J. Chem.

Thermodynamics 144 (2020) 106065

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Experimental densities and derived thermodynamic properties of pure

p-cymene, a-pinene, limonene and citral under high pressure conditions
Jovana Ilić Pajić a, Gorica Ivaniš b, Ivona Radović b, Aleksandar Grujić a, Jasna Stajić-Trošić a,
Mirko Stijepović b, Mirjana Kijevčanin b,⇑
a
University of Belgrade, Institute for Chemistry, Technology and Metallurgy, Njegoševa 12, 11000 Belgrade, Serbia
b
University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia

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

Article history: In order to reduce negative influence of fossil fuels on environment, use of various renewable resources is
Received 27 May 2019 highly promoted. Terpenes, naturally occurring in plants, can be added to petroleum fuel as its substitute
Received in revised form 13 January 2020 up to a certain share. Thermodynamic properties of a fuel under high pressure and moderate temperature
Accepted 20 January 2020
conditions are of significant importance for engine efficiency. This work reports density measurements of
Available online 24 January 2020
pure p-cymene, a-pinene, limonene and citral at temperatures (293.15–413.15) K and pressures (0.1–
60) MPa, applying an Anton Paar DMA HP measuring cell. Density data were fitted by modified
Keywords:
Tammann-Tait equation where the absolute average percentage deviation between measured and calcu-
Pure terpenes
High pressure
lated densities was about 0.010%. The obtained parameters were used to estimate the isothermal com-
Density pressibility, the isobaric thermal expansion coefficient, the internal pressure, and the difference
Thermodynamic properties between specific heat capacity at constant pressure and at constant volume. For examined compounds,
all thermodynamic properties, except the internal pressure, decrease with pressure rise along an iso-
therm and increase as temperature increases at a constant pressure. The intersection point of isotherms
for the isobaric thermal expansion coefficient for pure citral was registered at pressure 47 MPa, while for
other analyzed terpenes the intersection point is above 60 MPa, outside the measurements pressure
range.
Ó 2020 Elsevier Ltd.

1. Introduction
The attention to fuels with high energy density, low viscosity
and efficient and clean combustion, which can be applied for heavy
trucks, ships, aerospace or in the military, has been increased
[1–6]. Due to chronic need for transport fuels and rigorous envi-
ronmental regulation policy, the development of fuel production
from various renewable and economically cost-effective feedstock
is required [5,7–9]. The fact that fossil fuel reserves are limited and
environment shows signs of saturation, the utilization of
biodegradable, non-toxic and non-hazardous energy sources is
highly encouraged [10–13]. The growth of air transport has
increased the need for the development of fuel production from
bioresources which would lead to a reduction of CO2 emissions
[7,14–18]. Nevertheless, the utilization of alternative fuels was
limited in current air transport due to specific requirements pre-
scribed for aviation fuels [19]. In aerospace vehicles the effect of
⇑ Corresponding author.
E-mail address: mirjana@tmf.bg.ac.rs (M. Kijevčanin).
density and volumetric energy content of used liquid fuels are
the most important aspects for the propulsion performance. These
vehicles are usually volume-limited, so small tanks loaded with
fuel of high energy density are preferred. Biofuels with mentioned
properties should be synthesized from biomass feedstock includ-
ing terpene, hemicellulose, cellulose and lignin.
Group of natural chemical compounds, terpenes, are attractive
candidates as ‘‘drop-in” aviation fuels. They represent natural pro-
duct, secondary metabolites of plants, and can be produced either
from algal biomass or induced by bacteria in decomposition of
wood residues during a storage period [12,20,21]. Terpenes are
good alternative and sustainable energy sources since they usually
do not have oxygen content, contrarily to biodiesel and alcohol
[12,15,22–24]. Also, due to their properties such as boiling point,
flash point, freezing point, low viscosity, high energy density, sev-
eral terpenes have arose scientific interest [1,4,5,22,23]. They could
be found in cyclic and acyclic forms, where the cyclic structure was
preferred as a resource for a biofuel due to their higher energy den-
sity [9,23], although fuels of high energy density could also be syn-
thesized from some acyclic forms [23]. Based on isoprene units
these hydrocarbon compounds were classified as monoterpenes

https://doi.org/10.1016/j.jct.2020.106065
0021-9614/Ó 2020 Elsevier Ltd.
2 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065

(C10), sesquiterpenes (C15) and diterpenes (C20) [5,11,23–26].In 2. Experimental

order to improve volumetric energy content when it is needed, ter-
penes can be used in mixtures with the conventional fuels [27]. 2.1. Materials
Commonly used terpenes, which are by-product of wood, paper
industry, citrus fruits and leaves of many plants, are p-cymene, The terpenes were purchased from Acros Organics and details
a-pinene, limonene and citral. are listed in Table 1. All pure chemicals were ultrasonically
Knowledge of high pressure thermodynamic properties of a degassed before measurements. The mass fraction purity was
potential fuel is of high importance for engine efficiency develop- checked by gas chromatography. All chromatograms were shown
ment. The thermophysical and transport properties depend on in the Supplementary material to this paperin Fig. S1.
pressure and temperature, so the goal of this paper was to investi-
gate thermodynamic behavior of four pure terpenes at high pres-
sures (up to 60 MPa) and moderate temperatures (up to 2.2. GC/FID and GC/MS analyses
413.15 K). Terpenes with the wide industrial application have been
chosen, three cyclic terpenes without oxygen atom, p-cymene, GC/FID and GC/MS analyses were carried out with an Agilent
(1S)-(
)-a-pinene, (+)-limonene (in the further text referred as 7890A apparatus equipped with an 5975C MSD, FID, and a HP-
a-pinene and limonene) and the acyclic terpene with one oxygen 5MSI fused-silica capillary column (30 m  0.25 mm, film thick-
atom (citral). Citral has been chosen in order to compare the ther- ness 0.25 lm). The oven temperature was programmed from 60
modynamic behavior of an oxygen-containing organic compound to 315 °C at 3 °C/min then held isothermal for 5 min. Injector:
and hydrocarbons as the fuel precursors. The structures of the 250 °C; FID detector: 300 °C; carrier gas, He (1.0 mL/min at
selected compounds are presented in Fig. 1 [22]. According to the 210 °C), injection volume 1 lL split ratio, 3:1. EI-MS (70 eV), m/z
available literature there are few density data at high pressures
for a-pinene and limonene [28](pressures up to 40 MPa and tem-
Table 1
peratures up to 358.15 K). In order to complement the density Samples details.
database, densities of p-cymene, a-pinene, limonene, and citral
Chemical Name Source CAS number Purity mass
were determined at pressures from (0.1 to 60) MPa and tempera-
fractiona
tures from (293.15 to 413.15) K and presented in this paper. Den-
p-cymene Acros Organics 99-87-6 0.994
sities were fitted by the modified Tammann-Tait equation and
(1S)-(
)-a-pinene Acros Organics 7785-26-4 0.986
compared with reported literature data. Furthermore, important (+)-limonene Acros Organics 5989-27-5 0.994
mechanical properties were also calculated (i.e. isothermal com- citral (mixture of neral Acros Organics 5392–40-5 0.969 (0.476 neral;
pressibility, the isobaric thermal expansion coefficient, the internal and geranial) 0.493 geranial)
pressure, and the difference of specific heat capacity at constant a
Verified by gas chromatography with the relative uncertainty of 3% (confidence
pressure and at constant volume) and analyzed. level of 95%).

Fig. 1. Chemical structure of (a) p-cymene, (b) (1S)-(
)-a-pinene, (c) (+)-limonene, and (d) citral (mixture of geranial and neral).
 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065
range 40–550. Compound identification: identification of all com-
pounds in analyses was match by comparison of their linear reten-
tion indices (relative to C8–C36 n-alkanes on the HP-5MSI column)
and MS spectra with those of authentic standards from NIST11
database. The difference in retention times of neral (tR = 17.5 min)
and geranial (tR = 18.7 min) is 1.2 min and they were identified
according to the MS spectra and NIST11 database. Kovatsz index
for neral is 1238 (1234 theoretical) and for geranial 1268 (1265
theoretical), (see Fig. S1).
2.3. Measurement method
The densities were measured applying two different devices by
Anton Paar supplier, DSA 5000 M and DMA HP. Employing DSA
5000 M experimental values were determined at atmospheric
pressure and temperature T = (293.15–323.15) K with the standard
uncertainty of the density measurementsu (q) = ±0.09 kgm
3, con-
fidence level of 68%. The usage of the DSA 5000 M digital vibrating
U-tube densimeter is very similar to the DMA 5000, which is
explained in detail in previous works [29–31].The device was cal-
ibrated using ambient air and ultra-pureMilliporewater every day
prior to measurements.
At high pressures (up to 60 MPa) and temperatures (up to
413.15 K), experimental density measurements have been per-
formed applying an Anton Paar DMA HP measuring cell. Apparatus
was designed to measure the oscillation period of U tube filled
with a sample. It was connected with Anton Paar DMA 5000 vibrat-
ing densitymeter, which served as a reading device, by S-BUS inter-
faces. The set temperatures, and measured pressures and
oscillation periods were recorded by APSoftPrint software pro-
gram. The details about the experimental setup and the operating
method which was used in our laboratory has been described in
previous works [29,32–35]. Hence, the experimental density val-
ues were not obtained directly and it was crucial to carry out clas-
sical one-fluid calibration method [36,37].Calibration fluid for
measurements at temperatures equal or lower than 363.15 K and
at all pressures was water. At atmospheric pressure and tempera-
tures equal or higher than 373.15 K the calibration fluid was
n-decane. The calibration procedure was explained in details else-
where [32].
The pressures from (0.1–60) MPa have been achieved by High
Pressure Generator from High Pressure Equipment Co, model 50-
6-15, using acetone as pressurizing fluid. Pressure within the sys-
tem is measured using pressure sensor WIKA Alexander Wiegand
GmbH & Co, S-10, with the standard uncertainty of ±0.05 MPa, con-
fidence level of 68%. An integrated Peltier thermostat was
employed to control and regulate temperatures with a stability
of ±0.05 K and the standard uncertainty with level of confidence
of 68% for the temperature was estimated to u(T) = ±0.05 K. Bran-
son 3210 ultrasound bath was applied to degassing p-cymene,
a-pinene, limonene and citral for at least 10 min before measure-
ment. It is well known that sample’s viscosity affects oscillation of
measuring U tube in densimeter, so the density corrections have
been calculated according to viscosity values found in the litera-
ture and for all investigated terpenes they were less than
0.2 kgm
3 [38–41]. The standard uncertainty of densities of the
used chemicals (confidence level 68%) was estimated taking into
account aforementioned uncertainties of temperature, pressure
and density correction due to damping effect. It was u(q) = ±0.5 k
gm
3 (293.15 K  T  363.15 K) and ± 0.7 kg∙m
3 (373.15 K 
T  413.15 K). The described apparatus was used to measure oscil-
lation period for selected four pure terpenes under high pressures
up to 60 MPa and over range of temperatures (293.15–413.15) K.
Purity of the used chemicals influences the uncertainty of
reported results, so that was considered and estimated according
to the equation proposed by Chirico et al. [42]. The relative uncer-
3
tainties for the densities of p-cymene and limonene (0.994 mass
fraction) were estimated to 610
4, whereas for a-pinene (0.986
mass fraction) and citral (0.969 mass fraction) they were higher
due to poorer purity, 1.410
3 and 3.110
3, respectively.
3. Results and discussion
3.1. Density measurements
Densities, q, of p-cymene, a-pinene, limonene and citral were
obtained from the measured oscillation period. The pressures from
(0.1 to 60) MPa and temperatures from (293.15 to 413.15) K have
been covered by measurements. The experimental data of four
compounds were collected in Table 2 and presented in Fig. 2.
Experimental density values of p-cymene, a-pinene, (+)-
limonene, and citral, obtained by two different devices, DSA
5000 M and DMA HP, have been compared with available literature
and shown in Table 3. Good agreement of mentioned data addi-
tionally approve the quality of used chemicals.
As Fig. 2 and Table 2 show densities of the investigated terpenes
decrease in the following order: citral > a-pinene > p-cymene > li
monene. In order to better understand the density behavior a
molecule structure of each compound is shown in Fig. 1. All the
compounds consist of 10 carbon atoms, where p-cymene is an aro-
matic, a-pinene and limonene have cyclic structure, while citral
has an acyclic molecule structure (see Fig. 1). First three com-
pounds are hydrocarbons while citral, as an aldehyde has one oxy-
gen atom in its structure. Contrarily to the first three hydrocarbons,
citral shows hydrogen bond accepting abilities, but not hydrogen
donor ability so as hydrogen bonding is not possible. Due to a high
polarity of the citral molecules, 4.39 D they are capable to form
dipole-dipole interactions, while hydrocarbons mainly interact
through weaker dispersion forces (dipole moments for the
p-cymene, limonene and a-pinene amount to 0, 1.570 and 0.360
D, respectively) [60,61].With its acyclic structure and one oxygene
atom, citral shows the best packing and the highest densities at the
same conditions, comparing to the other three hydrocarbons
(Table 2 and Fig. 2). As it was expected the influence of pressure
and temperature on densities is opposite, i.e. for each compound
densities increase with pressure rise and with temperature
decrease. However, the temperature and pressure influences are
not the same for each compound which is explained in details in
the Section 3.3, where derived volumetric properties, isothermal
compressibility jT and the isobaric thermal expansion coefficient
ap, are analyzed.
Comparison between experimental densities obtained by both
devices, DSA 5000 M and DMA HP, at atmospheric pressure (see
Table 3 and Fig. S2) and literature reported values [38–59] shows
the density deviations less than 0.25% which confirms validity of
the applied measuring methods.
Experimental densities at high pressures measured with DMA
HP were also compared with available literature data (see Fig. 3).
The densities under high pressure conditions were found for
a-pinene and limonene [28]. Reported values include densities at
five pressures over the range (20–40) MPa and at six temperatures
from (283.15 to 358.15) K [28]. The temperature T = 313.15 K was
the only one of all isotherms that coincide with our measuring con-
ditions [28]. In order to widen the comparison, the parameters of
the modified Tammann-Tait equation reported by Langa et al.
[28] were used for calculation of densities at temperatures and
pressures examined in this paper, (293.15–353.15) K and
(0.1–60) MPa, respectively, and obtained results are shown in
Fig. 2. The absolute average percentage deviations, AAD were
0.11% and 0.10% for a-pinene and limonene, respectively. Very
4 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065

Table 2
Density of the p-cymene, (1S)-(
)-a-pinene, (+)-limonene, and citral at temperatures T = (293.15–413.15) K and pressures p = (0.1 to 60) MPa.

qa(kgm
3)
pa(MPa) p-cymeneb (1S)-(
)-a-pinenec (+)-limoneneb citrald
e
T = 293.15 K
0.1 856.8 858.2 842.3 887.8
1 857.5 858.9 842.9 888.2
5 860.2 861.8 845.5 890.5
10 863.4 865.3 848.7 893.4
15 866.6 868.7 851.8 896.2
20 869.6 872.0 854.8 898.9
25 872.6 875.2 857.7 901.6
30 875.5 878.3 860.5 904.1
35 878.3 881.3 863.2 906.7
40 881.0 884.2 865.9 909.1
45 883.6 887.0 868.4 911.5
50 886.1 889.7 870.9 913.9
55 888.6 892.2 873.3 916.2
60 890.9 894.7 875.6 918.4
Te = 303.15 K
0.1 848.9 850.0 834.5 879.7
1 849.5 850.7 835.1 880.3
5 852.3 853.8 837.9 882.7
10 855.8 857.5 841.2 885.7
15 859.1 861.1 844.5 888.6
20 862.3 864.6 847.6 891.5
25 865.4 867.9 850.7 894.2
30 868.4 871.2 853.6 896.9
35 871.4 874.3 856.5 899.6
40 874.2 877.3 859.3 902.1
45 876.9 880.2 861.9 904.6
50 879.5 883.0 864.5 907.1
55 882.0 885.6 866.9 909.4
60 884.4 888.2 869.3 911.7
Te = 313.15 K
0.1 840.8 841.7 826.7 871.7
1 841.5 842.5 827.3 872.3
5 844.5 845.7 830.2 874.8
10 848.1 849.6 833.8 877.9
15 851.6 853.4 837.2 881.0
20 855.0 857.1 840.5 883.9
25 858.2 860.6 843.7 886.8
30 861.4 864.0 846.8 889.5
35 864.4 867.3 849.8 892.2
40 867.4 870.4 852.6 894.9
45 870.2 873.4 855.4 897.4
50 872.9 876.3 858.1 899.8
55 875.5 879.1 860.6 902.2
60 878.0 881.9 863.2 904.8
Te = 323.15 K
0.1 832.7 833.4 818.8 863.6
1 833.5 834.2 819.5 864.2
5 836.6 837.6 822.5 866.9
10 840.4 841.8 826.2 870.2
15 844.1 845.8 829.8 873.4
20 847.6 849.6 833.3 876.5
25 851.1 853.3 836.7 879.4
30 854.4 856.9 839.9 882.4
35 857.6 860.3 843.0 885.2
40 860.6 863.6 846.0 887.9
45 863.5 866.7 848.9 890.5
50 866.4 869.7 851.7 893.1
55 869.0 872.6 854.3 895.5
60 871.6 875.3 856.8 897.9
Te = 333.15 K
0.1 824.7 825.1 810.8 855.6
1 825.4 825.9 811.6 856.2
5 828.7 829.5 814.8 859.0
10 832.7 833.9 818.7 862.5
15 836.6 838.1 822.5 865.8
20 840.3 842.1 826.2 869.0
25 843.9 846.0 829.7 872.2
30 847.4 849.7 833.1 875.2
35 850.7 853.3 836.4 878.1
40 853.9 856.7 839.5 881.0
 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065 5

Table 2 (continued)

qa(kgm
3)
pa(MPa) p-cymeneb (1S)-(
)-a-pinenec (+)-limoneneb citrald
45 856.9 860.0 842.5 883.7
50 859.9 863.1 845.3 886.4
55 862.7 866.1 848.1 888.9
60 865.3 868.9 850.7 891.4
Te = 353.15 K
0.1 808.2 808.1 794.8 839.2
1 809.1 809.0 795.6 839.9
5 812.8 813.1 799.2 843.1
10 817.2 817.9 803.6 846.8
15 821.5 822.6 807.8 850.5
20 825.6 827.1 811.8 854.1
25 829.6 831.4 815.7 857.5
30 833.4 835.5 819.5 860.8
35 837.0 839.5 823.0 864.0
40 840.5 843.2 826.4 867.1
45 843.8 846.7 829.7 870.1
50 846.9 850.1 832.7 872.9
55 849.9 853.2 835.7 875.6
60 852.8 856.2 838.4 878.2
Te = 373.15 K
0.1 791.4 790.6 778.3 822.7
1 792.6 791.9 779.5 823.7
5 796.7 796.5 783.6 827.2
10 801.7 801.9 788.5 831.4
15 806.4 807.2 793.2 835.4
20 811.0 812.2 797.6 839.3
25 815.4 816.9 801.9 843.1
30 819.5 821.4 806.0 846.7
35 823.5 825.7 809.9 850.2
40 827.3 829.8 813.6 853.5
45 830.9 833.6 817.1 856.7
50 834.2 837.2 820.4 859.8
55 837.4 840.6 823.5 862.7
60 840.4 843.7 826.4 865.4
Te = 393.15 K
0.1 774.4 773.1 761.9 806.3
1 775.6 774.4 763.1 807.3
5 780.3 779.6 767.6 811.2
10 785.8 785.7 773.1 815.9
15 791.1 791.5 778.3 820.3
20 796.2 797.1 783.3 824.6
25 801.0 802.4 788.0 828.8
30 805.6 807.4 792.6 832.7
35 810.0 812.1 796.8 836.5
40 814.1 816.5 800.9 840.1
45 818.0 820.6 804.7 843.5
50 821.6 824.4 808.2 846.8
55 825.0 828.0 811.5 849.9
60 828.1 831.3 814.6 852.8
Te = 413.15 K
0.1 757.1 755.2 745.2 790.0
1 758.2 756.4 746.3 790.9
5 763.4 762.2 751.4 795.2
10 769.7 769.1 757.5 800.4
15 775.7 775.7 763.4 805.4
20 781.3 781.9 768.9 810.1
25 786.7 787.8 774.2 814.7
30 791.7 793.3 779.1 819.0
35 796.5 798.5 783.8 823.1
40 801.0 803.3 788.2 827.0
45 805.1 807.7 792.3 830.8
50 809.0 811.8 796.1 834.3
55 812.6 815.6 799.6 837.6
60 815.9 819.0 802.8 840.7

where u stands for standard uncertainties and ur for relative uncertainties (confidence level of 68%).
a
u(p) = ±0.05 MPa.
b
ur(q) = 0.06% (293.15 K  T  363.15 K) and 0.09%(373.15 K  T  413.15 K).
c
ur(q) = 0.14%.
d
ur(q) = 0.31%.
e
u(T) = ±0.05 K.
6 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065

a) b)
920 920

900 900

880 880

860 860

840 840
-3

-3
820 820
/ kgm

/ kgm
800 800

780 780

760 760

740 60 740 60

300 300
30 30
350 Pa 350 Pa
/M /M
p p
T/ T/ 400
K 400 K 0
0

c) d)
920 920

900 900

880 880

860 860

840 840
-3

-3

820 820
/ kgm

/ kgm

800 800

780 780

760 760

740 60 740 60

300 300
30 30
a a
MP MP
350 350
p/ p/
T/ 400 T/ 400
K 0 K 0

Fig. 2. Densities q as function of pressure p = (0.1–60) MPa and temperature T = (293.15–413.15) of pure (a) p-cymene, (b) (1S)-(
)-a-pinene, (c) (+)-limonene, and (d) citral.

good agreement between experimental and literature density data First the parameters ai were fitted to Eq. (2) by using density
indicates the accuracy of the applied measuring method. data at atmospheric pressure, i.e. pref. Other four parameters have
been determined by applying Eqs. (1)–(3) to density data at pres-
3.2. Density modeling sures above 0.1 MPa [29,34].
In order to confirm accuracy of density correlation, the absolute
Experimental density data of pure p-cymene, a-pinene, limo- average percentage deviation, AAD, the percentage maximum devi-
nene and citral have been correlated applying the modified ation, MD, the average percentage deviation, Bias, and the standard
Tammann-Tait equation [29,34,35,62]: deviation, r, were calculated. All the equations for quality criteria
were reported previously [29,32–34]. The optimized parameters of
qref
ðTÞ the modified Tamman-Tait equation ai, bi and C, as well as devia-
qðT; pÞ ¼  ð1Þ
1
Cln BðTÞþp tions between experimental and calculated densities data are
BðTÞþpref
shown in Table 4. AAD values for p-cymene, a-pinene, limonene
and citral were 0.013%, 0.015%, 0.012% and 0.010%, respectively.
X
2
The obtained results for the pure terpenes verified correctness of
qref ðTÞ ¼ ai T i ð2Þ
i¼0 the used correlation procedure.

X
2
3.3. Derived thermodynamic properties
BðTÞ ¼ bi T i ð3Þ
i¼0
Very important thermodynamic and mechanical properties can
where T and p represent defined temperatures and pressures, B(T) is be calculated from the density data measured over the wide tem-
a temperature dependent parameter, while C is temperature inde- perature and pressure ranges [62]. Therefore, the obtained densi-
pendent. qref denotes reference density at reference pressure, pref, ties and parameters of the modified Tammann-Tait equation
which is herein chosen to be 0.1 MPa. were applied in calculating of the isothermal compressibility jT,
 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065 7

Table 3
Comparison between experimental and literature density data for the investigated compounds at temperature T and atmospheric pressure, 0.1MPaa.

Component Tb (K) qc(kgm
3) qd(kgm
3) Lit.

e
p-cymene 293.15 857.0 856.8 856.1 [43]; 857.1 [44,45]
298.15 853.0 852.1 [43]; 853.47 [46]; 852.88 [47]; 852.93 [48]; 852.99 [49]; 852.9 [38,50]; 852.91 [41]
303.15 848.9 848.9 848.6 [43]
308.15 844.9 844.5 [43]; 843.5 [45]; 845.59 [46]; 844.89 [48]; 844.94 [49];
313.15 840.9 840.8 840.6[43]; 840.85[50]
318.15 836.8 837.4 [43]; 838.46 [46]; 836.81 [48]; 836.86 [49]
323.15 832.8 832.7 832.6 [43]; 831.0[45]
(1S)-(
)-a-pinenef 293.15 858.3 858.2 858.5 [43]; 857.63 [51]; 857.6 [39]
298.15 854.2 854.8 [43]; 854.03 [46]; 853.9 [47,50]; 853.62 [51]; 853.88[38,52]; 853.7 [39]
303.15 850.0 850.0 851.9 [43]; 849.6 [51]
308.15 845.9 846.9 [43]; 845.79 [46]; 845.58 [51]
313.15 841.7 841.7 842.9 [43]; 841.4 [50]
318.15 837.6 839.4 [43]; 838.64 [46]
323.15 833.4 833.4 835.2 [43]
(+)-limonenee 293.15 842.3 842.3 844.8 [39]; 845.7 [53]; 814.7 [54]
298.15 838.4 841.0 [39]; 842.16 [53]; 837.31 [55]; 837.17 [56]; 838.8 [57]; 810.7 [54]
303.15 834.5 834.5 837.0 [39]; 837.68 [53]; 807.2 [54]
308.15 830.6 834.33 [39,53]
313.15 826.6 826.7 829.0 [39]; 830.3 [53]; 799.8 [54]
318.15 822.7 821.75 [58]
323.15 818.7 818.8 821.1 [39]; 792.2 [54]; 817.78 [58]
citralg 293.15 887.6 887.8 888.4 [39]
298.15 883.6 884.7 [39,40]; 884.8 [59]
303.15 879.6 879.7 880.4 [39]
313.15 871.6 871.7 872.3 [39]
323.15 863.6 863.6 864.3 [39]

where u stands for standard uncertainties and ur for relative uncertainties (confidence level of 68%).
a
u(p) = ±0.05 MPa.
b
u(T) = ±0.05 K.
c
Density measured by DSA 5000.
d
Density measured by DMA HP.
e
ur(q) = 0.06%.
f
ur(q) = 0.14%.
g
ur(q) = 0.31%.

Fig. 3. Comparison of the experimental densities with literature data for (a) (1S)-(
)-a-pinene [28] and (b) (+)-limonene [28] at different pressures p = (0.1–60) MPa and
temperatures:(j) 293.15 K, (d) 303.15 K, (N) 313.15 K, (.) 323.15 K, (J) 333.15 K, and (I) 353.15 K.

 
the isobaric thermal expansion coefficient ap, the internal pressure 1 @q C
jT ¼ ¼
 ð4Þ
pint, and the difference of specific heat capacities at constant pres- q @p T ðBðTÞ þ pÞ 1
Cln BðTÞþpref
BðTÞþp
sure and at constant volume, cp -cv.
The dependence of density on pressure change at a constant The temperature influence on density at a constant pressure is
temperature has been described by the isothermal compressibility described by isobaric thermal expansion coefficient apand the fol-
[62]. It can be calculated from Eq. (4) in combination with Eq. (1): lowing expression is presented as [62]:
8 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065

Table 4
Parameters of the modified Tammann-Tait equation and comparison criteria for the pure p-cymene, (1S)-(
)-a-pinene, (+)-limonene, and citral at temperatures 293.15–413.15 K
and at pressures up to 60 MPa.

p-cymene (1S)-(
)-a-pinene (+)-limonene Citral

a0 (kgm
3) 1061.140 1064.825 1045.999 1115.188
a1 (kgm
3K
1)
0.601740
0.595625
0.614032
0.747713
a2 (kgm
3K
2)
0.32456010
3
0.37248810
3
0.27605310
3
0.95768310
4
b0 (MPa) 427.765 405.267 429.229 487.271
b1 (MPa K
1)
1.506447
1.444942
1.516401
1.638352
b2 (MPa K
2) 0.14052210
2 0.135793110
2 0.142027110
2 0.147289810
2
C 0.86081510
1 0.86110210
1 0.85679110
1 0.89729610
1
AADa (%) 0.013 0.015 0.012 0.010
MDb (%) 0.069 0.084 0.065 0.056
Biasc (%)
0.002
0.002
0.002
0.003
rd (kgm
3) 0.149 0.185 0.142 0.123

where N denotes thenumber of experimental data and m is the number of parameters which were optimized.
PN qexp
qcal 
a
AAD ¼ 100  i exp i 
N  qi 

i¼1  exp 
q
qcal 
b
MD ¼ max 100 qexp i  ; i ¼ 1; N
 i

c PN qexp
qcal
Bias ¼ 100
N
i
qexp
i

i¼1 i
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P exp cal 2
N
ðqi
qi Þ
d
r ¼ i¼1 N
m

Fig. 4. Isothermal compressibility (jT) vs. pressure (p) for (a) p-cymene, (b) (1S)-(
)-a-pinene, (c) (+)-limonene, and (d) citral at (j) 293.15 K, (d) 303.15 K, (N) 313.15 K, (.)
323.15 K, (J) 333.15 K, (I) 353.15 K, (r) 373.15 K, ( ) 393.15 K, and ( ) 413.15 K.
 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065 9

 
1 @q C [33]. The description of the change of internal sample’s energy dur-
ap ¼
¼
 ð5Þ
q @T p
BðTÞþp
ðBðTÞ þ pÞ 1
Cln BðTÞþp ref
ing its isothermal contraction or expansion is shown by the Eq. (9)
[33,62]:
The incorporation of equation (1) into equation (5) leads to:    
@U @p T ap
pint ¼ ¼T
p¼
p ð9Þ
B0 ðTÞðpref
pÞ @V T @T q jT

q ref0
ðTÞ C ðBðTÞþpÞðBðTÞþpref Þ
ap ¼
ð6Þ
qref ðTÞ BðTÞþp
1
Cln BðTÞþpref
where U and V are internal energy and volume of the sample,
respectively.
Furthermore, it was very important to determine the difference
where B0 (T) and qref (T) denote the first derivative of B(T) and qref(T)
0

of specific heat capacities at constant pressure and constant vol-

with respect to T, respectively, and they are shown in following
ume. If the specific heat capacity of a constant pressure is known,
equations:
it will allow calculating the specific heat capacity at constant vol-
X
2 ume from the corresponding expression [62]:
qref0 ðTÞ ¼ iai T i
1 ð7Þ
ap T
i¼0 cp
ct ¼ ð10Þ
qjT
X
2 The obtained values of given thermodynamic properties for
B0 ðTÞ ¼ ibi T i
1 ð8Þ examined pure p-cymene, a-pinene, limonene and citral, at pres-
i¼0
sures (0.1–60) MPa and temperatures (293.15–413.15) K, are pre-
When above mentioned thermodynamic properties are known sented in Tables S1-S4 in the supplementary material to this paper.
and calculated it is very simple to obtain the internal pressure pint. Langa et al. [28] investigated densities of a-pinene and limo-
It gives information about intermolecular interactions in a sample nene at pressures up to 40 MPa at five temperatures (283.15–

Fig. 5. Isobaric thermal expansion coefficient (ap) of (a) p-cymene, (b) (1S)-(
)-a-pinene, (c) (+)-limonene, and (d) citral at (j) 293.15 K, (d) 303.15 K, (N) 313.15 K, (.)
323.15 K, (J) 333.15 K, (I) 353.15 K, (r) 373.15 K, ( ) 393.15 K, and ( ) 413.15 K.
10 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065
358.15) K. Values of jT and ap were also calculated. The absolute
average percentage deviations between literature and jT obtained
here at 313.15 K and under pressures (20 to 40) MPa, were 4.19%
for limonene and 3.85%, for a-pinene. AAD of ap under same condi-
tions were 2.68% and 1.47%, for a-pinene and limonene, respec-
tively [28].
The graphical representation of jT and ap vs. p obtained in this
work at selected temperatures is given in Figs. 4 and 5,
respectively.
As shown in Figs. 4 and 5 isothermal compressibility and iso-
baric thermal expansion coefficient of the pure compounds
decreases in the following order: a-pinene > p-cymene  limone
ne > citral. This means that the structure of citral is the most
rigid for compression or expansion, presumable due to different
shape and an existence of the molecule dipole-dipole interac-
tions. Both jT and ap increase with temperature increase and
decrease with pressure increase, as expected. Also, the tempera-
ture influence on jT and ap reduces as pressure increases. For p-
cymene, a-pinene and limonene ap isotherms do not intersect at
examined pressure range. The ‘‘crossing point” indicates pressure
at which the isobaric thermal expansion coefficient is tempera-
ture independent. At that pressures the dependence of ap on
temperature changes; at pressures lower than the one of }cross-
Fig. 6. Internal pressure (pint) of (a) p-cymene, (b) (1S)-(
)-a-pinene, (c) (+)-limonene, and (d) citral at (j) 293.15 K, (d) 303.15 K, (N) 313.15 K, (.) 323.15 K, (J) 333.15 K,
(I) 353.15 K, (r) 373.15 K, ( ) 393.15 K, and ( ) 413.15 K.
ing point} isobaric thermal expansion coefficient rises with
increase in temperature, at pressures higher than the }crossing
point} the behaviour of ap becomes opposite-decreases when
temperature goes up. ap isotherms for the limonene intersect
at pressures slightly above 60 MPa (see Fig. 5c), while the inter-
section point for pure citral is visible at pressure around 47 MPa
(see Fig. 5d).
Isobaric thermal expansion coefficient is an important property
since it provides significant information about the engine power
loss. The higher values of ap indicate the greater change in density
as response to temperature change. Since fuel injection system in
an engine is volume-based, the density decrease leads to decrease
in mass of injected fuel which means lower energy content. There-
fore, higher isobaric thermal expansion coefficient results in
greater engine power loss due to fuel heating [33]. From this point
of view, it seems that a-pinene is least acceptable due to the high-
est ap values.
Internal pressures presented in Fig. 6 show the influence of an
expansion or contraction of a system at constant temperature on
its internal energy. Internal pressure has the same decreasing order
as for density: citral > a-pinene > p-cymene > limonene, showing
that the internal energy of citral is mostly influenced by the expan-
sion/contraction. The pressure influence on pint at lower tempera-
 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065
tures is almost negligible, however as temperature approaches
boiling point of a sample, internal pressure visible increases with
the pressure raise. It is also evident that the internal pressure
decreases with temperature increase. The lowest internal pressure
is at highest temperature and at atmospheric pressure, meaning
that at this point liquid’s internal energy shows the lowest change
upon expansion/contraction.
The difference of specific heat capacity at constant pressure and
constant volume acts the same like jT and ap, rises as temperature
increasing and drops with pressure increases (Tables S1–S4).
4. Conclusion
Densities of pure p-cymene, a-pinene, limonene and citral have
been examined at pressures up to 60 MPa and at temperatures up
to 413.15 K. It was shown that densities of the investigated terpe-
nes decrease in the following order: citral > a-pinene > p-cymen
e > limonene possibly because citral has the best packing compar-
ing to the other three hydrocarbons at the same conditions due to
its acyclic structure and one oxygen atom.
The densities were correlated employing modified Tammann-
Tait equation. Very low values of the absolute average percentage
deviation, of about 0.010%, between experimental and literature
data confirm the correctness of the correlation method. From the
measured density data and optimized parameters of modified
Tammann-Tait equation isothermal compressibility, the isobaric
thermal expansion coefficient, the internal pressure, and the differ-
ence of specific heat capacities at constant pressure and at constant
volume were derived. It was established that the isothermal com-
pressibility, the isobaric thermal expansion coefficient and the dif-
ference of specific heat capacity at constant pressure and at
constant volume decrease with pressure rising and increase as
temperature increases. The isothermal compressibility and the iso-
baric thermal expansion coefficient decrease in the following
order: a-pinene > p-cymene  limonene > citral, showing that
the citral is most rigid upon volume change. The isotherms for
the isobaric thermal expansion coefficient of citral intersect at
pressure about 47 MPa, while for the other analyzed terpenes the
intersection point is expected at pressures higher than 60 MPa.
The measured and calculated properties provide significant infor-
mation for further research of terpenes and their potential applica-
tion as additives in biofuels.
CRediT authorship contribution statement
JovanaIlić Pajić: Investigation, Writing - original draft. Gorica
Ivaniš: Methodology, Data curation, Writing - original draft. Ivona
Radović: Methodology, Writing - review & editing. Aleksandar
Grujić: Validation. Jasna Stajić-Trošić: Formal analysis. Mirko Sti-
jepović: Formal analysis. Mirjana Kijevčanin: Methodology,
Resources, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge the financial support
received from the Ministry of Education, Science and Technological
Development of Republic of Serbia under projects TR37001,
III45019 and OI172063.
11
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jct.2020.106065.
References
[1] B. Yuan, Z. Wang, X. Yue, F. Yu, C. Xie, S. Yu, Biomass high energy density fuel
transformed from a-Pinene catalyzed by Brönsted-Lewis acidic heteropoly
inorganic-organic salt, Renew. Energy 123 (2018) 218–226.
[2] L.E. Fried, M.R. Manaa, P.F. Pagoria, R.L. Simpson, Design and synthesis of
energetic materials, Mater. Res. 31 (31) (2001) 291–321.
[3] A.-K. Sikder, N. Sikder, A review of advanced high performance, insensitive and
thermally stable energetic materials emerging for military and space
applications, J. Hazard. Mater. 112 (1–2) (2004) 1–15.
[4] H.A. Meylemans, L.C. Baldwin, B.G. Harvey, Low-temperature properties of
renewable high-density fuel blends, Energy Fuels 27 (2013) 883–888.
[5] S.-M. Cho, J.-H. Kim, S.-H. Kim, S.-Y. Park, J.-C. Kim, A comparative study on the
fuel properties of biodiesel from woody essential oil depending on terpene
composition, Fuel 218 (2018) 375–384.
[6] B.G. Harvey, W.W. Merriman, T.A. Koontz, High-Density renewable diesel and
jet fuels prepared from multicyclic sesquiter panes and a 1-hexene-derived
synthetic paraffinic kerosene, Energy Fuels 29 (2015) 2431–2436.
[7] P. Oßwald, R. Whitside, J. Schäffer, M. Köhler, An experimental flow reactor
study of the combustion kinetics of terpenoid jet fuel compounds: farnesane,
p-menthane and p-cymene, Fuel 187 (2017) 43–50.
[8] H.A. Meylemans, R.L. Quintana, B.R. Goldsmith, B.G. Harvey, Solvent-free
conversion of linalool to methylcyclopentadiene dimers: a route to renewable
high-density fuels, ChemSusChem 4 (2011) 465–469.
[9] H.A. Meylemans, R.L. Quintana, M.L. Rex, B.G. Harvey, Low-temperature,
solvent-free dehydration of cineoles with heterogeneous acid catalysts for the
production of high-density biofuels, J. Chem. Technol. Biotechnol. 89 (2014)
957–962.
[10] O. Reichert, T. Zeiner, G. Sadowski, Measurement and modeling of phase
equilibria in systems of acetonitrile, n-alkanes, and b-myrcene, Ind. Eng. Chem.
Res. 54 (2014) 1153–1160.
[11] J.-L.F. Monteiro, C.O. Veloso, Catalytic conversion of terpenes into fine
chemicals, Top. Catal. 27 (1–4) (2004) 169–180.
[12] W. Wu, R.W. Davis, One-pot bioconversion of algae biomass into terpenes for
advanced biofuels and bioproducts, Algal Res. 17 (2016) 316–320.
[13] C. DejoyeTanzi, M. AbertVian, F. Chemat, New procedure for extraction of algal
lipids from wet biomass: a green clean and scalable process, Bioresour.
Technol. 134 (2013) 271–275.
[14] R. Parker, M. Lathoud, Green, aero-engines: technology to mitigate aviation
impact on environment, Proc. Inst. Mech. Eng., Part C: J. Mech. Eng. Sci. 224
(2010) 529–538.
[15] F.L. Dryer, Chemical kinetic and combustion characteristics of transportation
fuels, Proc. Combust. Inst. 35 (1) (2015) 117–144.
[16] L. Rye, C. Wilson, The influence of alternative fuel composition on gas turbine
ignition performance, Fuel 96 (2012) 277–283.
[17] S. Blakey, L. Rye, C.-W. Wilson, Aviation gas turbine alternative fuels: a review,
Proc. Combust. Inst. 33 (2011) 2863–2885.
[18] M. Braun-Unkhoff, T. Kathrotia, B. Rauch, U. Riedel, About the interaction
between composition and performance of alternative jet fuels, CEAS Aeronaut.
J. 7 (2016) 83–94.
[19] ASTM D1655-19a, Standard Specification for Aviation Turbine Fuels, ASTM
International, West Conshohocken, PA, 2019..
[20] S. Laitinen, J. Laitinen, L. Fagernas, K. Korpijärvi, L. Korpinen, K. Ojanen, M.
Atamila, M. Jumpponen, H. Koponen, J. Jokiniemi, Exposure to biological and
chemical agents at biomass power plants, Biomass Bioenergy 93 (2016) 78–86.
[21] K. Rupar, M. Sanati, The release of terpenes during storage of biomass, Biomass
Bioenergy 28 (2005) 29–34.
[22] H.A. Meylemans, R.L. Quintana, B.G. Harvey, Efficient conversion of pure and
mixed terpene feedstocks to high density fuels, Fuel 97 (2012) 560–568.
[23] R. Mewalal, D.K. Rai, D. Kainer, F. Chen, C. Külheim, G.F. Peter, G.A. Tuskan,
Plant-derived terpenes: a feedstock for specialty biofuels, Trends Biotechnol.
35 (3) (2017) 227–240.
[24] B. Rotavera, A.M. Scheer, H. Huang, D.L. Osborn, C.A. Taatjes, Influence of
temperature and resonance-stabilization on the ortho-effect in cymene
oxidation, Proc. Combust. Inst. 35 (2015) 543–552.
[25] F.-X. Niu, Q. Lu, Y.-F. Bu, J.-Z. Liu, Metabolic engineering for the microbial
production of isoprenoids: carotenoids and isoprenoid-based biofuels, Synth.
Syst. Biotechnol. 2 (2017) 167–175.
[26] I. Fichen, C. Larroche, J.B. Gros, Water solubility vapor pressure, and activity
coefficients of terpenes and terpenoids, J. Chem. Eng. Data 44 (1999) 56–62.
[27] X. Zhang, L. Pan, L. Wang, J.-J. Zou, Review on synthesis and properties of high-
energy-density liquid fuels: hydrocarbons, nanofluids and energetic ionic
liquids, Chem. Eng. Sci. 180 (2018) 95–125.
[28] E. Langa, A.F. Palavra, C.A. Nieto de Castro, A.M. Mainar, P, q, and T
measurements of the limonene + a-pinene mixtures, J. Chem. Eng. Data 56
(4) (2011) 1709–1713.
[29] M.A. Aissa, G.R. Ivaniš, I.R. Radović, M.Lj. Kijevčanin, Experimental
investigation and modeling of thermophysical properties of pure methyl and
ethyl esters at high pressures, Energy Fuels 31 (7) (2017) 7110–7122.
12 J. Ilić Pajić et al. / J. Chem. Thermodynamics 144 (2020) 106065
[30] M.Lj. Kijevčanin, E.M. Živkovic, B.D. Djordjević, I.R. Radović, J. Jovanović, S.P.
Šerbanovic, J. Chem. Thermodyn. 56 (2013) 49–56.
[31] D.M. Bajić, E.M. Živković, J. Jovanović, S.P. Šerbanović, M.Lj. Kijevčanin, Fluid
Phase Equilib. 399 (2015) 50–65.
[32] G.R. Ivaniš, A.Ž. Tasić, I.R. Radović, B.D. Ðordević, S.P. Šerbanović, M.Lj.
Kijevčanin, An apparatus proposed for density measurements in compressed
liquid regions at the pressures 0.1-60 MPa and the temperatures 288.15-
413.15 K, J. Serb. Chem. Soc. 80 (8) (2015) 1073–1085.
[33] G.R. Ivaniš, I.R. Radović, V.B. Veljković, M.Lj. Kijevčanin, biodiesel density and
derived thermodynamic properties at high pressures and moderate
temperatures, Fuel 165 (2016) 244–251.
[34] G.R. Ivaniš, I.R. Radović, V.B. Veljković, M.Lj Kijevčanin, Thermodynamic
properties of biodiesel and petro-diesel blends at high pressures and
temperatures, experimental and modeling, Fuel 184 (2016) 277–288.
[35] O.G. Sas, G.R. Ivaniš, M.Lj. Kijevčanin, B. González, A. Domínguez, I.R. Radović,
Densities and derived volumetric properties of ionic liquids with [Nf2] and
[NTf2] anions at high pressures, J. Chem. Eng. Data 63 (4) (2018) 954–964.
[36] B. Lagourette, C. Boned, H. Saint-Guirous, P. Xans, H. Zhou, Densimeter
calibration method versus temperature and pressure, Meas. Sci. Technol. 3
(1992) 699–703.
[37] M.J.P. Comuñas, J.P. Bazile, A. Baylaueq, C. Boned, Density of siethyladipate
using a new vibrating tube densimeter from (293.15 to 403.15) K and up to
140 MPa. Calibration and measurements, J. Chem. Eng. Data 53 (2008) 986–
994.
[38] R. Francesconi, C. Castellari, F. Comelli, Viscosities densities refractive indices,
and excess molar enthalpies of Methyl tert-Butyl Ether + components of pine
resins and essential oils at 298.15 K, J. Chem. Eng. Data 46 (2001) 1520–1525.
[39] R.A. Clará, A.C. Gómez Marigliano, H.N. Sólimo, Viscosity density and refractive
index in the range (283.15 to 353.15) K and vapor pressure of r-Pinene, d-
Limonene, (+)-Linalool, and citral over the pressure range 1.0 kPa atmospheric
pressure, J. Chem. Eng. Data 54 (2009) 1087–1090.
[40] P.M. Florido, I.M.G. Andrade, M.C. Capellini, F.H. Carvalho, K.K. Aracava, C.C.
Koshima, C.E.C. Rodrigues, C.B. Gonçalves, Viscosities and densities of systems
involved in the deterpenation of essential oils by Liquid-liquid extraction: new
UNIFAC-VISCO parameters, J. Chem. Thermodyn. 72 (2014) 152–160.
[41] F. Comelli, S. Ottani, R. Francesconi, C. Castellari, Viscosities densities and
refractive indices of binary mixtures containing n-Hexane + components of
pine resins and essential oils at 298.15 K, J. Chem. Eng. Data 47 (2002) 93–97.
[42] R.D. Chirico, M. Frenkel, J.W. Magee, V. Diky, C.D. Muzny, A.F. Kazakov, K.
Kroenlein, I. Abdulagatov, G.R. Hardin, W.E. Acree Jr., J.F. Brenneke, P.L. Brown,
P.T. Cummings, T.W. de Loos, D.G. Friend, A.R.H. Goodwin, L.D. Hansen, W.M.
Haynes, N. Koga, A. Mandelis, K.N. Marsh, P.M. Mathias, C. McCabe, J.P.
O’Connell, A. Pádua, V. Rives, C. Schick, J.P.M. Trusler, S. Vyazovkin, R.D. Weir, J.
Wuu, Improvement of quality in publication of experimental
thermophysicalproperty data: challenges, assessment tools, global
implementation, andonline support, J. Chem. Eng. Data 58 (2013) 2699–2716.
[43] A. Ribeiro, G. Bernardo-Gil, densities and refractive indices of components of
pine resin, J. Chem. Eng. Data 35 (2) (1990) 204–206.
[44] S.R.M. Ellis, M. Razavipour, Vapour-liquid equilibria at reduced pressures: n-
butanol-ethyl benzene; aniline-p-cymene, Chem. Eng. Sci. 11 (2) (1959) 99–
107.
[45] V.W. Strubell, p-Cymene and its derivatives: 38. The thermodynamic
properties of p-Cymene, J. fürpraktischeChemie 26 (1964) 319–323.
[46] D.-K. Liao, X.-L. Meng, Z.-F. Tong, D.-X. Zheng, D.-Y. Peng, B.C.-Y. Lu, Excess
molar enthalpies of p-Cymene + r-Pinene + a-Pinene at (298.15, 308.15, and
318.15) K and at atmospheric pressure, J. Chem. Eng. Data 52 (2007) 808–811.
[47] F. Comelli, R. Francesconi, C. Castellari, Excess molar enthalpies and excess
molar volumes of binary mixtures containing dialkyl carbonates + pine resins
at (298.15 and 313.15) K, J. Chem. Eng. Data 46 (1) (2001) 63–68.
[48] J.F. Martínez-López, J.I. Pardo, J.S. Urieta, A.M. Mainar, Isobaric molar heat
capacities of the mixture (p cymene+ethanol) at several temperatures and
atmospheric pressure, J. Chem. Thermodyn. 111 (2017) 142–148.
[49] J. F. Martínez-López, J. I. Pardo, S. Liu, A. M. Mainar, Thermophysical and
volumetric study of mixtures {p-cymene + propan-1-ol} at several
temperatures and atmospheric pressure. Modeling with COSMO-RS, 123
(2018) 1–7..
[50] R. Francesconi, C. Castellari, F. Comelli, excess molar enthalpies and excess
molar volumes of binary mixtures containing 1,3-Dioxolane or 1,4-Dioxolane +
Pine Resins at (298.15 and 313.15) K and at atmospheric pressure, J. Chem.
Eng. Data 46 (2001) 577–581.
[51] M. Fujisawa, T. Matsushita, T. Kimura, Excess molar heat capacities of (r-(+)-
alpha Pinene + s-(-)-alpha Pinene) at temperatures between 293.15-308.15 K,
J. Therm. Anal. Calorim. 81 (1) (2005) 137–139.
[52] K. Tamura, H. Li, Mutual solubilities of terpene in methanol and water and
their multicomponent liquid-liquid equilibria, J. Chem. Eng. Data 50 (2005)
2013–2018.
[53] A. Tavares Sousa, C.A. Nieto de Castro, Density of alpha-Pinene, beta-Pinene,
limonene, and essence of turpentine, Int. J. Thermophys. 13 (2) (1992) 295–
301.
[54] R.A. Clará, A.C. Gómez Marigliano, V.d.V. Campos, H.N. Sólimo, Density,
viscosity, vapour liquid equilibrium, excess molar enthalpy, and their
correlations of the binary system [1-pentanol + R-(+)-limonene] over the
complete concentration range, at different temperatures, Fluid Phase Equilib.
293 (2010) 151–156.
[55] H. Li, K. Tamura, Ternary and quaternary (Liquid + Liquid) equilibria for (Water
+ Ethanol + a-Pinene, +b-Pinene, or +Limonene) and (Water + Ethanol + a-
Pinene + Limonene) at the temperature 298.15 K, J. Chem. Thermodyn. 38
(2006) 1036–1041.
[56] A. Arce, A. Marchiaro, A. Soto, Liquid-liquid equilibria of Linalool+Ethanol
+Water, Water+Ethanol+Limonene, and Limonene+Linalool+Water Systems, J.
Solution Chem. 33 (5) (2004) 561–569.
[57] W.V. Steele, R.D. Chirico, A.B. Cowell, S.E. Knipmeyer, A. Nguyen,
Thermodynamic properties and ideal-gas enthalpies of formation for
methyl benzoate, ethyl benzoate, (R)-(+)-Limonene, tert-Amyl Methyl Ether,
trans-crotonaldehyde, and diethylene glycol, J. Chem. Eng. Data 47 (2002)
667–688.
[58] G.A. Leeke, R. Santos, M.B. King, Vapor-liquid equilibria for the carbon dioxide
+ carvacrol system at elevated pressures, J. Chem. Eng. Data 46 (2001) 541–
545.
[59] D. Gonçalves, M.F. Paludetti, P.M. Florido, C. Tonetti, C.B. Gonçalves, C.E.C.
Rodrigues, Physical behavior of the phases from the liquid-liquid equilibrium
of citrus essential oils systems at 298.2 K, J. Chem. Eng. Data 63 (2018) 2718–
2737.
[60] C. Amelynck, B. Mees, N. Schoon, P. Bultinck, FA-SIFT study of the reactions of
H3O+(H2O)n (n=0, 1, 2), NO+ and O2+ with the terpenoid aldehydes citral
citronellal and myrtenal and their alcohol analogues, Int. J. Mass Spectrometry
379 (2015) 52–59.
[61] C.L. Yaws, Thermophysical Properties of Chemicals and Hydrocarbons, second
ed., Elsevier, Oxford, UK, 2014.
[62] G.R. Ivaniš, A.Ž. Tasić, I.R. Radović, B.D. Ðordević, S.P. Šerbanović, M.Lj.
Kijevčanin, Modeling of density and calculations of derived volumetric
properties for n-Hexane, toluene and dichloromethane at pressures 0.1-60
MPa and temperatures 288.15-413.15 K, J. Serb. Chem. Soc. 80 (11) (2015)
1423–1433.
JCT 2019-445