Experimental Study of VLE Properties of N Tetradecane in The Supercritical Binary Solvent (0.367 Propane/0.633

International Journal of Thermophysics (2023) 44:114
https://doi.org/10.1007/s10765-023-03220-3
Experimental Study of VLE Properties of n‑Tetradecane

in the Supercritical Binary Solvent (0.367 Propane/0.633
n‑Butane)
Vener F. Khairutdinov1 · Ilnar Sh. Khabriev1 · Talgat R. Akhmetzyanov1 ·

Lenar Yu. Yarullin1 · Farizan R. Gabitov1 · Ilmutdin M. Abdulagatov1,2,3
Received: 16 May 2023 / Accepted: 18 May 2023 / Published online: 26 June 2023
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature
2023
Abstract
A high-temperature and high-pressure optical cell VLE apparatus has been applied
to measure phase equilibrium properties of n-tetradecane in the supercritical binary
solvent (0.367propane + 0.633 n-butane mass fraction) at temperatures of 413.15 K,
433.15 K, and 453.15 K between of pressures (0.9 and 6.6) MPa. The combined
expanded uncertainty of the temperature, pressure, and concentration measurements
at 0.95 confidence level with a coverage factor of k = 2 is estimated to be 0.15 K,
0.0022, and 0.035, respectively. The critical parameters (TC, PC, wC ) were deter-
mined based on the measured isothermal phase equilibrium data of the ternary sys-
tem n-tetradecane + propane/n-butane. It is shown that the critical temperature and
pressure of the n-tetradecane + propane/n-butane system increases with concentra-
tion of n-tetradecane increases.
Keywords Critical point · Critical curve · n-Tetradecane + propane/butane mixture ·

Phase diagram · Supercritical solvent · VLE measurements
1 Introduction
Measurement of the solubility (VLE properties) of compounds in supercritical

fluids (SCF) and fluid mixtures is great important to optimize and control SCF
processes. This is because the properties of SCF solvent (temperature, pressure,
* Ilmutdin M. Abdulagatov
ilmutdina@gmail.com
1
Kazan National Research Technological University, Kazan, Russian Federation
2
Department of Physical and Organic Chemistry, Dagestan State University, Makhachkala,
Russian Federation
3
Geothermal and Renewal Energy Institute of the High Temperature Joint Institute of the Russian
Academy of Sciences, Makhachkala, Russian Federation
13
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114 Page 2 of 21 International Journal of Thermophysics (2023) 44:114
concentration of binary solvent) can be readily adjusted by changing their compo-

sitions for specific needs. Most measurements in the literature are focused on the
solubility of compounds in pure SC such as CO2 or light n-alkanes, etc., at dif-
ferent temperatures and pressures. Also, there are many reported solubility data
of compounds in SC CO2 + co-solvent such as acetone, methanol, ethanol, etc.
to enhance the solubility. Our research team has been active for many years in
study of the VLE properties of compounds in supercritical fluids and fluid mix-
tures (see, for example [1–12]). As a part of a long-term laboratory project on
study of the VLE properties of oil compound in SC fluids and fluid mixtures,
the phase equilibrium (VLE properties) of n-tetradecane, as a model of heavy
oil, in SC binary propane/butane solvent is studied. In our recent publication [1]
phase equilibrium properties (VLE, PTwL wG data) of n-tetradecane in the single
SC CO2 have been studied. The propane/n-butane is widely used previously as
a binary solvent for study supercritical fluid extraction processes (extraction of
heavy hydrocarbons from oil sludge and oil emulsions, treatment of oil-bearing
sands, and utilization of wood railway sleepers, etc.) associated with heavy oil
[6–11].
Accurate phase equilibrium data (VLE, PTwL wG ) in hydrocarbon mixtures is
required for simulation of the of oil reservoirs, effective optimization of process-
ing equipment, and separation processes. The supercritical fluid solvent mixtures
can be used in the same manner as pure liquids and have solvent properties which
can be easily manipulated by varying the concentration. The Rose Process uses
near-critical propane and n- butane or their mixture for the extraction of high
molecular weight components from oil residues. Near- and supercritical propane
is also used in the Solexol Process for the purification and separation of vege-
table and fish oils. Thus, phase equilibrium study is one of the most important
fundamental sciences for process development in the chemical industry. Reliable
VLE data provides useful tools for modeling the phase equilibrium. VLE data is
a necessity for the development and validation of the predictive thermodynamic
models. Accordingly, accurate VLE data are required for the calculation of inter-
action energies between functional groups for group contribution methods such
as PC-SAFT, CP- PC-SAFT, E-PPR78, and PSRK [1, 4, 12]. More measurements
have to be done to improve the accuracy of prediction VLE properties in com-
plex thermodynamic systems like n-tetradecane + propane/n-butane mixture near
the critical point. Deeper understanding of the phase equilibrium (PTxy) relations
in the multicomponent systems containing supercritical component can lead to a
significant improvement of their industrial applications.
This study is part an on-going research program investigating the phase equi-
librium properties of binary and ternary mixtures involved in SCF processes. In
our previous series publications, we have studied the phase equilibrium properties
of the binary C O2 + tetradecane [1], propane + n-butane [2], propane + naphtha-
lene [2], propane + phenol [12], and ternary SC (propane/n-butane) + acetophe-
none [3], propane/n-butane + n-hexadecane [4], and propane/n-butane + naph-
thalene [2], and CO2 + toluene/dichloromethane [5] mixtures using the same
technique (high-pressure optical cell). The efficiency of the supercritical extrac-
tion process essentially depends on correct choice of the supercritical solvent.
13
International Journal of Thermophysics (2023) 44:114 Page 3 of 21 114
The light alkanes, such as propane, n-butane and their mixtures, are good super-
critical solvents due to their chemical affinity to oil and the relatively low critical
pressures.
To the best of our knowledge no VLE data have been published previously for
the n-tetradecane + propane/n-butane ternary system, therefore, the phase equilib-
rium data (PTxy) presented herein for this system are new data. Only three VLE
data sources [13–15] are listed in the NIST Source Data Archive [16] for the binary
sub-systems propane + n-tetradecane and n-butane + n-tetradecane. Schwarz et al.
[13] studied the influence of functional end groups on the high-pressure phase equi-
libria of long chain molecules (n-tetradecane) in supercritical propane at tempera-
tures from (378 to 408) K and at pressures between (2.97 and 6.48) MPa. Gonzalez
et al. [14] reported the solubility of propane and butane in mixtures of n-alkanes
in the temperature range from (298 to 323) K. High-pressure (up to 4.4 MPa and
323–453 K) experimental and theoretical studies VLE for binary sub-systems of
the quaternary system N2 + CH4 + C4H10 + C14H30 have been done by de Leeuw
[15]. VLE properties of binary propane + n-butane mixture was detailed study by
many authors [17–31]. Detailed review of these works was provided in our previ-
ous publication Khairutdinov et al. [11]. The reported reliable VLE data [17–31]
for well-studied binary propane + n-butane mixture was used for validation of the
present VLE apparatus. The present study deals with the solubility of n-tetradecane
in the supercritical solvent mixture (0.367 propane/0.633 n-butane, mass fraction) at
three selected isotherms of 413.15 K, 433.15 K, and 453.15 K in the pressure range
from (0.9 to 6.6) MPa. By varying the propane or n-butane concentrations in the
propane/n-butane mixture, the critical parameters of the SC solvent can be manipu-
lated without changing the solvent quality.
2 Experiment of VLE
2.1 Chemicals
Binary mixture of propane/n-butane, with fixed composition of 0.633 mass fraction

of n-butane, has been used as a binary solvent to study phase equilibrium (VLE)
properties with heavy hydrocarbon (n-tetradecane), due to its commercial avail-
ability. This mixture is an affordable and cheap solvent with low critical parameters
(TC = 408.79 K and PC = 4.128 MPa [2]). The mixture 0.367propane/0.633n-butane
was purchased from OOO «UralOrgSynthesis». Pure propane (purity 0.9980 mass
fraction) and n-butane (purity 0.9975 mass fraction) were purchased from OOO
MONITORING (Moscow). Purity of n-tetradecane is 0.99 mass fraction (from
OOO “REACHIM”, Moscow). The suppliers, the CAS numbers, the stated purities
and water content for the chemicals used in the present measurements are given in
Table 1. All chemicals were used as received without further purification.
13
114
13
Page 4 of 21
Table 1 Description of the samples of propane, n-butane, n-tetradecane, and the propane/n-butane mixture used in this work
Chemical CAS Water content (mass Purity (mass fraction) Supplier
%)
Propane 74–98-6 Not found ≥ 0.9980 (NMR) OOO MONITORING (Moscow)

n-Butane 106–97-8 < 0.05 > 0.9975 (NMR) OOO MONITORING (Moscow)
n-Tetradecane 629–59-4 N/A ≥ 0.9900 (GC) OOO “REACHIM” (Moscow)
0.367 mass fraction (propane) / 0.633 – Not found – OOO «UralOrgSynthesis»
mass fraction (n-butane)a
a
GC NMR analysis, and the water content provided by the suppliers
International Journal of Thermophysics (2023) 44:114
2.2 Experimental VLE Apparatus and Procedure of Measurements
The experimental VLE apparatus and the procedure of the measurements have been
detailed discussed in our previous several publications (see, for example [1–5, 12]).
2.2.1 High‑Temperature and High‑Pressure Optical Cell
The schematic diagram and details of the design of the experimental VLE apparatus
for the phase equilibrium property (PTxy) measurements is presented in our pre-
vious publication [2, 3]. The measurements were performed using a high-pressure
optical cell. The method is based on gravimetrically analyzing the liquid and vapor
phase samples taken from an optical cell at equilibrium conditions. The experimen-
tal VLE apparatus mainly consists of following units: (1) the unit supplying a mix-
ture sample; (2) the temperature control unit; (3) the pressure creating, regulating,
and measuring unit; (4) the high-pressure optical cell; (5) the vacuuming system;
(6) the stirring mechanism; (7) the sampling system; and (8) the analytical part. A
main part of the VLE apparatus is the high-pressure optical cell. The stainless steel-
flanged sapphire cell operates up to 50 MPa and at temperatures from the ambient to
473 K. An optical cell consists of the sapphire windows on opposite sides installed
between the cover and the stainless steel body of the apparatus. Its working volume
is 117 cm3. The windows provide visual confirmation that the experimental equi-
librium conditions are in the two-phase region, i.e., stability of the phase boundary.
The copper jacket was used for smoother temperature control and uniform heat-
ing of the measuring cell. The optical cell temperature was measured using the
chromel–alumel thermocouples. The thermocouples were pre-calibrated using a 10
Ω reference platinum resistance thermometer (PRT-10). The PRT-10 was calibrated
by the VNIIFTRI (Russian NIST, Moscow) against the ITS-90 with an uncertainty
of 2 mK. The temperature in the VLE cell was measured at 5 points (different places
of the cell). Two thermocouples were placed inside the cell for each phase and three
on the copper jacked (high precision temperature control system, HPTC). At steady
state condition, the thermocouples should show the same value. The thermocouples
reading allows to determine the absence of temperature gradients in the system.
The thermocouples reading difference keeps within 0.03 K. Therefore, the stabil-
ity of the temperature (temperature fluctuation) inside the measuring cell was con-
trolled within 0.03 K. In order to avoid the temperature changes (cooling) due to the
Joule–Thomson effect, the sampling was performed very slowly and after rocking
for 30–40 min and adjusting, the temperature reaches to its original value. The com-
bined expanded absolute uncertainty of the temperature measurements (at 0.95 con-
fidence level, a coverage factor of k = 2) is 0.15 K (see also below sec. 2.2.5). The
pressure in the high-pressure optical cell was generated using a high-pressure pump
TharTechnology (Supercritical- 24). The dead weight pressure gage was used for
pressure measurements in the optical cell. The combined expanded relative uncer-
tainty of the pressure measurements with taking into account fluctuations due to
temperature change (at 0.95 confidence level, a coverage factor of k = 2) is 0.0022
(or 0.22%, see also below sec. 2.2.5).
13
2.2.2 Procedure of Measurements
During the experiment, one third of the optical cell was filled with n-tetradecane
through an open sapphire window. Then, a whole system was evacuated using the
vacuum pump. Next, the optical cell was heated to the desired temperature and
ready to use 0.367propane/ 0.633 n-butane mass fraction mixture was supplied into
it by the high-pressure pump until the required pressure was reached. Before per-
forming the composition analyses, a phase equilibrium study is required for identi-
fication of the equilibrium condition. In order to reach equilibrium conditions in the
two-phase (liquid + gas) system, the samples were vigorously stirred for 30–40 min
using the stirring mechanism (rocking, see details [3]). Stirring of the mixture was
performed by rotating the measuring cell 90 degrees around its axis with a fre-
quency of 8 rpm using the electric motor and linkage mechanism (see, for exam-
ple Khairutdinov et al. [3]). There are number of criteria of equilibrium conditions
(see also Review paper [38]). Most authors define the equilibrium condition as the
condition at which a measured property remains constant or fluctuate within experi-
mental uncertainties. For example, (a) temperature and pressure remains constant
[39–42]; (b) Pressure remains constant [43, 44]; (c) pressure remains steady within
1 kPa [45]; (d) pressure fluctuates within 1 kPa during a period 10 min [46]; (e) tem-
perature remains within ± 0.0005 K for 30 min and pressure remains within ± 0.01%
[47]; and (f) pressure and interfacial levels remain constant [48]. In the present, the
equilibrium state was established when both temperature and pressure achieved con-
stant values and the phase interface was well stabilized. The phase boundary level
stability indicates the completion of mixing. This means that T and P remain nearly
constant, while their fluctuations are within the experimental uncertainty range (see
below).
After reaching the equilibrium condition in the optical cell the sample stirring
was stopped. After a complete separation of the phases (at least 30–40 min after
the mixing has stopped), a sampling of each phase was carried out at constant
values of T and P. Then the optical cell was mounted in an upright position and
held for 40 min. The sampler with a relatively large volume of 4.1 cm3 was used
for sampling to reduce experimental uncertainty in determination of compositions.
The gravimetric method was used for analyzing liquid and vapor phase samples
taken from an optical cell. The phase compositions were measured by the follow-
ing procedure. Prior to sampling, the empty sampler was weighed using the Vibra
electronic balance with an uncertainty of 10–4 g. The extracted sample in the sam-
pler is a blend of the (propane/n-butane) mixture as a solvent and n-tetradecane
as a solute. The propane/n-butane mixture has been separated using the procedure
described below (see sec. 2.2.3., see also some details in our previous publications
[1–5, 12]). The mass of the separated (propane/n-butane) mixture in the sampler was
determined as a difference between the full and the empty sampler. Analogously,
the mass of n-tetradecane was calculated as a difference between the mass of the
substance remaining after completely releasing the vapor phase (propane/n-butane
mixture) and empty sampler. The n-tetradecane mass fractions in the liquid wL or
vapor wG phases can be obtained as
13
mC14
w(L/G) =
mC3+C4 + mC14
, (1)
where mC14 is the mass of n-tetradecane dissolved in the SC (propane/n-butane) mix-

ture; mC3+C4 is the mass of the (propane/n-butane) mixture. The combined expanded
relative uncertainty of the composition measurements (at 0.95 confidence level, a
coverage factor of k = 2) was estimated as 0.035 (see below).
Sampling (i.e. mass taken out from the system to be investigated) from a closed
high-pressure equilibrium VLE cell, leads to two effects: (1) to a drop of pressure
in the equilibrium cell if no counter pressure and (2) to a change of the total com-
position only in the phase equilibrium cell. The well-known procedure of keeping
pressure constant by adding mixture components during sampling has been used to
check the constant composition of the phase at equilibrium condition and for repeat-
ability uncertainty estimation (see below). Additional mass of propane/n-butane
mixture has been added to the phase equilibrium cell to keep the pressure in the
cell constant during sampling. The mass loss due to sampling has been compen-
sated. The amount of adding mass depends on pressure drop after sampling. This
is a very well-known depressurization procedure to add one of the components of
the mixture. The change of total composition in the equilibrium cell occurs when
the composition of the sample is different from the total composition (exception of
azeotropic systems). While pressure and temperature stay constant during sampling,
the change of composition usually does not negatively influence subsequent sam-
ples. This is because the new total composition lies on the original tie line so that
the compositions of the equilibrium phases remain constant, only the volume of the
phase that was sampled becomes smaller [49]. Due to the pressure drop the sys-
tem is no longer in phase equilibrium, a new equilibration begins that finally leads
to a new equilibrium state with phase compositions that different from the origi-
nal compositions. After some time (rocking the system and waiting for 30–40 min)
when the system complete mixed, the pressure reaches a plateau within fluctuations.
Before taking samples from the coexisting phases, the mixture is given sufficient
time (30 min) without rocking for the separation of the phases. Otherwise, the sam-
ple might not be homogeneous but contain material from another phase.
2.2.3 Separating Procedure
The procedure separating of the extracted sample (blend of n-tetradecane and

propane/n-butane mixture) into gaseous (propane/n-butane) and solid or liquid
(n-tetradecane), depending on separation temperature, components was carried out
by cooling the sampler to 294 K (at room temperature). The extracted sample was
kept at 294 K for 40 min to separate the (propane/n-butane) gaseous mixture from
the liquid n-tetradecane. At this temperature, n-tetradecane, previously dissolved in
the supercritical (propane/n-butane) mixture, is precipitating into the heavy (con-
densable) liquid -phase (the melting temperature of n-tetradecane is Tm = 278.95 K)
and light (non-condensable) gas-phase (propane/n-butane) mixture completely
separating from the liquid phase (n-tetradecane). In order to completely remove the
13
gas-phase (propane/n-butane) mixture from the liquid n-tetradecane, after release

the first amount of (propane/n-butane) mixture, then a vacuum is created in the
container to remove the rest of the (propane/n-butane) gas from the liquid -phase
(n-tetradecane). This procedure ensures that all of the (propane/n-butane) gas-phase
is completely removed from the liquid n-tetradecane. It was experimentally found
that the most optimal temperature for separating (propane/n-butane) gas- phase and
liquid phase (n-tetradecane) is the room temperature (294 K). We have tried cooling
the sample to crystallization temperature (below Tm). However, no significant dif-
ference in determination of the concentration of n-tetradecane was found. In order
to avoid possible removal of n-tetradecane from the vapor phase during its release
from the sampler, the particle trap was mounted to the outlet valve of the sampler
(for details see [1–5]). Thus, in this study we have assumed that the vapor fraction
removed from an extracted sample does not contain n-tetradecane. This assumption
was additionally verified by chromatographic analyses of both separated liquid and
vapor phases. Therefore, this method does not require a chromatographic analysis
of the compositions of the extracted samples, since the mass of the vapor and liquid
phases is directly determined. Chromatographic analysis was used in this work only
to verify the gravimetric analysis by determining a presence of traces of each com-
ponent in the separated (propane/n-butane) and n-tetradecane samples.
In the present work we are not measured of the composition (mole fractions) of
the gas and liquid phases in the n-tetradecane + propane/n-butane system. The deter-
mination of the composition (mole fraction) of the n-tetradecane and the compo-
nents of the propane/butane mixture is problem in this method, since it is impossible
within the present method precisely determine the propane / n-butane ratio in the liq-
uid and vapor phases. It is no guaranty that propane/n-butane ratio is constant at any
experimental temperatures and pressures. In this case it is very useful to use com-
bined, both gravimetric and chromatographic methods to precisely measure of the
mole fractions of components in the gas and liquid phases. Therefore, in the present
work we present the mass fractions of n-tetradecane and propane/n-butane mixture
in the gas- and liquid phases, i.e., provide VLE properties (solubility of n-tetrade-
cane in SC binary mixture of propane/n-butane) for the n-tetradecane + propane/n-
butane system in mass fraction for n-tetradecane and (propane/n-butane) without
separating concentrations of propane and n-butane (see below, Table 2).
According to the present method, the sampling from gas and liquid phases are
performed separately. After a quick sampling from any phase (gas or liquid using
different valves) at the given T and P, the phase equilibrium composition and pres-
sure are shifting. Therefore, with the present method the next sampling from another
phase at the same T and P conditions becomes impossible. Consequently, the next
sampling was performed after vigorously stirring the sample for 30–40 min using
rocking mechanism and reaching equilibrium condition at another experimen-
tal T and P condition. After some time (approximately 30–40 min), the pressure
reaches a plateau the mixing has stopped for the complete mixing. Once the equilib-
rium is reached, small samples are taken from the vapor or liquid phases and their
composition is analyzed. For convenience, the phases (liquid or gas) were analyzed
separately, at the different T and P conditions.
13
Table 2 Experimental Pressure P/(MPa) Mass fraction of Mass fraction of

VLE data in n-tetrade- n-tetradecane (propane/ n-butane)
cane + (0.367propane/0.633n- mixture
butane mass fraction) system at
selected isotherms T = 413.15 K
Liquid phase
1.00 0.928 0.072
1.15 0.888 0.112
1.57 0.840 0.160
1.69 0.828 0.172
2.42 0.735 0.265
3.08 0.607 0.393
3.38 0.511 0.489
3.89 0.379 0.621
4.53 0.257 0.743
4.85 0.162 0.838
Gas-phase
1.11 0.153 0.847
1.93 0.025 0.975
2.23 0.018 0.982
3.03 0.019 0.981
3.37 0.016 0.984
4.25 0.018 0.982
4.82 0.032 0.968
T = 433.15 K
Liquid -phase
0.88 0.962 0.038
1.26 0.929 0.071
1.63 0.899 0.101
2.30 0.827 0.173
3.05 0.736 0.264
3.77 0.629 0.371
4.35 0.535 0.465
5.30 0.357 0.643
5.78 0.244 0.756
Gas phase
1.05 0.170 0.830
1.75 0.069 0.931
2.57 0.032 0.968
3.39 0.027 0.973
4.24 0.030 0.970
5.05 0.047 0.953
5.90 0.207 0.793
T = 453.15 K
Liquid phase
1.09 0.960 0.040
13
Table 2 (continued) Pressure P/(MPa) Mass fraction of Mass fraction of

n-tetradecane (propane/ n-butane)
mixture
1.40 0.939 0.061

2.00 0.897 0.103
2.64 0.850 0.150
3.12 0.800 0.200
3.72 0.742 0.258
4.82 0.618 0.382
5.71 0.477 0.523
6.38 0.356 0.644
Gas-phase
1.20 0.106 0.894
1.99 0.061 0.939
2.45 0.049 0.951
3.65 0.042 0.958
4.54 0.053 0.947
5.08 0.052 0.948
5.99 0.122 0.878
6.59 0.169 0.831
Standard absolute u(0.95 level of confidence) and( relative ur uncer-

tainties
( ) are: u(T) = 0.075 K; ur(P) = 0.0011; ur wL = 0.018; and
)
ur wG = 0.018
2.2.4 Validation
The apparatus and the experimental procedure presented above were checked for binary
(SC CO2 + toluene), (propane + n-butane), CO2 + n-tetradecane mixtures at high- tem-
peratures and high -pressures for which reliable experimental VLE data is available in
the NIST/TRC Data Base (see Refs. [1, 4, 5]). Experiments for binary mixtures (SC
CO2 + toluene) and (propane + n-butane) were conducted at various temperatures and
pressures, in order to check the apparatus and experimental procedure described above.
The same apparatus was successfully used to measure VLE properties of hexadecane,
naphthalene, acetophenone, and dichloromethane in supercritical binary (propane
/n-butane) solvent [1–5]. Also, the measured critical property parameters (the critical
temperature, pressure, and density) for pure propane using the same VLE apparatus [2]
agreed with the reference data [34] within 1.2 K, 0.0003, and 0.03, respectively, while
the measured values of the critical parameters for the selected mixture of (0.367pro-
pane + 0.633 n-butane) (TC = 407.4 K and PC = 4.121 MPa) were in good agreement
(deviations are within 1.4 K and 0.006 MPa, respectively) with the reported data
[17–19, 32, 33] (see below, Figs. 1 and 2). The value of the critical density is in good
agreement (deviation of 0.6%) with the value reported by Nysewander et al. [19]. Thus,
this generally good agreement provides some confidence in the experimental VLE data
for n-tetradecane + (0.367propane/0.633 n-butane) obtained using the same apparatus
and procedure.
13
427
CP (C4H10)
417
407
TC / K
397
387
377
CP (C3H8)
367
0.0 0.2 0.4 0.6 0.8 1.0
x / mole fraction of propane

C3+C4 -Tc-x
Fig. 1 The critical temperature of binary propane/n-butane mixture as a function of concentration

(TC − x ) reported by various authors from the literature. ▲—Juntarachat et al. [33]; ×—Barber [17]; —
Nysewander et al. [19]; ○—Soo et al. [32]; ●—Kay [18]; □—Khairutdinov et al. [2] (using the present
method). Dashed line is calculated from correlation equation by Soo et al. [32]
2.2.5 Uncertainty Assessment
The uncertainty of pressure and temperature measurements consist of (1) the maxi-
mum instrumental uncertainty of pressure uP,ins = 0.025 bar and temperature uT,ins =
0.05 K; and (2) the deviation of temperature and pressure due to temperature fluctua-
tion (uT,fluc = 0.03 K for temperature and uP,fluc due to temperature instability). There-
fore, the standard uncertainties in the temperature u(T) and the pressure u(P) are
√
u(T) = u2T,ins + u2T,fluc < 0.06 K
√
and u(P) = u2P,ins + u2P,fluc depends on experimental temperature and pressure
changes due to temperature instability (fluctuations). The value of uP,fluc changes
within the present experimental conditions within 0.006 to 0.05. The maximal value
of u(P) at the temperature P and T conditions is about 0.056 bar (or maximal relative
standard uncertainty is ur (P) = 0.0011). Thus, the total combined expanded uncer-
tainty of temperature measurements (at 0.95 confidence level, a coverage factor of
k = 2) is 0.15 K (standard uncertainty is 0.075 K). The combined expanded relative
13
4.5
4.4
CP (C3H8)
4.3
4.2
PC / MPa
4.1
4.0
3.9
3.8
CP (C4H10)
3.7
0.0 0.2 0.4 0.6 0.8 1.0
x / mole fraction of propane
C3+C4 -Pc-x
Fig. 2 The critical pressure of binary propane/n-butane mixture as a function of concentration ( PC − x )

reported by various authors from the literature. ▲—Juntarachat et al. [33]; × -Barber [17]; —Nysewan-
der et al. [19]; ○—Soo et al. [32]; ●—Kay [18]; □—Khairutdinov et al. [2] (using the present method).
Dashed line is calculated from correlation equation by Soo et al. [32]
uncertainty of the pressure measurements (at 0.95 confidence level, a coverage fac-
tor of k = 2) is 0.0022 (standard uncertainty is 0.0011).
The uncertainty of the composition measurements in the present work were esti-
mated by the guidelines from NIST [37]. The uncertainty assessment based on the
relation for variance of phase concentrations (wL and wG ). The final uncertainty of
the liquid (wL) and gas (wG) concentration measurements has been calculated using
following expressions
√
ucal (z) = u2 + u2rep , (2)
√
√
√ Nsam
( Nsam
)2
( ) √ 1 ∑ 1 ∑ (3)
urep zi = √ zi − z ,
Nsam i=1 i
( )
Nsam − 1 i=1
where z is (wL or wG), urep is an uncertainty due to repeatability and Nsam is a num-
ber of sampling (5–6 for each fixed T and P). Series (i = 5–6) of experiments were
13
carried out by extracting the samples for analysis at fixed P and T using the pro-
cedure of keeping pressure constant by adding component (propane/n-butane mix-
ture) during sampling (see above). The experimental compositions were the result
of averaging the all obtained values of zi . These data zi were used to estimate the
uncertainty due to reputability as described above.
Assuming that all of the input parameters in working Eq. 1Xi ( mC14, mC3+C4, T, P)
are independent, the variance of phase concentrations (x and y) is
( )2 ( )2
𝜕z 𝜕z
u2 (z) = u2 mC14 + u2 mC3+C4
( ) ( )
𝜕mC14 C3+C4,P,T 𝜕mC3+C4 C14,P,T
( )2 ( )2 (4)
𝜕z 2 𝜕z 2
+ u (T) + u (P),
𝜕T mi ,P 𝜕P mi ,T
where u Xi are the standard

( ) (uncertainties (of the
) independent measured parameters
( )
)
Xi (mC14,mC3+C4,T ,P ); 𝜕m , 𝜕T
𝜕z 𝜕z
, and 𝜕P
𝜕z
are the sensitivity coefficient for
i mi ,P mi ,T
the phase concentrations, Eq. 1. The combined standard uncertainty is the square
(root )of the variance, u (z) [37]. All required derivatives of the concentrations,
2
𝜕z
𝜕Xi X
are can be explicitly derived from the working equation Eq. 1. The values
j≠i ( ) ( )
of partial derivatives 𝜕T𝜕z
and 𝜕P𝜕z
were approximately estimated from the pre-
p T
sent experimental VLE data. The relative combined expanded uncertainty Ur (z) of
phase concentrations (z) with a level of confidence of 0.95 can be calculated by the
following equation Ur (z) = ku(z)∕z(k = 2 is the inclusion factor). The combined
expanded (k = 2) absolute and relative uncertainty of the pressure, temperature, and
phase concentrations measurements at 0.95 confidence level is estimated to be
0.0022, 0.15 K, and 0.035, respectively. The standard uncertainty due to repeatabil-
ity is urep = 0.002. The relative combined expanded uncertainty of the concentration
measurements due to repeatability is Urep (z) = kurep (z)∕z = 0.01.
3 Results and Discussion
3.1 Experimental VLE Results
The isothermal phase equilibrium (VLE,PTwL wG ) properties of n-tetradecane

in the SC propane/n-butane solvent was measured at three temperatures of
T = (413.15, 433.15, and 453.15) K, which are above the critical temperature of
the binary ready to use solvent mixture of 0.367 mass fraction (propane) / 0.633
mass fraction (n-butane) or 0.433 mol fraction of propane/0.567 mol fraction of
n-butane (TC = 405.49 K and PC = 4.174 MPa [2]) used. Therefore, the critical
temperature of the binary solvent mixture lower than the critical temperature of
pure n-butane (TC = 425.13 K), while the critical pressure slightly above the criti-
cal pressure of pure n-butane ( PC = 3.796 MPa). The critical property data (TC-x,
PC-x, and PC-TC ) for the propane + n-butane binary mixture have been reported in
13
our previous publication [2] together with other available data from the literature
[17–19, 32]. These critical properties data [2] for propane + n-butane mixture has
been measured using the same method described above. Reported TC-x and PC-x
projections of the critical curves of binary propane/n-butane solvent are depicted
in Figs. 1 and 2. Our results for the critical properties data [2] of propane/n-
butane mixture were measured using the current experimental method (the same
VLE apparatus described above). This is good validation of the method and cor-
rectly operation of the VLE apparatus used for the present study. As shown in
Figs. 1 and 2, the agreement between the present and reported critical property
data is good. The TC-x curve of the propane/n-butane mixture is continuous with
a small curvature. The critical temperatures and the critical pressures of the mix-
tures lie between the pure component values. However, the critical pressures (see
Fig. 2) pass through a maximum around x = 0.8 mol fraction of propane which is
slightly higher than the critical pressures of the pure components.
Table 2 reports the experimental phase equilibrium ( PTwL wG ) results for three
temperatures T = 413.15 K, 433.15 K, and 453.15 K (see also Fig. 3 a,b,c in P-wL/wG
projections). As can be note, the concentration of n-tetradecane in the vapor phase is
negligible small at pressures between (2 to 5) MPa for each measured isotherm. The
concentration of n-tetradecane in the vapor phase sharply increases when approaches
to the critical pressure of the mixture. The present VLE data were used to estimate
the values of the critical properties of the system of n-tetradecane + propane/n-
butane, based on the well-known relation wL = wG . In the P- wL/wG-wG projection at
constant temperature (see Fig. 3 a-c), the pressure where composition of both, liquid
(wL) and gas (wG), phases is the same (wL = wG ), is the critical point of the mixture,
i.e., other words, the pressure where both liquid (full symbols, see Fig. 3a-c) and gas
(open symbols) branches of the isothermal VLE (P-w) curve are intersecting (where
both liquid and gas phases become identical) is the critical pressure. The derived
values of the critical parameters of n-tetradecane + propane/n-butane mixture
are: w = 0.093 mass fraction of n-tetradecane, PC = 5.03 MPa, and TC = 413.15 K;
w = 0.225 mass fraction of n-tetradecane, PC = 5.85 MPa, and TC = 433.15 K; and
w = 0.254 mass fraction of n-tetradecane, PC = 6.7 MPa, and TC = 453.15 K. Fig-
ure 4 illustrates the critical curve of the binary sub-systems (propane + n-butane,
propane + n-tetradecane, and n-butane + n-tetradecane). This figure contains also the
vapor- pressure curves calculated from the reference (REFPROP [34]) EoS for pure
propane and n-butane, and n-tetradecane calculated from vapor-pressure equation
by Camin and Rossini [35] (NIST recommended). As Fig. 4 shows, the slope of the
critical line (dPC/dTC ) is positive. This means that complete dissolution of n-tetrade-
cane in the propane/n-butane solvent increases with temperature increasing.
The type of the phase behavior, according to the van Konynenburg and Scott [36]
classification, depends on the shape of the critical lines. The critical curves behav-
ior for n-tetradecane + propane/n-butane is very less- known. Figure 5 illustrates
TC − w, PC − w, and PC − TC critical lines of the n-tetradecane + propane/n-butane
system based on the present experimental data. TC − w projection of the critical
line gradually increases with concentration of n-tetradecane and linking the critical
points of the pure n-tetradecane (TC = 693.0 K) and the critical temperature of the
binary mixture of 0.367propane/0.633n-butane (TC = 408.79 K). The critical curve
13
Fig. 3 a–c Measured isothermal 6
VLE phase diagram of n-tetra- (a)

decane + (0.367propane/0.633n- 5
butane mass fraction) system at
three constant temperatures. ×— T = 413 K
4
is the critical point of the mix-
ture where wL = wG ; ○-composi-
P / MPa
tion of the vapor phase, wG is 3
mass fraction of n-tetradecane
in gas phase; •—composition
2
of the liquid phase, wL is mass
fraction of n-tetradecane in
liquid phase. Dashed curves are 1
interpolated values (smoothed

data) 0
0.0 0.2 0.4 0.6 0.8 1.0
w (mass fraction of tetradecane)
C3+C4 + Tetradecane Pxy T413
(b)
6
T = 433 K
5
4
P / MPa
0
0.0 0.2 0.4 0.6 0.8 1.0
7
(c)
T = 453 K
6
5
P / MPa
0
0.0 0.2 0.4 0.6 0.8 1.0
13
12.0
7
10.5
9.0 5
6
7.5
P / MPa
6.0
4.5
1
3.0 4
2
1.5 3
0.0
300 350 400 450 500 550 600 650 700
T/K
C3+C4 -Tetradecane P-T, CrLines
Fig. 4 PC-TC projection of the critical curves of ternary n-tetradecane + (0.367propane/0.633n-butane

mass fraction) system and binary sub-systems. Solid lines are the vapor-pressures of pure propane (1)
and n-butane (2) calculated from REFPROP [34] and n-tetradecane (3) calculated from correlation by
Camin and Rossini [35]. ×—is the critical points of pure components; ●—is the critical points of the
n-tetradecane + propane/n-butane mixture (this work); Dashed-dotted curve (4) is VLE curve of the
binary 0.367propane/0.633n-butane system [17–29]. Other symbols are the critical property data for
binary propane + n-butane mixture from [17–19] (TDE/NIST Date Base [16]). Dashed lines are the criti-
cal curves of binary sub-systems (propane + n-tetradecane -7 and n-butane + n-tetradecane-5) guide for
the eye
of the n-tetradecane + propane/n-butane mixture in PC − x projection also is con-

necting the critical pressure of the pure n-tetradecane ( PC = 1.57 MPa) and the criti-
cal pressure of binary mixture of 0.367propane/0.633n-butane ( PC = 4.128 MPa).
The present critical pressure data confirm that the critical curve PC − w of n-tet-
radecane + 0.367propane/0.633n-butane passes through a maximum (see Fig. 5).
The P–T phase diagram and the critical curves of the binary n-tetradecane + CO2
[1], and ternary n-tetradecane + propane/n-butane (the present work) and CO2 + pro-
pane + n-butane (calculated from mixture –model by Lemmon et al. [34]) systems
in the ( PC-TC) projections are demonstrate in Fig. 6. This figure also is including
the critical curve and the P–T phase diagram of the ternary mixture CO2 + pro-
pane + n-butane predicted by mixture-model EoS by Lemmon et al. [34] based on
the reference EoS for pure components (REFPROP [34]). As Fig. 6 shows, the pre-
sent critical curve and P–T phase diagram data for n-tetradecane + propane/n-butane
system are in good consistence with the predicted data from the NIST mixture-
model for multicomponent system [34].
13
725 CP (C 14H 30)

7
625
PC / MPa
TC / K
5
525
CP (C 3H 8/n-C 4H 10)
425 3
CP (C 3H 8/n-C 4H 10) CP (C 14H 30)
325 1
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
w / mass fraction of n-tetradecane w / mass fraction of n-tetradecane
6
P / MPa
CP (C 3H 8/n-C 4H 10)
4
2 CP (C 14H 30)
0
300 400 500 600 700
T/K
Tetradecane +(C3+C4) Pc-x,Tc-x,Pc-Tc.AXD
Fig. 5 TC-w, PC-w, and PC-TC projections of the critical curves of n-tetradecane + propane/n-butane sys-
tem. Solid curve is the vapor-pressure of pure n-tetradecane [35]. Dashed -dotted curve is the P–T phase
equilibrium curve of (0.367propane/0.633n-butane mass fraction) [17–29]. Dashed lines are the critical
curves of n-tetradecane + propane/n-butane mixture guided for the eye
4 Conclusions
Isothermal vapor–liquid equilibrium ( PTwL wG ) data have been measured for n-

tetradecane in binary SCF solvent of (0.367 propane/0.633 n-butane mass frac-
tion) by using a high-pressure optical cell (VLE apparatus) for three isotherms of
413.15 K, 433.15 K, and 453.15 K in the pressure range from (0.9 to 6.6) MPa.
The critical parameters (w = 0.093 mass fraction of n-tetradecane, PC = 5.03 MPa,
and TC = 413.15 K; w = 0.225 mass fraction of n-tetradecane, PC = 5.85 MPa, and
TC = 433.15 K; and w = 0.254 mass fraction of n-tetradecane, PC = 6.7 MPa, and
TC = 453.15 K) were determined using the present experimental VLE data for the
(n-tetradecane + 0.367 propane/0.633 n-butane) system. We have experimentally
observed that concentration of n-tetradecane in the vapor phase is small at pres-
sures between (2 to 5) MPa for each measured isotherm. Also, the concentration
of n-tetradecane in the vapor phase sharply increases when approaches to the crit-
ical pressure of the mixture. The present VLE data indicates that complete dis-
solution of n-tetradecane in the 0.367 propane/0.633 n-butane solvent increases
with temperature increasing.
13
30
25
20
P / MPa
15
10 5
1
5 6
2
3
0
250 320 390 460 530 600 670
T/K
C3+C4 -Tetradecane & CO2- P-T, CrLines
Fig. 6 P–T phase diagram and the critical curves of the binary n-tetradecane + CO2, and ternary n-tet-
radecane + propane/n-butane and CO2 + propane + n-butane systems in the ( PC-TC) projections. 1- is
the vapor-pressure of pure CO2 [34], 2- is the VLE curve of the 0.367propane/0.633n-butane mixture
[17–19]; 3- is the vapor-pressure of pure n-tetradecane [35]. 4- and 5- are the critical curves of the n-tet-
radecane + CO2 and n-tetradecane + propane/n-butane mixtures guided for the eye; 6-is the VLE curve
of the ternary mixture of C
O2 + propane + n-butane (mixture-model based on the reference EoS for pure
components by Lemmon et al. [34], REFPROP); •-this work (experiment); ○- Khairutdinov et al. [1]
(experiment)
Acknowledgements The work was financially supported by the Ministry of Science and Higher Educa-
tion of the Russian Federation within the framework of the state assignment No. 075-01508-23-00 of
December 29, 2022 (Supercritical fluid technologies in polymer processing FZSG-2023-0007). The study
was carried out using the equipment of the Center for Collective use «Nanomaterials and Nanotechnol-
ogy» of the Kazan National Research Technological University.
Author Contributions VFK: investigation, supervision and editing software; ISK: formal analysis, soft-
ware; TRA: writing—review and editing software; LYY: investigation, resources; FRG: conceptualiza-
tion, methodology; IMA: writing—original draft.
Funding The Ministry of Science and Higher Education of the Russian Federation (075-01508-23-00)
and (FZSG-2023-0007).
Availability of Data and Materials All data generated or analyzed during this study are included in this
published article.
13
Declarations
Competing interest The authors have no competing interests, or other interests that might be perceived to
influence the results and/or discussion reported in this paper.
Ethical Approval Not applicable.
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Experimental Study of VLE Properties of N Tetradecane in The Supercritical Binary Solvent (0.367 Propane/0.633

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Experimental Study of VLE Properties of N Tetradecane in The Supercritical Binary Solvent (0.367 Propane/0.633

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International Journal of Thermophysics (2023) 44:114

Experimental Study of VLE Properties of n‑Tetradecane

Vener F. Khairutdinov1 · Ilnar Sh. Khabriev1 · Talgat R. Akhmetzyanov1 ·

Keywords Critical point · Critical curve · n-Tetradecane + propane/butane mixture ·

Measurement of the solubility (VLE properties) of compounds in supercritical

concentration of binary solvent) can be readily adjusted by changing their compo-

Binary mixture of propane/n-butane, with fixed composition of 0.633 mass fraction

Propane 74–98-6 Not found ≥ 0.9980 (NMR) OOO MONITORING (Moscow)

2.2 Experimental VLE Apparatus and Procedure of Measurements

2.2.1 High‑Temperature and High‑Pressure Optical Cell

where mC14 is the mass of n-tetradecane dissolved in the SC (propane/n-butane) mix-

The procedure separating of the extracted sample (blend of n-tetradecane and

gas-phase (propane/n-butane) mixture from the liquid n-tetradecane, after release

Table 2 Experimental Pressure P/(MPa) Mass fraction of Mass fraction of

Table 2 (continued) Pressure P/(MPa) Mass fraction of Mass fraction of

1.40 0.939 0.061

Standard absolute u(0.95 level of confidence) and( relative ur uncer-

x / mole fraction of propane

Fig. 1 The critical temperature of binary propane/n-butane mixture as a function of concentration

Fig. 2 The critical pressure of binary propane/n-butane mixture as a function of concentration ( PC − x )

where u Xi are the standard

3 Results and Discussion

3.1 Experimental VLE Results

The isothermal phase equilibrium (VLE,PTwL wG ) properties of n-tetradecane

Fig. 3 a–c Measured isothermal 6

VLE phase diagram of n-tetra- (a)

interpolated values (smoothed

C3+C4 + Tetradecane Pxy T413

Fig. 4 PC-TC projection of the critical curves of ternary n-tetradecane + (0.367propane/0.633n-butane

of the n-tetradecane + propane/n-butane mixture in PC − x projection also is con-

725 CP (C 14H 30)

Isothermal vapor–liquid equilibrium ( PTwL wG ) data have been measured for n-

Ethical Approval Not applicable.

49. S. Peper, R. Dohrn, J. Supercrit. Fluids 66, 2–15 (2012). https://​doi.​org/​10.​1016/j.​supflu.​2011.​09.​

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2.2 Experimental VLE Apparatus and Procedure of Measurements

2.2.1 High‑Temperature and High‑Pressure Optical Cell

3 Results and Discussion

3.1 Experimental VLE Results

49. S. Peper, R. Dohrn, J. Supercrit. Fluids 66, 2–15 (2012). https://doi.org/10.1016/j.supflu.2011.09.