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The volume characteristics of solution of naphthalene in heptane-ethanol

mixtures at 298.15 K

Article  in  Russian Journal of Physical Chemistry · August 2008

DOI: 10.1134/S0036024408080037

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ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2008, Vol. 82, No. 8, pp. 1258–1261. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.A. Dyshin, O.V. Eliseeva, M.G. Kiselev, G.A. Al’per, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 8, pp. 1419–1422.

PHYSICAL CHEMISTRY
OF SOLUTIONS

The Volume Characteristics of Solution of Naphthalene

in Heptane–Ethanol Mixtures at 298.15 K
A. A. Dyshin, O. V. Eliseeva, M. G. Kiselev, and G. A. Al’per
Institute of the Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
e-mail: eov@isc-ras.ru
Received April 12, 2007

Abstract—The solubility of naphthalene was studied by the isothermal saturation method, and the density of
naphthalene–heptane–ethanol solutions at 298.15 K was measured using an oscillating tube densimeter. The
results were used to calculate the volume characteristics of naphthalene in the systems specified. The solubility
of naphthalene in heptane was substantially higher than in ethanol. The composition dependences of apparent
partial molar volumes contained extrema. The reason for such nonlinear dependences can be a sharp change in
the contribution to the entropy of mixing related to the packing of molecules of different diameters (naphthalene
and heptane). Another possible mechanism of these anomalies can be related to the stabilization of the structure
of alkanols in the solvation sheath of alkanes noticed earlier.
DOI: 10.1134/S0036024408080037

INTRODUCTION
Knowledge of the thermodynamic functions of mix-
tures containing polycyclic aromatic hydrocarbons
(PAHs) and alkanes is of importance because these
mixtures are used in petroleum industry. Most of the
PAHs are accompanying components of fuels and, on
the other hand, carcinogenic compounds. For this rea-
son, studies of their extraction conditions are of current
interest.
Studies of mixtures of PAHs with alkanes [1, 2]
showed that deviations from ideality are not large for
these systems. For this reason, the influence of a cosol-
vent can be determining in extraction processes.
One of the most suitable cosolvents is n-alcohols.
The thermodynamic properties of mixtures of
n-alkanols with alkanes [3–18] are characterized by
substantial deviations from ideality, that is, large excess
thermodynamic values, especially excess heat capacity.
This phenomenon is explained on the assumption of the
partial dissociation of H-bonds between alcohol mole-
cules. On the other hand, complex studies of some
n-alkanol–alkane systems showed the presence of some
stabilization of the structure of alcohols in the solvation
sheaths of alkane molecules [19]. It was, in particular,
found that the number of hydrogen bonds increased in
the second solvation shell of alkanes in methanol–hep-
tane, ethanol–heptane, and ethanol–octane mixtures.
These systems were characterized by nonlinear concen-
tration dependences of their volume characteristics
[19]. In this work, we studied the volume characteris-
tics and solubility of naphthalene, which, among PAHs,
has the simplest molecular structure, in binary ethanol–
heptane mixtures.
EXPERIMENTAL
Solubility was studied by the isothermal saturation
method at 298.15 K. The temperature was maintained
accurately to within ±0.01 K. Equilibrium was estab-
lished in two days.
Density measurements were performed with the use
of an oscillating tube densimeter designed by Korolev
[20]. The advantage of this instrument was the possibil-
ity to work with small solution volumes. Measurement
errors were of ±2 × 10–6 g/cm3.
We used heptane of kh. ch. (chemically pure) grade
for chromatography without additional purification.
Ethanol was dried as recommended in [21]. Residual
water was determined by amperometric titration
according to Fischer; its concentration was 0.002%.
Naphthalene was purchased from Riedel-de Hafin and
used without additional purification. Working solutions
were prepared gravimetrically using a VLR-200 bal-
ance with an accuracy of ±0.00005 g.
RESULTS AND DISCUSSION
The experimental data on the solubility of naphtha-
lene (Table 1) clearly show that the solubility in hep-
tane is substantially larger compared with ethanol. This
result closely agrees with the experimental data
obtained by Ruelle et al. [22]. The theoretical approach
suggested by Huyskens, which is based on the concept
of labile structures [23], gives close agreement with the
data obtained in the approximation taking into account
nonspecific cohesion forces and H-bonds [24]. The
lower solubility in ethanol is then related to the contri-
bution of the entropy of mixing. Interestingly, even
small admixtures of heptane to the alcohol increase the

1258
 THE VOLUME CHARACTERISTICS OF SOLUTION OF NAPHTHALENE 1259

Table 1. Solubility of naphthalene in ethanol–heptane mix- The experimental density data (Table 2) were used
tures at 298.15 K to calculate the partial and apparent molar volumes of
naphthalene. The error in apparent molar volumes was
x, mole fractions m, mol/kg
less than 0.01 cm3/mol. The calculations were per-
0 0.90690 formed by the equations
0.0200 0.92210
10 ( ρ 0 – ρ ) M 2
3
0.0404 0.94325
VΦ = --------------------------- + ------- ,
0.0600 1.15012 mρρ 0 ρ
1.0000 1.30125
M ( 10 + mM 2 ) ∂ρ
3
Note: x is the concentration of heptane, and m is the solubility of
naphthalene. V 2 = -------2 – ------------------------------
- -------,
ρ ρ
2 ∂m

solubility of naphthalene. A probable explanation of this where ρ is the density of the solution, g/cm3; ρ0 is the
effect in terms of the Huyskens theory can be a negative density of the pure solvent, g/cm3; M2 is the molecular
contribution of the entropy of mixing related to a relative weight of the solute, g/mol; m is the molal concentra-
increase in cavity volumes in solution (Table 1). tion of the solution, mol/kg; VΦ is the apparent molar

Table 2. Densities of ethanol–heptane–naphthalene mixtures at 298.15 K

m ρ m ρ m ρ
x=0 x = 0.0200 x = 0.0600
0 0.785043 0.48940 0.791960 0.92108 0.792564
0.01686 0.785480 0.71891 0.797431 0.95823 0.793415
0.05098 0.786263 0.89186 0.801454 0.96222 0.793579
0.06693 0.786658 x = 0.0404 0.98614 0.794159
0.09189 0.787332 0 0.774012 1.02280 0.794965
0.11145 0.787888 0.04740 0.775243 1.15012 0.798109
0.13200 0.788495 0.08571 0.776400 x = 1.0000
0.15100 0.788900 0.16416 0.778676 0 0.679473
0.17248 0.789492 0.23881 0.780605 0.01368 0.679853
0.19252 0.790311 0.29991 0.782183 0.02169 0.680076
0.21259 0.790869 0.40480 0.784829 0.03395 0.680601
0.22748 0.791189 0.49888 0.787106 0.04450 0.681060
0.33929 0.794182 0.69101 0.791766 0.05267 0.681081
0.39374 0.795119 0.86486 0.796014 0.05932 0.681214
0.56178 0.799320 0.92068 0.797345 0.07122 0.681503
0.72211 0.803105 0.94325 0.797923 0.08047 0.681953
0.83721 0.805738 x = 0.0600 0.09647 0.682368
0.90690 0.807259 0 0.768787 0.20391 0.685905
x = 0.0200 0.04709 0.770233 0.32102 0.689039
0 0.779033 0.10096 0.771714 0.45299 0.692945
0.02648 0.780023 0.20071 0.774419 0.59767 0.696962
0.05571 0.780974 0.30035 0.777031 0.74601 0.701045
0.09897 0.782205 0.50011 0.782244 0.93374 0.706083
0.15299 0.783509 0.69621 0.787098 1.09892 0.710181
0.30261 0.787222 0.81362 0.789926 1.30125 0.715457
Note: x is the mole fraction of heptane; m is the molality of naphthalene, mol/kg; and ρ is the density of solutions, g/cm3.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 82 No. 8 2008

1260 DYSHIN et al.

VΦ, Òm3/mol V2, Òm3/mol

123 123

122 122

121 121

120 120
1
119 2
3 119
118 4
5 118
117 117
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
m, mol/kg 116
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
m, mol/kg
Fig. 1. Apparent molar volumes of naphthalene in the etha-
nol–heptane–naphthalene system at 298.15 K, x = (1) 0.00,
(2) 0.0200, (3) 0.0404, (4) 0.0600, and (5) 1.0000 mole frac- Fig. 2. Partial molar volumes of naphthalene in the ethanol–
tions; x is the concentration of heptane, and m is the molal- heptane–naphthalene system at 298.15 K; see Fig. 1 for
ity of naphthalene. notation.

volume, cm3/mol; and V2 is the partial molar volume, entropy of mixing [24]. Another possible mechanism of
cm3/mol. these anomalies can be related to the stabilization of
The dependence of the density of solutions on the alkanol structures in the solvation sheaths of alkanes
concentration of naphthalene is linear at all mixed noticed earlier [19]. For a solution of heptane in etha-
solvent compositions. It is described by the equation nol, the concentration of maximum stabilization of the
structure of the alcohol in the solvation sheath is 0.02–
ρ = a + bm, (1) 0.04 alkane mole fractions.
where ρ is the density of the solution, g/cm ; m is the
3
The nonlinear concentration dependences of vol-
molal concentration of the solution, mol/kg; and the a ume properties are much more pronounced for the par-
and b coefficients are listed in Table 3. Quite a different tial molar volumes, which increase as the concentration
picture is observed for the concentration dependence of of naphthalene grows at 0.04 and 0.02 heptane mole
volume characteristics. fractions (Fig. 2). The extrema of the dependences of
The solute concentration dependences of the appar- partial molar volumes flatten as the concentration of
ent molar volume pass a low maximum for both pure heptane increases.
and mixed solvents (Fig. 1). Interestingly, small admix- The possible reason for the nonlinear dependence
tures of heptane (0.02 or 0.04 mole fractions) substan- observed was studied by Satou et al. [25]. These
tially change the apparent molar volumes compared authors showed that the molar volumes of PAHs were
with solutions in pure ethanol; namely, at low naphtha- substantially smaller than those of alkanes at equal
lene concentrations, VΦ is smaller than in pure solvents. numbers of carbon atoms in the component molecules.
Such nonlinear dependences can be caused by a sharp This effect is related to a high conformational mobility
change in the contribution of packing of molecules of of alkanes, which, on the other hand, presupposes a
different geometries (naphthalene and heptane) to the substantial increase in the volume of voids created by
alkane molecule compared with PAHs. This can, in
Table 3. Coefficients of Eq. (1) turn, result in the partial overlapping of volumes occu-
pied by these molecules when they are mixed and, as a
x, mole fractions a b consequence, a sharp decrease in the partial molar vol-
ume of naphthalene.
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