J. Phys. Chem.

B 2007, 111, 4109-4115

4109

Solubility of Phosphonium Ionic Liquid in Alcohols, Benzene, and Alkylbenzenes

Urszula Doman ska*, and Lidia M. Casa s,
Physical Chemistry DiVision, Faculty of Chemistry, Warsaw UniVersity of Technology, Noakowskiego 3,
00-664 Warsaw, Poland, and Chemical Engineering Department, Faculty of Sciences, UniVersity of Vigo,
Lagoas Marcosende s/n, 36200 Vigo, Spain

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ReceiVed: January 13, 2007; In Final Form: February 20, 2007

The (solid + liquid) phase equilibria and (liquid + liquid) phase equilibria of binary mixtures containing
quaternary phosphonium salt-tetrabutylphosphonium methanesulfonate and alcohols or alkylbenzenes were
investigated. The systems {[(CH3CH2CH2CH2)4P][CH3SO3] + 1-butanol, or 1-hexanol, 1-octanol, 1-decanol,
or 1-dodecanol} and {[(CH3CH2CH2CH2)4P][CH3SO3] + benzene, or toluene, ethylbenzene, or propylbenzene}
have been measured by a dynamic method at a wide range of temperatures from 220 to 386 K. Solid-liquid
equilibria with immiscibility in the liquid phase were detected with the aromatic hydrocarbons ethylbenzene
and propylbenzene. The basic thermodynamic properties of pure ionic liquidsthe melting point, enthalpy of
fusion, enthalpy of solid-solid-phase transition, and glass transitionshave been determined by differential
scanning calorimetry. The experimental data of systems with alcohols were correlated by means of the
UNIQUAC ASM and NRTL1 equations and of systems with alkylbenzenes with Wilson and NRTL equations
utilizing parameters derived from the (solid + liquid) equilibrium. The root-mean-square deviations of the
solubility temperatures for all calculated data are dependent upon the particular system and the particular
equation used.

Introduction
An understanding of solid-liquid equilibria is of paramount
importance for the design of separation processes, especially
antisolvent crystallization. There is a pressing need to develop
better solvents for separation, especially in the cases of nonideal
complexing mixtures. There are numerous publications reporting
the suitability of imidazolium ionic liquids (ILs) as entrainers
for extractive distillation and as separation solvents for liquidliquid extraction.1-6 With an increasing awareness of how the
structure of an IL affects its physical properties, the advantages
of ILs as compared to volatile organic solvents become evident.
Until now, we have focused on the determination of phase
equilibria, (solid + liquid) phase equilibria (SLE) and (liquid
+ liquid) phase equilibria (LLE), of ionic liquids based on the
imidazolium cation with popular organic solvents.7-11 The main
disadvantage of imidazolium-based ionic liquids is their relatively high cost for bulk applications, whereas very well-known
quaternary ammonium salts seem to be much cheaper. The
ammonium ionic liquids presented in our previous work were
tetraalkylammonium bromides with a hydroxyl group as a side
chain.12-15 To the best of our knowledge, the phase equilibria
of phosphonium ionic liquids were not measured. The results
can be compared to the generally known ammonium ILs, which
could be used as a phase-transfer catalyst or as the additive to
new processes for large-scale electroplating, or as substanceenhancing lubricating properties of motor oils, or as substances
exhibiting antimicrobial and antifungal activity and antielectrostatic effects.15
More complex substances with functional groups or polar
anions (here, [CH3SO3]-) are capable of having additional
* To whom correspondence should be addressed. E-mail: ula@
ch.pw.edu.pl.
Warsaw University of Technology.
University of Vigo.
On leave at Warsaw University of Technology.

interactions with polar solvents. Given their structure and

diversity of functionality, they are capable of most types of
interactions (i.e., dispersive, -, n-, hydrogen bonding,
dipolar, ionic/charge-charge, van der Waals forces). In every
solution, there can be a number of different (in terms of type
and strength) and often simultaneous solute-solvent interactions.16-19 The ILs can be totally miscible or immiscible with
alcohols or alkylbenzenes that depend on the structure of cation,
or anion. Complete understanding of the phase behavior of ILs
with organic solvents is an important issue.
The majority of studies have focused upon the solid-liquid
or liquid-liquid phase behavior of ionic liquids with alcohols
and the subsequent determination of the upper critical solution
temperatures (UCST).10-16,19-24
Many factors that control the phase behavior of ionic liquids
with other liquids, especially with alcohols, have been discussed
in recently published papers focusing on pyridinium ILs, as
opposed to imidazolium ILs,20 or on ammonium ILs, as opposed
to imidazolium ILs.14 The impact of different alcohol and IL
characteristics, including alcohol chain length, cation (alkyl or
alkoxy) chain length, and cations with different substituent
groups on the nitrogen in ammonium ILs, have been discussed.7,10,12-16,19-24 In every system measured, the LLE or, for
the crystalline solutes, the SLE were observed as a simple
eutectic binary mixture with immiscibility in the liquid phase.
All systems exhibit UCSTs, with low solubility of the IL in the
alcohol and high solubility of the alcohol in the IL. Increasing
the alkyl chain length on the alcohol causes an increase in the
UCST of the system. By contrast, increasing the alkyl chain
length on the cation (imidazolium salts) results in a decrease in
the UCST of the system or in an increase in the solubility
(ammonium salts).
The solubility of imidazolium or ammonium IL in alkylbenzenes showed UCST behavior with very low solubility of an
aromatic solvent in the IL. An increase in the alkyl chain length

10.1021/jp070293j CCC: $37.00 2007 American Chemical Society

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4110 J. Phys. Chem. B, Vol. 111, No. 16, 2007

Domanska and Casas

TABLE 1: Investigated Compound: Structure, Name, and Abbreviation of Name

structure

name

abbreviation

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tetrabutylphosphonium methanesulfonate
[(CH3CH2CH2CH2)4P][CH3SO3]

of an n-alkane at a benzene ring resulted in an increase in the

UCST.8,9,11,15
Recently published by us, SLE and LLE of (benzyl)dimethylalkylammonium nitrate demonstrated the influence of
the structure of the IL on its phase behavior.25
Although the main interest in ILs is still focused on organic
chemistry synthesis or electrochemistry, various aspects of
physical chemistry in ionic liquids are being discussed now in
the literature. The wide overview of the physicochemical aspects
of air- and water-stable ionic liquids was recently presented by
Endres and Al Abedin.26 The other review, more about
thermodynamic and thermophysical properties, such as phase
equilibria VLE, LLE, and SLE; activity coefficients; heats of
mixing; gas solubility data; densities; and transport properties
such as viscosity, electric conductivity, and mutual diffusion
coefficients, speed of sound, and other properties, were presented
by Heintz27 and Hu and Xu.28
In our previous work, the LLE or SLE of binary systems
comprising 1-hexyloxymethyl-3-methylimidazolium bis(trifluoromethylsylfonyl)imide with an alcohol (1-butanol, 1-hexanol,
or 1-octanol), a ketone (3-pentanone, or cyclopentanone), or
water were measured, as were binary systems comprising
1-hexyloxymethyl-3-methylimidazolium tetrafluoroborate with
an alcohol (methanol, ethanol, 1-butanol, 1-hexanol, or 1octanol), a ketone (3-pentanone, or cyclopentanone), or water.11
In addition, the solubility of two dialkoxyimidazolium salts, 1,3dihexyloxymethylimidazolium bis(trifluoromethylsylfonyl)imide
in an alcohol (1-butanol, 1-hexanol, 1-octanol, or 1-decanol),
in a hydrocarbon (benzene, hexane, or cyclohexane), and in
water along with the systems 1,3-dihexyloxymethylimidazolium
tetrafluoroborate, in an alcohol (1-hexanol, 1-octanol, or 1-decanol) and in water, have been previously determined in our
laboratory.11
SLE of quaternary ammonium ILs in alcohols, hydrocarbons,
and water have previously been measured, as well.12-15,25 The
experimental SLE phase diagrams investigated for four quaternary ammonium salts, ethyl(2-hydroxyethyl)dimethylammonium
bromide, C2Br; (2-hydroxyethyl)dimethylpropylammonium bromide, C3Br; butyl(2-hydroxyethyl)dimethylammonium bromide,
C4Br; and hexyl(2-hydroxyethyl)dimethylammonium bromide,
C6Br; in water and alcohols, have been published in the
literature.12,13 Other anions, including [BF4]-, [PF6]-, [(CN)2N
]-, and [NTf2]-, have also been investigated.14,15
This paper follows the discussion of room-temperature ionic
liquids and is a continuation of our systematic study of the
impact of different factors on the phase behavior of ILs. This
work includes physicochemical properties and the phase equilibria measurements of the quaternary phosphonium salt
tetrabutylphosphonium methanesulfonate [(CH3CH2CH2CH2)4P][CH3SO3], (B4PCH3SO3), with 1-butanol, 1-hexanol,
1-octanol, 1-decanol, or 1-dodecanol and with benzene, toluene,
ethylbenzene, propylbenzene. The chemical name and the
abbreviation of the substance under study are presented in Table
1. Characteristics investigated here include the effect of the alkyl

B4PCH3SO3

TABLE 2: Thermophysical Constants of Pure Salt (DSC

Data) and Some Solvents
compound

Tfus,1
K

fusH1
kJ mol-1

Ttr,1
K

trH1
kJ mol-1

B4PCH3SO3
1-octanolb
1-decanolb
1-dodecanolb
benzenec

335.35
258.35
280.15
296.95
278.61

11.105
23.70
28.79
38.42
9.834

307.09; 227.7 (g)a

3.19

a (g), glass transition. Cp at the glass transition is 126 J mol-1

K-1. b Ref 29. c Ref 30.

chain length of the alcohol (solvent) and the effect of the alkyl
chain length at the benzene ring (solvent).
For a better understanding of the IL behavior and with a view
to application in chemical engineering or development of
thermodynamic models, reliable experimental data are required.
A basic IL can be expected to interact with solvents with both
accepting and donating sites. On the other hand, polar solvents
such as alcohols are very well-known to form a hydrogenbonded net with both high enthalpies and constants of association. In this work, higher interaction may be expected between
the anion of the phosphonium salt and the polar solvent as an
alcohol. The better solubility of an IL in a chosen solvent means
possible hydrogen bonding between the IL and the solvent. The
determination of the IL-solvent interaction of this IL via the
solubility measurements, especially with alcohols and alkylbenzenes, has been performed. The characterization and purity
of the compounds were obtained by the water content (Fischer
method) and differential scanning microcalorimetry (DSC). The
melting point, the glass transition temperature, enthalpy of
fusion, and enthalpy of solid-solid-phase transition were
determined by DSC.
Experimental Procedures and Results
Materials. Investigated tetrabutylphosphonium methanesulfonate (CAS 98342-59-7) was obtained from Flucka,
BuchsGG, Switzerland. The samples purity was g98 mass %,
and it was used without any purification.
All solvents were delivered from Sigma-Aldrich Chemie
GmbH, Stenheim, Germany. Before direct use, they were
fractionally distilled over different drying reagents to the mass
fraction purity g99.8 mass %. The solvents were stored over
freshly activated molecular sieves of type 4 (Union Carbide).
The brief characterization of IL and some solvents is presented
in Table 2. All compounds were checked by GLC analysis, and
no significant impurities were found.
Water Content. Water content was analyzed by the Karl
Fischer titration technique (method TitroLine KF). Samples of
all compounds were dissolved in methanol and titrated with steps
of 2.5 L. Analysis using the Karl Fischer technique showed
that the water content in the solvents was <0.02 mass %.
Samples of the ionic liquids used in the experiment have been
checked regularly concerning water content using Karl Fischer
titration. In all cases, the content of water was <140 ppm.

Solubility of Phosphonium Ionic Liquid

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TABLE 3: Eutectic Temperatures, T1,e, and Compositions,

x1,e, Detected Graphically for (B4PCH3SO3 (1) + 1-Alcohol
(2)) and (C4PCH3SO3 (1) + Benzene (2)) Binary Systems
mixture

T1,e/K

x1,e

C4PCH3SO3 + 1-octanol
C4PCH3SO3 + 1-decanol
C4PCH3SO3 + 1-dodecanol
C4PCH3SO3 + benzene

247.64
265.10
279.83
271.87

0.2372
0.2929
0.3350
0.1977

Differential Scanning Microcalorimetry. The melting point,

the enthalpy of fusion, and the enthalpy of the solid-solid phase
transition of B4PCH3SO3 were measured using differential
scanning microcalorimetry at a scan rate of 5 K min-1, with a
power sensitivity of 16 mJ s-1, and with a recorder sensitivity
of 5 mV. The instrument (Perkin-Elmer Pyris 1) was calibrated
each time with the 99.9999 mol % purity indium sample. The
uncertainty of the calorimetric measurements was estimated to
be (1%. The average melting temperature for four scans was
(335.35 ( 0.05) K. The repeatability of the measured melting
temperature (visual method as for SLE) was (0.05 K. The
enthalpy of melting was (11.11 ( 0.01) J mol-1, and the glass
transition temperature was (227.7 ( 0.2) K with a Cp of 126
J K-1 mol-1.
As for the many ionic liquids, the maximum of the peak
temperature in DSC was closer to the visual method for the
melting temperature and solid-solid-phase transition temperature (the characteristic inflection on the liquidus curve). The
thermophysical properties are shown in Table 2.
(Solid + Liquid) Phase Equilibria Apparatus and Measurements. Solid solubilities have been determined using a
dynamic (synthetic) method described previously.31 The compound was provided under nitrogen in the drybox. Mixtures of
solute and solvent were prepared by weighing the pure
components to within 1 10-4 g. The sample of solute and
solvent was heated very slowly (at less than 2 K h-1 near the
equilibrium temperature) with continuous stirring inside a Pyrex
glass cell placed in a thermostat. The crystal disappearance
temperatures, detected visually, were measured with a calibrated
Gallenkamp Autotherm II thermometer totally immersed in the
thermostating liquid. The measurements were carried out over
a wide range of solute mole fraction from 0 to 1. The uncertainty
of temperature measurements was (0.05 K, and that of the mole
fraction did not exceed (0.0005.
Results. To our knowledge, this is the first time the
solubilities of phosphonium IL has been measured. The
experimental data for alcohols and alkylbenzenes are shown in
Tables 1S, 2S and 3S of the Supporting Information. Tables
1S and 2S include the direct experimental results of the SLE,
temperatures; T1 versus x1; the mole fraction of the solute; and
1, the activity coefficient of the IL in the saturated solution.
Table 3S includes the experimental LLE temperatures, T1 versus
x1, and the mole fraction of the solute in binary systems of (IL
+ ethylbenzene or propylbenzene).
Experimental phase diagrams of SLE investigated in this work
are shown in Figures 1-6. The solubility of B4PCH3SO3 in
1-alcohols decreases when the alkyl chain of an alcohol
increases, as was observed for other types of ILs. These results
are presented in Figures 1-5. Complete miscibility in the liquid
phase at room temperature was observed for the binary systems
containing B4PCH3SO3 and 1-alcohols. It was observed in our
previous work for binary systems of 1-butyl-3-methylimidazolium 2-(2-methoxyethoxy)-ethylsulfate, with methanol, ethanol,
1-butanol, and 1-octanol;32 for solutions of 1,3-dimethylimidazolium methylsulfate with an alcohol (methanol, ethanol, or
1-butanol) and with water;10 and for solutions of 1-butyl-3-

Figure 1. (Solid + liquid) phase equilibria of (B4PCH3SO3 (1) +

1-alcohol (2)) binary systems: (b) 1-butanol; (0) 1-hexanol; (2)
1-octanol; (]) 1-decanol; and (/) 1-dodecanol.

Figure 2. (Solid + liquid) phase equilibria of (B4PCH3SO3 (1) +

1-alcohol (2)) binary systems: (b) 1-butanol; (2) 1-hexanol. Solid line
designated by the UNIQUAC ASM equation. Solid line at constant
temperature is a solid-solid-phase transition temperature.

methylimidazolium methylsulfate with an alcohol (methanol,

ethanol, 1-butanol, 1-hexanol, 1-octanol, or 1-decanol) and with
water,10 as well as for solutions of 1-butyl-3-methylimidazolium
octylsulfate, with an alcohol (methanol, 1-butanol, 1-hexanol,
1-octanol, or 1-decanol) at a temperature of 310 K.10,33 It is
evident that it is mainly the anion that is responsible for the
strong interaction when the polar solvent is either alcohol or
water. Similarly to the previous results, the oxygen atoms from

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4112 J. Phys. Chem. B, Vol. 111, No. 16, 2007

Domanska and Casas

Figure 3. (Solid + liquid) phase equilibria of ((B4PCH3SO3 (1) +

1-octanol (2)) binary system. Points are the experimental results. Solid
line designated by the NRTL 1 equation. Solid line at constant
temperature is a solid-solid-phase transition temperature.

Figure 5. (Solid + liquid) phase equilibria of ((B4PCH3SO3 (1) +

1-dodecanol (2)) binary system. Points are the experimental results.
Solid line designated by the NRTL 1 equation. Solid line at constant
temperature is a solid-solid-phase transition temperature.

Figure 4. (Solid + liquid) phase equilibria of ((B4PCH3SO3 (1) +

1-decanol (2)) binary system. Points are the experimental results. Solid
line designated by the NRTL 1 equation. Solid line at constant
temperature is a solid-solid-phase transition temperature.

Figure 6. (Solid + liquid) phase equilibria of ((B4PCH3SO3 (1) +

benzene (2)) binary system. Points are the experimental results. Solid
line designated by the NRTL equation. Solid line at constant temperature
is a solid-solid-phase transition temperature.

the anion [CH3SO3]- are responsible for the strong interaction

with an alcohol.
The solubility of B4PCH3SO3 in alcohols increases in the
order from 1-dodecanol to 1-butanol (see Figure 1). The results
mainly depend on the melting temperature of the solvent. It
can be stated that a better solubility was observed at the lowest
melting temperature of the solvent.

The solid-solid-phase transition of B4PCH3SO3 is shown as

a characteristic inflection on the liquidus curve (see Figures
2-5).
Due to the complete phase diagrams of investigated compounds in 1-octanol, 1-decanol, and 1-dodecanol, the eutectic
points were found graphically. Table 3 lists temperatures and
compositions of the eutectic points for the investigated mixtures.

Solubility of Phosphonium Ionic Liquid

J. Phys. Chem. B, Vol. 111, No. 16, 2007 4113

Cp1 for B4PCH3SO3 was not determined, and eq 1 was used in
the calculations without the third term. Equation 1 may be used
if one assumes simple eutectic mixtures with full miscibility in
the liquid and immiscibility in the solid phases. When the solidsolid-phase transition exists and the enthalpy of phase transition
is known, two equations have to be used: eq 1 for temperatures
below the phase transition temperature (T < Ttr,1) and eq 2 at
higher temperatures (Ttr,1 < T < Tfus,1).

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-ln x1 )

Figure 7. (Solid + liquid) and (liquid-liquid) phase equilibria of (B4PCH3SO3 (1) + alkylbenzene (2)) binary systems: (b) toluene; (])
ethylbenzene; (9) propylbenzene. Solid line designated by the experimental points.

Increasing the alkyl chain length on the alcohol causes an

increase in the eutectic temperature and shifts the composition
of the eutectic point to a higher IL mole fraction.
The solubilities of B4PCH3SO3 in benzene and in alkylbenzenes (toluene, ethylbenzene, propylbenzene) are presented in
Figures 6 and 7, respectively. The observed eutectic point for
the mixture of (C4PCH3SO3 + benzene) is also given in Table
3. The eutectic point of the system (B4PCH3SO3 + benzene) is
shifted toward a much lower IL mole fraction in comparison to
that of (B4PCH3SO3 + 1-alcohol). Experimental phase diagrams
of SLE and LLE with alkylbenzenes investigated in this work
are characterized mainly by the following: (1) a simple eutectic
system exists in the (B4PCH3SO3 + benzene, or toluene) binary
mixtures, (2) the liquidus curve exhibits similar shapes for
benzene and toluene, (3) the mutual solubility of B4PCH3SO3
in ethylbenzene and propylbenzene decreases with an increase
in the alkyl substituent at the benzene ring, (4) the UCST of
the system increases when the alkyl chain length at benzene
ring increases (see Figure 7). The immiscibility gap was found
low concentration of the IL.
Correlation of (Solid + Liquid) Equilibrium. The solubility
of a solid, 1, in a liquid may be expressed in a very general
manner by eq 1

-ln x1 )

fusH1 1
trH1 1
1
1
+
R
T1 Tfus,1
R T1 Ttr,1
T1
Tfus,1
fusCp1
ln
+
- 1 + ln 1 (1)
R
Tfus,1
T1

where x1, 1, fusH1, fusCp1, Tfus,1, and T1 stand for mole

fraction, activity coefficient, enthalpy of fusion, difference in
solute heat capacity between the liquid and solid at the melting
temperature, melting temperature of the solute (1), and equilibrium temperature, respectively. The trH1 and Ttr,1 are the
enthalpy of solid-solid-phase transition and transition temperature of the solute, respectively. Unfortunately, the value of fus-

fusH1 1
1
R
T1 Tfus,1
T1
Tfus,1
fusCp1
ln
+
- 1 + ln 1 (2)
R
Tfus,1
T1

In this study, two methods were used in the systems (B4PCH3SO3 + 1-alcohol) to derive the solute activity coefficients,
1, from the so-called correlation equations that describe the
Gibbs free energy of mixing, (GE), the UNIQUAC ASM34 and
NRTL1.35 The UNIQUAC associated-solution theory has been
proposed to reproduce the (vapor + liquid), (liquid + liquid),
and (solid + liquid) phase equilibria of binary (alcohol +
unassociated component, or alcohol) mixtures as well as for
ternary mixtures of two alcohols with one nonpolar component.
The model postulates the formation of linear multisolvated
complexes from i-mers of one or two alcohols. The association
equilibrium constants were assumed to be independent of the
degree of association and solvation.35 The modified form of the
NRTL equation proposed by Renon was presented by Nagata
and co-workers35 by substituting a local surface fraction for the
local mole fraction and further by including Guggenheims
combinatorial entropy for athermal mixtures whose molecules
differ in size and shape. The resulting equations involve three
adjustable parameters and are extended to multicomponent
systems without adding ternary parameters.
Two adjustable parameters of the equations were found by
an optimization technique using Marquardts or Rosenbrocks
maximum likelihood method of minimization,
n

[T exp
- T calcd
(x1i,P1,P2)]2

i
i
i)1

(3)

where is the objective function; n is the number of

experimental points; T exp
and T calcd
denote the experimental
i
i
and calculated equilibrium temperatures, respectively, corresponding to the concentration x1i. P1 and P2 are model
parameters resulting from the minimization procedure. The rootmean-square deviation of temperature is defined as follows:

(
n

T )

i)1

(T exp
- T calcd
)2
i
i
n-2

1/2

(4)

Parameters ri and qi of the UNIQUAC ASM model were

calculated with following relationships:

ri ) 0.029 281Vm
qi )

(Z - 2)ri 2(1 - li)

+
Z
Z

(5)
(6)

where Vm is the molar volume of pure compound i at 298.15

K. The molar volume of solute Vm1 (298.15) as a hypothetical
subcooled liquid was calculated by the group contribution
method36 and was assumed to be 387.3 cm3 mol-1. The

4114 J. Phys. Chem. B, Vol. 111, No. 16, 2007

Domanska and Casas

TABLE 4: Correlation of the (Solid + Liquid) Phase

Equilibrium Data of the (B4PCH3SO3 (1) + 1-Alcohol (2))
Binary Mixtures by Means of the UNIQUAC ASM and
NRTL1 Equations: Values of Parameters and Measures of
Deviations
parameters

solvent
1-butanol
1-hexanol
1-octanol
1-decanol

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1-dodecanol

deviations

parameters

UNIQUAC ASM NRTL 1

u12
u12
UNIQUAC ASM NRTL1a
u21
u21
Tb
Tb
J mol-1
J mol-1
K
K
965.39
-1982.62
913.01
-1654.02
-499.63
-388.67
-1192.82
608.30
3288.14
-2193.92

6185.81
-1668.10
5781.57
-1276.49
6782.24
-2105.24

TABLE 5: Correlation of the (Solid + Liquid) Phase

Equilibrium Data of the (B4PCH3SO3 (1) + Alkylbenzene
(2)) Mixtures by Means of the Wilson and NRTL
Equations: Values of Parameters and Measures of
Deviations

solvent

3.77

benzene

3.16

toluene

1.66

1.45

ethylbenzene

1.50

1.16

propylbenzene

1.24c

1.14d

a Calculated with the third nonrandomness parameter, R ) 0.9.

According to eq 4 in the text. c Calculated with Mecke-Kempter
model of association. d Calculated with the third nonrandomness
parameter, R ) 0.6.

coordination number Z was assumed to be 10, and the bulk

factor li was assumed to be 0 for the linear molecule. The
calculations were carried out by the use of the data set of
association presented in Table 4S of the Supporting Information.
The temperature dependence of association constants was
calculated from the vant Hoff relation, assuming the enthalpy
of hydrogen bond formation to be temperature-independent. The
Kretschmer-Wiebe model of association was used. The correlation for the two equations used was presented with the
developing of two adjustable parameters. In this work, the value
of parameter R, a constant of proportionality similar to the
nonrandomness constant of the NRTL 1 equation, had different
values in the calculations for different binary systems (see Table
4).
Values of model parameters obtained by fitting solubility
curves together with the corresponding standard deviations are
given in Table 4. For systems with alcohols, the description of
(solid + liquid) phase equilibrium was given by the average
standard mean deviation (T) equal to 2.27 and 1.29 K for
UNIQUAC ASM and NRTL 1 equations, respectively. A
comparison of the experimental points and one of these two
equations used is shown in Figures 2-5, where the solid-liquid
phase equilibrium diagrams are presented together with curves
calculated by the UNIQUAC ASM or the NRTL1 equation.
For the (B4PCH3SO3 + an alkylbenzene) binary systems, in
which the solvent is not an associating compound, the Wilson41
and the NRTL42 equations were used. The molar volumes of
solvents are listed in Table 5S of the Supporting Information.
For the NRTL equation, the value of parameter R had different
values in the calculations for different binary systems (see Table
5). The equation parameters together with the corresponding
standard deviations are given in Table 5. The description of
(solid + liquid) phase equilibrium is given by the average
standard mean deviation (T) equal to 4.6 and 2.5 K for Wilson
(only for benzene and toluene systems) and NRTL equations,
respectively. The results of the correlations are shown in Figure
6, where the solid-liquid phase equilibrium diagram is presented together with a curve calculated by the NRTL equation.
Positive and negative deviations from ideality were found.
The values of activity coefficients in the saturated solution of
IL in 1-alcohols were very close to the one, 1 1 (see Table
1S of the Supporting Information). This is the evidence for a

Wilson
g12-g22
g21-g11
J mol-1

NRTL
u12
u21
J mol-1

-4449.83
10629.75
5093.35
3613.18

6073.23
1349.48
8594.17
7871.37
4257.08
7094.63
3814.96
8133.74

deviations
Wilson
Ta
K

NRTL
Ta
K

2.53

1.77b

6.76

3.10c
2.91c
2.44d

a According to eq 4 in the text. b Calculated with the third nonrandomness parameter, R ) 0.9. c Calculated with the third nonrandomness
parameter, R ) 0.6. d Calculated with the third nonrandomness
parameter, R ) 0.5.

strong IL-solvent interaction. In Table 2S of the Supporting

Information, the activity coefficients in the systems with
alkylbenzenes are listed. The deviations from ideality are much
higher, and the values of the activity coefficients, > 1 are
observed; the solubility is lower than the ideal.
Concluding Remarks
New experimental results for the solubility of quaternary
phosphonium salt-tetrabutylphosphonium methanesulfonate in
alcohols and in alkylbenzenes for temperatures from 220 to
386 K at ambient pressure are presented. Relatively high
solubility in alcohols (no immiscibility in the liquid phase),
which is a result of polar anion-solvent interaction, was
observed. The phenomenon of solid-solid-phase transitions for
B4PCH3SO3 has been observed at a temperature of 307 K.
Solid-solid-phase transition as a result of changing structure
of a solid phase at constant temperature and pressure is widely
used in energy storage. The (solid + liquid) phase diagrams
with alcohols, benzene, and toluene have shown simple eutectic
mixtures with complete miscibility in the liquid phase. The
results of the correlation were acceptable, with better results
with the UNIQUAC ASM model when taking into account the
association of alcohols. The solubility of the B4PCH3SO3 in
alcohols was close to the ideal. However, the specific shape of
the area of liquid-liquid equilibria in the (B4PCH3SO3 +
ethylbenzene, or propylbenzene) binary systems causes a
problem of possible joint correlation of solid-liquid equilibrium
and liquid-liquid equilibrium with the same parameters.
Generally, the trend observed in the solubility changes of a
phosphonium salt is the same as was observed for ammonium
salts. An increase in the alkyl chain length of an alcohol or of
an alkyl substituent at a benzene ring decreases the solubility
of IL.
Acknowledgment. L. M. Casas expresses thanks for the
financial support from the Programa FPU of Ministerio de
Educacion y Ciencia, Spain. Funding for this research was also
provided by the Polish Committee for Scientific Research (Grant
3 T09B 004 27).
Supporting Information Available: Supporting Information
available is phase equilibrium data and calculated activity

Solubility of Phosphonium Ionic Liquid

coefficients in Tables 1S, 2S, and 3S and association parameters
of solvents. This material is available free of charge via the
Internet at http://pubs.acs.org.

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Publication Date (Web): March 29, 2007 | doi: 10.1021/jp070293j

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