Fluid Phase Equilibria 518 (2020) 112630

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Thermodynamic properties of a model hydrocarbon ternary mixture

in the vicinity of critical point: Measurements and modeling with
crossover equation of state
M.Yu. Belyakov a, *, V.D. Kulikov a, A.R. Muratov a, A.F. Sharipov a, b
a
Oil & Gas Research Institute of the Russian Academy of Sciences, Gubkina 3 St, Moscow, 119333, Russia
b
Gazprom VNIIGAZ LLC, Moscow Region, Razvilka, 142717, Russia

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

Article history: In the framework of the proposed theoretical model crossover and scaling equations of state for near-
Received 28 January 2020 critical multicomponent hydrocarbon mixture were obtained. To elaborate the equations of state the
Received in revised form experimental data measured on the serial setup intended for comprehensive pressure-volume-
23 April 2020
temperature (PVT) research of a natural gas-condensate systems were used. The information concern-
Accepted 29 April 2020
Available online 7 May 2020
ing the mixture composition was not involved. The obtained equations describe the experimental data
with the accuracy not exceeding the measurement inaccuracy. It has been shown that in extended range
of thermodynamic parameters the crossover equation of state looks more reliable. The crossover model
Keywords:
Multi-component mixture
describes the transition from the scaling behavior to the mean-field behavior, which is typical for cubic
Equation of state and multiparameter equations of state. The model was extended for calculation of the volume fractions
Critical point of gas and liquid phases needed for practical applications. In addition, the expression for isothermal
Crossover model compressibility has been derived. It was demonstrated that the isothermal compressibility has a cusp-
Dew-bubble curve like anomaly in the close vicinity of the critical point.
Isothermal compressibility © 2020 Elsevier B.V. All rights reserved.

1. Introduction composition, which often is defined rather poorly. Besides, in case

An equation of state (EOS) of fluids is widely employed in
modern computational simulators for modeling of various tech-
nological processes. Different modifications of a cubic equation of
state are commonly used for these purposes [1e3]. The simplicity of
cubic EOS and the possibility of calculation of various thermo-
physical properties play here the crucial role. At the same time, the
accuracy of such calculations as a rule does not exceed 2e5%. Note
also that the calculation of extensive quantities (density variables)
is usually significantly less accurate than the calculation of inten-
sive variables (fields). To obtain more accurate results one can use
multiparameter equations of state [4e7]. These equations enable to
provide the better description of various thermodynamic proper-
ties in a wide range of state parameters. In practice, cubic and
multiparameter EOS are convenient for most technological needs.
At the same time, these EOS have significant restrictions. To find the
parameters of the equation one has to know the mixture
* Corresponding author.
E-mail addresses: belyakov@ogri.ru, belyakov@ipng.ru (M.Yu. Belyakov).
of a multicomponent mixture the tuning of cubic or multiparam-
eter equations requires the determination of a large number of
binary interaction coefficients. Another significant disadvantage of
these equations consists in incorrect description of the critical point
vicinity [8].
The point is that the cubic and multiparameter equations of
state are mean-field equations. Strictly speaking, these equations
are not able to describe specific features of near-critical behavior of
fluids. If the quantitative description of critical point vicinity is
needed, the approaches based on the scaling theory have to be
used. Evidently, scaling models can not replace cubic and multi-
parameter equations, since they do not describe the complete
phase diagram of fluids. At the same time scaling theory being valid
in near-critical region allows to formulate scaling EOS of a fluid
system. In addition, there is a principal possibility to develop the
universal approach that incorporates scaling and mean-field EOS
[9e12].
Initially, the scaling EOS for mixtures was elaborated within the
scope of isomorphism conception [13e19]. An appreciable success
was achieved in the description of thermophysical properties of
near-critical fluid systems. However, the developed theoretical

https://doi.org/10.1016/j.fluid.2020.112630
0378-3812/© 2020 Elsevier B.V. All rights reserved.
2 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630
models prove to be rather complicated and actually they can be
applied only to binary mixtures. In recent decade an alternative
approach which did not use the isomorphism concept was pro-
posed and developed [20e23]. The theoretical EOS of a fluid
mixture with fixed composition has been obtained in the vicinity of
its critical point. It was demonstrated that the form of EOS does not
depend on mixture composition. The suggested EOS is written as
the power decompositions of thermodynamic parameters over the
characteristics of a scaling model. The coefficients of these expan-
sions depend on the composition of the studied mixture and are
non-universal parameters. For a given mixture the values of these
system-dependent parameters are determined by the fitting of the
EOS to the available experimental data. In particular, the parame-
ters of the EOS in the above mentioned articles were determined by
the processing of P
T (pressure-temperature) data measured on
various isochores.
In present work the experimental study was carried out on an
industrial PVT apparatus. As a result the data set for the pressure-
density (P
r) isotherms of methane - propane - n-pentane
mixture with the composition 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mole
fractions has been obtained. The main purpose of the given study
was the determination of the critical parameters of the artificial
mixture modeling natural gas-condensate based on the data ob-
tained on the serial setup. Note that the mixture with similar
composition was studied earlier by the adiabatic calorimetry method
[20]. It turned out that the difference of experimental results of the
earlier study and the recent study exceeds both the experimental
uncertainty and the inaccuracy of the theoretical description of given
dataset. The probable reason of the discrepancy is that compositions
of the studied samples were different. Due to this fact the set of
experimental data at isotherms was used to elaborate a new equa-
tion of state of the studied system. It is essential the actual compo-
sition of the studied sample was not employed in this procedure.
As a matter of fact in present work we obtained two equations of
state of the studied mixture, namely, crossover and scaling equa-
tions of state. This circumstance allowed us to compare the abilities
of different theoretical models both in close vicinity of the critical
point and in extended range of thermodynamic parameters.
Moreover, the theoretical models were completed by the calcula-
tion of volume fractions of coexisting liquid and gas phases in the
two-phase region of a mixture, which often is needed for practical
applications. The corresponding calculations will be presented
below. In addition, we carried out the calculations of the isothermal
compressibility in the vicinity of the mixture critical point.
2. Experiment description
The ternary hydrocarbon mixture composed of 0.5 mol fr. of
methane, 0.35 mol fr. of propane and 0.15 mol fr. of n-pentane has
been chosen as an object of the study. For this mixture the critical
point is located between the cricondenbar and cricondentherm on
PeT phase diagram. Experimental studies were fulfilled on a serial
PVT apparatus Ruska (model 2370). This setup is intended for
comprehensive PVT studies of natural gas-condensate systems for
the needs of oil and gas industry. The general scheme of this setup
and its measuring capabilities are described in Ref. [24]. The range
of the pressure measurements is 0e70 MPa and the available
temperature range is 293e470 K. The measuring unit includes two
thermo stabilized high-pressure cells. One cell with a volume of
400 ml has a piston with a mechanical drive and a viewing window
in the upper part to observe the processes of phase trans-
formations. The second cell with a volume of 600 ml is equipped
with a “floating” piston, having a hydraulic drive from an external
pump. The PVT measurements are controlled by a computer unit, so
that the measurements can be performed in both cells.
The studied mixture was recombined from pure components in
the cell with mechanical drive. Each component was loaded into
the cell at a single-phase condition. The reduction of the mixture to
a single-phase state was carried out at a constant temperature with
permanent stirring. The standard uncertainties u of measurements
are uðPÞ ¼ 0:0018 MPa for the pressure, uðTÞ ¼ 0:05 K for the
temperature, and uðVÞ ¼ 0:0003 cm3/g for the specific volume. The
mixture was prepared from pure chemicals supplied by the
“Monitoring” LLC (Saint-Petersburg, Russia). The purities of pure
compounds were: methane 0.999 vol fr., propane 0.998 vol fr., and
n-pentane 0.990 mass fr., respectively (see also Table 1 for details).
The compounds were used in the experiments without further
purification. The needed amount of each component was loaded
into the cell at fixed temperature with the use of NIST reference
data (see Ref. [25]). The component concentrations in the studied
mixture (including combined expanded uncertainties) are esti-
mated as 0.5 ± 0.0012 mol fr. of methane, 0.35 ± 0.0010 mol fr. of
propane and 0.15 ± 0.0018 mol fr. of n-pentane.
The permanent stirring by a magnetic stirrer has been used to
achieve the equilibrium state in the cell. The dependence of the
pressure on the cell volume at fixed temperature was measured.
Note that the mass of the mixture in the cell during the measure-
ments was constant. The current values of the pressure and the
volume of the system were controlled by the computer and were
recorded. The measurement process was started in the one-phase
region of the mixture. Before the measurement of certain
isotherm the mixture was stirred during 30 min to reach the
equilibrium in single state of the fluid at the pressure on 5e10 MPa
larger than the saturation pressure. After the stabilization of the
temperature, the measurements were performed at the stepwise
decrease of the pressure. The appearance of the second phase, as
well as its type (liquid or vapor) was determined visually. The
pressure value at which the formation of the second phase was
observed was taken as the saturation pressure.
The PVT data along ten isotherms were measured in the experi-
ment and the obtained data are presented in Table 2. The tempera-
ture range of measurements was 303.15e368.15 K while the
pressure range was 9.6e16 MPa. The results of the experiments are
shown in Fig. 1. The points of liquid-vapor phase transitions were
determined for each isotherm. In addition, the critical parameters of
the mixture were estimated by the interpolation of the experimental
information concerning the type of new phase (dew or bubble)
appearing at the pressure decrease. The estimates of the critical
pressure and temperature are the following: Pc ¼ 10:51±0:12 MPa
and Tc ¼ 355:8±2:8 K.
3. Theoretical model
The general method of derivation of the theoretical EOS for
near-critical fluids was described in detail in Ref. [23]. The EOS
presents the set of relations for thermodynamic quantities
expressed in terms of some scaling model. The scaling model is
characterized by the three field variables hk ðk ¼ 1; 2; 3Þ. The fields
h1 and h2 are considered as independent variables whereas the
field h3 is considered to be dependent on h1 and h2 and the
appropriate differential takes the form:
dh3 ¼ f1 dh1 þ f2 dh2 (1)
where fi ði ¼ 1; 2Þ are the scaling densities conjugated to h1 and h2 .
In the critical point vicinity the scaling fields hk are assumed to be
related to the pressure P, the temperature T, and chemical poten-
tials of the mixture components mj ðj ¼ 1…NÞ. It is convenient to
consider the pressure P as the thermodynamic potential of fluid
mixture. Since the composition of the mixture is supposed to be
 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630 3

Table 1
Description of pure chemicals.

Chemical Name Notation Source Initial Purity Purification Method Final Purity Analysis Method

methane C1 “Monitoring” LLC 0.999 vol fr. e 0.999 vol fr. e

propane C3 “Monitoring” LLC 0.998 vol fr. e 0.998 vol fr. e
n-pentane n-C5 “Monitoring” LLC 0.99 mass fr. e 0.99 mass fr. e

fixed, the critical parameters are constant and can be used to make
the thermodynamic values dimensionless. In this case the pressure
differential has the form
dDP ¼ s dt þ rx1 dDm1 þ rx2 dDm2 þ / þ rxN dDmN
To calculate thermodynamic properties in two-phase region one
needs to put h1 ¼ 0 in Eqs. (3)e(6). In this case we are able to
calculate specific curves with a fixed volume ratio of coexisting
phases (isopleths). In the two-phase region, the average density of
(2) the liquid mixture is written as

Here DP ¼ ðP
Pc Þ=rc RTc is the reduced pressure, R is the uni-

versal gas constant, rc and Tc are the critical molar density and
temperature of the mixture. Besides, s ¼ s=rc R is the dimensionless
entropy per unit volume, r ¼ r=rc is the reduced density, t ¼ T=Tc

1 is the reduced temperature, and Dmj ¼ ðmj
mjc Þ=RTc is the
reduced chemical potential of the j-th component. According to the
hypothesis of thermodynamic fields mixing [26,27], we suppose
that the scaling fields hk are analytical functions of the thermody-
namic variables Dmi , t, and DP, i.e. the mixing is written in the form
of so-called “complete scaling” [28e30]. In the vicinity of the crit-
ical point, the variables hk ðDP; t; Dmi Þ can be expanded in a Taylor
series. Using the relations (1) and (2), it is easy to find the ex-
pressions for thermodynamic densities s and rxj . The expansions of
fields hk and the expressions for densities form a system of Nþ 4
equations with respect to Dmi , t, DP, s, and r. The solution of the
system can be found as the expansions of thermodynamic quanti-
ties in powers of the characteristics of the scaling model [23]:
Dr ¼ r
1
¼ cr1 f1 þ cr2 f2 þ cr3 h2 þ cr4 h1 þ cr5 h3 þ cr6 f21 þ cr7 f1 f2
þ/
t ¼ ~ct1 Dr þ ~ct2 f2 þ ~ct3 h2 þ ~ct4 h1 þ ~ct5 h3 þ ~ct6 f22 þ /
DP ¼ ~cP1 Dr þ ~cP2 f2 þ ~cP3 h2 þ ~cP4 h1 þ ~cP5 h3 þ ~cP6 f22 þ /
Ds ¼ s
sc ¼ ~cs1 Dr þ ~cs2 f2 þ ~cs3 h2 þ ~cs4 h1 þ ~cs5 h3 þ ~cs6 f22 þ /
This system presents the theoretical EOS of a multicomponent
mixture. The coefficients ~czm in Eqs. (4)e((6) have the form
ð1Þ ð2Þ
~czm ¼ czm þ czm Dr þ czm Dr2 þ /
ðnÞ
where czm and czm in Eq. (7) are non-universal parameters. These
parameters depend on the concentrations of the components, but
the form of expressions (3)e(7) remains the same for any fluid
mixture with a fixed average composition.
r ¼ rL V L þ rG V G (8)
where rL;G and V L;G ¼ VL;G =V are the densities and the volume
fractions of the liquid and gas phases. Introducing the parameter u
as
u ¼ VL
VG (9)
and taking into account that V L þ V G ¼ 1, one can express the
volume fractions
1 1
V L ¼ ð1 þ uÞ; VG ¼ ð1
uÞ (10)
2 2
In addition, using the expression (3) in the two-phase region
ðh1 ¼ 0Þ; for the densities of coexisting phases we have


rL;G ¼ rc 1 ± cr1 jf1 j þ cr2 f2 þ cr3 h2 þ cr5 h3 þ cr6 f21 þ /
(11)
where the sign “þ” at f1 in the latter equation relates to liquid
phase while the sign “e” corresponds to gas phase. The substitution
(3) of expressions (10) and (11) in (8) yields


(4) r ¼ rc 1 þ u cr1 jf1 j þ cr2 f2 þ cr3 h2 þ cr5 h3 þ cr6 f21 þ /
(12)
(5) Expression (12), (4), and (5) allow us to calculate the isopleths
for different values of the parameter u. The parameter u varies
from
1 to 1, so that the curve at u ¼
1 corresponds to the gas
branch of the dew-bubble curve while u ¼ 1 corresponds to the
(6)
liquid branch. In this paper, we do not study the behavior of iso-
pleths. Such analysis has been carried out in Ref. [31], both for the
case of complete scaling and for traditional scaling when the fields
h1 and h2 depends only on t and Dmi .
(7) An important characteristic for a number of applications is the
coefficient of isothermal compressibility bT ¼ r
1 ðvr=vPÞT;x. The
expression for this value in the vicinity of the critical point of a
multicomponent fluid mixture can be obtained directly from the
expressions (3)e(5):


  ct2 c~ 2ð1;2Þ þ ct3 þ /
1 vDr 1
bTð1;2Þ ¼ ¼
 (13)
rRTc vDP T;x rRTc ðct2 cP1
ct1 cP2 Þc~ ð1;2Þ þ ðct3 cP1
ct1 cP3 Þ þ /
2
4 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630

Table 2
a,b
Near-critical isotherms T for 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture: the pressure P and the specific volume V values .
3 3
T/K P/MPa V/cm /g T/K P/MPa V/cm /g T/K P/MPa V/cm3/g

303.15 16 2.309 322.65 16 2.551 343.75 16 2.894

303.15 15.3 2.328 322.65 15 2.599 343.75 15 2.971
303.15 15 2.336 322.65 14 2.653 343.75 14 3.067
303.15 14 2.366 322.65 13 2.716 343.75 13 3.189
303.15 13 2.399 322.65 12.5 2.756 343.75 12.5 3.265
303.15 12 2.438 322.65 12 2.8 343.75 12 3.355
303.15 11.5 2.46 322.65 11.5 2.852 343.75 11.8 3.396
303.15 11.2 2.477 322.65 11.3 2.878 343.75 11.6 3.441
303.15 11 2.488 322.65 11.15 2.899 343.75 11.5 3.464
303.15 10.9 2.493 322.65 11.07* 2.911* 343.75 11.4 3.488
303.15 10.8 2.498 322.65 11 2.923 343.75 11.3 3.516
303.15 10.7 2.504 322.65 10.9 2.964 343.75 11.2 3.544
303.15 10.6 2.51 322.65 10.8 3.007 343.75 11.1 3.574
303.15 10.52* 2.515* 322.65 10.7 3.05 343.75 11 3.607
303.15 10.5 2.516 322.65 10.6 3.092 343.75 10.95* 3.620*
303.15 10.45 2.523 322.65 10.5 3.132 343.75 10.9 3.644
303.15 10.4 2.544 322.65 10.4 3.179 343.75 10.85 3.656
303.15 10.38 2.552 343.75 10.8 3.694
303.15 10.35 2.563 333.15 16 2.717 343.75 10.75 3.718
303.15 10.2 2.621 333.15 15 2.774 343.75 10.7 3.744
303.15 10.1 2.661 333.15 14 2.844
303.15 9.9 2.744 333.15 13 2.936 348.65 16 2.987
333.15 12.5 2.989 348.65 15 3.074
313.15 16 2.427 333.15 12 3.048 348.65 14 3.178
313.15 15 2.461 333.15 11.8 3.074 348.65 13 3.315
313.15 14 2.5 333.15 11.6 3.111 348.65 12 3.483
313.15 13 2.546 333.15 11.4 3.145 348.65 11.2 3.695
313.15 12 2.601 333.15 11.3 3.164 348.65 11.1 3.725
313.15 11 2.675 333.15 11.2 3.185 348.65 11 3.757
313.15 10.9 2.689 333.15 11.11* 3.198* 348.65 10.95 3.774
313.15 10.88* 2.692* 333.15 11.1 3.199 348.65 10.9 3.791
313.15 10.8 2.702 333.15 11 3.245 348.65 10.85 3.808
313.15 10.7 2.74 333.15 10.9 3.288 348.65 10.82* 3.817*
313.15 10.6 2.782 333.15 10.8 3.335 348.65 10.8 3.829
313.15 10.5 2.819 333.15 10.7 3.382 348.65 10.78 3.836
313.15 10.4 2.867 348.65 10.75 3.846

T/K P/MPa V/cm3/g T/K P/MPa V/cm3/g T/K P/MPa V/cm3/g

348.65 10.71 3.87 358.65 11.1 4.102 363.65 10.4 4.633

348.65 10.69 3.882 358.65 11 4.144 363.65 10.35 4.658
348.65 10.66 3.888 358.65 10.9 4.186 363.65 10.3 4.693
348.65 10.63 3.917 358.65 10.85 4.21 363.65 10.25 4.722
348.65 10.6 3.931 358.65 10.8 4.233 363.65 10.18 4.765
348.65 10.57 3.953 358.65 10.75 4.254 363.65 10.15* 4.786*
348.65 10.54 3.968 358.65 10.7 4.28 363.65 10.1 4.82
358.65 10.65 4.304 363.65 10.05 4.855
353.45 16 3.074 358.65 10.6 4.331 363.65 10 4.879
353.45 15 3.179 358.65 10.55 4.359 363.65 9.95 4.92
353.45 14 3.304 358.65 10.5 4.39 363.65 9.9 4.956
353.45 13 3.464 358.65 10.45 4.418
353.45 12 3.679 358.65 10.41* 4.438* 368.15 16 3.346
353.45 11.5 3.817 358.65 10.4 4.443 368.15 15 3.479
353.45 11.3 3.878 358.65 10.35 4.468 368.15 14 3.645
353.45 11.2 3.911 358.65 10.3 4.496 368.15 13 3.858
353.45 11.1 3.947 368.15 12 4.123
353.45 11 3.983 363.65 16 3.262 368.15 11 4.518
353.45 10.9 4.02 363.65 15 3.381 368.15 10.5 4.765
353.45 10.85 4.04 363.65 14 3.533 368.15 10.4 4.814
353.45 10.8 4.057 363.65 13 3.734 368.15 10.3 4.869
353.45 10.75 4.076 363.65 12 3.988 368.15 10.2 4.914
353.45 10.7 4.103 363.65 11.5 4.152 368.15 10.15 4.957
353.45 10.65* 4.123* 363.65 11.3 4.232 368.15 10.1 4.988
353.45 10.6 4.145 363.65 11.1 4.301 368.15 10.05 5.022
353.45 10.55 4.167 363.65 11 4.35 368.15 10 5.052
353.45 10.5 4.19 363.65 10.9 4.381 368.15 9.95 5.086
353.45 10.45 4.213 363.65 10.85 4.406 368.15 9.9 5.123
363.65 10.8 4.429 368.15 9.88* 5.130*
358.65 16 3.16 363.65 10.75 4.454 368.15 9.85 5.143
358.65 15 3.269 363.65 10.7 4.472 368.15 9.8 5.182
358.65 14 3.407 363.65 10.65 4.503 368.15 9.75 5.231
358.65 13 3.589 363.65 10.6 4.528 368.15 9.7 5.265
 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630 5

Table 2 (continued )

T/K P/MPa V/cm3/g T/K P/MPa V/cm3/g T/K P/MPa V/cm3/g

358.65 12 3.826 363.65 10.55 4.554 368.15 9.65 5.307

358.65 11.5 3.969 363.65 10.5 4.584
358.65 11.3 4.033 363.65 10.45 4.607
a
Liquid-vapor phase transition points are marked by superscript “star”.
b
Standard uncertainties u are uðPÞ ¼ 0:0018 MPa, uðTÞ ¼ 0:05 K, and uðVÞ ¼ 0:0003 cm3/g.

where the superscript (1,2) refers to the one-phase or two-phase asymptotical Wegner critical exponent [32,35]. Besides, the
region. The values c ~ ð1Þ ~ ð2Þ
2 ¼ c2
c12 =c1 and c2 ¼ c2 are deter-
2 following notations were introduced for the universal coefficients
mined by means of the generalized susceptibilities of the scaling of the model:
model, namely, c1 ¼ ðvf1 =vh1 Þh2 , c2 ¼ ðvf2 =vh2 Þh1 , and c12 ¼
2b g
1 2a k
ðvf2 =vh1 Þh2 ¼ ðvf1 =vh2 Þh1 . Note that the form of expression (13) is k¼ ; k ¼ ; k ¼1
; k ¼ 1 ; k
g 1 1
a 2 1
gk 3 1 þ k 4
similar to the expressions for the isochoric heat capacity Cr;x and
1
k2 k1 1
k
the derivative ðvP=vTÞr;x presented in Refs. [20,22,23]. It means that ¼ ; w2S ¼ ; b2 ¼ (15)
k1 1
k 1
gk
the compressibility bT on the critical isotherm has a cusp-like sin-
gularity in the critical point vicinity. The crossover functions in Eq. (14) are written as
At last, to complete constructing the EOS for a multicomponent
   
mixture, it is necessary to specify the scaling model. Here, we use a g rD 1
1
k2 q2
crossover linear model, which was described in details in Ref. [23]. YðrÞ ¼ 1 þ r D ; Fðq; rÞ ¼ (16)
g rD þ 1
ð1
kÞq2
This model provides a smooth transition from the asymptotic
scaling behavior in the immediate vicinity of the critical point to the It is essential, that the expressions (14) and (16) are universal
mean-field behavior which is typical for cubic and multiparameter functions of the variables r and q. The positive variable r controls
EOS. The model can be formulated in a parametric form: the distance from the critical point. This variable is responsible for
the transition of the system from the asymptotic scaling behavior
2ab2 gþb g
2b
 g
2b ðr≪1Þ to the mean-field behavior ðr[1Þ. The variable q charac-
Y 2D q 1
q
k3 Fðq;rÞ ; f1 ¼ r b Y 2D q
2
h1 ¼ r terizes the deviation from the boundary of the two-phase region at
k3
r ¼ const. The two-phase region is defined by the conditions h1 ¼ 0
and qs0. As it follows from the expression (14) such conditions are

   satisfied when
g
1 1
2b a
1
b2 q ; f2 ¼ gk4 r 1
a Y D w2S
q þ
2 2
h2 ¼ r Y D Fðq;rÞ sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi !
gk4

 k ð1
kÞg k3 r D
h3 ¼ r 2
a
Y
ðg
2bÞ
1
k4 ðk1 þ k2 Þq þ k4 k2 q
2ab q Fðq;rÞ
2 4 2 2 q2
¼ q21 ¼1
ðg k3 r D þ 1Þ 1þ4
1
2ð1
kÞ
D
ðg k3 r D þ 1Þ2
(14) (17)

where a ¼ 0:11, b ¼ 0:325, and g ¼ 2
a
2b ¼ 1:24 are the where k3 ¼ ð2g
1Þ =ð1
aÞ. Expression (17) defines the
asymptotic critical exponents [32e34], and Dx0:51 is the non-

Fig. 1. Isotherms of the 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture measured in one-
phase and two-phase regions on P
r plane. Corresponding absolute temperatures
are shown in the figure legend. Big empty squares mark the experimental estimations
of the phase transition points. Large circle shows the position of the critical point
estimation.
Fig. 2. Experimental points of liquid-gas phase transitions for the 0:5 C1 þ 0:35 C3 þ
0:15 n-C5 mixture in P
T variables measured by two different techniques. The points
obtained by the adiabatic calorimetry method [20] are denoted by filled squares. Solid
line represents the phase envelope calculated within the scope of the EOS elaborated
in Ref. [20]. The empty squares correspond to experimental data presented in this
work. Empty circles indicate the positions of measured critical points.
6 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630

Table 3
Fitting parameters of the crossover EOS for 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture.

Non-universal parameters in Eqs. (19) and (20) for Dr

cr1 cr2 cr3 cr6

1.2624 0 e 3.9057 e 0.4691
Non-universal parameters in Eqs. (19) and (20) for t
ct1 ð1Þ ð2Þ ð3Þ ct2 ð1Þ c t3 ð1Þ
ct1 ct1 ct1 ct2 ct3

0.1973 0.0888 0.5136 e 0.1619 0.1826 0 1.9445 2.7207
Non-universal parameters in Eqs. (19) and (20) for DP
cP1 ð1Þ ð2Þ ð3Þ cP2 ð1Þ cP3 ð1Þ
cP1 cP1 cP1 cP2 cP3
0.004267
0.004914 0.020753 0.000891 0 e 0.0940 0.1078 0.6597
Critical parameters
Tc ¼ 357:867 K Pc ¼ 10:446 MPa rc ¼ 0:2282 g=cm3

boundary of the two-phase region for the crossover linear model. form:
Inside the two-phase region q2 ¼ q21 , so that the liquid and gas
branches relate to q ¼ q1 and q ¼
q1 respectively. The value q21 Dr ¼ cr1 f1 þ cr2 f2 þ cr3 h2 þ cr6 f21 ; t
varies in the range from unity, in the limit r≪1, to q21 ¼ 1
¼ ~ct1 Dr þ ~ct2 f2 þ ~ct3 h2 ; DP ¼ ~cP1 Dr þ ~cP2 f2 þ ~cP3 h2
k k3 =k2 x0:944, when r[1. It can be easily seen that in immediate (19)
vicinity of the critical point (r≪1) expressions (14)e(16) reproduce
the linear model Here

2ab2 gþb
 ð1Þ

h1 ¼ r q 1
q2 ; f1 ¼ r b q
k3



f2 ¼ g k4 r 1
a w2S
q
2 2
h2 ¼ r 1
b2 q ;


h3 ¼ r 2
a 1
k4 ðk1 þ k2 Þq þ k4 k2 q
2 4
which also can be used as a scaling model to establish the relation
between the fields hk and densities fi . Thus, expressions (3)e(7)
together with (14)e(17) (or along with (15) and (18)) completely
determine the EOS for a near-critical fluid mixture. Thus, any
thermodynamic quantities can be computed in terms of r and q.
4. Comparison with the experiment
As it was mentioned above the mixture with the same compo-
sition was studied previously by adiabatic calorimetry on various
isochores. The results of this study were presented in Ref. [20]. It
turned out that the results of measurements on isochores and
recent PVT data measured on isotherms are significantly different.
Fig. 2 exhibits a comparison of the experimental and calculated
dew-bubble curves on P
T plane. As it can be seen from this
picture, the differences in pressures are about 0:4
0:5 MPa, i.e.
they exceed significantly the measurement uncertainty. We believe
that the observed discrepancies are caused by slightly different
compositions of studied samples. In particular, the pure compo-
nents used in these experiments were taken from different sources.
We cannot state which mixture composition is closer to the
announced one. At the same time, the available set of experimental
data at isotherms allows us to obtain the EOS of the near-critical
mixture even if the composition is unknown.
Note that expressions (3)e(7) present the general equation of
state of any near-critical fluid mixture with an arbitrary composi-
tion. To obtain the EOS for certain mixture it is necessary to
formulate the fitting model. For this purpose, one needs to restrict
the expansions (3)e(7) and to choose the scaling model to connect
hk and fi . In present paper the expansions (3)e(7) were taken in the
~cz1 ¼ cz1 þ cz1 ð2Þ
Dr þ cz1 ð3Þ
Dr2 þ cz1 Dr3 ;
ð1Þ ð1Þ
~cz2 ¼ cz2 þ cz2 Dr; ~cz3 ¼ cz3 þ cz3 Dr (20)
(18) where subscript z means t or P. Note that expressions (19) have
been modified in comparison with the works [22,23] due to the
terms with coefficients cr2 , cr3 , and cr6 . The addition of these terms
allows to calculate the volumes of coexisting phases. Besides, the
crossover relations (14)e(16), as well as the linear model (15) and
(18) were employed to connect the fields hk and densities fi in
expressions (19). Corresponding models are called as the crossover
model or the scaling model. Thus, one can obtain the EOS of the
mixture within the scope of the specific model with non-universal
parameters in expressions (19) and (20) to be determined by fitting
procedure.
In present work both crossover EOS and scaling EOS of the
studied mixture were obtained as a result of independent fitting of
the models to the entire set of available experimental data. The
obtained values of non-universal parameters are shown in
Tables 3 and 4. Parameters cr2 and cP2 appeared to be statistically
insignificant for the studied mixture, so they were put equal to
zero. Note that the parameter cr1 is not adjustable one for the
scaling model. This coefficient can be set equal to unity by the
replacement of the variable r on b r ¼ cr1 1=b r in Eqs. (18). Essentially
that the values of the critical parameters in the framework of both
EOS turned out to be close. As a consequence, the parameters ct1
and cP1 are also close, since they determine the slopes of the
mixture dew-bubble curves at the critical points of the obtained
equations of state. The other parameters in both EOS are different.
Since the variable r at the boundaries of the studied density range
is of order of 0.1, the simple estimation gives that the correction
term in the crossover function YðrÞ is about 30%. Thus the cross-
over function effects appreciably on the thermodynamic behavior.
Fig. 3 demonstrates the comparison of two models in the
extended range of pressures and densities. As it is seen from the
figure, both equations practically coincide in the region of existing
data. At the same time, the scaling EOS demonstrates the non-
physical behavior in the more wide region, for example, at pres-
sures about 7e8 MPa. Therefore the crossover model looks more
reliable and it permits us to obtain the EOS of near-critical fluid in
 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630 7

Table 4
Fitting parameters of the scaling EOS for 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture.

Non-universal parameters in Eqs. (19) and (20) for Dr

cr1 cr2 cr3 cr6

1 0
1.5462 0.2103
Non-universal parameters in Eqs. (19) and (20) for t
c t1 ð1Þ ð2Þ ð3Þ c t2 ð1Þ ct3 ð1Þ
ct1 c t1 ct1 ct2 ct3

0.1966 0.0812 0.6343 e 0.1818 0.0971 0.6795 1.0026 0
Non-universal parameters in Eqs. (19) and (20) for DP
cP1 ð1Þ ð2Þ ð3Þ cP2 ð1Þ cP3 ð1Þ
cP1 cP1 cP1 cP2 cP3
0.004325
0.005004 0.023559 0.002393 0 e 0.0339 0.0542 0.3122
Critical parameters
Tc ¼ 358:246 K Pc ¼ 10:430 MPa rc ¼ 0:2270 g=cm3

the more wide range of thermodynamic values. Taking in mind
this fact, the comparison with the experiment will be carried out
further only for the crossover EOS.
Fig. 4 represents the calculated isotherms in comparison with
the experimental data. This figure shows also the calculated dew-
bubble curve in P
r variables. As it can be seen, the obtained
EOS provides a good agreement with the measurement results. The
average deviation of calculated values from the experimental
points is about 0:25 % and maximal deviation does not exceed
0:8 %. Fig. 5 presents the calculation results according to the
crossover EOS as well as Peng-Robinson EOS (PR EOS) [36]. Binary
interaction coefficients were taken from the article [37]. The
mixture critical parameters determined from PR EOS are equal to
TcPR ¼ 356:7 K, PcPR ¼ 10:54 MPa, and rPR 3
c ¼ 0:2442 g=cm : The
figure shows the calculated dew-bubble curves together with two
isotherms T ¼ 322:65 K and T ¼ 353:45 K in P
r variables. The
isotherm T ¼ 322:65 K is one of the isotherms presented in Fig. 3.
The second isotherm T ¼ 353:45 K is near-critical both for the
crossover EOS and PR EOS. It is well-known that cubic EOSs allow to
calculate thermophysical properties with the accuracy of the order
of 2e5%. In this regard, Fig. 5 demonstrates that the crossover EOS
improves significantly the accuracy of the description of the near-
critical region of the studied mixture.
Fig. 6 illustrates the calculation results of the mixture dew-
bubble curves on T
r and P
T planes together with the exper-
imental data for the phase transition points. The calculated values
are in a good agreement with the experimental results. In addition,
Fig. 6 shows the isopleth lines computed from the expressions (12),
(19), (20), and (14)e(16). Each line with fixed u is terminated by the
critical point of the mixture. In present paper, the approach based
on the complete scaling has been used. As it was demonstrated in
Ref. [31], in this case the slopes of all isopleths at the critical point
including the line at u ¼ 0, are the same. For the traditional scaling
when there is no pressure mixing in the fields h1 and h2 , the slope
of the line at u ¼ 0 should be different [31]. It turns out that the
asymptotic near-critical behavior of the line at u ¼ 0 takes place in
a very narrow region, namely, jDrj < 10
3 and jtj < 10
4 . Practically,
this fact does not allow us to make a choice between complete or
traditional scaling. Anyway, the volumes of coexisting phases were
not measured during the experimental study, so it is impossible to
estimate the accuracy of our calculations. Despite this, the possi-
bility of isopleth calculations supplements the proposed model.
Fig. 7 exhibits the behavior of the coefficient of isothermal

Fig. 3. Comparison of the crossover and the scaling models in extended region of
thermodynamic parameters for the 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture. Symbols
denote experimental data: open squares indicate the DBC curve in P
r plane, small
filled squares represent the measured isotherms corresponding to 322:65 Kand
368:15 K, big black circle means the experimental estimation of the critical point. Lines
demonstrate the calculations within the scope of the crossover EOS (red lines) and the
scaling EOS (blue lines). Solid lines relate to the dew-bubble curve (DBC), while dashed
lines correspond to the isotherms. Lines marked by (1) and (2) present the curves with
equal volumes of coexisting phases. Insertion illustrates the behavior of the vapor
branch of DBC and the isotherm at T ¼ 322:65 K.
Fig. 4. Experimental points for the 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture and
calculated isotherm dependencies. Filled squares exhibit the experimental data for all
isotherms in one-phase and two-phase regions. Empty squares correspond to exper-
imental estimates of liquid-gas phase transition points. Solid lines represent the iso-
therms and the dashed line depicts the P
r dew-bubble curve calculated in
accordance with crossover EOS obtained in this work. Empty circle denotes the critical
point calculated within the scope of crossover EOS.
8 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630

Fig. 5. Comparison of the crossover EOS and PR EOS calculations for the DBC and two
isotherms T ¼ 322:65 K and T ¼ 353:45 K of the studied mixture. The notations for the
experimental data and for the curves calculated on the base of crossover EOS are the
same as in Fig. 4. Green lines represent PR EOS calculations: dashed line exhibits the
DBC and solid lines denote isotherms. Green empty circle indicates the critical point of
PR EOS.

compressibility bT in the vicinity of the critical point. The lines

calculated within the scope of the crossover EOS as well as the
results of numerical differentiation of experimental data are shown
in Fig. 7a. In the one-phase region, the calculated results are in a
good agreement with the experimental points. In the two-phase
region there are systematic deviations which possibly are the
result of non-equilibrium state of the system just after the
appearance of the second phase. We believe that in the two-phase Fig. 6. Calculated dew-bubble curves of the 0:5 C1 þ 0:35 C3 þ 0:15 n-C5 mixture
region, and especially in the critical point vicinity, the complete together with experimental data in T
r and P
T planes. Filled squares are the
relaxation of the system to equilibrium state requires more waiting experimental estimates of phase transition points; solid lines exhibit the calculated
dew-bubble curves within the crossover EOS. Dashed lines represent the calculated
time. The figure shows a cusp-like singularity of the isothermal
curves with fixed volume ratio ðu ¼ constÞ of liquid-gas coexisting phases. The location
compressibility in the close vicinity of the critical point. Note also of the mixture critical point is marked by empty circle.
that the calculated jump of the derivative ðvr=vPÞT;x on the dew-
bubble curve changes its sign before the cricondetherm point.
This is an unexpected fact which we cannot comment in this paper.
typical result for the standard study on the industrial serial setup.
Fig. 7b shows a comparison of the isothermal compressibility
Two types of equations of states were based on different theoretical
calculated from the crossover EOS and PR EOS. The compressibility
models, namely, scaling model and crossover model. Both proposed
was calculated for the isotherms presented in Fig. 5. The behavior of
EOS of the mixture describe the experimental results with the ac-
the compressibility on the isotherm T ¼ 322:65 K calculated within
curacy not worse than the experimental uncertainty. Note that the
the scope of the crossover EOS and PR EOS is similar, though the
information concerning the mixture composition was not involved
densities corresponding to the transition points are slightly
in the processing. In the framework of the obtained equations, the
different. At the same time the compressibility behavior on the
critical parameters Pc , Tc , and rc of the studied mixture were
near-critical isotherm T ¼ 353:45 K differs qualitatively for these
determined, and the dew-bubble curves were calculated. The dis-
equations. Unfortunately, the quality of experimental data obtained
tinctions of determined critical parameters and corresponding
on the standard PVT setup does not allow us to observe the cusp-
experimental estimates are less than 2 K ð0:6%Þ for the temperature
like behavior of compressibility unlike such behavior established
and 0:07 MPa ð0:7%Þ for the pressure. This confirms the consistency
earlier for isochoric heat capacity Cr;x and the derivative ðvP=vTÞr;x
of the obtained equations of state. Let us also remark that the ability
[20,23]. The distinction of the crossover EOS from PR EOS clearly to elaborate EOS for a mixture of unknown composition, as well as
demonstrates that the mean field EOS can not describe correctly the ability to calculate the necessary thermodynamic characteristics
the anomalous behavior of thermophysical properties of a near- may be interesting for practice. It is known that in some cases a
critical fluid. natural fluid mixture in oilfield can be in a near-critical state. The
results of standard studies often do not make it possible to attribute
5. Conclusions reliably the deposit to an oil or gas-condensate type. This fact leads
to significant difficulties in designing the development of such de-
Let us summarize the main results of the work. Two different EOS posits. The use of a cubic EOS generally is not a reliable way for the
of a near-critical hydrocarbon mixture were elaborated on the basis determination of critical parameters of a natural fluid mixture.
of PVT data measured on isotherms. Earlier we did not use such data Mean-field equations reproduce qualitatively only strong anomalies
set for the optimization of fitting models although it represents a of thermodynamic quantities rather than weak anomalies like the
 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630
Fig. 7. (a) Isothermal compressibility bT calculated by the crossover EOS. (b) The
comparison with PR EOS calculations for the same isotherms as in Fig. 5. Symbols
indicate experimental points on the studied isotherms. Solid red and magenta lines in
figures (a) and (b) present the crossover EOS computations in one-phase region and in
two-phase region respectively. Dashed blue lines in both figures exhibit the jumps of
bT at the phase transition points. Green lines in figure (b) correspond to PR EOS cal-
culations: solid lines show the compressibility behavior and dashed lines indicate the
jumps at the transition points in the framework of PR EOS.
anomaly of isochoric heat capacity and etc. In this respect the
elaboration and using of scaling-based EOS can present a substantial
interest. The proposed approach permits one to improve the un-
derstanding of phase behavior of a fluid provided some additional
experimental information is available. Scaling-based models allow
us to process the datasets which involve both strong and weak
anomalies of thermodynamic properties to develop more reliable
EOS of a mixture in the vicinity of its critical point.
The comparison of the crossover and scaling equations of state is
presented in the article for the first time. It is demonstrated that the
crossover EOS provides more reliable description in the extended
region of thermodynamic parameters. The obtained crossover EOS
of the mixture is based on the crossover linear model. Such model
allows one to take into account the transformation from the
asymptotic scaling behavior to the mean-field behavior, which is
typical for cubic and multiparameter equations of state. This per-
mits us to extend the range of description of the experimental data
and to provide more reliable results in the region where the
experimental data are not available. We would like to remark that
the crossover linear model results from the scaling theory which is
valid in the vicinity of the critical point. Strictly speaking, there is no
rigid criterion which could determine in mixtures the range of
validity of the proposed approach. For this reason, to estimate the
applicability range of the crossover EOS state we need experimental
9
data in a more wide region of thermodynamic parameters.
In the given paper the model was modified by the inclusion of
the terms with coefficients cr2 , cr3 , and cr6 in Eqs. (12) and (19). This
allows us to calculate the lines of constant ratios of coexisting phase
volumes on the base of obtained equations. We note that the added
new terms produce small effect on the quality of the description of
the available experimental data. For this reason, these coefficients
were not previously used in fitting models [22,23]. However, it is
these coefficients that determine the behavior of the line with
equal volumes of phases ðu ¼ 0Þ. Moreover, as one can see from
Fig. 3 the lines of equal phase volumes obtained from crossover
(line 1) and scaling EOS (line 2) differ essentially, so the behavior of
isopleths depends strongly on the specified model. Unfortunately,
the liquid and gas coexisting phase volumes were not measured in
this experimental study. As a result, we cannot estimate the accu-
racy of calculated curves. Note that the knowledge of coexisting
phase volumes allows to study in particular the non-equilibrium
behavior of a system. This problem is known to be especially
important in the vicinity of the critical point. Thus, the possibility to
calculate isopleths and to analyze their behavior is a significant
supplement to the model.
The experimental data obtained on isotherms allows us to
determine the isothermal compressibility bT and to analyze its
behavior near the liquid-vapor critical point of a multicomponent
fluid mixture. Earlier studies were restricted mainly by the in-
vestigations of binary mixtures. In the present work the theoret-
ical expression (13) for the isothermal compressibility of a
multicomponent mixture was first obtained. It has been shown
that in close vicinity of the critical point the isothermal
compressibility demonstrates the singular cusp-like behavior. As
it is seen from Fig. 7a, the cusp-like behavior on the liquid branch
of DBC is lacked for the densities r > 0:29 g=cm3 which correspond
to isotherms with the temperatures T < 340 K. For these isotherms
the behavior of isothermal compressibilities calculated by means
of crossover EOS and PR EOS (see Fig. 7b) is qualitatively consis-
tent. For the temperatures larger than 340 K the corresponding
compressibilities reveal a qualitative difference. Taking into ac-
count the specific peculiarities of the compressibility behavior one
can assume that the immediate vicinity of the critical point of the
studied mixture on the liquid branch of DBC is restricted by the
temperature interval 340 K < T < Tc or by the density interval
rc < r < 0:29 g=cm3 respectively. The cusp-like anomaly is indeed
observable in this region. Note that a similar behavior is typical in
the vicinity of a critical point of a fluid mixture. Earlier such
anomalies have been observed experimentally in Refs. [20,23] for
the isochoric heat capacity Cr;x and for the derivative ðvP=vTÞr;x . In
this way, the problem of determination of immediate (fluctuation)
vicinity of the critical point of the fluid mixture arises together
with the question relating to the applicability criterion of the
crossover EOS. There are also some more points regarding the
behavior of the isothermal compressibility in fluid mixtures that
are beyond the scope of the article. These issues will be considered
in other papers.
Funding
The research was supported by the state program N АААА-
А19-119030690057-5.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
10 M.Yu. Belyakov et al. / Fluid Phase Equilibria 518 (2020) 112630
CRediT authorship contribution statement
M.Yu. Belyakov: Conceptualization, Methodology, Software,
Investigation, Writing - original draft, Writing - review & editing.
V.D. Kulikov: Conceptualization, Formal analysis, Investigation,
Writing - original draft, Writing - review & editing. A.R. Muratov:
Conceptualization, Formal analysis, Investigation, Writing - original
draft, Writing - review & editing. A.F. Sharipov: Investigation,
Validation.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.fluid.2020.112630.
References
[1] A. Anderko, Cubic and generalized van der Waals equations, in: J.V. Sengers,
R.F. Kayser, C.J. Peters, H.J. White (Eds.), Equations of State for Fluids and Fluid
Mixtures, vol. 5, Elsevier, 2000, pp. 75e126.
[2] I.G. Economou, Cubic and generalized van der Waals equations of state.
Applied Thermodynamics of Fluids, Royal Society of Chemistry, Cambridge,
2010, pp. 53e83.
[3] N.I. Diamantonis, G.C. Boulougouris, E. Mansoor, D.M. Tsangaris,
I.G. Economou, Evaluation of cubic, SAFT, and PC-SAFT equations of state for
the vapor-liquid equilibrium modeling of CO2 mixtures with other gases, Ind.
Eng. Chem. Res. 52 (2013) 3933e3942.
[4] E.W. Lemmon, R. Span, Multi-parameter equations of state for pure fluids and
mixtures, in: A. Goodwin, C. Peters, J.V. Sengers (Eds.), Applied Thermody-
namics of Fluids, Royal Society of Chemistry, Cambridge, 2010, pp. 394e432.
[5] O. Kunz, W. Wagner, The GERG-2008 wide-range equation of state for natural
gases and other mixtures: an expansion of GERG-2004, J. Chem. Eng. Data 57
(2012) 3032e3091.
[6] R. Smith, H. Inomata, C. Peters, Chapter 6 - equations of state and formulations
for mixtures, in: Supercritical Fluid Science and Technology, vol. 4, Elsevier,
2013, pp. 333e480.
[7] M. Thol, M. Richter, E.F. May, E.W. Lemmon, R. Span, Eos-Lng, A fundamental
equation of state for the calculation of thermodynamic properties of liquefied
natural gases, J. Phys. Chem. Ref. Data 48 (36) (2019), 033102.
[8] A. Firoozabadi, S. Arbabi, B. Dindoruk, Near-critical phase behavior of mixtures
using equations of state, Can. J. Chem. Eng. 72 (1994) 134e141.
[9] S.B. Kiselev, Cubic crossover equation of state, Fluid Phase Equil. 147 (1998)
7e23.
[10] A. Kostrowicka Wyczalkowska, J.V. Sengers, M.A. Anisimov, Critical fluctua-
tions and the equation of state of van der Waals, Physica A 334 (2004)
482e512.
[11] M.Yu Belyakov, E.E. Gorodetskii, Universal crossover approach to equation of
state for fluids, Int. J. Thermophys. 27 (2006) 1387e1405.
[12] A. Jamali, A.P.C.M. Vinhal, H. Behnejad, W. Yan, G.M. Kontogeorgis, Compari-
son of two crossover procedures for describing thermodynamic behavior of
normal alkanes from singular critical to regular classical regions, Fluid Phase
Equil. 495 (2019) 33e46.
[13] S.S. Leung, R.B. Griffiths, Thermodynamic properties near the liquid-vapor
critical line in mixtures of He3 and He4, Phys. Rev. A 8 (1973) 2673e2686.
[14] M.R. Moldover, J.C. Rainwater, Interfacial tension and vapor-liquid equilibria
in the critical region of mixtures, J. Chem. Phys. 88 (1988) 7772e7780.
[15] M.A. Anisimov, S.B. Kiselev, Universal crossover approach to description of
thermodynamic properties of fluids and fluid mixtures, in: A.E. Sheindlin,
V.E. Fortov (Eds.), Sov. Phys. Rev. B -Therm. Phys., vol. 3, Harwood Acad. Publ.,
1992, pp. 1e121.
[16] M.Yu Belyakov, S.B. Kiselev, J.C. Rainwater, Crossover Leung-Griffiths model
and the phase behavior of dilute aqueous ionic solutions, J. Chem. Phys. 107
(1997) 3085e3097.
[17] V.A. Agayan, M.A. Anisimov, J.V. Sengers, Crossover parametric equation of
state for Ising-like systems, Phys. Rev. E 64 (19) (2001), 026125.
[18] M.A. Anisimov, J.V. Sengers, Critical region, in: J.V. Sengers, R.F. Kayser,
C.J. Peters, H.J. White (Eds.), Equations of State for Fluids and Fluid Mixtures,
vol. 5, Elsevier, 2000, pp. 381e434.
[19] H. Behnejad, J.V. Sengers, M.A. Anisimov, Thermodynamic behaviour of fluids
near critical points, in: A. Goodwin, C. Peters, J.V. Sengers (Eds.), Applied
Thermodynamics of Fluids, Royal Society of Chemistry, Cambridge, 2010,
pp. 321e367.
[20] M.Yu Belyakov, V.P. Voronov, E.E. Gorodetskii, V.D. Kulikov, Phase behavior
and anomalies of thermodynamic properties in a multi-component near-
critical fluid mixture, Chem. Phys. 362 (2009) 85e90.
[21] M.Yu Belyakov, E.E. Gorodetskii, V.D. Kulikov, A.R. Muratov, V.P. Voronov,
B.A. Grigoriev, A.N. Volkov, Anomalous properties of dew-bubble curves in the
vicinity of liquid-vapor critical points, Fluid Phase Equil. 358 (2013) 91e97.
[22] M.Yu Belyakov, E.E. Gorodetskii, V.D. Kulikov, V.P. Voronov, B.A. Grigoriev,
Scaled equation of state for multi-component fluids, Chem. Phys. 445 (2014)
53e58.
[23] M.Yu Belyakov, V.D. Kulikov, A.R. Muratov, V.P. Voronov, Crossover equation
of state of a multi-component fluid mixture in the vicinity of liquid-vapor
critical points, Chem. Phys. 513 (2018) 149e155.
[24] S. Rahman, M.A. Barrufet, A new technique for simultaneous measurement of
PVT and phase equilibria properties of fluids at high temperatures and
pressures, J. Petrol. Sci. Eng. 14 (1995) 25e34.
[25] B.A. Younglove, J.F. Ely, Thermophysical properties of fluids e II. Methane,
ethane, propane, isobutene and normal butane, J. Phys. Chem. Ref. Data 16
(1987) 577e793.
[26] V.L. Pokrovskii, Feasibility of experimental verification of the conformal
invariance hypothesis, JETP Lett. (Engl. Transl.) 17 (1973) 156e158.
[27] A.Z. Patashinskii, V.L. Pokrovskii, Fluctuation Theory of Phase Transitions,
Pergamon, Oxford, 1979.
[28] M.E. Fisher, G. Orkoulas, The Yang-Yang anomaly in fluid criticality: experi-
ment and scaling theory, Phys. Rev. Lett. 85 (2000) 696e699.
[29] Y.C. Kim, M.E. Fisher, G. Orkoulas, Asymmetric fluid criticality. I. Scaling with
pressure mixing, Phys. Rev. E 67 (21) (2003), 061506.
[30] J. Wang, C.A. Cerdeirin~ a, M.A. Anisimov, J.V. Sengers, Principle of isomorphism
and complete scaling for binary fluid criticality, Phys. Rev. E 77 (12) (2008),
031127.
[31] Pablo de Castro, Sollich Peter, Critical phase behavior in multi-component
fluid mixtures: complete scaling analisys, J. Chem. Phys. 149 (21) (2018)
204902.
[32] A.J. Liu, M.E. Fisher, The three-dimensional Ising model revised numerically,
Physica A 156 (1989) 35e76.
[33] R. Guida, J. Zinn-Justin, Critical exponents of the N-vector model, J. Phys. A 31
(1998) 8103e8122.
[34] Jan V. Sengers, Joseph G. Shanks, Experimental critical-exponent values for
fluids, J. Stat. Phys. 137 (2009) 857e877.
[35] F.G. Wegner, Corrections to scaling laws, Phys. Rev. B 5 (1972) 4529e4536.
[36] D.-Y. Peng, D.B. Robinson, A new two-constant equation of state, Ind. Eng.
Chem. Fundam. 15 (1976) 59e64.
[37] H. Nishiumi, T. Arai, Generalization of the binary interaction parameter of the
Peng-Robinson equation of state by component family, Fluid Phase Equil. 42
(1986) 43e62.