ISSN 0018-151X, High Temperature, 2016, Vol. 54, No. 2, pp. 210–214. © Pleiades Publishing, Ltd., 2016.

Original Russian Text © S.M. Rasulov, S.M. Orakova, I.A. Isaev, 2016, published in Teplofizika Vysokikh Temperatur, 2016, Vol. 54, No. 2, pp. 223–227.

THERMOPHYSICAL PROPERTIES
OF MATERIALS

Thermal Properties and Phase Diagrams

of Water–Hydrocarbon Systems*
S. M. Rasulova, S. M. Orakovaa,b, and I. A. Isaeva
aAmirkhanov Institute of Physics, Dagestan Scientific Center, Russian Academy of Sciences,
Makhachkala, 367003 Russia
b
Dzhambulatov Dagestan State Agricultural University, Makhachkala, 367032 Russia
e-mail: orakova.s@mail.ru
Received January 20, 2015

Abstract—The phase equilibria of immiscible binary systems (water–n-hexane, water–n-pentane) are inves-
tigated using a constant-volume piezometer. The measurements were performed under normal conditions,
based on P,V,T,x-data obtained in the temperature range of 300–680 K, pressures up to 60 MPa, and in a wide
range of densities. Based on the experimental data, we constructed phase diagrams in the P–T and T–x coor-
dinates and determined the Krichevskii parameters for the system of water–n-hexane near the critical point
of the pure solvent.

DOI: 10.1134/S0018151X16020164

INTRODUCTION In this paper, we report the results of studying

The interest in binary layering mixtures of n-alkanes
containing a polar component (water) is due to not only
practical applications (development and optimization
of processes for oil and petrochemical industry, power
engineering, and chemical technology) but also research
purposes (analysis of the phase behavior of systems that
are immiscible under normal conditions) [1–6]. Phase
diagrams of these mixtures have complex character and
various forms, which also stimulates intense investiga-
tions of thermophysical properties of such systems.
The thermodynamic behavior of dilute mixtures is
crucial for understanding the molecular interactions
of the solute and solvent. All thermodynamic proper-
ties of dilute mixtures in the vicinity of the critical
point of the pure solvent can be found by the
Krichevskii parameter [7], which is determined as the
( )
∞
derivative ∂ P calculated at the critical point of the
∂ x TcVc
pure solvent (for example, n-hexane or water). The
Krichevskii parameter also determines the shape of
the condensation and boiling curves. In the limit of
infinite dilution, many partial molar properties of the
solute (such as volume V 2∞ , enthalpy H 2∞ , and isobaric
∞
heat capacity Cp 2 ), which are related to the
Krichevskii parameter, have a strong discrepancy at
the critical point of the pure solvent.
* Based on the Proceedings of the XIV Russian Conference on the
Thermophysical Properties of Substances (RCTP-14), Kazan,
October 2014.
phase equilibria of binary systems that are immiscible
under normal conditions (water–n-hexane, water–
n-pentane) based on measuring P, V, T, x data and
determining the Krichevskii parameter near the criti-
cal point of pure n-hexane and pure water. The ther-
mal properties were found at the following water con-
centrations (in molar fractions): 0.166, 0.201, 0.234,
0.257, 0.347, 0.615, 0.827, 0.918, 0.935, and 0.964 for
the water–n-hexane system; 0.110, 0.143, 0.174, 0.203,
0.209, 0.214, 0.572, 0.800, 0.862, 0.881, 0.903, 0.925,
0.942, 0.973, and 0.987 for water–n-pentane system;
and in the temperature range of 300–680 K, at pres-
sures up to 60 MPa, and in a wide range of densities.
The measurements were carried out using a constant-
volume piezometer [5, 8].
To test the setup and estimate the measurement
accuracy, the ρ–T data for triple distilled pure water
over one of the isochores were measured, and the
results were compared with the values obtained from
the IAPWS formulation [9]. The experimental and
calculated values are in quite good agreement: the
maximum deviation is 0.3% and the absolute average
deviation is 0.16%. This consistency confirms the reli-
ability and high accuracy of data measured by the
described setup.
For each concentration, the measurement were
performed over 10–11 isochores covering a wide
region of the vapor and liquid states (Fig. 1). Most
measured isochores exhibit two inflection or kink
points (Fig. 2).

210
 THERMAL PROPERTIES AND PHASE DIAGRAMS 211

P, MPa P, MPa
70 12
169.9 kg/m3
254.9
60
339.9 10
50 424.8
509.8 3 4
40 594.7 8
679.7
30 764.7
6
20
10 4
1
0
2 2
320 350 400 450 500 550 600 650 700
T, K 0
330 350 370 390 410 430 450 470
T, K
Fig. 1. Isochores of the water–n-hexane system for 0.935 mol
fractions of water.
Fig. 3. Phase P–T diagram of a binary mixture of water–
n-hexane for the concentration of 0.257 mol fractions of
RESULTS AND DISCUSSION water along two liquid isochores: (1) three-phase line
(l–l–g) [9], (2) saturation vapor pressure of pure n-hexane
[10], and (3) 607.5 and (4) 540.0 kg/m3.
The inflection points in the P–T and T–x diagrams
correspond to the phase transitions occurring in these
binary mixtures (Figs. 3–5). The first phase transition their critical parameters approach each other with
(at lower temperatures) corresponds to the dissolution increasing water concentration in the mixture. At a
of hydrocarbon in water [(l1–g) g] or the three-phase concentration of 0.257 mol fractions of water for the
layering (g–l1–l2) into a two-phase equilibrium [l1/g–l2], system water–n-hexane and 0.209 mol fractions for
and the second is the phase transition of liquid–gas of the system water–n-pentane, the lines of phase equi-
the solution (l2 is an aqueous solution of hydrocarbon) libria l–l and l–g have a point of contact and their crit-
into vapor [(l2–l1) → g] or a two-phase equilibrium ical parameters are the same (Fig. 5).
(g–l2 or g1–g2) with the transition into the homoge- This point is called the upper critical end point
neous supercritical fluid (fl) [(l2–g) or (g1–g2) → fl]. (UCEP); it is a point of the azeotrope with all three
Connecting the breakpoints, we obtain the phase phases coexisting in it: hydrocarbon liquid, aqueous
equilibrium lines separating the three-phase area from liquid, and gas. The parameters of this point for the
the two-phase and the two-phase area from the single- water–n-pentane system are Tc = 463.8 K and Pc =
phase. The lines of phase transitions l—l and l–g and 4.57 MPa, and for the water–n-hexane system, they
are Tc = 495.3 K and Pc = 5.28 MPa, which are in good
agreement with published data [1–4]. Above the con-
P, MPa P, MPa centration corresponding to the UCEP along the iso-
1.4 20 chore, first, the transition of hydrocarbon liquid into
18 vapor occurs, and then aqueous fluid transits into
1.2 16 vapor. The critical transition temperatures and pres-
1 2
14
sures of the hydrocarbon liquid into vapor are the
1.0 same as for the UCEP, up to high concentrations of
12 water in the mixture; however, the critical densities
0.8 10 differ. Above the concentration corresponding to the
8 UCEP, the dependence of P(T) is smooth and mono-
0.6 6 tonic without any features. For these concentrations in
4 the phase diagrams, the critical conditions are not
0.4 2 realized. The critical points appear again for concen-
380 400 420 440 480 540 600 660 trations above 0.882 mol fractions. The local tempera-
T, K ture maximum and minimum are manifested in the
isopleths. With increasing concentration, the differ-
ence between the extremes increases (Fig. 6). In the
Fig. 2. Regions of (1) the first and (2) the second phase
transitions along the isochore of ρ = 89 kg/m3 of the area of high pressure, all isopleths show a steep rise. A
water–n-hexane system at a concentration of 0.964 mol temperature minimum is detected in the upper locus
fractions of H2O. of critical points, corresponding to concentrations of

HIGH TEMPERATURE Vol. 54 No. 2 2016

212 RASULOV et al.

P, MPa T, K
Тc (H2O)
50 650
g1–g2 4
2 1 g–l2
40 Two phases Single phase 600 DCP

30 550
Тc (H2O)
20 500 Тc (C5H12)
l –g l21–g
UCEP 2
10 UCEP (C6H14) 2
UCEP (C5H12) 450 g–l1–l2 3 5
l12–g 1
0
400 450 500 550 600 650 700 0 0.2 0.4 0.6 0.8 1.0
T, K x, mole fraction of H2O

Fig. 4. Critical diagram of water–n-hexane and water– Fig. 5. Critical diagram of the water–n-pentane system:
n-pentane: (1) and (2) the upper regions of the critical line (1, 3, and 5) three-phase equilibrium lines and (2) the
for pentane and hexane, respectively. lower and (4) the upper regions of the critical line.

0.935 and 0.925 mol fractions of water. The point cor- ical point of pure hydrocarbon Tc(C5H12) and ends at
responding to the minimum temperature divides the the upper critical point of separation (UCEP) at 463.8 L
two-phase region into two parts. The right side of the and 4.5 MPa. The heterogeneity of equilibrium in the
critical line corresponds to equilibrium g = l2; it UCEP (g = l1–l2), in the absence of reliable data on
approaches the critical point of water with increasing the density and composition of coexisting phases, sug-
temperature. The left side corresponds to equilibrium gests the use of only average values of the density of the
g1–g2 of the second type and continues above the crit- mixture and solutions (485 kg/m3) for the plotting of
ical temperature of water further into the region of this equilibrium on the phase diagram.
high pressures and temperatures. The point where the
curves g1–g2 and g = l2 are closed is called the double The upper critical curve (l2 = g and g1 = g2, curve 4)
critical point (DCP). In the P–T diagram, the phase begins at the critical point of water Tc(H2O) and, pass-
equilibrium region of g1–g2 is limited by the curve ing through the minimum temperature, tends to the
going from the DCP to higher T and P and the iso- region of higher temperatures and pressures. A region
therm coming from the DCP to higher pressures. With of absence of critical points is located between these
an increasing number of carbon atoms in the hydro- critical curves; in this region, there is either a homoge-
carbon, the critical curve is shifted to lower pressures neous solution or a two-phase equilibrium (two equi-
and to higher concentrations of water. The following
parameters were obtained for the DCP of water–
n-pentane and water–n-hexane systems: Tc = 625.5 K P, MPa
and Pc = 33.7 MPa and Tc = 627.7 K and Pc = 30.9 MPa, 70 5
2
respectively. 4
The phase diagram of the binary system of water– 60 1
n-pentane in T–x coordinates is presented in Fig. 5, 8 6
50
built based on our experimental data and the data of
[2, 3]. There, l12 is the liquid solution of water in 40
hydrocarbon, and l21 is the liquid solution of hydrocar- 30
bon in water. According to the classification of the
phase diagrams by Scott and van Konynenburg [10], 20
the studied system refers to type III, and it is charac- 10 7 9 10
terized by the absence of a continuous critical curve 3
connecting the critical points of the pure components. 0
The phase diagram of type III is divided into three 400 450 500 550 600 650
temperature areas: the region of the lower branch of T, K
the critical points (l1 = g), the region where the critical
points are absent (g1 = g2), and the region of the upper Fig. 6. Phase equilibrium lines of aqueous liquid–gas of the
water–n-pentane systems: (1) 0.214, (2) 0.572, (3) 0.800,
branch of the critical points (g = l2). The lower branch (4) 0.862, (5) 0.881, (6) 0.903, (7) 0.925, (8) 0.942, (9) 0.973,
of the critical points (l1 = g, curve 2) begins at the crit- and (10) 0.987 mol fractions.

HIGH TEMPERATURE Vol. 54 No. 2 2016

 THERMAL PROPERTIES AND PHASE DIAGRAMS 213

P, MPa P, MPa of the solvent and solute. In general, the thermody-

7 namic behavior of diluted mixtures near the critical
39 point of the solvent can be described completely by the
Krichevskii parameter.
35 6 The Krichevskii parameter can be determined from
the initial slopes (at x = 0), (dTc dx ) and (dPc dx ) of
31 5 the critical lines Tc(x) and Pc(x) of the critical value of
1 the mixture and the slope of the saturated vapor pres-
2 4 sure curve ( dPS dT ) CXC of the pure solvent at their
27 C

critical points. Krichevskii obtained the relationship

23 3 Тc (C6H14) between the slopes of the critical lines and derivative
Тc (H2O)
(∂P ∂x )T∞V , that is,
c c
19 2

( ) ( ) ( ) ( )
0 0.05 0.10 0.15 0.20 0 0.1 0.2 0.3 0.4 0.5 ∞ C C C
x, mole fraction of C6H14 x, mole fraction of H2O
∂P =
dPc
−
dPS dTc
,
∂ x VcTc dx CRL dT CXC dx CRL

Fig. 7. Pressure vs. concentration along the critical iso- or in an equivalent form

chore of pure components of (left) water and (right) n-hexane:
(1) our data and (2) data [12].
librium solution), and the transition from supercritical
vapor to a supercritical liquid-like solution (with
increasing pressure) occurs continuously without crit-
ical phenomena.
In the P–T diagram, the region of phase equilib-
rium gas–gas is limited by the critical curve of liquid
(l1) and vapor (g) (380–460 K), the homogenization
curve of high-temperature the two-phase equilibria in
the vicinity of the critical curve (l2 = g, g1 = g2, 570–
630 K), coming from Tc(H2O) (g1–g2), passing from the
DCP to higher temperatures and pressures, and the iso-
therm coming from the DCP to higher pressures.
Curve 1 (Fig. 5) corresponds to the composition of
the liquid organic phase l1, occurring in a three-phase
equilibrium of l1–l2–g. The composition of the second
liquid phase l2 is reflected by curve 5, drawn through
one data point in the region of a high water content.
The horizontal line corresponds to the invariant equi-
librium in the UCEP (l1 = g–l2) and connects the crit-
ical phase compositions (l1 = g) and the noncritical
liquid phase (l2).
The double critical point (according to [2, 11]) cor-
responds to a composition of 75.487 wt % of water with
the critical parameters of T(DCP) = 625.5 K and
P(DCP) = 33.7 MPa. This point divides the phase
diagram near the curve of the high-temperature criti-
cal system into two parts. The lower part (by pressure)
corresponds to the equilibrium of liquid–vapor, and
the upper part is for the equilibrium of gas–gas. These
values of temperature and pressure of the line of g–g
phase equilibrium and its critical parameters are in
good agreement with the data published [2, 3].
The thermodynamic behavior of a strongly dilute
solution is completely determined by the properties of
the solvent itself and the interaction of the molecules
( ) ( ) ( )
∂P
C ⎡⎛ dP ⎞ C dPS
C ⎤ dTc C
= ⎢⎜ c ⎟ − ⎥ ,
∂x V cTc ⎣⎢⎝ dTc ⎠ CRL dT CXC ⎦⎥ dx CRL
where subscripts CXC and CRL refer to the curves of
the saturated vapor pressure and the critical line,
respectively [7]. The modes of behavior of a near-crit-
ical dilute solution depend strongly on the signs and
magnitudes of the initial slopes of the critical curves
and on the slope of the saturated vapor pressure curve
at the critical point of the pure solvent, that is, on the
magnitude and sign of the Krichevskii parameter.
We calculate the Krichevskii parameter in the
vicinity of the pure solvent (n-hexane and water),
based on direct measurements of the P,V,T,x-data for
the water–n-hexane system using different methods
[12–15]. The value of the Krichevskii parameter near
the critical point of pure n-hexane is 10.5 ± 2 MPa
(n-hexane as a solvent), and for pure water, it is 161.51 ±
40 MPa (Fig. 7). The Krichevskii parameter obtained
from direct measurements is consistent with the values
of the initial slopes of the upper and lower critical lines
of 11.72 ± 2 MPa (n-hexane as a solvent) and 159.36 ±
40 MPa (water as a solvent).
CONCLUSIONS
Experimental P,V,T,x-data for the binary mixtures
of water–n-hexane and water–n-pentane were
obtained.
The phase diagrams in various coordinates were
plotted based on the experimental data, and the values
of the Krichevskii parameter for the water–n-hexane
system were calculated.
REFERENCES
1. Yiling, T., Berger, Th.M., and Franck, E.U., J. Chem.
Thermodyn., 1991, vol. 23, p. 105.
2. Brunner, E., J. Chem. Thermodyn., 1990, vol. 22,
p. 335.

HIGH TEMPERATURE Vol. 54 No. 2 2016

214 RASULOV et al.
3. De Loos, Th.W., Penders, W.G., and Lichtenthaler, R.N.,
J. Chem. Thermodyn., 1983, vol. 10, p. 279.
4. Kamilov, I.K., Stepanov, G.V., Malysheva, L.V., Rasu-
lov, A.R., Rasulov, S.M., and Shakhbanov, K.A., High
Temp.—High Pres., 1997, vol. 29, p. 491.
5. Rasulov, S.M. and Orakova, S.M., High Temp., 2013,
vol. 51, no. 1, p. 60.
6. Rasulov, S.M. and Isaev, I.A., High Temp., 2006,
vol. 44, no. 1, p. 847.
7. Krichevskii, I.R., Zh. Fiz. Khim., 1967, vol. 41, p. 1332.
8. Rasulov, S.M. and Khamidov, M.M., Prib. Tekh. Eksp.,
1999, no. 1, p. 148.
9. Wagner, W. and Pruss, A., J. Phys. Chem. Ref. Data,
2002, vol. 31, p. 387.
10. Van Konynenburg, P.H. and Scott, R.L., Philos. Trans. R.
Soc. London, 1980, vol. 298, no. A1442, p. 495.
11. Rasulov, S.M. and Rasulov, A.R., Russ. J. Phys. Chem. A,
2009, vol. 83, no. 5, p. 756.
12. Abdulagatov, I.M., Bazaev, A.R., Magee, J.W.,
Kiselev, S.B., and Ely, J.F., Ind. Eng. Chem. Res., 2005,
vol. 44, p. 1967.
13. Orakova, S.M., Rasulov, S.M., and Abdulagatov, I.M.,
J. Mol. Liq., 2013, vol. 187, p. 7.
14. Orakova, S.M., Rasulov, S.M., and Abdulagatov, I.M.,
J. Phys. Chem. Liq., 2014, vol. 52, no. 1, p. 130.
15. Rasulov, S.M., Orakova, S.M., and Abdulagatov, I.M.,
Russ. J. Phys. Chem. A, 2015, vol. 89, no. 1, p. 61.
Translated by O. Zhukova
HIGH TEMPERATURE Vol. 54 No. 2 2016