J. Chem.

Thermodynamics 47 (2012) 203208

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Volumetric and surface properties of pure ionic liquid n-octyl-pyridinium nitrate

and its binary mixture with alcohol
Haichao Jiang a,b, Jianying Wang b, Fengyun Zhao b, Guodi Qi b, Yongqi Hu a,b,
a
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
b
College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China

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

Article history: The density and surface tension for pure ionic liquid N-octyl-pyridinium nitrate were measured from
Received 11 May 2011 (293.15 to 328.15) K. The coefcient of thermal expansion, molecular volume, standard entropies, and
Received in revised form 10 October 2011 lattice energy were calculated from the experimental density values. The critical temperature, surface
Accepted 18 October 2011
entropy, surface enthalpy, and enthalpy of vaporization were also studied from the experimental surface
Available online 25 October 2011
tension results. Density and surface tension were also determined for binary mixtures of (N-octyl-
pyridinium nitrate + alcohol) (methanol, ethanol, and 1-butanol) systems over the whole composition
Keywords:
range at 298.15 K and atmospheric pressure. Excess molar volumes and surface tension deviations for
Ionic liquid
Alcohol
the binary systems have been calculated and were tted to a RedlichKister equation to determine the
Thermophysical properties tting parameters and the root mean square deviations. The partial molar volume, excess partial molar
Density volume, and apparent molar volume of the component IL and alcohol in the binary mixtures were also
Surface tension discussed.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Ionic liquids (ILs) are organic molten salts that remain liquid at
room temperature. Compared with traditional organic solvents,
they have many unique properties such as thermal stability, con-
trollable polarity, nonvolatility, recyclability, and good solvation
ability for organic or inorganic materials [1]. Due to these unique
properties, ILs have potential applications in synthesis [2], electro-
chemistry [3], catalysis [4], and separation engineering [57]. Such
potential applications make it is necessary to know the thermody-
namic characteristics, such as density [8,9], surface tension [10],
viscosity [11,12], solubility [1317], and dynamics [1821] not
only for pure ILs, but also for the mixture with other solvents,
e.g. alcohols.
Presently, most of the studies focused on the imidazolium-based
ILs [2228], and properties of pyridinium-based ILs and its mixtures
with other solvents are scarce. In addition, N-alkyl-pyridinium-based
ILs has gained widespread attractions. They can be used as catalysts
[2932] and electrolytes [33], and have excellent effect of extraction
desulfurization on oil [3438]. The knowledge of physical properties
Corresponding author at: College of Chemical and Pharmaceutical Engineering,
Hebei University of Science and Technology, Shijiazhuang 050018, China. Tel./fax:
+86 311 88632175.
E-mail address: huyq2000@126.com (Y. Hu).
of pyridinium-based ILs and its mixtures with other solvents may
help to reveal new applications for these types of liquids [39].
In this work, the density and surface tension for pure ionic li-
quid N-octyl-pyridinium nitrate ([Ocpy][NO3]) were measured
from (293.15 to 328.15) K. The thermodynamic properties of pure
[Ocpy][NO3] were obtained from experimental density and surface
tension values. Density and surface tension were also determined
for binary mixtures of {[Ocpy][NO3] + alcohol} (methanol, ethanol,
and 1-butanol) systems over the whole composition range at
298.15 K and atmospheric pressure. Excess molar volumes and sur-
face tension deviations for the binary systems were calculated and
tted to a RedlichKister equation. The partial molar volume, ex-
cess partial molar volume and apparent molar volume of the com-
ponent IL and alcohol in the binary mixtures were also discussed.
2. Experimental
2.1. Materials
[Ocpy][NO3] (mass fraction > 99%) was obtained from Shanghai
Chengjie Chemical Co. (in China). The IL sample was dehydrated
under vacuum at 80 C for at least 48 h prior to the measurements
in order to reduce the water content. Water content in the ILs,
determined by Karl Fisher titration, was below 0.02% (mass frac-
tion). Methanol (mass fraction, 99.5%), ethanol (mass fraction,

0021-9614/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2011.10.013
204 H. Jiang et al. / J. Chem. Thermodynamics 47 (2012) 203208

99.5%), and 1-butanol (mass fraction, 99.9%) were supplied by
Beijing Chemical Reagent Co. and were used without further
purication.
2.2. Apparatus and methods
Mixtures were prepared by weighing on a Mettler AX-205 bal-
the tting line is 9.22  104 K1 for [Ocpy][NO3]. This value is com-
parable to coefcients of [Ocpy][BF4] (6.30  104 K1) [39].
The molecular volume of IL, Vm, is calculated from the experi-
mental density value using the following equation at 298.15 K:
V m M=N  q; 3
where M is the molar mass of [Ocpy][NO3], 254.14 g  mol , and N 1

ance covering the whole composition range; the uncertainty in
molar fraction being estimated as less than 1  104. The densities
of all the samples were measured using an Anton-Paar DMA4500
vibrating-tube densimeter and performed in nitrogen atmosphere
in order to avoid the adsorption of water. The repeatability of the
density measurement is 0.0002 g  cm3. The density measuring
cell was thermostated with a temperature stability of 0.01 K.
The apparatus calibration was performed periodically, and doubly
distilled, degassed water were used for calibration. The measure-
ments were done in three reduplicate runs and the average value
is considered for further study.
Measurements of surface tension were performed with a plati-
num plate with a DCAT21 (Dataphysics, Germany) digital tensiom-
eter. All surface tension measurements were performed in nitrogen
atmosphere to avoid surface contamination and the adsorption of
water. Samples were measured in a closed measuring cell with a
volume of about 40 cm3, and the temperature was controlled with-
in 0.02 K. Before a series of experiments, the plate and vessel were
thoroughly cleaned by immersion in a concentrated solution of ni-
tric acid for several hours. Then it was rinsed with distilled water,
carefully amed in a Bunsen burner, washed again with distilled
water and dried. Each reported value was an average of ve mea-
surements, where the maximum deviation from the average value
was always less than 0.5%. The uncertainty of the measurements is
0.15 mN  m1 [40].
3. Results and discussion
is the Avogadros constant. The calculated value of Vm for [Ocpy][-
NO3] is 0.3875 nm3.
The standard entropy can be expressed in terms of molecular
volume by the following equation:
1
S 298=J  mol  K1 1246:5V m =nm3 29:5: 4
Equation (4) was proposed by Glasser [41], and the value of stan-
dard entropy calculated for [Ocpy][NO3] is 512.5 J  mol1  K1.
Lattice energy reects the interaction of the cation and anion,
and density is also critically needed for the estimation of lattice en-
ergy (UPOT) of an ionic species which then can be utilized to calcu-
late the heat of formation [42]. According to Glassers theory [41],
UPOT, may be calculated using the following equation:
1
U POT =kJ  mol 1981:2q=M1=3 103:8: 5
The lattice energy of [Ocpy][NO3] calculated by equation (5) is
425.6 kJ  mol1. This value is less than those of series of imidazoli-
um-based ILs [41,43], which are in the range of (432 to
470) kJ  mol1. This indicates the interaction of cation and anion
of [Ocpy][NO3] IL is weaker than that of imidazolium-based ILs,
which have strong hydrogenbonding interaction between cation
and anion [44].
Experimental surface tension results were determined over the
temperature range from (293.15 to 328.15) K at atmospheric pres-
sure and are presented in table 1. An empirical equation of surface
tension was obtained as follows:

c=mN  m1 55:7  0:0668T=K: 6

3.1. Thermodynamic properties of pure [Ocpy][NO3]
The correlation coefcient is 0.9993. The surface entropy and sur-
Experimental density values were measured over the tempera- face enthalpy can be derived from the experimental surface tension
ture range from (293.15 to 328.15) K at atmospheric pressure and data. The surface entropy is obtained from the slopes Ss = (oc/oT)P
the results are presented in table 1. Density data for IL studied here of the temperature plots of the surface tension. The surface enthal-
were used to deduce the coefcient of thermal expansion. The den- pies Hs = c  T(oc/oT)P are constant in the temperature range of
sity values were tted by the method of the least-square. An (283.15 to 333.15) K. The surface entropy of [Ocpy][NO3] is
empirical equation was derived as follows: 0.0668 mJ  K  m2, which is smaller than that of [Bupy][NO3]
(0.0794 mJ  K  m2, [45]). The surface enthalpy [Ocpy][NO3] is
lnq=g  cm3  0:3601  9:2251104 T=K: 1
55.70 mJ  m2, and this value is also smaller than that of [Bupy][-
The correlation coefcient is 0.9993. The thermal expansion coef- NO3] (75.37 mJ  m2, [45]). This indicates the interaction of cation
cient of IL studied here is dened through the following equation: and anion of [Bupy][NO3] is stronger than that of [Ocpy][NO3], since
    the surface enthalpy is dependent on interaction energy (lattice en-
1 @V @ ln q ergy) between ions [46].
a  ; 2
V @T p @T p Critical temperatures (Tc) of ionic liquids is one of the most rel-
evant thermophysical properties since it can be used in many cor-
where a is the coefcient of thermal expansion, V is the volume of
responding states correlations for equilibrium and transport
the IL, and q is the density of the IL. The value of a obtained from
properties of uids [1]. However, it is hard to acquire reliable data
of Tc due to the intrinsic nature of ILs. Guggenheim [47] empirical
TABLE 1 equation was usually used to predict the critical temperature value
Experimental density and surface tension values of pure IL [Ocpy][NO3] at temper- by many research groups [1,47]. The empirical equation was de-
atures (293.15 to 328.15) K. scribed as follows:
T/K q/(g  cm3) c/(mN  m1)  11=9
T
293.15 0.01 1.0935 0.0001 36.12 0.09 cK 1 ; 7
298.15 0.01 1.0895 0.0001 35.76 0.08 Tc
303.15 0.01 1.0842 0.0001 35.50 0.12
308.15 0.01 1.0786 0.0001 35.18 0.11 where c is the surface tension, Tc is critical temperature, K is an
313.15 0.01 1.0734 0.0001 34.76 0.14 empirical constant. The equation reects the fact that c becomes
318.15 0.01 1.0686 0.0002 34.48 0.10 null at the critical point [1,47]. The estimated critical temperature
323.15 0.01 1.0638 0.0002 34.12 0.15
of [Ocpy][NO3] is 950 K, which is comparable to that of [Bupy][NO3]
328.15 0.02 1.0597 0.0001 33.78 0.10
(1089 K) [45].
 H. Jiang et al. / J. Chem. Thermodynamics 47 (2012) 203208 205

Rebelo et al. [48] proposed an expression of estimating the nor- xIL M 1 1  xIL M 2 xIL M 1 1  xIL M 2
VE   ; 9
mal boiling temperature, Tb, in terms of critical temperature, Tc, q q1 q2
which is Tb = 0.6Tc. The normal boiling temperature value esti-
mated from Guggenheim and expression is 570 K. where xIL is mole fraction of [Ocpy][NO3] in the binary mixtures; q,
Low vapor pressure is one of the most important properties of q1, and q2 are densities of binary mixture, pure ionic liquid [Ocpy][-
ILs, and can be studied by the enthalpy of vaporization. The mea- NO3] and alcohol, respectively; M1 and M2 are molar mass of [Oc-
surable vapor pressures in a temperature interval are large enough py][NO3] and alcohol, respectively. The values of VE are presented
for a proper evaluation of thermodynamic parameters such as en- in table 2. The excess quantities of the binary mixtures have been
thalpy of vaporization. Zaitsau et al. [49] propounded an empirical tted to a RedlichKister [5153] type equation:
equation of estimating the enthalpy of vaporization, X
M

2=3 Z xIL 1  xIL BP 2xIL  1p ; 10

Dgl Hm AcV M N1=3 B; 8 p0

where N is Avogadros constant, VM is molar volume, A and B are
empirical parameters and their values are (0.01121 and
2.4) kJ  mol1, respectively. The molar enthalpy of vaporization
for [Ocpy][NO3] estimated from equation (8) is 130.7 kJ  mol1,
which is smaller than that of imidazolium-based ILs [43,50].
3.2. Binary mixtures of {[Ocpy][NO3] + alcohols}
where Z is the excess property, xIL is the mole fraction of [Ocpy][-
NO3], BP is the tting parameter, and M is the degree of the polyno-
mial expansion, which was optimized using the Marquardts
algorithm. The tting parameters BP are listed in table 3 together
with the standard deviations (r). These deviations were calculated
by employing the following expression:
"n #1=2
Xdat

The experimental data of density for the binary systems r zexp  zcal 2 =ndat ; 11
{[Ocpy][NO3] + methanol}, {[Ocpy][NO3] + ethanol}, and {[Ocpy] 1

[NO3] + 1-butanol} were determined over the whole composition
range. The results are listed in table 2. It can be found that the den-
sity value increase with the increase of molar fraction of IL (xIL) for
all the three binary systems.
Excess molar volume is important in understanding the nature
of molecular aggregation that exits in binary mixtures. The excess
molar volume VE was calculated from the measured densities by
using the following equation:
where zexp, zcal, and ndat present the experimental value, calculated
value, and the number of experimental data, respectively.
Figure 1 shows the experimental points and tting curve of VE. It
is evident that in the case of {[Ocpy][NO3] + 1-butanol} mixture, the
values of VE are all positive and show maximum at xIL = 0.6. While
for {[Ocpy][NO3] + methanol} and {[Ocpy][NO3] + ethanol}, the val-
ues of VE appear negative over the entire molar fraction of IL, and
become more negative with the decrease of alkyl chain length of
alcohols. Similar behaviors were observed for the mixtures of

TABLE 2
Volumetric properties for the binary mixture of {[Ocpy][NO3] + alcohols} at different molar fraction of [Ocpy][NO3] (xIL) at 298.15 K and atmospheric pressure.

xIL q/(g  cm3) VE/(cm3  mol1) V IL / (cm3  mol1) V S /(cm3  mol1) V EIL /(cm3  mol1) V ES /(cm3  mol1) VuIL/(cm3  mol1) VuS/(cm3  mol1)

{[Ocpy][NO3] + methanol}
0.0000 0.7853 0.0001 0.00 229.71 40.75 3.42 0.00 40.75
0.1026 0.9102 0.0001 0.31 230.24 40.13 2.89 0.62 230.10 40.40
0.2063 0.9743 0.0001 0.59 230.84 39.72 2.29 1.03 230.25 40.00
0.3072 1.0113 0.0001 0.77 231.34 39.52 1.78 1.23 230.62 39.64
0.4225 1.0384 0.0002 0.89 231.75 39.49 1.38 1.25 231.02 39.20
0.5067 1.0526 0.0001 0.96 231.97 39.58 1.16 1.17 231.23 38.80
0.6067 1.0650 0.0002 0.95 232.20 39.83 0.93 0.91 231.56 38.32
0.8534 1.0844 0.0001 0.72 232.86 42.46 0.27 1.72 232.29 35.84
0.9360 1.0875 0.0001 0.32 233.07 44.86 0.07 4.11 232.78 35.70
1.0000 1.0895 0.0001 0.00 233.13 47.69 0.00 6.94 233.13
{[Ocpy][NO3] + ethanol}
0.0000 0.7848 0.0001 0.00 231.59 58.61 1.54 0.00 58.61
0.2000 0.9393 0.0001 0.26 231.90 58.11 1.23 0.50 231.81 58.28
0.3035 0.9814 0.0002 0.39 231.93 57.87 1.20 0.74 231.84 58.05
0.4063 1.0115 0.0001 0.50 231.96 57.66 1.16 0.96 231.89 57.77
0.5087 1.0342 0.0002 0.61 232.06 57.53 1.07 1.08 231.92 57.36
0.5903 1.0485 0.0001 0.67 232.20 57.57 0.93 1.04 232.00 56.98
0.7456 1.0694 0.0001 0.70 232.59 58.38 0.53 0.24 232.19 55.84
0.7910 1.0739 0.0002 0.64 232.73 58.90 0.40 0.287 232.33 55.57
0.8760 1.0815 0.0001 0.49 232.96 60.38 0.17 1.77 232.57 54.62
1.0000 1.0895 0.0001 0.00 233.13 64.18 0.00 5.56 233.13
{[Ocpy][NO3] + 1-butanol}
0.0000 0.8056 0.0001 0.00 243.75 91.86 10.62 0.00 91.86
0.1245 0.8753 0.0001 0.69 235.71 92.82 2.58 0.96 238.68 92.65
0.2008 0.9100 0.0001 0.80 234.53 92.80 1.40 0.95 237.11 92.86
0.3038 0.9486 0.0002 0.88 234.70 93.04 1.58 1.18 236.02 93.12
0.4019 0.9781 0.0001 0.98 235.20 93.58 2.07 1.72 235.57 93.50
0.5012 1.0020 0.0002 1.21 235.24 93.98 2.11 2.12 235.55 94.29
0.6025 1.0230 0.0001 1.36 234.71 93.56 1.58 1.71 235.38 95.26
0.7010 1.0417 0.0001 1.27 233.92 91.98 0.79 0.12 234.94 96.09
0.8005 1.0590 0.0001 0.99 233.28 89.46 0.15 2.40 234.36 96.81
0.8990 1.0749 0.0002 0.50 233.06 87.36 0.07 4.50 233.69 96.85
1.0000 0.8056 0.0001 0.00 233.13 0.00 233.13
206 H. Jiang et al. / J. Chem. Thermodynamics 47 (2012) 203208

TABLE 3 12
Fitting parameters and root mean square deviations (r) for the three binary mixtures
of {[Ocpy][NO3] + alcohols} at 298.15 K.

B0 B1 B2 B3 r 8
{[Ocpy][NO3] + methanol}

-1
VE/(cm3  mol1)

V IL/cm mol
3.800 0.917 1.384 0.844 0.022
dc/(mN  m1) 14.589 10.386 20.214 14.396 0.138

3
4
{[Ocpy][NO3] + ethanol}
VE/(cm3  mol1) 0.007

E
2.412 1.905 1.140 0.105
dc/(mN  m1) 4.813 7.232 11.467 39.549 0.128
{[Ocpy][NO3] + 1-butanol} 0
VE/(cm3  mol1) 11.564 1.519 2.091 0.247 0.059
dc/(mN  m1) 19.208 15.794 11.739 7.622 0.110

-4
0.0 0.2 0.4 0.6 0.8 1.0
xIL

1.6 FIGURE 2. Excess partial molar volumes of the IL against molar fraction of IL: j
{[Ocpy][NO3] + methanol}; d {[Ocpy][NO3] + ethanol}; and N {[Ocpy][NO3] + 1-
butanol}.
1.2

0.8 !
E @V E
V S V M;S V xIL ; 13
-1

@xIL
V /cm mol

0.4
P;T
3

0.0 where V IL and V S are the partial molar volumes of the IL and the sol-
E

vent alcohol, VM,IL and VM,S are molar volume of the pure ionic liquid
-0.4 and the solvent, and (oVE/oxIL)P,T is calculated from equation (10).
The excess partial molar volumes in a binary mixture can be deter-
-0.8 mined from the equation:

-1.2 V EIL V IL  V M;IL ; 14

0.0 0.2 0.4 0.6 0.8 1.0
xIL V ES V S  V M;S : 15

FIGURE 1. Excess molar volumes of binary mixtures against molar fraction of IL: j The molar volume of the binary mixture (VM) was calculated by
{[Ocpy][NO3] + methanol}; d {[Ocpy][NO3] + ethanol}; N {[Ocpy][NO3] + 1-buta- the following equation:
nol}; and line, tting curves using RedlichKister equation.
xIL M IL 1  MIL M S
VM ; 16
q
{[emim][CH3SO4] + methanol} and {[emim][CH3SO4] + ethanol}
where MIL and MS are the molar mass of the IL and the solvent, xIL is
[40]. Compared with {[Ocpy][NO3] + 1-butanol} mixture, the VE of
the molar fraction of the IL, and q is the density of the mixture.
mixture of {[emim][CH3SO4] + 1-butanol} are all negative over the
The apparent molar volume of a component i in the binary mix-
entire molar fraction of IL [40]. For {[Ocpy][NO3] + methanol}, the
ture is dened as:
VE show minimum at around xIL = 0.5, and shifted to xIL = 0.8 for
{[Ocpy][NO3] + ethanol} system. V M  xj V Mj
V/i ; 17
In fact, there are two main factors inuence the excess molar xi
volume: (1) the strength of intermolecular interactions between
ions (e.g. hydrogen bonding and electrostatic interactions) in the
mixture and (2) the molecular shape and size as well as the pack- 8
ing effect of molecules [54]. The molar volume of [Ocpy][NO3] is
233.13 cm3  mol1 at 298.15 K, which is much larger than those
of alcohols (VM,methanol = 40.75 cm3  mol1, VM,ethanol = 58.61 cm3
 mol1). This makes small alcohol molecules get into the inter- 4
-1

stices upon mixing with ILs, and interact with the cation and anion
V S /cm mol

of IL molecules. These all contribute to the negative values of the

3

molar excess volumes. The positive values of excess molar volume

0
E

of {[Ocpy][NO3] + 1-butanol} binary mixture indicate a positive

deviation from ideal behavior and imply that the 1-butanol mole-
cules reduce and even break the strong electrostatic interactions
between cation and anion of the pure IL during the mixing process
-4
[55].
The partial molar volumes of IL and alcohols over the whole
composition range have been calculated using equations (12) and 0.0 0.2 0.4 0.6 0.8 1.0
(13) [56,57]: xIL
!
E @V E FIGURE 3. Excess partial molar volumes of the solvent alcohols against molar
V IL V M;IL V 1  xIL ; 12
@xIL fraction of IL: j {[Ocpy][NO3] + methanol}; d {[Ocpy][NO3] + ethanol}; and N
P;T {[Ocpy][NO3] + 1-butanol}.
 H. Jiang et al. / J. Chem. Thermodynamics 47 (2012) 203208 207

TABLE 4
Surface tension, c, and their deviations, dc, for the three binary mixtures of {[Ocpy][NO3] + alcohols} at 298.15 K.

xIL c/(mN  m1) dc/(mN  m1) xIL c/(mN  m1) dc/(mN  m1)
{[Ocpy][NO3] + methanol}
0.0000 22.09 0.06 0.00 0.00 0.5067 32.80 0.12 3.79 0.05
0.1026 27.40 0.08 3.91 0.02 0.6067 33.43 0.11 3.04 0.04
0.2063 30.11 0.05 5.20 0.01 0.8534 35.19 0.12 1.43 0.04
0.3072 30.78 0.10 4.49 0.03 0.9360 35.72 0.07 0.83 0.01
0.4225 32.00 0.10 4.14 0.03 1.0000 35.76 0.08 0.00 0.00
{[Ocpy][NO3] + ethanol}
0.0000 21.55 0.04 0.00 0.00 0.5903 30.75 0.05 0.82 0.01
0.2000 26.44 0.04 2.05 0.01 0.7456 30.92 0.06 1.23 0.01
0.3035 27.83 0.08 1.97 0.03 0.7910 31.13 0.14 1.66 0.07
0.4063 28.74 0.12 1.42 0.06 0.8760 31.27 0.06 2.73 0.02
0.5087 29.75 0.11 0.97 0.05 1.0000 35.76 0.08 0.00 0.00
{[Ocpy][NO3] + 1-butanol}
0.0000 23.67 0.10 0.00 0.00 0.6025 28.08 0.07 2.88 0.02
0.1245 25.17 0.13 0.01 0.03 0.7010 28.65 0.09 3.50 0.01
0.2008 25.84 0.08 0.25 0.02 0.8005 29.79 0.08 3.56 0.01
0.3038 26.35 0.04 0.99 0.05 0.8990 31.31 0.08 3.23 0.01
0.4019 26.92 0.06 1.60 0.03 1.0000 35.76 0.08 0.00 0.00
0.5012 27.53 0.03 2.20 0.06

region of V EIL of [Ocpy][NO3] at low IL molar fraction, and then

the V EIL increases and becomes almost constant with a value of
36 V EIL  0 at higher bulk mole fraction of IL. The negative value of
V EIL reveals the negative deviation from ideal behavior at low IL mo-
lar fraction. With the increase of the chain length of alcohols, the
32 values of V EIL increase and become positive from negative values
when the solvent methanol and ethanol were replaced by 1-buta-
-1
/ mNm

nol. This conrms the strong interactions of ionic liquid and alco-
28 hols around this composition in the bulk phase and this kind of
specic interactions weakened by the increasing length of the alco-
hol chain.
24 The surface tension deviations (dc) were calculated by

X
2

20 dc c  xi ci ; 20
0.0 0.2 0.4 0.6 0.8 1.0 i1

xIL
FIGURE 4. Surface tensions of binary mixtures against molar fraction of IL: j
{[Ocpy][NO3] + methanol}; d {[Ocpy][NO3] + ethanol; and N {[Ocpy][NO3] + 1-
butanol}.
where VM is the molar volume of mixture, xi is the mole fraction of
component i in the mixture, VMj is the molar volume of the second
component j. Combination of equations (9) and (17) gives the fol-
lowing equations:
VE
V/IL V M;IL ; 18
xIL
VE
V/S V M;S : 19
xS
The value of the partial molar volumes, the excess partial molar
volumes and the apparent molar volumes of IL and alcohols at
298.15 K are listed in table 2. It is evident that the V IL , V ES , and
V/IL of {[Ocpy][NO3] + methanol} and {[Ocpy][NO3] + ethanol} in-
crease with the increase of molar fraction of IL in the mixture while
the {[Ocpy][NO3] + ethanol} system appears an opposite trend. V S
and V/S increase with the increase of length of the alcohol chain.
The excess partial molar volumes of the IL and the solvent alco-
hols against molar fraction of IL are plotted in gures 2 and 3,
respectively. It can be seen from gure 2 that the excess partial
molar volumes of {[Ocpy][NO3] + methanol} and {[Ocpy][NO3] +
ethanol} binary mixtures appear similar tendencies: there is a
where c and ci is the surface tensions of the mixture and the com-
ponent i, and xi is the mole fraction of the component i. The data of c
and dc of {[Ocpy][NO3] + alcohols} binary mixtures are recorded in
table 4. In contrast to the bulk phase, the surface presents a differ-
ent behavior as shown in the variation of surface tension (gure 4)
for the three studied mixtures. As for the {[Ocpy][NO3] + ethanol}
and {[Ocpy][NO3] + 1-butanol} systems, at low bulk ionic liquid mo-
lar fraction, the values of surface tension increase slowly, while at
high molar fraction of ILs (xIL > 0.9), the values of surface tension in-
crease rapidly. This break point (xIL  0.9) is the location of the
aggregation onset (AO) [58]. This phenomenon reveals there are rel-
atively more alcohol molecules to be presented at the surface before
the AO, but at high ionic liquid molar fraction, there seems an ionic
liquid region formed at the phase boundary. While the AO of
{[Ocpy][NO3] + methanol} binary mixture system appears at
xIL  0.2. This indicates there are more IL molecules congregate at
the phase boundary at low ionic liquid molar fraction, which is dif-
ferent with the {[Ocpy][NO3] + ethanol} and {[Ocpy][NO3] + 1-buta-
nol} systems.
The surface tension deviations were tted to a RedlichKister
equation as mentioned above. The corresponding tting parame-
ters BP and the standard deviations (r) are also given in table 3.
The surface tension deviations are positive for {[Ocpy][NO3] +
methanol} system and negative for {[Ocpy][NO3] + 1-butanol} sys-
tem over the whole range of composition. These behaviors are sim-
ilar with the mixtures of {[emim][CH3SO4] + methanol} and
{[emim][CH3SO4] + 1-butanol} [40]. The surface tension deviations
for {[Ocpy][NO3] + ethanol} system are positive at low IL molar
208 H. Jiang et al. / J. Chem. Thermodynamics 47 (2012) 203208
fraction and negative at high IL molar fraction. The values of dc for
{[Ocpy][NO3] + alcohol} mixtures increase with the decrease of al-
kyl chain length of alcohols over the entire composition range. In
addition, the values of dc show maximum at xIL  0.2 for
{[Ocpy][NO3] + methanol} system, and show minimum at xIL  0.8
for {[Ocpy][NO3] + 1-butanol} mixture.
4. Conclusions
The density and surface tension of pure ionic liquid [Ocpy][NO3]
have been measured as a function of temperature at atmospheric
pressure, and decrease with increasing temperature for the range
covered in the current study. The thermal expansion coefcient
of [Ocpy][NO3] was determined using the experimental density re-
sults. The molecular volume, standard entropy, and lattice energy
of the IL were calculated from the experimental densities at
T = 298.15 K.
The surface entropy and the surface enthalpy value for the [Oc-
py][NO3] are obtained from the surface tension values in the tem-
perature range of (283.15 to 333.15) K. The critical temperature
and the normal boiling temperature were obtained by using the
Guggenheim equation.
Density and surface tension have been determined over the
whole composition range for [Ocpy][NO3] with alcohols (methanol,
ethanol, and 1-butanol) binary systems at 298.15 K. The density
and surface tension values increase with the increase of molar frac-
tion of the IL in the binary mixture. The excess molar volumes VE
were calculated from the measured densities and were tted
appropriately to a RedlichKister equation. The excess molar vol-
umes are positive for the {[Ocpy][NO3] + 1-butanol} binary mixture
and negative for {[Ocpy][NO3] + methanol} and {[Ocpy][NO3] +
ethanol} binary mixtures over the entire composition range. The
values of VE in these binary mixtures increase with the increase
of alkyl chain length of alcohol and decrease with the increasing
temperature.
The excess partial molar volume of alcohol, partial molar vol-
ume and apparent molar volume of IL for {[Ocpy][NO3] + metha-
nol} and {[Ocpy][NO3] + ethanol} systems increase with the
increase of molar fraction of IL, while the {[Ocpy][NO3] + ethanol}
system appears an opposite trend. The partial molar volume and
apparent molar volume of alcohol increase with the increase of
length of the alcohol chain. The surface tension values of the three
binary mixtures increase with the increase of molar fraction of IL.
The surface tension deviations were tted to a RedlichKister
equation.
Acknowledgement
The authors are grateful for the nancial support of National
Natural Science Foundation of China (No. 20776037).
References
[1] M.G. Freire, P.J. Carvalho, A.M. Fernandes, I.M. Marrucho, A.J. Queimada, J.A.P.
Coutinho, J. Colloid Interface Sci. 314 (2007) 621630.
[2] J. Howarth, P. James, R. Ryan, Synth. Commun. 31 (2001) 29352942.
[3] J. Fuller, R.T. Carlin, R.A. Osteryoung, J. Electrochem. Soc. 144 (1997) 3881
3885.
[4] W. Chen, L. Xu, C. Chatterton, J. Xiao, Chem. Commun. (1999) 12471248.
[5] J. Palgunadi, H.S. Kim, J.M. Lee, S. Jung, Chem. Eng. Process. 49 (2010) 192198.
[6] P. Cserjsi, N. Nemestthy, K. Bla-Bak, J. Membrane Sci. 349 (2010) 611.
[7] S.M. Mahurin, J.S. Lee, G.A. Baker, H.M. Luo, S. Dai, J. Membrane Sci. 353 (2010)
177183.
[8] C.P. Fredlake, J.M. Crosthwaite, D.G. Hert, S.N.V.K. Aki, J.F. Brennecke, J. Chem.
Eng. Data 49 (2004) 954964.
[9] Z. Gu, J.F. Brennecke, J. Chem. Eng. Data 47 (2002) 339345.
[10] G. Law, P.R. Watson, Langumir 17 (2001) 61386141.
[11] J. Zhang, W. Wu, T. Jiang, H. Gao, Z. Liu, J. He, B. Han, J. Chem. Eng. Data 48
(2003) 13151317.
[12] P. Bonhte, A.P. Dias, N. Papageogiou, K. Kalyanasundaram, M. Grtzel, Inorg.
Chem. 35 (1996) 11681178.
[13] A. Chaumont, E. Engler, G. Wipff, Inorg. Chem. 42 (2003) 53485356.
[14] A. Chaumont, G. Wipff, Chem. Eur. J. 10 (2004) 39193930.
[15] A. Chaumont, G. Wipff, Inorg. Chem. 43 (2004) 58915901.
[16] A. Chaumont, G. Wipff, Phys. Chem. Chem. Phys. 5 (2003) 34813488.
[17] C.G. Hanke, A. Johansson, J.B. Harper, R.M. Lynden-Bell, Chem. Phys. Lett. 374
(2003) 8590.
[18] M.H. Ghatee, M. Zare, F. Moosavi, A.R. Zolghadr, J. Chem. Eng. Data 55 (2010)
30843088.
[19] S. Wang, S. Li, Z. Cao, T.Y. Yan, J. Phys. Chem. C 114 (2010) 990995.
[20] M.G. Del Ppolo, G.A. Voth, J. Phys. Chem. B 108 (2004) 17441752.
[21] A. Chandran, K. Prakash, S. Senapati, Chem. Phys. 374 (2010) 4654.
[22] A.B. Pereiro, A. Rodrguez, J. Chem. Thermodyn. 39 (2007) 978989.
[23] A.B. Pereiro, P. Verda, E. Tojo, A. Rodrguez, J. Chem. Eng. Data 52 (2007) 377
380.
[24] A.B. Pereiro, F. Santamarta, E. Tojo, A. Rodrguez, J. Tojo, J. Chem. Eng. Data 51
(2006) 952954.
[25] U. Domnska, A. Pobudkowska, A. Wisniewska, J. Solution Chem. 35 (2006)
311334.
[26] U. Domnska, A. Pobudkowska, M. Rogalski, J. Colloid Interface Sci. 322 (2008)
342350.
[27] J.S. Torrecilla, J. Palomar, J. Garca, F. Rodrguez, J. Chem. Eng. Data 54 (2009)
12971301.
[28] L.I.N. Tom, P.J. Carvalho, M.G. Freire, I.M. Marrucho, I.M.A. Fonseca, A.G.M.
Ferreira, J.A.P. Coutinho, R.L. Gardas, J. Chem. Eng. Data 53 (2008) 19141921.
[29] K. Pajuste, A. Plotniece, K. Kore, L. Intenberga, B. Cekavicus, D. Kaldre, G.
Duburs, A. Sobolev, Cent. Eur. J. Chem. 9 (2011) 143148.
[30] K.X. Li, L. Chen, Z.C. Yan, H.L. Wang, Catal. Lett. 139 (2010) 151156.
[31] B. Ni, Q.Y. Zhang, A.D. Headley, Tetrahedron Lett. 49 (2008) 12491252.
[32] F.G. Deng, B. Hu, W. Sun, J. Chen, C.G. Xia, Dalton Trans. (2007) 42624267.
[33] L. Mayrand-Provencher, S. Lin, D. Lazzerini, D. Rochefort, J. Power Sources 195
(2010) 51145121.
[34] D.S. Zhao, Y.N. Wang, E.H. Duan, J. Zhang, Fuel Process. Technol. 91 (2010)
18031806.
[35] A. Arce, M. Francisco, A. Soto, J. Chem. Thermodyn. 42 (2010) 712718.
[36] D.S. Zhao, Y.N. Wang, E.H. Duan, Molecules 14 (2009) 43514357.
[37] H.S. Gao, Y.G. Li, Y. Wu, M.F. Luo, Q. Li, J.M. Xing, H.Z. Liu, Energy Fuels 23
(2009) 26902694.
[38] H.S. Gao, M.F. Luo, J.M. Xing, Y. Wu, Y.G. Li, W.L. Li, Q.F. Liu, H.Z. Liu, Ind. Eng.
Chem. Res. 47 (2008) 83848388.
[39] B. Mokhtarani, A. Shari, H.R. Mortaheb, M. Mirzaei, M. Ma, F. Sadeghian, J.
Chem. Thermodyn. 41 (2009) 323329.
[40] J.Y. Wang, F.Y. Zhao, Y.M. Liu, X.L. Wang, Y.Q. Hu, Fluid Phase Equilib. (2010),
doi:10.1016/j.uid.2011.03.008.
[41] L. Glasser, Thermochim. Acta 421 (2004) 8793.
[42] C.F. Ye, J.M. Shreeve, J. Phys. Chem. A 111 (2007) 14561461.
[43] J.Y. Wang, H.C. Jiang, Y.M. Liu, Y.Q. Hu, J. Chem. Thermodyn. 43 (2011) 800
804.
[44] Y.Q. Hu, H.C. Jiang, X.C. Zhang, Z.P. Liu, J. Ren, R.J. Liu, J. Mol. Struct.:
THEOCHEM 915 (2009) 132140.
[45] J. Wang, X. Zhang, Y. Hu, G. Qi, L. Liang, J. Chem. Thermodyn. 45 (2012) 4347.
[46] J.Z. Yang, Q.G. Zhang, B. Wang, J. Tong, J. Phys. Chem. B 110 (2006) 22521
22524.
[47] E.A. Guggenheim, J. Chem. Phys. 13 (1945) 253258.
[48] L. Rebelo, L. Canongia, J. Esperana, E. Filipe, J. Phys. Chem. B 109 (2005) 6040
6043.
[49] D.H. Zaitsau, G.J. Kabo, A.A. Strechan, Y.U. Paulechka, J. Phys. Chem. A 110
(2006) 73037306.
[50] J. Tong, Q. Liu, P. Zhang, J. Yang, J. Chem. Eng. Data 52 (2007) 14971500.
[51] E. Gomez, B. Gonzalez, N. Calvar, E. Tojo, A. Dominguez, J. Chem. Eng. Data 51
(2006) 20962102.
[52] A.B. Pereiro, A. Rodrguez, J. Chem. Eng. Data 52 (2007) 600608.
[53] E.J. Gonzlez, B. Gonzlez, N. Calvar, . Domnguez, J. Chem. Eng. Data 52
(2007) 16411648.
[54] M. Anouti, A. Vigeant, J. Jacquemin, C. Brigouleix, D. Lemordant, J. Chem.
Thermodyn. 42 (2010) 834845.
[55] L.A.S. Ries, F.A. do Amaral, K. Matos, E.M.A. Martini, M.O. de Souza, R.F. de
Souza, Polyhedron 27 (2008) 32873293.
[56] H.J. Wang, L.J. Hu, Y.H. Wu, J. Chem. Thermodyn. 37 (2005) 11191129.
[57] H.A. Zarei, J. Mol. Liq. 130 (2007) 7478.
[58] A.P. Frba, P. Wasserscheid, D. Gerhard, H. Kremer, A. Leipertz, J. Phys. Chem. B
111 (2007) 1281712822.
JCT-11-180