Fluid Phase Equilibria 243 (2006) 166170

Osmotic and activity coefficients of dilute aqueous solutions

of symmetrical and unsymmetrical quaternary
ammonium bromides at 293.15 K
Amado G. Eliseo a, , Luis H. Blanco b,1
a

IBEAR, Universidad de Pamplona, Pamplona, Colombia

LIB, Universidad Nacional de Colombia, A.A. 078 Bogota, Colombia

Received 22 July 2005; received in revised form 24 February 2006; accepted 6 March 2006

Abstract
The osmotic coefficients of Bu4 NBr, sec-Bu4 NBr, iso-Bu4 NBr, Bu2 Et2 NBr and Bu3 EtNBr have been measured by isopiestic method at 293.15 K
in dilute aqueous solutions. A branched isopiestic cell was used. The osmotic coefficients of tetraalkylammonium solutions were analyzed comparing
these with the DebyeHuckel limiting law. The order of the osmotic coefficient variation is used for qualitative deduction of the solutesolvent
interactions occurring in these solutions. The osmotic coefficients have been correlated using the ion interaction model of Pitzer. The results show
that the Pitzer model successfully correlate the osmotic coefficients.
2006 Elsevier B.V. All rights reserved.
Keywords: Activity coefficient; Osmotic coefficient; Unsymmetrical quaternary ammonium bromides; Pitzer model; TAABr

1. Introduction
Thermodynamic aspects of the hydration and mutual interaction in water of electrolytic systems have been a challenge during
the last 50 years [17]. The tetraalkylammonium salts (TAAX)
(X = Cl, F, Br and I) with alkyl chains R ranging from methyl
to n-butyl (or in a few cases to n-pentyl) under environmental conditions haves been a model compounds for the study of
hydrophobic interactions [8,9]. The effects due to the interaction
of the apolar groups with the water are known as hydrophobic
hydration and it could be the cause of the low solubility as well
as of their large positive heat capacity changes upon solvation
found by Franks [10].
The evaluation of the effect of changing the length of the alkyl
chains (R1 R2 R3 R4 NX) as it was proposed by Lowe and Rendall
[11] over the activity coefficients and other related magnitudes,
such as osmotic coefficients, solvent activity, excess free energy

Corresponding author. Fax: +57 75685303.

E-mail addresses: eamado@unipamplona.edu.co (A.G. Eliseo),
lhblancoc@unal.edu.co (L.H. Blanco).
1 Tel.: +57 13150188.
0378-3812/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.03.001

of the solutions at lower temperatures may give insights about

changes in the structural features of liquid water phenomena.
Thermodynamic studies of TAAX salts in aqueous solution, including Bu4 NBr have been done in relation with semiclathrates crystal structure and it was found that the ammonium
ions with long alkyl chains have a strong tendency to enable the
surrounding water molecules to form clathrate-like structures
even in aqueous solution and with high water crystallization
[1217]. Different hydration numbers to the Bu4 NBr have been
described on the basis of the phase diagram analysis [1820].
The formation of clathrate polyhydrates seems evident from differential thermal analysis [2123]. Also it has been found that in
the region of relatively diluted solutions, polyhydrates may be
formed in which water molecules together with the anion buildup of the host framework [24]. Shimada et.al. [25] consider that
the growth mechanism of Bu4 NBr semi-clathrate hydrate crystals may be extremely affected by interfacial kinetics.
This study was carried out using the isopiestic technique
which is an accurate way to determine solvent activity using
an isopiestic chamber and good thermal contact with sample
containers, keeping the whole apparatus at a constant temperature. The vapour space is evacuated and the volatile component is transported through the vapour phase until the solutions

A.G. Eliseo, L.H. Blanco / Fluid Phase Equilibria 243 (2006) 166170

reach equilibrium. The quality of the attainment of isopiestic equilibrium depends on the equalization of temperature
between the solutions, so that chemical potentials of the solvent in each of the solutions within the isopiestic apparatus
must be identical. The order of the osmotic coefficient the systems at 298.15 K was Bu2 Et2 N+ > BuEt3 N+ > sec-Bu4 N+ > isoBu4 N+ > n-Bu4 N+ [26].
Data from osmotic and activity coefficients of the tetra-alkyl
bromides were determined by Lindenbaum et.al. [27] and then
the osmotic coefficients were determined as function of temperature to aqueous solutions of TAAX (X = Cl, F and I) [28].
The objective of this work is to test the ability of a conventional electrolyte model to describe activity coefficients
of quaternary ammonium salts at low concentration in water
and at temperatures below 298.15 K. In future work, we will
address lower temperatures and we anticipate that the salts would
not be fully dissociated. In the long term, we hope that this
approach will provide some insight of the effect of the geometric
structure on the solutesolvent interactions and ion association
phenomena.
2. Experimental procedure
2.1. Apparatus
The isopiestic apparatus employed in the present work and
the procedure is essentially similar to the one used previously
described by Amado and Blanco [29]. The twelve cups of the
apparatus were set as follows: two cups contained the standard
NaCl solutions, nine cups containing the solution of the salts
and the remaining cup was used as a water reservoir. Other processes were sometimes used. Fresh, doubly distilled deionized
water was used to prepare the solutions. The sample sizes were
used in the range 1.21.5 g. All the weighing were done around
room temperature at 20 2 C. The analytical balance Metler
AT261, used to weigh the sample cups and solution samples has
a precision of 1 105 g. Each isopiestic sample cup was closed
at the equilibrium temperature. All apparent sample masses were
converted to masses using buoyancy corrections. Both NaCl (aq)
isopiestic reference standard stock solutions were prepared by
mass from oven-dried analytical reagent grade NaCl (analytical)
and purified water. Molar masses used for molality calculations
or gravimetric analysis of solutions are 58.443 g mol1 for NaCl.

167

The average relative uncertainty in the observed water activity

was less than 0.005%. At 293.15 K an equilibration time between
8 and 20 days was required. No longer equilibrium times were
used to reach equilibrium at the lowest molalities. The molalities
are accurate to 0.002 m.
The air was slowly removed from the branched cell with a
vacuum pump until the pressure of 4.5 kPa. It was found that
with this procedure isopiestic equilibrium was achieved with
good consistency between the replicate samples. At low molalities the rate of approach to isopiestic equilibrium is controlled
mainly by mass transport through the vapor phase.
2.2. Results and discussions
2.2.1. Experimental results
Isopiestic equilibrium molalities of the investigated solutions
with reference standard aqueous solutions of NaCl as reported
in Table 1 enabled the calculation of the osmotic coefficient of
the investigated solutions, * from
r mr
= r
(1)
m
in which and m are, respectively, the total number of ions
produced by one mole of the salt and the molality of the
salt; r stands for isopiestic standard solution and strike indicates the TAABr solution. The osmotic coefficient of NaCl was
determined as a function of molality and temperature from the
extended BradleyPitzer correlation proposed by Archer [30].
2.2.2. Correlation of data
The modified equations for excess Gibbs energy from expressions for activity coefficient are derived The equations to the
activity coefficient and osmotic coefficient of an electrolyte of
the 1:1 charge type (the present case) in a solution containing
an indefinite number of cations, c, and anions, a, are given by:




Gex
4A I
=
ln(1 + 1.2 I)
(nw RT )
1.2

T
+
mc ma (2Bca + ZCca
)
(2)
c

ln(c ) = z2c F +

T
ma (2Bca + ZCca
)

(3)

Table 1
Isopiestic molalities of aqueous solutions of TAABr salts at 293.15 K
NaCl (m)

Bu4 NBr (m)

sec-Bu4 NBr (m)

iso-Bu4 NBr (m)

Bu2 Et2 NBr (m)

BuEt3 NBr (m)

0.1002
0.1936
0.2755
0.3606
0.4550
0.5841
0.7029
0.8062
0.9167
0.9805

0.1029
0.2029
0.2937
0.3908
0.5010
0.6556
0.8031
0.9326
1.0731
1.1550

0.1025
0.2021
0.2924
0.3889
0.4972
0.6492
0.7924
0.9187
1.0574
1.1369

0.1024
0.2019
0.2918
0.3862
0.4918
0.6406
0.7817
0.9046
1.0391
1.1181

0.1026
0.2012
0.2896
0.3816
0.4845
0.6255
0.7551
0.8687
0.9899
1.0601

0.1030
0.2018
0.2893
0.3826
0.4871
0.6316
0.7681
0.8880
1.0158
1.0900

Units: m (mol kg1 ).

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A.G. Eliseo, L.H. Blanco / Fluid Phase Equilibria 243 (2006) 166170

ln(a ) = z2X F +

T
mc (2Bca + ZCca
)

(4)

A is a solvent dependent parameter and can be computed using

the pure solvent properties via the equation:
A =

1.5
e2
1
2No d1
3
4o DkT

(5)

in which n is the number of data, and exp and cal stand for
experimental and calculated values.
3. Results and discussion



A I 3/2
2

1 = 
(1 + 1.2 I)
i mi

T
mc ma (Bca + ZCca
)
+

On Table 3 the standard deviations of Pitzers equation in the

osmotic coefficients, (), is defined as:


2
i (exp cal )i
(12)
() =
n

(6)

Where, F, the long-range electrostatic term, is given by:





2
I
+
F = A
ln(1 + 1.2 I)
1.2
1 + 1.2 I

(7)

From the present results, it can be concluded that the multiple

isopiestic cell used here is appropriate equipment for collecting
data of osmotic coefficients at 293.15 K of aqueous solutions of
TAABr.
Table 2 contains the osmotic and activity coefficients of aqueous solutions of TAABr salts at 293.15 K. From the osmotic
coefficients data shown in Fig. 1, it was noticed that larger deviations from the limiting law to small cations as Bu2 Et2 N+ was
found. The order of the osmotic coefficient variation at 293.15 K

In the above equations, I is the molality based on ionic strength;

the equations also contain the following functions:

Z=
mi |zi |
(8)
i

0
1
+ ca
g(ca I)
Bca = ca

(9)

where
g(x) =

2[1 (1 + x) exp(x)]
x2

(10)

g (x) = exp(x) g(x)

(11)

where d1 and D are density and dielectric constant of the pure

solvent. No , o and k are Avogadro number, permittivity of the
vacuum and Boltzmann constant, respectively. The value of A is
0.3915 (kg mol1 )1/2 . Details of the Pitzers equation are given
elsewhere, see reviews by Pitzer [31,32] or Clegg and Whitfield
[33]. Details of the model are not present here.

Fig. 1. Concentration dependence of the osmotic coefficients for aqueous solutions of TAABr salts at 293.15 K compared to limiting law and to data of aqueous
solutions of Bu4 NBr at 298.15 K from Lindenbaum and Boyd [28].

Table 2
Osmotic and activity coefficients of aqueous solutions of TAABr at 293.15 K
NaCl (m)

Bu4 ()a

NBr ( )b

sec-Bu4 ()

NBr ( )

iso-Bu4 ()

NBr ( )

Bu2 Et2 ()

NBr ( )

BuEt3 ()

NBr ( )

0.1002
0.1936
0.2755
0.3606
0.4550
0.5841
0.7029
0.8062
0.9167
0.9805

0.9078
0.8813
0.8636
0.8487
0.8356
0.8215
0.8094
0.8021
0.7957
0.7927

0.7336
0.6641
0.6229
0.5898
0.5602
0.5277
0.5029
0.4845
0.4672
0.4581

0.9114
0.8848
0.8675
0.8530
0.8420
0.8296
0.8203
0.8142
0.8076
0.8053

0.7367
0.6690
0.6291
0.5971
0.5690
0.5381
0.5149
0.4976
0.4811
0.4727

0.9123
0.8856
0.8693
0.8589
0.8512
0.8407
0.8316
0.8269
0.8218
0.8189

0.7371
0.6708
0.6321
0.6018
0.5754
0.5463
0.5245
0.5086
0.4937
0.4858

0.9106
0.8888
0.8759
0.8692
0.8641
0.8611
0.8609
0.8610
0.8626
0.8637

0.7378
0.6744
0.6391
0.6127
0.5906
0.5684
0.5532
0.5427
0.5338
0.5294

0.9070
0.8861
0.8769
0.8669
0.8594
0.8528
0.8463
0.8423
0.8406
0.8400

0.7398
0.6760
0.6398
0.6115
0.5870
0.5611
0.5422
0.5285
0.5162
0.5099

Units: m (mol kg1 ).

a : osmotic coefficient.
b Activity coefficients of the TTA (aq) were calculated from the parameters of the Pitzer equation.

A.G. Eliseo, L.H. Blanco / Fluid Phase Equilibria 243 (2006) 166170

169

negative second osmotic virial coefficients are found. But it is

not a clear effect of the increasing chain lengths on the second
virial term.
4. Conclusions
Experimental osmotic coefficient data were obtained for
the aqueous solutions of Bu4 NBr, sec-Bu4 NBr, iso-Bu4 NBr,
Bu2 Et2 NBr and Bu3 EtNBr by isopiestic method at 293.15 K.
The order of osmotic coefficients has been interpreted qualitatively in terms of solutesolvent interactions. Experimental
osmotic coefficient data for the investigated systems are satisfactorily correlated by the ion interaction model of Pitzer with
good precision.
Fig. 2. Concentration dependence of the activity coefficients for aqueous solutions of TAABr salts at 293.15 K.

Acknowledgements
To Dr. D. Archer, N.I.S.T., for his kind collaboration with his
computer programs. To Prof. Luis F. Hernandez for his critical
observations. To Colciencias for its financial support.
List of symbols
m
molality (mol kg1 )
M
molecular weight (g mol1 )
R
gas constant (J mol1 K1 )
T
absolute temperature (K)
Greek letters

activity

chemical potential (J mol1 )

stoichiometric coefficient

osmotic coefficient

Fig. 3. Differences (residuals) between experimental osmotic coefficients and

least-squares fit values cal of TAABr salts as a function of m at T = 293.15 K,
for fits with the molality region (01.00) mol kg1 using Eq. (6). The parameter
C(o) was set equal to zero since it was not significant.

is Bu2 Et2 N+ > BuEt3 N+ > sec-Bu4 N+ > iso-Bu4 N+ > n-Bu4 N+ ,
the same order was seen at 298.15 K (Fig. 2).
This order may be related with increasing hydrophobic
interactions.
The residual values of the data suggest an excellent fit of the
data to the Pitzer model with two parameters with a maximum
variation around 0.003 at lower concentrations. At concentrations of m > 0.3, the residual values are around 0.002 (see
Fig. 3). Table 3 contains the least-squares coefficient values and
their standard errors for fits of the parameters of Eq. (6) to molality data. In the case of Bu4 NBr, sec-Bu4 NBr and BuEt3 NBr
Table 3
Coefficients 0 and 1 of ion-interaction parameters obtained by fitting Eq. (6)
to experimental data of aqueous solutions of the TAABr salts at 293.15 K
Parameter

Bu4 NBr

0
1
()

0.0184 0.0970
0.0444 0.0281
0.001
0.001

(): standard error.

sec-Bu4 NBr

iso-Bu4 NBr

Bu2 Et2 NBr

BuEt3 NBr

0.0027
0.0243
0.001

0.0561
0.1266
0.001

0.0239
0.0461
0.001

Subscripts
o
standard state
r
reference
s
solute
w
water or solvent
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