Article

pubs.acs.org/jced

Solubility of Binary and Ternary Systems Containing Vanillin and

Vanillic Acid in Supercritical Carbon Dioxide
Adrián Rojas-Á vila,†,‡ Alfredo Pimentel-Rodas,‡ Teresa Rosales-García,†,‡ Gloria Dávila-Ortiz,†
and Luis A. Galicia-Luna*,‡
†
Laboratorio de Proteínas Vegetales, Escuela Nacional de Ciencias Biológicas-Instituto Politécnico Nacional, UPALM, Av. Wilfrido
Massieu s/n, C.P.07738, Del. Gustavo A. Madero, Ciudad de México, México
‡
Laboratorio de Termodinámica, S.E.P.I.-E.S.I.Q.I.E. Instituto Politécnico Nacional, UPALM, Edif. Z, Secc. 6, 1ER piso Lindavista,
C.P. 07738, México D. F., México

ABSTRACT: Experimental solubility data of binary and

ternary systems containing vanillin and vanillic acid in
supercritical carbon dioxide were carried out in equipment
based on the static-synthetic method. Compositions of
dissolved solids were determined online via high-performance
liquid chromatography with a diode array detector. The carbon
dioxide + vanillin, carbon dioxide + vanillic acid, and carbon
dioxide + vanillin + vanillic acid systems were studied at
(315.00, 324.90, and 334.71) K, (314.91, 324.91, and 334.71)
K, and (314.13, 323.67, and 333.17) K, respectively. For all
systems the measurements were carried out at pressure range
between 8.00 and 30.00 MPa. For binary systems the
maximum solubilities were 5.215 × 10−3 and 2.911 × 10−5 in mole fraction for vanillin and vanillic acid, respectively. For
ternary systems the maximum solubilities were 4.669 × 10−3 and 2.213 × 10−5 for vanillin and vanillic acid, respectively. The
expanded uncertainties (k = 2) for the measured properties are estimated to be U(P) = 0.04 MPa, U(T) = 0.04 K, and Ur(y) =
0.0286 mole fraction. Méndez-Santiago and Teja, Bartle et al., Kumar and Johnston, and Chrastil models were used to correlate
the experimental data. The results from the correlation confirmed the consistency of the reported data.

1. INTRODUCTION A supercritical extraction process using a CO2-like solvent is

Vanilla (Vanilla planifolia Andrews) has been valued and
required because of flavor and aroma, and actually is considered
the most widely used flavoring agent in the food, flavors,
fragrances, and cosmetics industries.1 The aroma developed by
cured vanilla pods is naturally very complex and more than a
hundred volatile compounds are found and belong to various
kinds of chemical groups.2−4
Vanillin and vanillic acid are compounds present in vanilla
and participate in the global aroma composition which is
developed from a natural fermentation process.5 Green vanilla
pods are almost odorless. They develop a faint phenolic odor,
unlike that of cured beans. During the process called “curing”,
vanilla pods develop flavor as a consequence of enzymatic
action.6−9
Most of the components that are involved in aroma
composition are thermo-labile and volatile. The quality of the
final extract depends on the purification and extraction
methods of the vanilla extracts.10 Essentially, multistage
lixiviation is the principal extraction method for vanilla
oleoresin,11 or simple lixiviation at 353.00 K employing
ethanol, but if the process lacks temperature control,
degradation of vanilla and other aromatic compounds may
happen and a decrease of quality in the extract is expected.12
an excellent alternative to extract this kind of compounds given
its properties (not toxic, nonflammable, without environmental
impact).10 Furthermore, CO2 supercritical properties are easy
to reach (Tc = 304.13 K and Pc = 7.38 MPa) therefore it is
suitable for processing thermo-labile compounds.13 Super-
critical fluids have several advantages over organic solvents
about physical properties and information about solubility (y)
of solids in supercritical fluids is very important to be
determined.
Wells et al.14 have previously reported the solubility of
vanillin in supercritical CO2 (SC−CO2) for two isotherms,
308.15 and 318.15 K, covering a pressure range from 8.35 to
19.10 MPa; Škerget et al.15 also reported isotherms at 313.20,
308.20, and 318.20 K covering a pressure range from 8.00 to
27.65 MPa. For vanillic acid, Murga et al.16 reported three
isotherms (313.00, 323.00, and 333.00) K and a pressure range
from 8.50 to 50.00 MPa. Stassi et al.17 measured solubilities at
313.00 and 328.00 K and pressure range between 9.00 and
25.00 MPa. Deviations between the data published by these
authors were found, also the experimental uncertainties in these
Received: April 19, 2016
Accepted: July 19, 2016
Published: August 16, 2016

© 2016 American Chemical Society 3225 DOI: 10.1021/acs.jced.6b00322

J. Chem. Eng. Data 2016, 61, 3225−3232
Journal of Chemical & Engineering Data Article

works are not reported. Since these systems are of interest in two-position valve with a loop of 5 μL, a high performance
this work, the experimental solubilities and their experimental liquid chromatograph (HPLC), a syringe pump and a
uncertainties were determined and reported in this research, temperature regulator (heating by air). Figure 1 shows the
allowing comparisons between the data obtained in this work apparatus used in the measurements. Two sapphire windows
and the literature previously mentioned. are coupled to the visual high-pressure cell with the main
Furthermore, in order to study the behavior of vanillin and objective to observe the phase equilibria. This cell can be
vanillic acid as a function of temperature and pressure in the operated up to 30.00 MPa. The temperature of the visual high-
determination of solubility in supercritical carbon dioxide, a pressure cell was regulated with a temperature regulator and
ternary system consisting of the compounds mentioned before measured by two platinum probes (Pt 100 Ω, Specitec)
was performed. All measurements were carried out using a coupled to a digital display (Hart Scientific, Chub-E4).
static-analytic apparatus with online sampling.18 Platinum probes were calibrated against a 25 Ω reference
The solubility data of binary and ternary systems were probe (Rosemount, 162CE ± 0.005 K certified uncertainty)
correlated with Méndez-Santiago and Teja,19 Bartle et al.,20 coupled to a precision thermometry bridge (Automatic Systems
Kumar and Johnston,21 and Chrastil22 models over the entire Laboratories, F300). In this work, after calibration of platinum
experimental conditions. resistance thermometers, a maximum deviation of ±0.009 K
was obtained, while the expanded uncertainties with a level of
2. EXPERIMENTAL METHOD confidence of 95% (k = 2) in temperature for both probes are
2.1. Materials. Carbon dioxide (CAS No. 124-38-9) with 0.04 K.23
purity 99.995% was provided by Infra (México). Capsaicin The system pressure was regulated by injection of CO2 using
(CAS No. 404-86-4) with purity 97.0%, vanillin (CAS No. 121- a syringe pump and recorded by a pressure transducer (Druck,
33-5) with purity 99.0% and vanillic acid (CAS No. 121-34-6) PDCR 910-1756) connected to the top of the visual high-
with purity 98.0% were supplied from Sigma-Aldrich. Except for pressure cell to a pressure indicator (DPI 145, Druck) with a
CO2, all compounds were carefully degassed by agitation under resolution of ±1 × 10−7 MPa. The pressure transducer was
vacuum prior to injection into the system. Table 1 shows the calibrated against a dead-weight balance (Desgranges & Huot,
source and purity of the compounds used in this work. The model 5304) with a certified precision of the order of ±0.005%
physical properties of vanillin, vanillic acid, and capsaicin are (full scale). For this work, after calibration of pressure
presented in Table 2. transducer, a maximum deviation of the order of ±0.0074
MPa was obtained. The expanded uncertainty (k = 2) in
Table 1. Samples Information pressure was obtained corresponding to an estimated maximum
initial mass fraction purification analysis of the order of 0.04 MPa.23
name source puritya method method With the aim to obtain and record the real-time data, an
carbon Infra 0.99995 none GCb Electronic Acquisition Data (EAD) was programmed. The
dioxide acquisition program was programmed in Agilent VEE PRO
capsaicin Sigma- 0.97 none HPLCc RELEASE 9.32 software. The EAD was used in all measure-
Aldrich
vanillin Sigma- 0.99 none HPLCc
ments.
Aldrich 2.3. Composition Determinations. The procedure to
vanillic acid Sigma- 0.98 none HPLCc quantify the solid in the fluid phase consisted in performing
Aldrich high performance liquid chromatography methods with a
a
Provided by the manufacturer. bGas chromatography. cPerformance previous calibration. The apparatus used in this work for
liquid chromatography. composition analysis is integrated by a manual injector port
with a loop of 5 μL, a degassing module, a quaternary pump, a
2.2. Apparatus and Procedures. The equipment used in precolumn of 7.5 mm × 4.6 mm (Grace, Alltima C18), a
solubility determinations of solids in SC-CO2 is based on the column of 250 mm × 4.6 mm (Grace, Alltima C18), both of
static-analytic method. The main parts of this apparatus are a particle size of 5 μm, and a diode array detector (DAD). The
visual high-pressure cell with inner volume of 50 cm3, a six-port analytical method for the calibration and analysis of each solid

Table 2. Physical Properties of Vanillin, Vanillic Acid and Capsaicina

a
Reference 26.

3226 DOI: 10.1021/acs.jced.6b00322

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Figure 1. Experimental apparatus for measuring the solubility of solids in carbon dioxide: AB, air bath; EC, equilibrium cell; P, pressure transducer;
SD, stirring device; SP, syringe pump; SPV, six-port valve; T1 and T2, platinum resistance thermometers; HPLC, high-pressure liquid
chromatograph.
Table 3. HPLC Conditions for Calibration and Solubility Measurements
compound mobile phase
capsaicin acetonitrile/water
vanillin
water + 0.1% trifluoroacetic acid (TFA) (A)/acetonitrile +
0.09% TFA (B)
vanillic acid
in the fluid phase depends on the studied system. The
conditions of each HPLC method are given in Table 3.
2.4. Solubility Determinations. For all experimental
determinations, 2 g of pure solid (capsaicin, vanillin and/or
vanillic acid) was employed and placed inside of the visual high-
pressure cell. The experimental system (sampling circuit,
solvent feeding system, and the visual high-pressure cell) was
subjected to vacuum for 1 h. Then, the temperature was fixed
(within the experimental uncertainty) using an air bath, and
carbon dioxide was fed to the visual high-pressure cell using a
syringe pump. Subsequently, the binary mixture (carbon
dioxide + solid) was vigorously stirred with a magnetic bar
located inside the cell. Prior to measurements and while the
pressure and temperature were fixed (within the experimental
uncertainty), the initial samples were used as purge because
solid compositions are generally found either too low or not
repeatable. After the desired temperature was reached for at
least 5 h with the fluctuation less than ±0.01 K for more than
30 min, the pressure was recorded and the vapor composition
was analyzed by HPLC. After equilibrium was reached, samples
were sent online to the HPLC through the loop of 5 μL
coupled to a six-port two-position valve. The sampling
procedure was stopped when the solid solubility in the fluid
phase showed repeatability within 1% for at least three
consecutive samples. Those measurements were recorded,
and the average is reported as the solubility. The relationship
between the chromatographic peak areas and the mole fractions
were determined based on six calibration points obtained using
vanillin and vanillic acid with varying concentrations in the
3227
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wavelength
flow rate mL·min−1 % volume nm T/K
1 70/30 280 298.00
gradient:
at 0 min 5% (B)
at 12 min 65% (B)
at 14 min 90% (B)
1 280 303.00
at 16 min 90% (B)
at 16.01 min 5% (B)
at 21 min 5% (B)
atop at 21 min
range (0−50 μg·mL−1) prepared gravimetrically in the
laboratory. Two types of experimental uncertainties were
associated with the composition measurements:23 (A) repeat-
ability of the HPLC data, determined to be 0.0088 mole
fraction; (B) uncertainty regarding the aforementioned
calibration determined to be 0.0053 mole fraction. The relative
expanded uncertainty (k = 2) for the composition (Ur(y))
measurements was estimated to be 0.0286 mole fraction.23
3. RESULTS AND DISCUSSION
3.1. Binary Systems. The reliability of the equipment used
in this work in order to determine solubility data of solids in
supercritical carbon dioxide was validated by measuring the
solubilities of capsaicin in SC-CO2 and then comparing with
literature data.24,25 These measurements were performed at
313.15 and 323.15 K. The comparison between the
experimental solubility data for CO2 + capsaicin system with
the international literature24,25 is shown in Figure 2. According
to the results of these measurements, the data obtained in this
work are in good agreement with Elizalde-Solis and Galicia-
Luna24 in both isotherms in the entire pressure range with a
maximum deviation of 4.9% and with de la Fuente et al.25 at
313.00 K and up to 15.00 MPa with a maximum deviation of
6.01%. The highest deviations are found with de la Fuente et
al.25 after 15.00 MPa (maximum deviation of 18.41%). This
discrepancy could be ascribed to a systematic or experimental
error which was not account for; however, the solubility data of
de la Fuente et al. presents the highest deviations (≤15.00%) at
313 K and at high pressures. The experimental solubility data
DOI: 10.1021/acs.jced.6b00322
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Table 5. Experimental Solubilities of Vanillin in Supercritical

Carbon Dioxidea
T/K P/MPa vanillin y(103) ρCO2/kg·m−3
315.00 8.61 0.063 334.95
10.56 1.015 632.13
14.97 1.994 766.32
20.43 2.996 834.32
23.81 3.318 862.78
30.81 3.783 907.36
324.90 8.10 0.090 218.38
10.15 0.563 374.84
15.10 2.010 686.73
20.24 3.426 777.14
25.29 4.358 828.57
Figure 2. Solubility of capsaicin in SC-CO2; (○) Elizalde-Solis and 30.36 4.784 865.77
Galicia-Luna24 at 312.86 K; (△) Elizalde-Solis and Galicia-Luna24 at 334.71 10.28 2.075 297.61
322.91 K; (■) de la Fuente et al.25 at 313.00 K; (●) this work at 14.84 2.642 581.30
313.15 K; (▲) this work at 323.15 K. 19.17 3.342 699.05
25.54 4.787 784.25
Table 4. Experimental Mole Fraction Solubilities of 30.10 5.215 823.84
Capsaicin in Supercritical Carbon Dioxidea a
Expanded uncertainties (k = 2) for the measured properties are
T/K P/MPa 5
capsaicin y(10 ) estimated to be U(P) = 0.04 MPa, U(T) = 0.04 K, and Ur(y) = 0.0286
mole fraction. ρCO2 is the density of pure CO2 from the correlation of
313.15 10.78 5.74
ref 27.
12.56 7.82
15.08 9.95
17.53 12.77
Table 6. Experimental Solubilities of Vanillic Acid in
20.02 17.84
Supercritical Carbon Dioxidea
25.09 21.54 T/K P/MPa vanillic acid y(107) ρCO2/kg·m−3
30.09 25.75
314.91 8.57 9.601 328.56
323.15 10.76 5.92
10.56 23.457 632.13
12.50 8.05
14.67 68.072 760.92
15.10 13.08
20.25 112.293 832.53
17.53 16.95
23.81 129.076 862.78
20.02 21.23
30.81 145.056 907.36
25.09 25.70
324.91 8.42 21.912 236.08
30.09 29.10
a
9.63 40.919 323.81
Expanded uncertainties (k = 2) for the measured properties are 15.10 101.924 686.73
estimated to be U(P) = 0.04 MPa, U(T) = 0.04 K, and Ur(y) = 0.0286 20.24 148.740 777.14
mole fraction.
30.36 202.763 865.77
334.71 8.41 3.538 204.45
10.28 72.291 297.61
for capsaicin in SC-CO2 are given in Table 4. Once the method
14.84 162.161 581.30
was validated, the systems containing SC-CO2, vanillin, and
19.17 197.486 699.05
vanillic acid were measured.
25.54 259.998 784.09
The solubilities of vanillin and vanillic acid in carbon dioxide
30.10 291.108 823.84
were measured at 315.00, 324.90, and 334.71 K for vanillin and a
314.91, 324.91, and 334.71 K for vanillic acid. The pressure Expanded uncertainties (k = 2) for the measured properties are
range was 8−30 MPa for each isotherm in both systems. The estimated to be U(P) = 0.04 MPa, U(T) = 0.04 K, and Ur(y) = 0.0286
solubility of the vanillin and vanillic acid was measured based mole fraction. ρCO2 is the density of pure CO2.27
on the mole fraction (y), of the solute in supercritical CO2.
Tables 5 and 6 show the experimental results for CO2 +
vanillin and CO2 + vanillic acid systems, respectively. Over the after 14.00 MPa, perhaps due to the difference between
entire experimental conditions, the mole fraction of vanillin and experimental methods; however, the trend of the data of this
vanillic acid are in range of (6.300 × 10−5 to 5.215 × 10−3) and study is in good agreement with Wells et al.14 It is worth
(3.538 × 10−7 to 2.911 × 10−5), respectively. Figure 3 shows mentioning, there is a small difference between the
the comparison between the solubility data for CO2 + vanillin experimental temperature of this work and the references
system from the international literature14,15 with the exper- temperatures. Figure 4 shows the comparison between the
imental solubilities obtained in this work. According to the solubility data for CO2 + vanillic acid system from the
results of these measurements, the data obtained in this work international literature16,17 with the experimental solubilities
are in good agreement with Wells et al.14 at 308.15 K at all obtained in this work. According to the results, the solubility
pressures in the range and with Škerget et al.15 at 313.20 K and data obtained in this work are in good agreement with the
up to 14.00 MPa. Deviations are found with Škerget et al.15 international literature considering that there are differences
3228 DOI: 10.1021/acs.jced.6b00322
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Figure 3. Solubility of vanillin in SC-CO2: (■) Wells et al.14 at 308.15
K; (●) Škerget et al.15 at 313.2 K; (▲) this work at 315.00 K.
Figure 5. New experimental data for the systems: (●) SC-CO2 +
vanillin at 315.00 K; (▲) SC-CO2 + vanillic acid at 314.9 K; (○)
vanillin in ternary system (SC-CO2 + vanillin + vanillic acid) at 314.13
K; (△) vanillic acid in ternary system (SC-CO2 + vanillin + vanillic
acid) at 314.13 K.

Figure 4. Solubility of vanillic acid in SC-CO2: (●) Murga et al.16 at

313.00 K; (■) Stassi et al.17 at 313.00 K; (▲) this work at 314.91 K.

Table 7. Acid in Supercritical Carbon DioxideExperimental Figure 6. Comparison of the correlated results from the Mendez-
Solubilities of Vanillin and Vanillic in a Ternary Systema Santiago and Teja19 model with the experimental data for the binary
systems: (●) SC-CO2 + vanillin and (▲) SC-CO2 + vanillic acid; (○)
T/K P/MPa vanillic acid y2(107) vanillin y3(103) ρCO2/kg · m−3 vanillin in ternary system (SC-CO2 + vanillin + vanillic acid) and (△)
vanillic acid in ternary system (SC-CO2 + vanillin + vanillic acid). The
314.13 9.51 8.282 0.187 550.80
solid line represents the calculated data using the MST model for all
11.23 8.495 0.246 679.63 temperatures and up to 30 MPa.
14.61 9.344 0.308 766.65
19.99 1.255 0.674 834.56
23.99 20.079 1.113 867.98 From the data given in Tables 5 and 6 it can be observed that
28.77 25.567 1.349 899.13 for all temperatures an increase in pressure causes an increment
323.67 10.06 4.217 0.172 382.82 in solubility of vanillin and vanillic acid in SC-CO2. This can be
15.27 19.350 0.506 701.76 explained as being due to the increment on SC-CO2 density by
19.98 40.792 0.940 781.10 effect of an increment in pressure at fixed temperature. This
24.80 68.655 1.794 830.08 density enhancement is due to a lower intermolecular distance
29.99 86.693 2.230 868.28 which causes a higher solubility strength. Consequently, if the
333.17 10.69 6.460 0.303 335.44 system pressure increases, the solubility of vanilla and vanillic
12.74 39.796 0.511 488.37 acid increases. This effect is more significant at higher
19.53 132.138 3.076 715.97 temperatures.
23.82 180.137 4.046 774.05 Under the same conditions of temperature and pressure,
29.63 221.307 4.669 826.86 vanillin shows higher solubility than vanillic acid. This behavior
a
Expanded uncertainties (k = 2) for the measured properties are can be explained since both compounds contain hydroxyl and
estimated to be U(P) = 0.04 MPa, U(T) = 0.04 K, and Ur(y2) = Ur(y3) methoxy functional groups in an adjacent position, which
= 0.0286 mole fraction. ρCO2 is the density of pure CO2.27 cannot form an intramolecular hydrogen bond between the two
substituents.15 For this reason, the solubility of the compounds
between the experimental temperature reported in this work is not affected by these interactions. However, both compounds
and that reported in the international literature. contain a third functional group, aldehyde for vanillin and
3229 DOI: 10.1021/acs.jced.6b00322
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Journal of Chemical & Engineering Data
Figure 7. Comparison of the correlated results from the Bartle et al.20
model with the experimental data for the binary systems: (●) SC-CO2
+ vanillin and (▲) SC-CO2 + vanillic acid; (○) vanillin in ternary
system (SC-CO2 + vanillin + vanillic acid) and (△) vanillic acid in
ternary system (SC-CO2 + vanillin + vanillic acid). The solid line
represents the calculated data using the Bartle et al.20 model for all
temperatures and up to 30 MPa.
Figure 8. Comparison of the correlated results from the Kumar and
Johnston21 model with the experimental data for the binary systems:
(●) SC-CO2 + vanillin (▲) SC−CO2 + vanillic acid; (○) vanillin in
ternary system (SC-CO2 + vanillin + vanillic acid) and (△) vanillic
acid in ternary system (SC−CO2 + vanillin + vanillic acid). The solid
line represents the calculated data using the Kumar and Johnston21
model for all temperatures and up to 30 MPa.
carboxyl for vanillic acid. Therefore, the aldehyde group of
vanillin interacts with SC-CO2, providing more solubilization
power than provided by the carboxyl group present in the
vanillic acid.
3.2. Ternary System. The solubility data for the ternary
systems, containing CO2, vanillin and vanillic acid, were
determined at the same pressure and temperature adopted
for the binary systems. For ternary systems solubility
determination, 1 g of each pure solid (vanillin and vanillic
acid) was placed in the equilibrium cell to ensure a sufficient
amount of these components. Experimental solubility data for
the ternary systems are listed in Table 7. Just as mentioned in
the binary systems, vanillin has greater solubility than the
vanillic acid. However, because there are two compounds in the
ternary system, competition between them exists to solubilize
3230
Article
Figure 9. Comparison of the correlated results from the Chrastil22
model with the experimental data for the binary systems: (●) SC−
CO2 + vanillin and (▲) SC−CO2 + vanillic acid; (○) vanillin in
ternary system (SC−CO2 + vanillin + vanillic acid) and (△) vanillic
acid in ternary system (SC−CO2 + vanillin + vanillic acid). The solid
line represents the calculated data using the Chrastil22 model for all
temperatures and up to 30 MPa.
in SC-CO2, which causes a decrease in the solubility of both
compounds compared with solubility in binary systems. Figure
5 shows experimental solubility data of ternary systems
compared with binary systems.
3.3. Correlation of Experimental Solubility Data. In
this work the experimental solubilities data of vanillin and
vanillic acid in binary and ternary systems were correlated by
four density-based semiempirical models proposed by Méndez-
Santiago and Teja,19 Bartle et al.,20 Kumar and Johnston,21 and
Chrastil.22 These models were developed from theory of dilute
solutions, which involves the expansion of the Helmholtz
energy around the solvent critical point in order to describe
properties of infinite dilute solutions.
The equation proposed by Mendez-Santiago and Teja
(MST)19 was the first one tested. This equation was derived
considering a classical expansion of the Helmholtz energy near
the critical point of solvent to represent the mixture properties
at infinite dilution. It is considered a correlation with three
fitting parameters with the assist of a Clausius−Clapeyron
expression for the sublimation pressure. The consistency of the
reported data are considered as well, if all isotherms collapse to
a single straight line on a graph of the left-hand side of the
equation versus the density of the solvent. For details about this
model the reader is referred to the original literature source.19
With the aim to represent and/or modeling the experimental
results, the measured solubilities data were used to fit
parameters of the Mendez-Santiago and the Teja and Chrastil
models.
Comparison of the correlated results from the MST model
with experimental values for the systems CO2 + vanillin, CO2 +
vanillic acid and CO2 + vanillin + vanillic acid are presented in
Figure 6. Since all isotherms, for each system performed,
collapse to a single straight line on a graph of the left-hand side
of the equation versus the density of the solvent, we considered
that the experimental solubility data have a good consistency,
with a maximum absolute average relative deviation (AARD) of
4.64%.
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Table 8. Correlation Parameters for Experimental Solubility Data of Vanillin and Vanillic Acid in SC-CO2 in Binary and
Ternary Systems and AARD of Different Modelsa
correlation parameters
name equation solute system a0 a1 a2 AARD%
binary −2402.520 2.190 1.661 3.472
vanillin
ternary −3020.870 2.418 2.258 4.640
MST T ln(y2 P) = a0 + a1ρ + a 2T
binary −3696.790 1.539 −0.333 3.649
vanillic acid
ternary −3087.000 1.418 −2.183 2.892
binary −3.953 6.747 × 10−3 −950.562 3.030
⎛ y P⎞ vanillin
a ternary −3.747 7.436 × 10−3 −1332.360 3.898
Bartle ln⎜ 2 ⎟ = a0 + a1(ρ − ρref ) + 2
⎝ Pref ⎠ T binary −3.194 4.728 × 10−3 −2693.450 3.013
vanillic acid
ternary −5.262 4.361 × 10−3 −2071.360 2.409
binary −9.947 4.866 × 10−3 854.230 2.348
vanillin
a2 ternary −17.469 5.146 × 10−3 826.660 3.457
Kumar and Johnston ln y2 = a0 + a1ρ +
T binary −9.735 2.802 × 10−3 1149.380 2.447
vanillic acid
ternary −17.546 2.070 × 10−3 87.741 2.432
binary 0.999 3.613 −7423.310 2.759
vanillin
a2 ternary 5.727 4.244 −10573.900 4.568
Chrastil ln y2 = a0 + a1 ln ρ +
T binary 1.964 2.747 −7583.530 2.909
vanillic acid
ternary −2.176 4.450 −10327.300 3.464
a
ρ is the density of pure CO2 obtained from the reference.27

The second model used was that proposed by Bartle et al.20
This model takes a correlation of the so-called enhancement
factor and fits it to a function of density. However, vapor
pressures, needed to calculate the enhancement factor, are not
known for many compounds, particularly the solids. Therefore,
the first approach was based on a reference pressure and
density. Finally, Bartle et al. modified this equation using a
reference density. For details about this model the reader is
referred to the original literature source.20 The resulting
modeling data (binary and ternary systems) using the Bartle
et al. model are show in Figure 7. Through the correlation
results it can be seen that the model is in good agreement with
the experimental data with a maximum AARD of 3.90%.
The Kumar and Johnston21 model was the third equation
used. In this model, it is considered that the chemical potential
of the solute is the same in the condensed and supercritical
phases. In the first instance, the chemical potential is referred to
in terms of fugacities. Kumar and Johnston reformulated the
expression in terms of the density of the supercritical fluid as an
independent variable. For details about this model the reader is
referred to the original literature source.21 The experimental
data and correlating data results (binary and ternary systems)
using the Kumar and Johnston model are shown in Figure 8.
The correlation results show that the model is in good
agreement with the experimental data with a maximum AARD
of 3.46%.
The last density-based model tested was the one proposed by
Chrastil,22 which was developed on the basis of the solute with
solvent complex formation in the gas phase. The Chrastil
model is linear in a log−log graph of solubility versus density.
For details about this model the reader is referred to the
original literature source.22 Comparison of the correlated
results from the Chrastil model with experimental values for
the systems CO2 + vanillin, CO2 + vanillic acid, and CO2 +
vanillin + vanillic acid are shown in Figure 9. According to the
correlation results, it can be seen that the model used has a
good agreement with the data obtained in this work with a
maximum AARD of 4.57%.
The absolute average relative deviation AARD (%) was
calculated as follows:
3231
100
N
y exp − y cal
AARD(%) = ∑
N y exp
i=1 (1)
where N is the number of data points, yexp is the experimental
solubility, ycal is the solubility obtained from the correlation.
The optimal parameters and the AARD(%) from the
semiempirical models proposed by Méndez-Santiago and
Teja,19 Bartle et al.,20 Kumar and Johnston,21 and Chrastil22
using the experimental data of this work (over the entire range
of pressure and temperature) are reported in Table 8.
■ CONCLUSIONS
The solubility data of the vanillin and vanillic acid in
supercritical carbon dioxide at temperature and pressure
range of 308.15 to 338.15 K and 16.00 to 30.00 MPa,
respectively, were experimentally determined using a static-
analytic method. The obtained results in this work show that
vanillin and vanillic acid have solubility in carbon dioxide
(binary mixture) over the mole fraction range of (6.300 × 10−5
to 5.215 × 10−3) and (9.601 × 10−7 to 2.911 × 10−5),
respectively.
For ternary mixtures as it was expected, the solubilities of
both compounds are smaller than that obtained in binary
systems; however, the solubility of vanillin is still greater than
that of vanillic acid.
For all systems measured, the reported solubilities data show
that an increase in the pressure leads to an increase in the
solubilities with a higher impact of pressure on the solubility
enhancement at the higher temperatures.
The correlation results show that the calculated data from the
models used have a good agreement with the experimental data
obtained in this work with a maximum absolute average relative
deviation (AARD) of 4.64% obtained from the MST model.
The minimum AARD was 3.46% obtained from the Kumar and
Johnston model.
The results of this study are useful to help determine the
optimal conditions for performing vanilla extractions by using
supercritical fluid extraction.
DOI: 10.1021/acs.jced.6b00322
J. Chem. Eng. Data 2016, 61, 3225−3232
Journal of Chemical & Engineering Data

■
Article

AUTHOR INFORMATION Supercritical CO2 under Dynamic Conditions. J. Chem. Eng. Data
2000, 45, 161−165.
Corresponding Author (18) Elizalde-Solis, O.; Galicia-Luna, L. A. New Apparatus for
*Tel.: +52 55 5729 6000 ext. 55133. Fax: +52 55 5586-2728. E- Solubility Measurements of Solids in Carbon Dioxide. Ind. Eng. Chem.
mail: lgalicial@ipn.mx. Res. 2011, 50, 207−212.
Funding (19) Méndez-Santiago, J.; Teja, A. S. The solubility of solids in
The authors would like to thank the Instituto Politécnico supercritical fluids. Fluid Phase Equilib. 1999, 158−160, 501−510.
Nacional and CONACyT for the financial support of this (20) Bartle, K. D.; Clifford, A. A.; Jafar, S. A.; Shilstone, G. F.
Solubilities of Solids and Liquids of Low Volatility in Supercritical
research. Carbon Dioxide. J. Phys. Chem. Ref. Data 1991, 20, 713−756.
Notes (21) Kumar, S. K.; Johnston, K. P. Modelling the Solubility of Solids
The authors declare no competing financial interest. in Supercritical Fluids with Density as the Independent Variable. J.

■
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