 0.439
60.00 904.8 0.542 0.428
170 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Table 10 (Continued ) Table 11

Fitting parameters for the cubic polynomial equation, Eq. (10), for the studied ionic
p (MPa)  (kg m3 ) p (k K1 ) T (GPa1 ) liquids.
373.15 K p (MPa) A (kg m3 ) B (103 C (106 D (109
0.10 849.8 0.643 0.751 kg m3 K1 ) kg m3 K2 ) kg m3 K3 )
0.25 849.9 0.642 0.750
0.50 850.1 0.642 0.748 [C4 mim][Ntf2 ]
1.00 850.4 0.639 0.745 0.10 7.5324 1.2750 1.9244 2.0022
2.00 851.0 0.637 0.739 0.25 7.5330 1.2785 1.9327 2.0073
4.99 852.9 0.627 0.720 0.50 7.5331 1.2784 1.9311 2.0030
1.00 7.5319 1.2671 1.8993 1.9702
10.01 855.9 0.614 0.691
2.00 7.5317 1.2617 1.8833 1.9474
15.00 858.8 0.601 0.664
5.00 7.5298 1.2358 1.8064 1.8528
20.01 861.6 0.591 0.639
10.00 7.5289 1.2114 1.7315 1.7455
24.99 864.3 0.579 0.616
15.00 7.5292 1.1963 1.6805 1.6615
30.01 867.0 0.569 0.595
20.00 7.5278 1.1693 1.6011 1.5569
34.99 869.4 0.560 0.576
25.00 7.5251 1.1307 1.4877 1.4224
40.01 872.0 0.551 0.557
30.00 7.5244 1.1086 1.4210 1.3320
44.91 874.3 0.543 0.540 35.00 7.5230 1.0812 1.3394 1.2299
50.00 876.7 0.535 0.524 40.00 7.5219 1.0571 1.2684 1.1394
54.99 878.9 0.528 0.509 45.00 7.5211 1.0344 1.1997 1.0511
60.00 881.1 0.521 0.494 50.00 7.5214 1.0219 1.1613 0.9930
55.00 7.5194 0.9904 1.0688 0.8854
393.15 K
60.00 7.5183 0.9675 1.0039 0.8065
0.10 839.0 0.644 0.817
0.25 839.1 0.642 0.816 [C4 mim][dca]
0.50 839.2 0.642 0.814 0.10 7.2099 1.1247 1.3977 1.1989
1.01 839.6 0.640 0.810 0.25 7.2115 1.1369 1.4297 1.2256
2.00 840.3 0.636 0.802 0.50 7.2059 1.0871 1.2832 1.0816
4.99 842.2 0.626 0.780 1.00 7.2070 1.0960 1.3108 1.1072
10.01 845.5 0.611 0.746 2.00 7.2087 1.1110 1.3640 1.1650
14.99 848.5 0.597 0.715 5.00 7.1999 1.0287 1.1293 0.9320
20.00 851.5 0.585 0.686 10.00 7.2052 1.0636 1.2301 1.0107
25.01 854.4 0.574 0.659 15.00 7.2146 1.1356 1.4440 1.2038
30.00 857.2 0.563 0.635 20.00 7.2032 1.0345 1.1791 0.9606
34.99 859.8 0.553 0.613 25.00 7.1962 0.9609 0.9620 0.7327
40.00 862.5 0.544 0.592 30.00 7.1960 0.9568 0.9790 0.7619
44.99 865.0 0.535 0.572 35.00 7.1919 0.9073 0.8272 0.5937
50.00 867.4 0.528 0.554 40.00 7.1999 0.9735 1.0392 0.8026
54.99 869.7 0.519 0.537 45.00 7.1928 0.9000 0.8238 0.5790
50.00 7.1903 0.8735 0.7650 0.5276
60.00 872.1 0.512 0.521
55.00 7.1930 0.8886 0.8142 0.5674
413.15 K 60.00 7.1974 0.9240 0.9399 0.6995
0.10 828.2 0.647 0.889
[C2 mim][EtSO4 ]
0.25 828.3 0.644 0.888
0.10 7.3610 1.2035 1.8596 1.7519
0.50 828.5 0.644 0.886
0.25 7.3622 1.2132 1.8873 1.7775
1.00 828.9 0.643 0.881
0.50 7.3608 1.2019 1.8579 1.7511
2.00 829.6 0.638 0.872 1.00 7.3592 1.1844 1.8013 1.6904
5.00 831.7 0.627 0.846 2.00 7.3623 1.2102 1.8786 1.7633
10.01 835.2 0.609 0.805 5.00 7.3584 1.1707 1.7664 1.6488
15.00 838.5 0.594 0.769 10.00 7.3599 1.1717 1.7662 1.6297
20.00 841.7 0.580 0.736 15.00 7.3589 1.1539 1.7180 1.5719
24.99 844.6 0.572 0.705 20.00 7.3583 1.1386 1.6740 1.5155
30.00 847.6 0.559 0.678 25.00 7.3570 1.1174 1.6150 1.4483
34.99 850.4 0.547 0.652 30.00 7.3584 1.1171 1.6076 1.4220
40.00 853.1 0.537 0.628 35.00 7.3569 1.0950 1.5467 1.3544
45.00 855.7 0.528 0.606 40.00 7.3540 1.0607 1.4522 1.2560
50.00 858.3 0.521 0.586 45.00 7.3491 1.0086 1.3019 1.1015
54.99 860.8 0.510 0.567 50.00 7.3506 1.0121 1.3124 1.1003
60.00 863.2 0.502 0.549 55.00 7.3544 1.0359 1.3819 1.1565
*
60.00 7.3483 0.9743 1.2096 0.9865
[Aliquat 336 -derived][dca]; see Section 2.1.
[Aliquat][dca]*
0.10 7.0421 1.0957 1.1942 1.0498
0.25 7.0392 1.0658 1.0986 0.9489
seem in contradiction with previous results obtained for different 0.50 7.0418 1.0892 1.1689 1.0169
ionic liquids (including the [C4 mim][Ntf2 ] ionic liquid studied in 1.00 7.0522 1.1752 1.4072 1.2312
the present work) that exhibit a monotonous decrease of p with 2.00 7.0394 1.0646 1.1008 0.9431
5.00 7.0489 1.1370 1.3034 1.1076
increasing temperature [40,4446] in the 270350 K range. Fig. 3c
10.00 7.0275 0.9444 0.7755 0.5956
and d also depict those other data for [C4 mim][Ntf2 ] [46,47]. 15.00 7.0316 0.9677 0.8482 0.6380
It must be noted that this inverse proportionality between p 20.00 7.0188 0.8546 0.5599 0.3681
and T constitutes an anomalous behavior and most traditional liq- 25.00 7.0377 1.0102 1.0221 0.7934
30.00 7.0262 0.9006 0.7239 0.5001
uids exhibit direct proportionality. Moreover, the thermodynamics 35.00 7.0184 0.8260 0.5287 0.3071
of liquidvapor equilibrium dictates that at a sufciently high tem- 40.00 7.0170 0.8059 0.4915 0.2686
perature p ought to start rising with temperature increase because 45.00 7.0149 0.7811 0.4384 0.2127
at the liquidvapor critical point it must diverge to +. This appar- 50.00 7.0161 0.7881 0.4871 0.2651
55.00 7.0019 0.6558 0.1203 0.0912
ent contradiction between the present and previously published 60.00 6.9988 0.6237 0.0493 0.1579
data sets can be unraveled simply by noting that the previously *
[Aliquat 336 -derived][dca]; see Section 2.1.
reported results covered a rather small pT range where the non-
monotonous behavior was still not obvious.
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 171

Fig. 3. pVT behaviour of [C4 mim][Ntf2 ]: (a) density as a function of pressure for selected isotherms; (b) isothermal compressibility coefcient as a function of pressure (same
isotherms); (c and d) thermal expansion coefcient as a function of pressure and temperature. The top four unlabelled isobars in panel (d) correspond to pressures of 0.1,
0.25, 0.5, and 1 MPa. The red lines represent the boundaries of the data presented by Roman et al. (isotherms between 293 and 353 K and isobars between 5 and 50 MPa).
The green lines highlight the same boundaries in the present set of data. (For interpretation of the references to color in this gure legend, the reader is referred to the web
version of the article.)

Thus, the data determined in this work seem to constitute one of
the rst experimental proofs of the existence of such a previously
predicted crossover, from negative to positive, in the temperature
derivative of the thermal expansion coefcient of ionic liquids.
The position both in terms of temperature and pressure of such
crossover depends on the nature of the ionic liquid. Nonetheless,
these ndings should be taken with due care given the uncertainty
of the experimental data (including the systematic errors associ-
ated with the calibration of the high-pressure U-tube densimeter
used in this work) and the sensitivity to those uncertainties of the
derived quantities p and T .
to the high number of vibrational degrees of freedom of the methyl-
trialkyl (C8 , C8 , C10 )ammonium cation, namely its octyl and decyl
groups. The difference between the values of the two ionic liquids
with the same cation ([C4 mim], 1-n-butyl-3-methyl-imidazolium)
can be explained by the higher contribution of the vibrational
degrees of freedom of the two triuoromethanesulfonyl groups,
compared with those of the dicyanamide anion. In addition the
variation with temperature of the heat capacity of [Aliquat][dca]
is stronger.
The experimental values were tted as a function of tempera-
ture with the polynomial given by Eq. (12):

CP (J mol1 K1 ) = b1 + b2 (T /K) + b3 (T /K)2 (12)

3.2. Heat capacity
Measurements of the heat capacity of [C2 mim][EtOSO3 ],
[C4 mim][NTf2 ], [C4 mim][dca], and [Aliquat][dca], were obtained,
at 0.1 MPa, between 308 and 363 K and Table 13 shows the
results obtained. Fig. 7 shows the variation of heat capacity
with temperature. The results show that the heat capacity of
[C2 mim][EtOSO3 ] and [C4 mim][dca] are very similar, smaller than
that of [C4 mim][NTf2 ] and about 2.5 times smaller than [Ali-
quat][dca]. The high heat capacity of this compound is probably due
Table 14 shows the coefcients of regression for Eq. (12) and
the root mean square deviations associated with the ts for all
four ionic liquids, which is, respectively, 0.5206, 0.8354, 0.9689 and
0.8769 J mol1 K1 , always smaller than 0.20%, a value that gives an
idea of the reproducibility of the measurements. The uncertainty of
the values, is smaller than 1.5% (the ISO denition, with a coverage
factor k = 2 is used).
In Fig. 8 we compare the results obtained for [C2 mim][EtOSO3 ]
with results published by different authors. Data have been
172 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Fig. 4. pVT behaviour of [C4 mim][dca]: (a) density as a function of pressure for selected isotherms; (b) isothermal compressibility coefcient as a function of pressure (same
isotherms); (c and d) thermal expansion coefcient as a function of pressure and temperature. The top ve unlabelled isobars in panel (d) correspond to pressures of 0.1,
0.25, 0.5, 1 and 2 MPa.

reported by Zhang et al. [48], using a high-precision automatic adi-
abatic calorimeter, Fernandez et al. [49], Garcia-Miaja et al. [50,51],
Ficke et al. [52], Gee et al. [53] used DSC. A wide variation between
the datasets of up to 15% at room temperature is observed. This
situation is very uncommon in calorimetry; however it is known
that, apart from differences in sample purity, the DSC used must be
well calibrated and this may explain the systematic deviations of
the data. Fig. 9 shows the deviations between and other data. Our
data agrees with the data Garcia-Miaja et al. [50,51] to within 1.6%,
with the data Ge et al. [53] to within 0.7% up to 320 K, increasing
up to 6.8% at 360 K. The data of Ficke et al. [52] is 23% lower, while
that of Zhang et al. [48] is about 3.6% lower at 310 K, but deviates
up to 6.4% at 360 K. The data of Fernandez et al. [49] have a devia-
tion of +10% at 306 K, increasing to 35% at 360 K. All these numbers
are well within the mutual uncertainty of the data, except those of
Fernandez et al. [49].
Fig. 10 shows the variation of heat capacity with temperature
for [C4 mim][NTf2 ], together with the results obtained by different
authors. Data for this liquid has been reported by Holbrey et al. [54],
Fredlake et al. [55], Troncoso et al. [56], Shimizu et al. [57], Ge et
al. [53] and Blokhin et al. [58]. All the data was obtained by DSC,
except those of Blokhin et al. [58], obtained by adiabatic calorime-
try. Fig. 11 shows the deviations between and other data. For this
liquid, our data agrees very well with those of Troncoso et al. [56]
(within 0.4%), Shimizu et al. [57] (0.2% at 300 K) and Blokhin et
al. [58] (less than 0.5%), well within the mutual uncertainty of
the data. However the data of Holbrey et al. [54] deviates by 20%
at room temperature and 16% at 360 K, the data of Fredlake et
al. [55] deviates around 6% and the data of Ge et al. [53] around
6%. Again the possible justication are sample purity and decient
calibration of the DSC.
Fig. 12 shows the variation of heat capacity with temperature for
[C4 mim][dca], together with the two points obtained by Fredlake et
al. [55], the only set of data available, obtained by DSC. These data
is about 4% lower than our data, a value which is commensurate
with the mutual uncertainty of both sets of data. Fig. 13 shows the
departures from Eq. (9) from our experimental points and Fredlake
et al. [55] data, and the deviations can be justied by the same
reasons of those for [C4 mim][NTf2 ].
As referred above, there is no experimental data available in the
literature for [Aliquat][dca]. Our data is unique and was presented
in Fig. 7. Deviations from Eq. (9) are presented in Fig. 14.
As discussed before, ionic liquids can be considered excellent
heat transfer liquids, from cryogenic temperatures up to 200 C,
as their heat capacity per unit volume is signicantly greater
than current heating/cooling oils and can be considered as pos-
sible replacements of current silicon based heat transfer uids
[2,5,54,59]. In addition, they have very low vapor pressures, wide
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 173

Fig. 5. pVT behaviour of [C2 mim][EtSO4 ]: (a) density as a function of pressure for selected isotherms; (b) isothermal compressibility coefcient as a function of pressure
(same isotherms); (c and d) thermal expansion coefcient as a function of pressure and temperature. The top ve unlabelled isobars in panel (d) correspond to pressures of
0.1, 0.25, 0.5, 1 and 2 MPa.

liquid ranges, thermal stability (some can be used at tempera-
tures up to 500 C). These results show that high performance
commercial thermal uids, Paratherm HE and Dowtherm MXTM ,
Syltherm 800TM , Syltherm HFTM and Dowtherm ATM , have lower
heat capacities per unit volume than common imidazolinium sys-
tems. Fig. 15 shows the values of CP for the ionic liquids measured
compared with the values for the current heat transfer liquids.
The composition of the proprietary heat transfer uids is not
always detailed. However for the sake of consistence they are
included here: Dowtherm A is a eutectic mixture of two very sta-
ble compounds, biphenyl (C12 H10 ) and diphenyl oxide (C12 H10 O);
Dowtherm MX is a mixture of alkylated aromatics; Paratherm HE
is a parafnic hydrocarbon (Single Cut, M = 445 g mol1 ); Syltherm
800 and Syltherm HF are dimethyl polysiloxanes. From Fig. 15 we
can conclude that the heat capacities per unit volume of the liquids
studied, as for many other ionic liquids [5], is at 1.52 times greater
than the current heat transfer liquids, in all the temperature range
studied. This conclusion would have a great effect in heat transfer
engineering policies, but unfortunately, as described in the paper
by Franca et al. [5], the actual cost of ionic liquids ([C2 mim][EtOSO3 ]
300 US$/kg), produced at a laboratory or pilot quantities, is still
much bigger than the cost of these heat transfer liquids (roughly 12
US$/L). This situation might change in a near future, as ionic liquids
become used at multi-kilo or tonnage quantities.
3.3. Diffusion coefcients at innite dilution
The innite dilution diffusion coefcients of water in
[C4 mim][NTf2 ] and [C4 mim][dca], and of [C2 mim][EtOSO3 ] in
water were measured at 298.03 K and the results are presented
in Table 15. The diffusion of water in the ionic liquids studied is
more difcult that the diffusion of [C2 mim][EtOSO3 ] in water, a
fact that can be explained by the small dimension of the water
molecule, and by the lower viscosity of the solvent. However when
we are dealing with the diffusion of water in [C4 mim][NTf2 ] and
[C4 mim][dca], it can be seen from the data presented in Table 15
that the Stokes-Einstein relation is not obeyed, as lower viscosity
of the ionic liquid corresponds also to a lower value for the innite
dilution diffusion coefcient of water. This was also found in the
work by Sarraute et al. [33], where the diffusion coefcients of 1-
alkyl-3-methylimidazolium ionic liquids in water, methanol, and
acetonitrile at innite dilution have been presented. These authors
found that in general, the diffusivities are lower for diffusion in
water, followed by methanol and acetonitrile, and decrease with
an increase in the alkyl side chain of the imidazolium-based ionic
liquids, facts that do not follow the StokesEinstein relation but
could in principle be explained be explained by the solutesolvent
interactions. Further investigations are needed to explain better
these anomalous behaviors.
174 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Fig. 6. pVT behaviour of [Aliquat][dca]: (a) density as a function of pressure for selected isotherms; (b) isothermal compressibility coefcient as a function of pressure (same
isotherms); (c and d) thermal expansion coefcient as a function of pressure and temperature. The top four unlabelled isobars in panel (d) correspond to pressures of 0.1,
0.25, 0.5 and 1 MPa.

3.4. Surface tension
The surface tension data of dry [C2 mim][EtOSO3 ] is reported
in Table 16. The experimental values were tted as a function of
temperature with a linear equation given by Eq. (13):
(N m1 ) = a1 + a2 (T /K)
with a1 = 0.0630 0.0004 N m1 and a2 = 5.4 105 1 106
N m1 K1 , with a root mean square deviation of 4.0 105 N m1 .
In Fig. 16 we represent our data and the data obtained by other
authors, with different experimental methods and different sam-
ples. It is noteworthy the scattering of data, not only in absolute
values, but also in the rst temperature coefcient. The relative
deviations between the experimental data obtained in this work
and those reported by other authors are presented in Fig. 17. The
(13) data shows deviations between 8% and 10% with average deviations
lower than 4%, in respect to literature data.

Fig. 7. Heat capacity as a function of temperature for all the liquids measured. Fig. 8. Heat capacity of [C2 mim][EtOSO3 ] as a function of temperature. () Zhang et
() [C2 mim][EtOSO3 ]; () [C4 mim][NTf2 ]; () [C4 mim][dca]; () [Aliquat 336 - al. [48]; () Fernandez et al. [49]; () Garcia-Miaja et al. [50]; () Ficke et al. [52];
derived][dca]. () Garcia-Miaja et al. [51]; Ge et al. [53]; () present work.
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179 175

Table 12 Table 13
Fitting parameters of each isotherm using Tait equation, Eq. (11), for the studied Heat capacity of [C2 mim][EtOSO3 ], [C4 mim][NTf2 ], [C4 mim][dca], and
ionic liquids. [Aliquat][dca]* as a function of temperature.

T (K) A (105 m3 kg1 ) B (MPa) C (kg m3 ) T (K) CP (J mol1 K1 )

[C4 mim][Ntf2 ] [C2 mim][EtOSO3 ] [C4 mim][NTf2 ] [C4 mim][dca] [Aliquat][dca]*

293.15 6.62573 185.668 1441.78
303.15 6.55688 176.566 1432.27 308.16 393.42 573.13 381.78 972.94
313.15 6.47201 167.148 1422.81 313.16 396.97 575.92 384.86 981.03
323.15 6.36173 157.288 1413.48 318.16 399.33 577.32 382.81 987.97
333.15 6.38584 151.379 1404.22 323.16 402.06 581.51 386.92 997.21
343.15 6.35998 144.203 1394.98 328.22 405.24 584.31 386.92 1003.0
353.15 6.33236 137.059 1385.76 333.22 406.42 588.50 388.97 1012.2
363.15 6.35145 131.265 1376.56 338.19 408.78 588.50 391.02 1016.9
373.15 6.35391 125.090 1367.33 343.18 411.14 592.70 392.05 1023.8
393.15 6.48207 115.695 1348.78 348.25 414.69 595.49 394.10 1029.6
413.15 6.61089 106.220 1330.03 353.18 415.87 596.89 395.13 1034.2
433.15 6.79368 97.779 1310.98 358.25 418.23 599.68 396.15 1041.1
453.15 7.13482 91.731 1291.50 *
[Aliquat 336 -derived][dca]; see Section 2.1.
473.15 7.52985 85.951 1271.48

[C4 mim][dca]
293.15 7.60103 221.132 1064.37
303.15 7.83126 219.600 1057.87
313.15 7.84035 211.307 1051.48
323.15 7.85580 203.545 1045.22
333.15 7.97821 199.187 1039.03
343.15 8.19660 197.800 1032.90
353.15 8.21664 190.956 1026.84
363.15 8.11773 181.418 1020.85
373.15 8.32587 179.766 1014.92
393.15 8.30873 165.968 1003.20

[C2 mim][EtSO4 ]
293.15 6.80554 256.615 1241.30
303.15 6.71247 244.671 1234.32
313.15 6.73351 237.461 1227.47 Fig. 9. Deviations between our data for the heat capacity of [C2 mim][EtOSO3 ] and
323.15 6.82779 232.979 1220.73 other authors data from Eq. (9), as a function of temperature. () Zhang et al. [48];
333.15 7.01070 231.703 1214.05 ( ) Fernandez et al. [49]; () Garcia-Miaja et al. [50]; ( ) Ficke et al. [52]; () Ge
343.15 6.75504 214.713 1207.42 et al. [53]; (+) Garcia-Miaja et al. [51]; () present work.
353.15 6.73674 206.391 1200.85
363.15 7.02784 208.341 1194.32
373.15 6.84341 194.807 1187.80
393.15 6.93285 182.660 1174.81
413.15 7.04420 170.438 1161.75
433.15 7.34931 162.970 1148.57

[Aliquat][dca]*
293.15 8.28289 138.165 895.26
303.15 8.65145 137.336 889.37
313.15 8.66984 130.540 883.51
323.15 8.82248 126.653 877.72
333.15 9.04262 124.074 872.02
343.15 9.07482 118.714 866.41
353.15 9.00866 111.946 860.79
363.15 9.23500 109.735 855.28
373.15 9.20820 104.120 849.81
393.15 9.26339 95.016 838.97
413.15 9.34764 86.944 828.21
*
[Aliquat 336 -derived][dca]; see Section 2.1. Fig. 10. Heat capacity of [C4 mim][NTf2 ] as a function of temperature. () Holbrey
et al. [54]; ( ) Fredlake et al. [55]; () Troncoso et al. [56]; () Shimizu et al. [57];
() Ge et al. [53]; (+) Blokhin et al. [58]; () present work.

The data from Martino et al. [60] and from Santos and Baldelli
[61] show the largest negative and positive deviations respectively,
and while the former used a compound supplied by Sigma the latter
studied a compound synthesized in house and was not thoroughly
characterized. Yang et al. [62] also synthesized [C2 mim][EtOSO3 ],
do not provide a compound characterization and report values
slightly lower than those by Santos and Baldelli [61] but higher
than all other authors suggesting this disagreement may be linked
to low purity samples. Several other authors [6366] studied
[C2 mim][EtOSO3 ] supplied by Sigma, using the pendant drop tech-
nique, obtaining systematically higher values than those reported

Table 14
Coefcients of Eq. (12) for the studied ionic liquids.

Ionic liquid b1  b1 (J mol1 K1 ) b2  b2 (J mol1 K2 ) b3  b3 (104 J mol1 K3 )  (J mol1 K1 )

[C2 mim][EtOSO3 ] 107.40 64.03 1.3099 0.3822 12.339 5.692 0.5206

[C4 mim][NTf2 ] 281.36 102.74 1.2920 0.6133 11.224 9.133 0.8354
[C4 mim][dca] 393.02 119.17 0.3222 0.7113 9.306 10.593 0.9689
[Aliquat][dca]* 82.39 107.85 5.2000 0.6438 57.615 9.587 0.8770
*
[Aliquat 336 -derived][dca]; see Section 2.1.
176 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179

Fig. 11. Deviations between our data for the heat capacity of [C4 mim][NTf2 ] and
other authors data from Eq. (9), as a function of temperature. () Holbrey et al. [54];
() Fredlake et al. [55]; () Troncoso et al. [56]; ( ) Shimizu et al. [57]; () Ge et al.
[53]; () Blokhin et al. [58]; () present work.
Fig. 15. Heat capacity per unit volume for the ionic liquids studied. Data for
the heat transfer uids from their Material Safety Data Sheets available on-line.
() [C4 mim][NTf2 ]; () [C2 mim][C2 H5 SO4 ]; () [C4 mim][dca]; ( ) [Aliquat 336 -
derived][dca]; ( ) Syltherm 800TM ; ( ) Syltherm HFTM ; () Dowtherm ATM ;
( ) Dowtherm MXTM ; ( ) Paratherm HE .

Table 15
0
The innite dilution diffusion coefcients, D12 , of water in [C4 mim][NTf2 ] and
[C4 mim][dca], and of [C2 mim][EtOSO3 ] in water at 298.03 0.08 K. Also shown are
the viscosity and density of the solvents used.

Ionic liquid mixture 0

D12 (1010 m2 s1 )
solv (mPa s) solv (kg m3 )

9.62
[C2 mim][EtOSO3 ] 9.15 0.89252 997.08
in water 9.84 [73] [73]
9.79

3.69
Water in 3.97 51 1444
[C4 mim][NTf2 ] 4.13 [41] [32]
3.90

2.08
Fig. 12. Heat capacity of [C4 mim][dca] as a function of temperature. () Fredlake 2.13
et al. [55]; () present work. 2.11
Water in 2.03 28 1059
[C4 mim][dca] 1.98 [32] [32]
2.05
2.00
2.28

Table 16
Surface tension measurements of [C2 mim]
[EtOSO3 ] as a function of temperature.

T (K)  (103 N m1 )

292.91 47.165
298.26 46.901
303.00 46.595
308.61 46.349
313.41 46.115
322.71 45.505
Fig. 13. Deviations between our data for the heat capacity of [C4 mim][dca] and other 332.09 45.076
authors data from Eq. (9), as a function of temperature. () Fredlake et al. [55]; ()
present work.

Fig. 16. Surface tension of [C2 mim][EtOSO3 ] as a function of temperature. () Gomez

Fig. 14. Deviations of our data for the heat capacity of [Aliquat 336 -derived][dca] et al. [69]; Wandschneider et al. [68]; () Frba et al. [70]; () Fernandez et al.
from Eq. (9), as a function of temperature. [6366]; ( ) Yang et al. [62]; () Restolho et al. [6366]; () Restolho et al. [6366];
( ) Santos and Baldelli [61]; ( ) Martino et al. [60]; () present work.
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179
Fig. 17. Deviations between our data for the surface tension of [C2 mim][EtOSO3 ]
and other authors data from Eq. (13), as a function of temperature. () Gomez et al.
[69]; () Martino et al. [60]; ( ) Wandschneider et al. [68]; () Frba et al. [70];
() Fernandez et al. [6366]; () Yang et al. [62]; ( ) Santos and Baldelli [61]; (+)
Restolho et al. [6366]; () Restolho et al. [6366]; () present work.
here (0.82.3%), while the value reported by Martino et al. [60] is
signicantly lower suggesting this discrepancy may be associated
with the capillary rise method used, probably due to a higher water
content, resulting from extended equilibration periods in contact
with air, which is known [67] to decrease the surface tension.
Furthermore it is worth noticing that the data reported here
as well as all data pertaining to compounds with higher nominal
purities (99%), obtained either commercially [68] or synthesized
in house [69,70] always show lower surface tensions than those
obtained for [C2 mim][EtOSO3 ] supplied by Sigma, ndings which
are independent of the method used to measure surface tension. In
fact, except from the data reported by Wandschneider [68], which
pertains to a higher water content sample, and reports lower values
(34.5%). The data obtained by Gomez et al. [69] and Frba et al. [70]
agree well with the data presented here, falling within a 0.3% to
+0.5% interval over the whole temperature range.
Studies on IL surface tension dependence on temperature are
scarce and the discrepancies observed on [C2 mim][EtOSO3 ] coef-
cient a2 are also evident in terms of data published for [C4 mim][PF6 ]
[57,71] and have also been acknowledge by Ghatee and Zolghadr
[72] in studies involving several 1-alkyl-3-methylimidazolium-
based ionic liquids, authors that ascribed these inconsistencies to
poor control of ILs water content as well as thermal equilibra-
tion. The agreement between raw surface tension data obtained
in this work and the one by Gomez et al. [59] also indicates the
divergence in coefcient a2 may be a consequence of inaccurate
temperature assignments, an hypothesis reinforced by the fact that
the absolute values of both density and surface tension tempera-
ture dependence coefcients are smaller for the [C2 mim][EtOSO3 ]
sample studied in the present work. Furthermore, Freire et al. [67]
studies on the effect of low water contents on the surface tension,
for imidazolium-based ionic liquids, concluded small decreases
in the surface tension for increasing low water contents, were
irrelevant in terms of the linear coefcients for surface tension tem-
perature dependence, thus pinpointing towards the relevancy of
thermal equilibration/assignment within available literature data
for [C2 mim][EtOSO3 ].
4. Conclusions
New data on thermophysical properties of new and not-so-new
ionic liquids has been obtained, namely data on density, heat capac-
ity, innite dilution diffusion coefcients and surface tension. The
liquids were synthesized and characterized by NMR spectroscopy,
ESMS and elemental analysis. Supplementary material on the spec-
tra can be obtained from Supplementary Information (SI). Care has
177
been taken with the purity of the liquids synthesized, through a
detailed characterization, namely regarding the water and chloride
ion content.
The data obtained for density of [C4 mim][NTf2 ], [C4 mim][dca],
[C2 mim][EtOSO3 ] and [Aliquat][dca] is quite extensive, permitting
the calculation of the isothermal thermal expansion coefcient.
The data determined in this work seem to constitute one of the
rst experimental proofs of the existence of a previously predicted
crossover, from negative to positive, in the temperature derivative
of the thermal expansion coefcient of ionic liquids. The posi-
tion both in terms of temperature and pressure of such crossover
depends on the nature of the ionic liquid.
The heat capacity measurements are also signicant, not only
because they are the rst values for [Aliquat][dca] and the sec-
ond batch for [C4 mim][dca], but also because the scatter of the
literature data is much larger than usually, namely with the data
obtained with DSC methods. Our data, performed with a DSC care-
fully calibrated agree very well with the best values obtained with
adiabatic calorimetry and DSC measurements. A brief analysis of
the heat storage capacity of these ionic liquids and their potential
as alternatives to current engineering thermal uids is also pre-
sented, showing that although the mass production of ILs has not
yet been attained; however, when it should, we would be able to
replace actual non-biodegradable and environmental harmful heat
transfer uids.
From the innite dilution diffusion coefcients obtained we can
conclude that the StokesEinstein relation is not obeyed for the dif-
fusion of water in the ionic liquids, a fact that requires investigation
with other uids.
In the surface tension measurements of [C2 mim][EtOSO3 ],
namely in the comparisons with other authors data it is shown
that the temperature measurement in the cells is a critical mea-
surement, in addition to purity.
Finally we hope to report on further measurements on the ther-
mophysical properties of these ionic liquids in a near future, namely
in diffusion coefcients, surface tension, viscosity, electrical con-
ductivity, relative permittivity and thermal conductivity.
Acknowledgments
This paper is the rst report of project PTDC/QUI/66826/2006,
on Synthesis and Characterization of New and not so-New Ionic
Liquids, funded by FCT Fundaco para a Cincia e para a Tec-
nologia, Portugal. Elisa Langa thanks for a post-doctoral grant
SFRH/BPD/42035/2007.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.uid.2010.03.010.
References
[1] M. Earle, K. Seddon, Ionic liquids. Green solvents for the future, Pure Appl. Chem.
72 (2000) 13911398.
[2] C.A.N. de Castro, F.J.V. Santos, Measurement of ionic liquids properties Are
we doing it well? Chim. Oggi-Chem. Today 25 (2007) 2023.
[3] R.L. Gardas, J.A.P. Coutinho, Group contribution methods for the prediction of
thermophysical and transport properties of ionic liquids, AIChE J. 55 (2009)
12741290.
[4] V.M.B. Nunes, M.J.V. Lourenco, F.J.V. Santos, M.L.S.M. Lopes, C.A.N. de Castro,
Accurate measurements of physico-chemical properties on ionic liquids and
molten salts, in: K.R. Seddon, M. Gaune-Escard (Eds.), Ionic Liquids and Molten
Salts: Never the Twain, John Wiley, 2010, pp. 229263.
[5] J. Franca, C.A.N. de Castro, M. Lopes, V. Nunes, Inuence of thermophysical
properties of ionic liquids in chemical process design, J. Chem. Eng. Data 54
(2009) 25692575.
[6] C.A.N. de Castro, M.J.V. Lourenco, A.P.C. Ribeiro, E. Langa, S.I.V. Vieira, P.
Goodrich, C. Hardacre, Thermal properties of ionic liquids and ionanou-
178 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179
ids of imidazolinium and pyrrolinium liquids, J. Chem. Eng. Data 55 (2010)
653661.
[7] K.N. Marsh, J.F. Brennecke, R.D. Chirico, M. Frenkel, A. Heintz, J.W. Magee,
C.J. Peters, L.P.N. Rebelo, K.R. Seddon, Thermodynamic and thermophysi-
cal properties of the reference ionic liquid: 1-hexyl-3-methylimidazolium
bis(triuoromethyl)sulfonyl amide (including mixtures). Part 1. Experimen-
tal methods and results (Iupac Technical Report), Pure Appl. Chem. 81 (2009)
781790.
[8] R.D. Chirico, V. Diky, J.W. Magee, M. Frenkel, K.N. Marsh, Thermody-
namic and thermophysical properties of the reference ionic liquid:
1-hexyl-3-methylimidazolium bis (triuoromethyl)sulfonyl amide
(including mixtures). Part 2. Critical evaluation and recommended
property values (Iupac Technical Report), Pure Appl. Chem. 81 (2009)
791828.
[9] A.K. Burrell, R.E. Del Sesto, S.N. Baker, T.M. McCleskey, G.A. Baker, The large scale
synthesis of pure imidazolium and pyrrolidinium ionic liquids, Green Chem. 9
(2007) 449454.
[10] J.G. Huddleston, A.E. Visser, W.M. Reichert, H.D. Willauer, G.A. Broker, R.D.
Rogers, Characterization and comparison of hydrophilic and hydrophobic room
temperature ionic liquids incorporating the imidazolium cation, Green Chem.
3 (2001) 156164.
[11] D.R. MacFarlane, S.A. Forsyth, J. Golding, G.B. Deacon, Ionic liquids based on
imidazolium, ammonium and pyrrolidinium salts of the dicyanamide anion,
Green Chem. 4 (2002) 444448.
[12] J.D. Holbrey, W.M. Reichert, R.P. Swatloski, G.A. Broker, W.R. Pitner, K.R. Seddon,
R.D. Rogers, Efcient, halide free synthesis of new, low cost ionic liquids: 1,3-
dialkylimidazolium salts containing methyl- and ethyl-sulfate anions, Green
Chem. 4 (2002) 407413.
[13] N.M.T. Lourenco, S. Barreiros, C.A.M. Afonso, Enzymatic resolution of Indinavir
precursor in ionic liquids with reuse of biocatalyst and media by product sub-
limation, Green Chem. 9 (2007) 734736.
[14] M.J. Earle, C.M. Gordon, N.V. Plechkova, K.R. Seddon, T. Welton, Decolorization
of ionic liquids for spectroscopy, Anal. Chem. 79 (2007) 758764.
[15] J.P. Mikkola, P. Virtanen, R. Sojholm, Aliquat 336((R)) a versatile and affordable
cation source for an entirely new family of hydrophobic ionic liquids, Green
Chem. 8 (2006) 250255.
[16] G. Argiropoulos, R.W. Cattrall, I.C. Hamilton, R. Paimin, Determination of the
quaternary ammonium ion components of Aliquat 336 by electrospray mass
spectrometry, Anal. Chim. Acta 360 (1998) 167169.
[17] G.L. Lee, R.W. Cattrall, H. Daud, J.F. Smith, The analysis of Aliquat-336 by gas-
chromatography, Anal. Chim. Acta 123 (1981) 213220.
[18] T.L. Greaves, C.J. Drummond, Protic ionic liquids: properties and applications,
Chem. Rev. 108 (2008) 206237.
[19] C.F. Poole, Chromatographic and spectroscopic methods for the determination
of solvent properties of room temperature ionic liquids, J. Chromatogr. A 1037
(2004) 4982.
[20] F.J.V. Santos, C.A.N. de Castro, P.J.F. Mota, A.P.C. Ribeiro, Electrical conductiv-
ity and viscosity of 1-hexyl-3-methylimidazolium bis(triuorosulfonyl)imide,
[C6 mim] [(CF3 SO2 )2 N] (CAS-RN# 382150-50-7), Int. J. Thermophys. (2009),
doi:10.1007/s10765-009-0584-4.
[21] J. Lachwa, P. Morgado, J. Esperanca, H.J.R. Guedes, J.N.C. Lopes,
L.P.N. Rebelo, Fluid-phase behavior of {1-hexyl-3-methylimidazolium
bis(triuoromethylsulfonyl) imide, C(6)mim NTf2, plus C-2-C-8 n-alcohol}
mixtures: liquidliquid equilibrium and excess volumes, J. Chem. Eng. Data 51
(2006) 22152221.
[22] J.A. Widegren, A. Laesecke, J.W. Magee, The effect of dissolved water on the
viscosities of hydrophobic room-temperature ionic liquids, Chem. Commun.
(2005) 16101612.
[23] J.A. Widegren, J.W. Magee, Density, viscosity, speed of sound, and elec-
trolytic conductivity for the ionic liquid 1-hexyl-3-methylimidazolium
bis(triuoromethylsulfonyl)imide and its mixtures with water, J. Chem. Eng.
Data 52 (2007) 23312338.
[24] H. Kratzke, R. Niepmann, E. Spillner, F. Kohler, Residual helmholtz energies of
liquid benzene between 300 and 465 K and up to 60 MPa, Fluid Phase Equilib.
16 (1984) 287316.
[25] H. Kratzke, S. Muller, M. Bohn, R. Kohlen, Thermodynamic properties of satu-
rated and compressed liquid normal-pentane, J. Chem. Thermodyn. 17 (1985)
283294.
[26] W. Wagner, A. Pruss, The IAPWS formulation 1995 for the thermodynamic
properties of ordinary water substance for general and scientic use, J. Phys.
Chem. Ref. Data 31 (2002) 387535.
[27] A.M. Demiriz, P, V, T Messungen an ausgewahlten Methanderivaten, Ruhr-
Universitat, Bochum, 1987.
[28] J.W. Magee, T.J. Bruno, Isochoric (p, rho, T) measurements for liquid toluene
from 180 K to 400 K at pressures to 35 MPa, J. Chem. Eng. Data 41 (1996)
900905.
[29] C.A.N. de Castro, M.J.V. Lourenco, M.O. Sampaio, Calibration of a DSC: its
importance for the traceability and uncertainty of thermal measurements,
Thermochim. Acta 347 (2000) 8591.
[30] M.J.V. Lourenco, F.J.V. Santos, M.L.V. Ramires, C.A.N. de Castro, Isobaric specic
heat capacity of water and aqueous cesium chloride solutions for tempera-
tures between 298 K and 370 K at p = 0.1 MPa, J. Chem. Thermodyn. 38 (2006)
970974.
[31] A. Alizadeh, C.A.N. de Castro, W.A. Wakeham, The theory of Taylor dispersion
technique for liquid diffusivity measurements, Int. J. Thermophys. 1 (1980)
243284.
[32] W.C. Su, C.H. Chou, D.S.H. Wong, M.H. Li, Diffusion coefcients and conductiv-
ities of alkylimidazolium tetrauoroborates and hexauorophosphates, Fluid
Phase Equilib. 252 (2007) 7478.
[33] S. Sarraute, M.F.C. Gomes, A.A.H. Padua, Diffusion coefcients of 1-alkyl-3-
methylimidazolium ionic liquids in water, methanol, and acetonitrile at innite
dilution, J. Chem. Eng. Data 54 (2009) 23892394.
[34] M.L.S.M. Lopes, C.A.N. de Castro, Liquid-phase diffusivity measurements of n-
alkane binary mixtures, High Temp. -High Press. 17 (1985) 599606.
[35] M.L.M. Lopes, C.A.N. de Castro, C.M.P. Deoliveira, Mutual diffusivity in normal-
heptane + normal-hexane isomers, Fluid Phase Equilib. 36 (1987) 195205.
[36] M.L.M. Lopes, C.A.N. de Castro, Liquid mutual diffusivities of the H2 O/D2 O sys-
tem, Int. J. Thermophys. 7 (1986) 699708.
[37] M.I. Viseu, C.A.N. de Castro, S.M.B. Costa, Diffusion-coefcients of tetrazolium
blue in homogeneous and micellar solutions, Int. J. Thermophys. 12 (1991)
323331.
[38] M. Lopes, C.A.N. de Castro, J.V. Sengers, Mutual diffusivity of a mixture of
normal-hexane and nitrobenzene near its consolute point, Int. J. Thermophys.
13 (1992) 283294.
[39] I.M.S. Lampreia, A.F.S. Santos, M.J.A. Barbas, F.J.V. Santos, M. Lopes, Changes in
aggregation patterns detected by diffusion, viscosity, and surface tension in
water + 2-(diethylamino)ethanol mixtures at different temperatures, J. Chem.
Eng. Data 52 (2007) 23882394.
[40] R.G. de Azevedo, J. Esperanca, V. Najdanovic-Visak, Z.P. Visak, H.J.R.
Guedes, M.N. da Ponte, L.P.N. Rebelo, Thermophysical and thermodynamic
properties of 1-butyl-3-methylimidazolium tetrauoroborate and 1-butyl-3-
methylimidazolium hexauorophosphate over an extended pressure range, J.
Chem. Eng. Data 50 (2005) 9971008.
[41] M. Frenkel, Ionic Liquids Database (IL Thermo), NIST Standard Reference
Database #147, NIST, US Secretary of Commerce, 2006.
[42] M. Tariq, P.A.S. Forte, M.F.C. Gomes, J.N.C. Lopes, L.P.N. Rebelo, Densities and
refractive indices of imidazolium- and phosphonium-based ionic liquids: effect
of temperature, alkyl chain length, and anion, J. Chem. Thermodyn. 41 (2009)
790798.
[43] M. Tariq, A.P. Serro, J.L. Mata, B. Saramago, J.M.S.S. Esperanca, J.N.C. Lopes, L.P.N.
Rebelo, High-temperature surface tension and density measurements of 1-
alkyl-3-methylimidazolium bistriamide ionic liquids, Fluid Phase Equilib. 294
(2010) 131138.
[44] L. Rebelo, V. Najdanovic-Visak, Z. Visak, M. da Ponte, J. Szydlowski, C. Cerdeirina,
J. Troncoso, L. Roman, J. Esperanca, H. Guedes, H. de Sousa, A detailed thermo-
dynamic analysis of [C(4)mim][BF4] plus water as a case study to model ionic
liquid aqueous solutions, Green Chem. 6 (2004) 369381.
[45] J. Troncoso, C.A. Cerdeirina, P. Navia, Y.A.G.-S. Sanmamed, Diego, L. Roman,
Unusual behavior of the thermodynamic response functions of ionic liquids, J.
Phys. Chem. (2009), Letters Published (Web) November 16, 2009.
[46] P. Navia, J. Troncoso, L. Roman, Dependence against temperature and pressure
of the isobaric thermal expansivity of room temperature ionic liquids, J. Chem.
Eng. Data 55 (2010) 595599.
[47] P. Navia, J. Troncoso, L. Roman, Isobaric thermal expansivity for ionic liquids
with a common cation as a function of temperature and pressure, J. Chem. Eng.
Data 55 (2010) 590594.
[48] Z.H. Zhang, Z.C. Tan, L.X. Sun, J.Z. Yang, X.C. Lv, Q. Shi, Thermodynamic investiga-
tion of room temperature ionic liquid: the heat capacity and standard enthalpy
of formation of EMIES, Thermochim. Acta 447 (2006) 141146.
[49] A. Fernandez, J.S. Torrecilla, J. Garcia, F. Rodriguez, Thermophysical properties of
1-ethyl-3-methylimidazolium ethylsulfate and 1-butyl-3-methylimidazolium
methylsulfate ionic liquids, J. Chem. Eng. Data 52 (2007) 19791983.
[50] G. Garcia-Miaja, J. Troncoso, L. Roman, Excess properties for binary systems
ionic liquid plus ethanol: experimental results and theoretical description
using the ERAS model, Fluid Phase Equilib. 274 (2008) 5967.
[51] G. Garcia-Miaja, J. Troncoso, L. Roman, Excess enthalpy, density, and heat
capacity for binary systems of alkylimidazolium-based ionic liquids plus water,
J. Chem. Thermodyn. 41 (2009) 161166.
[52] L.E. Ficke, H. Rodriguez, J.F. Brennecke, Heat capacities and excess enthalpies
of 1-ethyl-3-methylimidazolium-based ionic liquids and water, J. Chem. Eng.
Data 53 (2008) 21122119.
[53] R. Ge, C. Hardacre, J. Jacquemin, P. Nancarrow, D.W. Rooney, Heat capacities
of ionic liquids as a function of temperature at 0.1 MPa. Measurement and
prediction, J. Chem. Eng. Data 53 (2008) 21482153.
[54] J. Holbrey, W. Reichert, R. Reddy, R. Rogers, Heat capacities of ionic liquids and
their applications as thermal uids, Ionic Liq. Green Solvent: Progr. Prospect.
856 (2003) 121133.
[55] C. Fredlake, J. Crosthwaite, D. Hert, S. Aki, J. Brennecke, Thermophysical proper-
ties of imidazolium-based ionic liquids, J. Chem. Eng. Data 49 (2004) 954964.
[56] J. Troncoso, C. Cerdeirina, Y. Sanmamed, L. Roman, L. Rebelo, Thermodynamic
properties of imidazolium-based ionic liquids: densities, heat capacities, and
enthalpies of fusion of [bmim][PF6] and [bmim][NTf2], J. Chem. Eng. Data 51
(2006) 18561859.
[57] Y. Shimizu, Y. Ohte, Y. Yamamura, K. Saito, Effects of thermal history on thermal
anomaly in solid of ionic liquid compound, C(4)mim Tf2N, Chem. Lett. 36 (2007)
14841485.
[58] A.V. Blokhin, Y.U. Paulechka, A.A. Strechan, G.J. Kabo, Physicochemical
properties, structure, and conformations of 1-butyl-3-methylimidazolium
bis(triuoromethanesulfonyl)imide C(4)mim NTf2 ionic liquid, J. Phys. Chem.
B 112 (2008) 43574364.
[59] J. Holbrey, Heat capacities of common ionic liquids potential applications as
thermal uids? Chim. Oggi-Chem. Today 25 (2007) 2426.
 C.A. Nieto de Castro et al. / Fluid Phase Equilibria 294 (2010) 157179
[60] W. Martino, J.F. de la Mora, Y. Yoshida, G. Saito, J. Wilkes, Surface ten-
sion measurements of highly conducting ionic liquids, Green Chem. 8 (2006)
390397.
[61] C.S. Santos, S. Baldelli, Alkyl chain interaction at the surface of room tempera-
ture ionic liquids: systematic variation of alkyl chain length (R = C-1-C-4, C-8)
in both cation and anion of RMIM R-OSO3 by sum frequency generation and
surface tension, J. Phys. Chem. B 113 (2009) 923933.
[62] J.Z. Yang, X.M. Lu, J.S. Gui, W.G. Xu, A new theory for ionic liquids the Interstice
Model Part 1. The density and surface tension of ionic liquid EMISE, Green Chem.
6 (2004) 541543.
[63] A. Fernandez, J. Garcia, J.S. Torrecilla, M. Oliet, F. Rodriguez, Volumetric, trans-
port and surface properties of [bmim][MeSO4 ] and [emim][EtSO4 ] ionic liquids
as a function of temperature, J. Chem. Eng. Data 53 (2008) 15181522.
[64] J.S. Torrecilla, E. Rojo, J. Garcia, M. Oliet, F. Rodriguez, Determination of toluene,
n-heptane, [emim][EtSO4 ], and [bmim][MeSO4 ] ionic liquids concentrations in
quaternary mixtures by UVvis spectroscopy, Ind. Eng. Chem. Res. 48 (2009)
49985003.
[65] J. Restolho, J.L. Mata, B. Saramago, Electrowetting of ionic liquids: contact angle
saturation and irreversibility, J. Phys. Chem. C 113 (2009) 93219327.
[66] J. Restolho, J.L. Mata, B. Saramago, On the interfacial behavior of ionic liquids:
surface tensions and contact angles, J. Colloid Interf. Sci. 340 (2009) 8286.
179
[67] M.G. Freire, P.J. Carvalho, A.M. Fernandes, I.M. Marrucho, A.J. Queirnada, J.A.P.
Coutinho, Surface tensions of imidazolium based ionic liquids: anion, cation,
temperature and water effect, J. Colloid Interf. Sci. 314 (2007) 621630.
[68] A. Wandschneider, J.K. Lehmann, A. Heintz, Surface tension and density of pure
ionic liquids and some binary mixtures with 1-propanol and 1-butanol, J. Chem.
Eng. Data 53 (2008) 596599.
[69] E. Gomez, B. Gonzalez, N. Calvar, E. Tojo, A. Dominguez, Physical properties
of pure 1-ethyl-3-methylimidazolium ethylsulfate and its binary mixtures
with ethanol and water at several temperatures, J. Chem. Eng. Data 51 (2006)
20962102.
[70] A.P. Froba, H. Kremer, A. Leipertz, Density, refractive index, interfacial tension,
and viscosity of ionic liquids [EMIM][EtSO4 ], [EMIM][NTf2], [EMIM][N(CN)(2)],
and [OMA][NTf2] in dependence on temperature at atmospheric pressure, J.
Phys. Chem. B 112 (2008) 1242012430.
[71] V. Halka, R. Tsekov, W. Freyland, Interfacial phase transitions in imidazolium-
based ionic liquids, J. Phys. Cond. Mater. 17 (2005) S3325S3331.
[72] M.H. Ghatee, A.R. Zolghadr, Surface tension measurements of imidazolium-
based ionic liquids at liquidvapor equilibrium, Fluid Phase Equilib. 263 (2008)
168175.
[73] E.W. Lemmon, M.L. Huber, M.O. McLinden, NIST Reference Fluid Thermody-
namic and Transport Properties Database (REFPROP): Version 8.0, 2007.