Physical Behavior of the Phases from the Liquid–Liquid Equilibrium of

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Physical Behavior of the Phases from the Liquid−Liquid Equilibrium of Citrus Essential Oils Systems at 298.2 K Daniel Gonçalves,* Mayara F. Paludetti, Priscila M. Florido, Camila Tonetti, Cintia B. Gonçalves,* and Christianne E. C. Rodrigues* Separation Engineering Laboratory (LES), Department of Food Engineering (ZEA/FZEA), University of Sao Paulo (USP), Avenida Duque de Caxias Norte 225, 13635-900 Pirassununga, Brazil

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S Supporting Information *

ABSTRACT: Solvent extraction is a fractionation process applied to separate terpenes and oxygenated compounds from citrus essential oils (EOs). Once the knowledge of the physical properties of phases was found to be crucial for equipment design and the scaling of tubes and accessories, this study focused on the evaluation of density, viscosity, and interfacial tension of phases from the liquid−liquid equilibrium of citrus EO systems. Model mixtures of orange and lemon EOs and real systems at 298.2 K were prepared, and the physical properties of their phases were thus evaluated. Increased water content in the solvent led to higher values of density, viscosity, and interfacial tension, whereas an increased amount of oxygenated compounds caused lower interfacial tensions. Densities estimated by the simple mixing rule provided good results. Parameters of the Grunberg−Nissan model adjusted to the model systems data exhibited a good description of the viscosities of real systems. The UNIFAC-VISCO model provided suitable predictions of viscosities of the solvent phases, and satisfactory results for the interfacial tensions were calculated by linear adjustment and the Bahramian−Danesh thermodynamic model, except for the real acid lime system.

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(linalyl acetate).8,12 The amount of terpenes and oxygenated compounds is also variable depending on the EO. The volatile fraction of orange EO is composed of ∼0.0127 mass fraction of oxygenated compounds,1,6 acid lime EO is 0.078 mass fraction,2,11 and bergamot EO is ∼0.57 mass fraction.8 The composition of the raw material has a direct relation with the partition of the components and the solvent selectivity in a fractionation process by liquid−liquid extraction, as was previously demonstrated in different systems, such as orange,6 lemon,9 acid lime,11 bergamot,8 and other EOs such as lavandin,8 eucalyptus,13 oregano,14 and mint.15 The composition of the phases from the fractionation also has a direct contribution to the physical properties, such as density and viscosity, as was observed by Florido et al.7 for bergamot, lemon, and mint model systems, and by Gonçalves et al.13 for eucalyptus model systems. The understanding of the values of physical properties is important for planning and scaling tubes, accessories, and industrial equipment as well as for process optimization. Another interesting property for separation processes by liquid−liquid extraction is the tension in the interface between phases (interfacial tension), which is related to the stability of the dispersed phase drops and the efficiency of the phase separation in equipment operations.16

INTRODUCTION Essential oils (EOs) are important commodities in the international market. These raw materials are widely used in cosmetics, pharmaceuticals, and food and beverage formulations.1,2 In 2016, the total value in EO exportation reached US $4.71 billion,3 and Brazil was ranked the main EO exporter at 52.7 thousand tons, denoting US $339 million in trade.4 Currently, Brazil is the main exporter of orange EOs, being responsible for ∼39% of the world’s exports,3 and has a slight but important participation in the lemon and lime EO markets.3−5 Citrus EOs, such as orange, lemon, acid lime, and bergamot, are predominantly composed of volatile components, subdivided into terpene hydrocarbons and oxygenated compounds. Several studies have demonstrated the importance and the technical evaluation of the fractionation of citrus EOs, focusing on the separation between terpenes and oxygenated compounds by liquid−liquid extraction, using ethanol/water mixtures as solvents.1,2,6−9 From this fractionation process, a product with improved sensorial qualities, stability, and solubility in aqueous solutions may be obtained. Limonene is the main terpene found in citrus EOs, whereas the composition of the oxygenated fraction is highly varied. For example, the oxygenated fraction of orange EO (varieties Valencia and Pera Rio) is mainly composed of aldehydes (octanal and citronellal) and alcohols (linalool),1,6,10 and acid lime and lemon EOs are more abundant in aldehydes (citral),2,9,11 whereas bergamot EO is rich in alcohol (linalool) and ester © XXXX American Chemical Society

Received: January 25, 2018 Accepted: June 4, 2018

A

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

This study aimed to evaluate the chemical composition of phases from the liquid−liquid equilibrium of citrus EOs over the behavior of their physical properties. The main EOs exported by Brazil, orange (Citrus sinensis L. Osbeck), and acid lime (Citrus latifolia Tanaka), were the focuses of this work. Model mixtures of orange (limonene, linalool, ethanol, and water)6 and lemon/lime (limonene, β-pinene, γ-terpinene, citral, ethanol, and water)9 EOs and real systems (crude orange or acid lime EO, ethanol, and water) were prepared at T = (298.2 ± 0.1) K, and the physical properties of their phases were evaluated. The experimental data of the model systems were used to adjust parameters of empirical models as the Grunberg−Nissan model17 and linear adjustment, which were used to predict the viscosity and interfacial tension of real systems, respectively. Kinematic viscosity was also predicted by the UNIFAC-VISCO thermodynamic model,18,19 and the interfacial tensions were also estimated by the Bahramian−Danesh model.20 All densities were estimated by the simple mixing rule.

analysis conditions were the same as the ones adopted for GC-FID analysis. The column interface temperature was 518.2 K; the ion source temperature was 473.2 K, and the mass spectral scanning ranged from 40 to 800 m/z with 70 eV of ion source energy. Samples were diluted in 1-propanol with a 1:1 mass ratio before GC-MS analysis. The components were identified via comparison with standards retention times and/or by similarity of the component mass spectra with the one contained in the Solutions GC-MS software (version 2.5, NIST 08 and NIST 08s libraries) and/or by comparison with the Kovats retention index (KIi) calculated for each component with the one from the literature6,8 for the same DB-FFAP capillary column. For KIi determination (eq 1), the alkane standards C10−C40 (Sigma-Aldrich, USA) were analyzed under the same GC-MS conditions. ÄÅ É ÅÅ ij log RTi − log RTi − 1 yzÑÑÑÑ ÅÅ j z zÑÑ KIi = 100·ÅÅCi − 1 + jj j log RTi + 1 − log RTi − 1 zzÑÑÑ ÅÅ (1) ÅÇ k {ÑÖ

MATERIALS AND METHODS Solvents and Reagents. Hydroalcoholic solvents with different water contents were prepared by diluting deionized water (Millipore, Milli-Q, USA) in absolute ethanol. Crude orange (C. sinensis) and acid lime (C. latifolia) EOs were obtained by cold pressing and were kindly donated by the Louis Dreyfus Company (Bebedouro/SP, Brazil). Limonene, linalool, ethanol, and water were used to prepare the orange model systems as proposed by Gonçalves et al.,6 whereas limonene, β-pinene, γ-terpinene, citral, ethanol, and water were used for the lemon/lime model systems as proposed by Koshima et al.9 For the real systems, crude orange EO or crude acid lime EO, ethanol, and water were mixed. The CAS registry numbers, suppliers, and experimental purities, sources, and experimental physical properties of the standards used for the model systems and of the hydroalcoholic solvents and the crude EOs, as well as values from the literature at T = (298.2 ± 0.1) K, are shown in Table 1.7,13,21−39

where Ci−1 is the number of carbons in the alkane immediately preceding the analyte, RTi is the analyte retention time, RTi−1 is the retention time of the alkane immediately preceding the analyte, and RTi+1 is the retention time of the alkane immediately after the analyte. The mass fraction of the components identified in the crude EOs was calculated by internal normalization in the GC-FID analysis, and components with mass fractions lower than 0.001 were not considered. Liquid−Liquid Equilibrium. The liquid−liquid equilibrium (LLE) was reached according to a method adopted for several EO systems.6,8−11,13−15,41,42 For the orange model systems, different mass proportions between limonene and linalool were prepared and contacted with the solvent using a mass ratio of 1:1. For the lime/lemon model systems, a stock solution composed of limonene, β-pinene, and γ-terpinene was prepared and mixed with citral at different mass proportions and then contacted with the solvent using the same 1:1 mass ratio. For the real systems, the crude EO was contacted with the solvent at different mass ratios depending on the solvent used. Mixtures were prepared in a capped polypropylene tube (15 or 50 mL, Corning, USA), and the masses were measured using an analytical balance (Adam, PW Model 254, USA, accurate to 0.0001 g). The tubes were vigorously agitated at 2800 rpm for 10 min at room temperature T = (298.2 ± 0.1) K, centrifuged for 30 min at 5000g at controlled temperature T = (298.2 ± 0.1) K (Thermo Electron Corporation, model CR3i, France), and maintained in a thermostatic bath (Marconi, model MA-184, Brazil) at T = (298.2 ± 0.1) K for 20 h to attain LLE. After that, two homogeneous and well-formed phases were obtained, the terpene- and solvent-rich phases, which were separately collected by syringes. The composition in terms of terpenes, oxygenated compounds, and ethanol was assessed by GC-FID analysis, and the water content was determined by Karl Fischer titration (Metrohm, 787 KF Titrino, Switzerland) using Karl Fischer reagents (CombiTitrant 5 mg H2O mL−1, Merck, Germany). The physical properties of the LLE phases were measured as described in the next section. Conventionally, each component existing in the systems was represented by numbers as follows: limonene (1), γ-terpinene (2), β-pinene (3), linalool (4), citral (5), ethanol (6), and water (7). In the case of the real systems, as adopted in previous

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EXPERIMENTAL PROCEDURES Standards Purities. The purities and retention times of standards were assessed using a gas chromatograph with a flame ionization detector (GC-FID, Shimadzu, model GC 2010 AF, Japan) and an automatic injector (Shimadzu, model AOC 20i, Japan). The capillary column used was a nitroterephthalic acidmodified polyethylene glycol (DB-FFAP, 0.25 × 10−6 m capillary thickness, 30 m length, 0.25 × 10−3 m internal diameter; Agilent, USA), and the analysis conditions were the same as adopted in previous studies:1,2,6,10,11,13,40 helium as the carrier gas at 1.13 mL min−1, 523.2 K injection temperature, 1 × 10−3 mL injection volume with a 50:1 split ratio, column temperature program from 373.2 to 513.2 K (at 8 K min−1) and held at 513.2 K for 1 min (18.5 min each analysis), and 553.2 K detection temperature. Samples were diluted in 1-propanol (0.999 mass fraction, Sigma-Aldrich, EUA) with a 1:1 mass ratio before GC-FID analysis. Chemical Characterization of the Crude Essential Oils. The chemical composition of the volatile fraction of crude orange (C. sinensis) and acid lime (C. latifolia) EOs was performed in a gas chromatograph coupled to a mass spectrometer (GC-MS, Shimadzu, model QP 2010 Plus, Japan) with an automatic injector (Shimadzu, model AOC-5000, Japan) as the method adopted in previous studies.1,6,11 The capillary column and B

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

C

152.2

46.07

18.02

128.2 130.2

citral (5)

ethanol (6)

water (7)

octanal 1-octanol

154.3 154.3 154.3 156.3

154.3

linalool (4)

(±)-citronellal α-terpineol geraniol decanal

136.2 136.2

γ-terpinene (2) (−)-β-pinene (3)

134.2 136.2

136.2

(R)-(+)-limonene (1)

p-cymene (+)-α-pinene

Mi/ g mol−1

material

106-23-0 98-55-5 106-24-1 112-31-2

99-87-6 7785-70-8

124-13-0 111-87-5

7732-18-5

64-17-5

5392-40-5

78-70-6

99-85-4 18172-67-3

5989−27-5

CAS number

0.980 0.900 0.970 0.950

0.970 0.990

0.950 0.980

0.998

0.960

0.970

0.970 0.990

0.970

supplier purity

0.990 0.900 0.970 0.950

0.970 0.990

0.950 0.990

0.999

0.990

0.992

0.977 0.999

0.988

experimental purityb

Sigma-Aldrich, Sigma-Aldrich, Sigma-Aldrich, Sigma-Aldrich,

USA USA USA USA

Sigma-Aldrich, USA Sigma-Aldrich, USA

Others Sigma-Aldrich, USA Sigma-Aldrich, USA

Merck, Germany

Sigma-Aldrich, USA

Sigma-Aldrich, USA

856.3 931.2 874.2 838.4

± ± ± ±

0.9 0.9 0.9 0.8

853.2 ± 0.9 854.7 ± 0.9

836.1 ± 0.8e 822.0 ± 0.8

997 ± 1

785.2 ± 0.9

884.8 ± 0.9

857.4 ± 0.9

845.2 ± 0.8 867.0 ± 0.9

841.4 ± 0.8

Standards Model Systems Sigma-Aldrich, USA

Sigma-Aldrich, USA Sigma-Aldrich, USA

exp.

source

lit.

853.821 853.739 850.0313

821.0722 821.5724 822.825 821.6225 821.6427 822.2529 821.8730

842.1621 837.1732 841.039 838.6833 840.7334 844.907 862.821 866.937 857.7432 857.739 856.8333 856.2534 884.739 883.427 786.1034 785.077 785.936 785.0822 997.057 997.038 997.0513 996.7029

ρ/kg m−3

1.740 37.32 6.690 3.039

0.777 1.284

1.864e 7.642

0.873

1.056

1.930

4.565

0.852 1.531

0.916

exp.

lit.

1.584913

1.30339

1.20022 7.68030

2.11138 2.01867 1.04034 1.12507 1.09635 1.0736 0.89047 0.8938 0.897613

4.4739 4.46934 4.34937

1.61627

0.89739 0.92834

η/mPa s

2.032 40.08 7.652 3.625

0.911 1.502

2.229e 9.300

0.875

1.345

2.181

5.324

1.008 1.766

1.089

exp.

lit.

1.86513

1.52639

1.46222 9.34530

0.8937 0.8937 0.900313

2.38639 2.2857 1.32334 1.4337 1.3636

5.21239 5.21934

1.8647

1.06739 1.10433

ν/mm2 s−1

23 32 30 24

27 26

23 25

71

22

32

25

25 27

28

exp.

25.6331

26.5227 27.131 27.0428 28.029

22.2535 21.8237 22.423 21.9731 72.0137 72.023 70.9131 71.9429

26.2231

26.0031

27.1831

lit.

σ/mN m−1

Table 1. Molar Masses (Mi), CAS Numbers, Supplier and Experimental Purities, Source and Experimental Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Surface Tension (σ) of Standards, Solvents, and Crude Essential Oils at T = 298.2 K and p = 1 × 105 Paa

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

± ± ± ± ± ±

0.002 0.005 0.003 0.001 0.002 0.008

137.7 155.4

terpene group (T)d oxygenated group (O)d

CAS number

supplier purity

experimental purityb

Louis Dreyfus Company, Brazil

Crude Essential Oils Louis Dreyfus Company, Brazil

Solventsc

source

0.925 3.438 1.234 1.006 4.000

845.4 ± 0.8 873.4 ± 0.9

2.235 2.180 1.799 1.798 1.731 1.676

841.7 ± 0.8 849.8 ± 0.8 864.6 ± 0.9

0.9 0.9 0.9 0.9 0.8 0.8

exp.

0.903

± ± ± ± ± ±

lit.

η/mPa s

841.1 ± 0.8

911.4 890.1 865.5 850.5 847.4 841.9

exp.

ρ/kg m−3 lit.

1.187 4.415

1.099 4.048 1.427

1.074

2.452 2.450 2.079 2.114 2.043 1.990

exp.

ν/mm2 s−1 lit.

25

25

28 27 26 25 25 25

exp.

23.8237

27.9637 26.2337 25.0137

lit.

σ/mN m−1

a

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(η) = 0.007 mPa s, u(ν) = 0.007 mm2 s−1, u(σ) = 1 mN m−1, and u(ρ) expressed after each mean value. bDetermined by GC-FID, given as mass fraction (wi) without further purification. cWater content in ethanol (w7,S) given as mass fraction followed by the standard uncertainty. dCalculated considering the composition of each pure component in the group and its respective physical property. eDeviations from the experimental values reported in the literature may be related to differences in the standard purity. Note that the purity of octanal does not strongly affect the experimental results because its content in the crude orange essential oil is very low (Table 2).

136.2 145.1

31.92 34.13 37.36 39.22 39.22 39.24

Mi/ g mol−1

terpene group (T)d oxygenated group (O)d acid lime (C. latifolia)

orange (C. sinensis)

0.508 0.426 0.311 0.247 0.235 0.206

material

Table 1. continued

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DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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studies,2,6,11 terpenes and oxygenated compounds were grouped; therefore, the LLE data were presented in terms of terpenes (T), oxygenated compounds (O), ethanol (6), and water (7). Standard uncertainties Type A were estimated43 in the LLE data to be equal to 0.001 mass fraction. Physical Properties. Standards, hydroalcoholic solvents, crude EOs, and phases from the LLE were submitted for experimental determination of their physical properties, such as density (ρ, in g cm−3), dynamic viscosity (η, in mPa s), and kinematic viscosity (ν, in mm2 s−1). The surface tension (σ, in mN m−1) of the crude EOs, solvents, and standards and the interfacial tension between the LLE phases (π, in mN m−1) were also measured. Densities were measured in a bench digital densimeter (Anton Paar, model DMA 4500, Austria) at T = (298.2 ± 0.1) K in triplicate with standard uncertainties assumed as 0.1% of the experimental value.44 Dynamic viscosities were determined in a falling ball automated microviscometer (Anton Paar, model AMVn, Austria) at T = (298.2 ± 0.1) K at three inclination angles (50, 60, and 70°) using a glass capillary with 1.6 × 10−3 m internal diameter. The measurement was repeated four times for each inclination angle, yielding a total of 12 measurements per sample according to the procedure conducted in previous studies.7,13 Kinematic viscosities were calculated by dividing the dynamic viscosity by the density (ν = η/ρ). The uncertainties were estimated to be equal to 0.007 mPa s for dynamic viscosity and 0.007 mm2 s−1 for kinematic viscosity. Both densimeter and the glass capillary were periodically calibrated assuming deionized water at T = 293.2 K as the reference fluid. Surface and interfacial tensions were evaluated using a force tensiometer (Attension, model Sigma 702, Finland) at T = (298.2 ± 0.1) K. The equipment balance was frequently calibrated using a reference weight. Values of water surface tension and soybean oil/water interfacial tension were measured at T = (298.2 ± 0.1) K and compared to the literature to ensure the data reliability. The surface tension was measured in triplicate, and the standard uncertainty was estimated to be equal to 1 mN m−1. Sample was placed inside a glass vessel, and a platinum Du Noüy ring submerged the sample until the higher tension registered.6 For the determination of interfacial tension between the solvent and terpene phases, the heavy phase (predominantly the solventrich phase) was first placed in a glass vessel, and the Du Noüy ring was immersed within that phase. The light phase (predominantly the terpene-rich phase) was then slowly placed above the heavy phase so that the LLE was not lost. Then, the ring made an upward movement and the equipment indicated the interfacial tension when the higher tension value was reached. The uncertainty for the interfacial tension was calculated by the deviation Type A43 of the three experimental values being equal to 0.1 mN m−1. Correlation and Prediction. Density. Density of each pure component was calculated by GCVOL model45 by eq 2. ρicalc /g cm−3 =

Mi M = K i Vi ∑ j = 1 nj ·Δvj

where A, B, and C are the GCVOL-60 parameters of each group j in molecule i from Ihmels and Gmehling,45 and T is the absolute temperature (298.2 K). Density values of the mixtures (crude EOs, phases from the LLE, and solvents) were estimated using the simple mixing rule (eq 4) in mass and molar basis. N

ρcalc /g cm−3 =

(4)

i=1

where ci is either the mass fraction (wi) or the molar fraction (xi) of component i, N is the number of components in the mixture, and ρi is the density of pure component i. For the complexity of the mixtures to be evaluated, the excess molar volume (VE) was calculated by eq 5. Small relative deviations in the density by the simple mixing rule are related to lower VE values.13 3

−1

V /cm mol

=

ij 1 1 yz − zzzz ρi { kρ

∑ xi·Mi ·jjjj N

E

i=1

(5)

where N is the total number of components in the mixture, xi is the molar fraction of component i, Mi is the molar mass of component i (g mol−1), ρ is the mixture density, and ρi is the density of pure component i. For the crude essential oils, the ρi of terpenes and oxygenated compounds group were estimated by weight considering the molar fraction of each component in the group and its density. Viscosity. Experimental viscosity values of the LLE phases from the model systems were used to adjust the interaction parameters of the Grunberg−Nissan model17 in eq 6. Although the original equation is for dynamic viscosity (η, in mPa s) and compositions in molar fraction (xi) in this study, we also considered kinematic viscosity (ν, mm2 s−1) and compositions in mass fraction (wi). N

ln Dcalc =

N

1 2 i=1

N

∑ ci·ln Di + ∑ ∑ ci·cj·Gij i=1

j=1 j≠i

(6)

where D can be assumed as dynamic (η) or kinematic viscosity (ν), ci is either the molar fraction (xi) or the mass fraction (wi) of component i or j (i ≠ j), Di is the experimental η or ν of component i, N is the number of components in the mixture, and Gij is the binary interaction parameter, adjusted by Matlab software (MathWorks, version R2015a, USA). The Gij values adjusted for the model systems were used to calculate the viscosity of the LLE phases of both model and real systems at T = (298.2 ± 0.1) K. For the orange real system, the terpene group was considered as limonene, and the oxygenated group was assumed as linalool, according to the approach adopted by Gonçalves et al.6 For the acid lime real system, the oxygenated group was considered as citral, and the terpene group was also considered as limonene, as assumed by Gonçalves et al.11 For that, other parameters were adjusted for the lemon/lime model system counting the terpenes (limonene, γ-terpinene, and β-pinene) as limonene, i.e., cT = c1 + c2 + c3 (c can be either mass or molar fraction). The kinematic viscosity of all LLE phases (from the model and real systems) was also predicted by the UNIFAC-VISCO model17,18 using the parameters adjusted by Florido et al.7 and the compositions in the molar fraction. The equations of the UNIFAC-VISCO model can be accessed in the Supporting Information.

(2)

where Mi is the molar mass of the component i (g mol−1), Vi is the molar volume (cm3 mol−1), K is the total number of GCVOL groups, nj is the amount of each GCVOL group j appearing in component i, and Δvj is the group volume increment calculated by eq 3. Δvj /cm 3 mol−1 = Aj + Bj ·T + Cj·T 2

∑ ci·ρi

(3) E

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Interfacial Tension. The tension between the LLE phases (π) of the model systems (orange and lemon/lime EOs) were correlated to phase compositions according to eq 7, as adapted from Treybal.46 Although the original equation refers to the composition in molar fraction, the mass fraction was also considered.

(mass fraction). The oxygenated fraction of acid lime EO is four times that of orange EO (0.044 and 0.011 mass fractions, respectively), and their compositions are also different. The acid lime EO oxygenated fraction is more abundant in citral (geranial 0.537 and neral 0.266 mass fraction), whereas the orange EO contains linalool (0.378), octanal (0.284), and citronellal (0.212) (mass fraction). Densities of each pure component calculated by the GCVOL model45 (eq 2) are also shown in Table 2. The relative deviations between experimental and calculated values (eq 8) were from 0.31 to 1.81%, demonstrating good agreement with experimental values. Therefore, the GCVOL model45 is a worthy tool to predict the density values of pure components. Densities and viscosities of terpenes and oxygenated groups of real systems were calculated using the xj composition and the property of each pure component. For the components for which the densities were not experimentally determined, the calculation by the GCVOL model45 was considered. Liquid−Liquid Equilibrium Experimental Data. The LLE data of the model systems are shown in Table 3 for orange EO and in Table 4 for lemon/lime EOs. The LLE data of the real systems are shown in Table 5 for orange EO and in Table 6 for acid lime EO. The crude EO compositions were represented by terpenes (1) and oxygenated compounds (2) groups. The physical properties (ρ, η, and ν), the excess volumes (VE) of each phase, and the interfacial tensions (π) are also presented in these tables. For all systems, the relative deviation on the tie-line (δ) was less than or equal to 0.5%, indicating good experimental quality.47 At this point, it is important to mention that the existence of two liquid phases was possible due to the presence of water in the system without which the EO and ethanol are completely soluble. Density and Viscosity. In all model or real systems, the increased water content in the phases led to higher density and dynamic viscosity values, mainly for the solvent phases, which are rich in ethanol and water. We can also observe in Table 1 that increasing water in the solvents led to higher physical property values. Increasing the amount of oxygenated compounds in the phases also related to higher density and viscosity values because these components have higher viscosities and, in general, higher density values (Table 1). The experimental data of lemon/lime model systems are in agreement with reports by Florido et al.,7 and the same tendencies were observed in bergamot,7 mint7 and eucalyptus13 model systems. Interfacial Tension. For orange and lemon/lime model systems (Tables 3 and 4, respectively) and for the orange real system (Table 5), the increased water content in the solvent also led to higher interfacial tension values. This can be attributed to the fact that water has the highest surface tension value (71 ± 1 mN m−1, Table 1) and decreases the solubility between the LLE phases,1,6,8,9,13,15,41 contributing to higher interfacial tension values. However, the increase in interfacial tension of the acid lime real systems with increasing water was less prominent than in the model systems. Conversely, the increased amount of oxygenated compounds was related to lower interfacial tension values because these components increase the solubility of the phases.6,13,15 The physical properties of the model and real orange systems were similar, confirming that the crude orange EO can be assumed to be a simple mixture of limonene and linalool. However, the interfacial tensions of the model and real acid lime systems were quite different, where the values of the model system

π calc/mN m−1 = a − b·ln(c1,SP + c 2,SP + c3,SP + c4,SP + c5,SP + c6,TP + c 7,TP)

(7)

where a and b were correlated by a least-squares fitting procedure by Origin Pro software (OriginLab, version 90E, USA), c can be either the molar fraction (xi) or the mass fraction (wi) of component i (1 to 7), and the subscripts SP and TP correspond to solvent- and terpene-rich phases, respectively. The parameters a and b, adjusted to the model systems, were used to calculate the interfacial tension of the real systems. The interfacial tension of all systems was also estimated by the thermodynamic model proposed by Bahramian and Danesh20 according to eq 8. Ä É N Å Å i α yÑÑ ∑ ÅÅÅÅÅ(xi ,TP·xi ,SP)0.5 ·expjjj i ·π calc/mN m−1zzzÑÑÑÑÑ = 1 k R·T {ÑÖ Ç (8) i=1 Å where xi is the mole fraction of component i in the terpene-rich (TP) and solvent-rich (SP) phases, R is the universal gas constant (8.3145 J mol−1 K−1), T is the absolute temperature (298.2 K), and αi is the molar surface area of component i (in m2). Evaluation of Experimental and Calculated Data. For the quality of the experimental data to be evaluated, the LLE phase masses (MTP + MSP) were estimated by the least-squares fitting procedure based on their experimental compositions, and the relative deviation between MTP + MSP and the initial mixture mass (MOC) was calculated by eq 9. According to Marcilla et al.,47 δ ≤ 0.5% indicates acceptable experimental quality. ÄÅ ÉÑ ÅÅÅ |(M TP + MSP) − MOC| ÑÑÑ ÑÑ·100 δ /% = ÅÅÅ ÑÑ ÅÅÇ MOC (9) ÑÖ The average relative deviations between the correlated or calculated physical properties and the experimental values (Δ) were calculated following eq 10. Δ/% =

N |y exp − y calc | 100 ·∑ i exp i N i=1 yi

(10)

where y can be assumed as density (ρ), dynamic viscosity (η), kinematic viscosity (ν), or interfacial tension (π); the superscripts exp and calc correspond to the experimental and calculated physical property, respectively; i is the value referring to the phase; and N is the total number of experimental data.

■

RESULTS AND DISCUSSION Crude Essential Oils Characterization. Table 2 summarizes the compositions of the crude orange and acid lime EOs both in mass fraction (wi) and molar fraction (xi) as well as the molar fraction of each component in the terpene or oxygenated group (xj). The chemical characterization of the crude EOs is in agreement with previous studies.6,10,11 The terpene fraction of orange EO is mainly composed of d-limonene (0.976) and α-pinene (0.024), whereas the acid lime EO is a complex mixture of hydrocarbons, predominantly d-limonene (0.634), γ-terpinene (0.155), β-pinene (0.139), and α-pinene (0.029) F

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 2. Chemical Characterization of Crude Orange and Acid Lime Essential Oils, Retention Times (RTi), Identification Procedure, Molar Masses (Mi), Kovats Index (KIi), Compositions in Mass Fraction (wi), Molar Fraction (xi), and Calculated Density by GCVOL Model (ρicalc) at T = 298.2 K and p = 1 × 105 Paa crude orange essential oil component (i)

RTi/min

Terpenes (T) α-pinene 2.58 β-pinene 2.47 myrcene 2.55 d-limonene 2.91 γ-terpinene 3.02 p-cymene 3.13 terpinolene 3.19 δ-elemene 4.58 β-caryophyllene 5.76 β-elemene 6.01 α-bergamotene 6.56 β-farnesene 6.82 β-bisabolene 7.39 β-germacrene 7.89 Oxygenated Compounds (O) octanal 3.23 decanal 4.83 citronellal 4.89 linalool 5.24 octanol 5.35 neral 6.95 α-terpineol 7.01 geranial 7.59 geranyl acetate 7.68 geraniol 8.20 bisabolol 8.72

KIib

c

identification

1487 1479 1485 1604 1617 1624 1628 1802 1860 1871 1894 1904 2034 2057

standard/ KIf standard/ KIf NIST-MS standard/ KIf standard/ KIf standard/ KIf NIST-MS NIST-MS NIST-MS/ KIf NIST-MS NIST-MS NIST-MS/ KIf NIST-MS/ KIf NIST-MS

136.2 136.3 136.3 136.2 136.2 134.2 136.2 204.4 204.4 204.4 204.4 204.4 204.4 204.4

1630 1815 1819 1837 1842 2012 2015 2042 2047 2070 2092

standard/ KIf standard/ KIf standard/ KIf standard/ KIf standard/ KIf standard/ KIf standard/ KIf standard/ KIf NIST-MS/ KIf standard/ KIf NIST-MS/ KIf

128.2 156.3 154.3 154.2 130.2 152.2 154.3 152.2 196.3 154.3 222.4

Mi/g mol

−1

wi

xi

xjd

0.987 0.024

0.990 0.024

1.000 0.024

0.963

0.966

0.976

0.011 0.003

0.010 0.003

1.000 0.284

0.003 0.004 0.001

0.001

0.002 0.004 0.001

0.001

0.212 0.378 0.067

0.059

crude acid lime essential oil wi

xi

xjd

ρicalc/kg m−3e

0.956 0.027 0.131 0.014 0.600 0.146 0.001 0.007 0.001 0.012 0.005 0.001 0.001 0.010 0.001 0.044

0.961 0.027 0.133 0.014 0.609 0.149 0.001 0.007 0.001 0.008 0.003 0.001 0.000 0.007 0.000 0.039

1.000 0.029 0.139 0.015 0.634 0.155 0.001 0.007 0.001 0.008 0.003 0.001 0.000 0.007 0.000 1.000

862.14 856.97 772.40 853.93 853.93 855.89 908.78 770.76 954.62 836.03 1093.1 814.05 808.91 817.03

0.001

0.000

0.012

0.002

0.002

0.047

0.011 0.002 0.023 0.002 0.001 0.001

0.010 0.002 0.021 0.001 0.001 0.001

0.266 0.048 0.537 0.036 0.034 0.018

819.92 826.28 850.03 850.59 824.27 872.33 937.95 872.33 593.72 875.75 835.09

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(w) = 0.001, u(x) = 0.001. bCalculated by eq 1. cIdentified by GC-MS (NIST-MS library) and by comparison with the standard retention time and/or with KI values from the literature. dComposition of component i in the group terpenes or oxygenated compounds. eCalculated by eq 2. fKovats Index in agreement with value previously reported in the literature.6,8 a

compounds in the terpene-rich phase. The discussion of each calculated physical property is presented next. Density. Table 7 contains the relative deviations for the estimated densities of the LLE phases by the simple mixing rule (eq 4) for compositions in either mass fraction or molar fraction. For the terpene-rich phases (TP), better results were calculated using the compositions in molar fraction (Δ = 0.10−1.68%), whereas for the solvent-rich phases (SP), the lower deviations were obtained using the compositions in mass fraction (Δ = 1.53−2.36%). The same tendency was observed by Gonçalves et al.13 for a eucalyptus model system. A good estimation of densities by the simple mixing rule can be confirmed by low excess volumes values (VE) calculated by eq 5 and shown in Tables 3−6. Relating the excess volume values, we can verify that they were positive for terpene-rich phases (with the exception of the acid lime real system, Table 6) and always negative for the solvent-rich phases. The breaking of cohesion forces and unfavorable interactions between distinct molecules are responsible for positive VE values, whereas the negative values are related to interactions among unlike molecules (e.g., terpenes and water) by charge−transfer and dipole−dipole interactions among the solvent molecules (ethanol and water).48 Furthermore, excess volumes of the terpene-rich phases from the model (Table 3) and real (Table 5) orange systems were very low (0.25− 0.58 cm3 mol−1), implying a high proximity to an ideal mixture.

were much higher than those of the real system. Some slight discrepancies can also be observed in density and viscosity values. These differences may be related to the complexity of the crude acid lime EO and the presence of other components in the real system, as nonvolatile compounds, such as waxes, pigments, acids, and so forth. For comparison purposes, the interfacial tension values between the crude EOs and pure deionized water were measured. The interfacial tension of the orange system varied from 7.4 to 10.2 mN m−1, whereas that of the acid lime system varied from 2.0 to 3.6 mN m−1. Because the citrus EOs were crude, nonvolatile compounds were present in the mixtures (composition not determined). However, it was visually observed that the acid lime systems had a higher nonvolatile amount than those of the orange systems. Lower interfacial tensions concerning the acid lime real systems are probably related to higher nonvolatile compound content in the interface. Correlated and Calculated Data. Experimental physical properties (as points) and the best results of their respective correlated or predicted values (as lines), according to the highlighted deviations in Table 7, are displayed in Figures 1 and 2 for orange and lemon/lime model systems, respectively, and in Figures 3 and 4 for orange and acid lime real systems, respectively. Because the solute (oxygenated compounds) migrates from the terpene-rich to the solvent-rich phase, the physical properties are related to the mass percentage of oxygenated G

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

H

0.426 ± 0.005

0.311 ± 0.003

0.387

0.388

0.005

0.005

0.005

0.010

0.010

0.010

0.015

0.015

0.015

0.020

0.020

0.020

0.500

0.493

0.495

0.495

0.490

0.490

0.490

0.484

0.485

0.484

0.478

0.479

0.477

0.353

0.005

0.005

0.005

0.010

0.010

0.010

0.016

0.015

0.015

0.020

0.020

0.020

0.025

0.025

0.025

0.493

0.494

0.479

0.490

0.488

0.487

0.485

0.477

0.485

0.479

0.479

0.479

0.474

0.475

0.475

0.500

0.341

0.500

0.281

0.350

0.341

0.342

0.352

0.352

0.352

0.350

0.347

0.341

0.354

0.352

0.351

0.366

0.352

0.342

0.500

0.388

0.386

0.387

0.386

0.386

0.385

0.385

0.385

0.385

0.385

0.385

0.387

0.386

w6

0.500

0.235 ± 0.002

w4

0.501

w1

w7,Sb

0.219

0.150

0.159

0.159

0.149

0.149

0.149

0.150

0.162

0.159

0.149

0.150

0.148

0.151

0.149

0.149

0.159

0.159

0.115

0.114

0.114

0.114

0.114

0.115

0.115

0.115

0.115

0.115

0.115

0.114

0.113

0.113

0.113

w7

overall composition (OC)

0.981

0.928

0.933

0.934

0.951

0.946

0.942

0.946

0.951

0.950

0.945

0.963

0.962

0.969

0.972

0.966

0.975

0.976

0.938

0.936

0.939

0.946

0.945

0.947

0.955

0.955

0.954

0.955

0.960

0.959

0.965

0.964

0.979

w1

0.026

0.026

0.025

0.017

0.019

0.020

0.015

0.015

0.016

0.010

0.010

0.010

0.005

0.005

0.005

0.016

0.016

0.016

0.012

0.012

0.012

0.008

0.008

0.008

0.004

0.004

0.004

w4

0.016

0.043

0.037

0.037

0.029

0.033

0.036

0.036

0.031

0.031

0.042

0.024

0.026

0.024

0.021

0.026

0.022

0.022

0.043

0.045

0.042

0.039

0.040

0.038

0.035

0.034

0.036

0.039

0.033

0.035

0.033

0.033

0.019

w6 0.002

0.002

0.003

0.003

0.004

0.003

0.002

0.003

0.003

0.004

0.003

0.003

0.003

0.003

0.002

0.003

0.003

0.003

0.002

0.003

0.003

0.003

0.003

0.003

0.003

0.003

0.003

0.002

0.003

0.002

0.002

0.002

0.003

837.4

837.7

837.3

837.6

837.5

837.4

837.4

837.3

837.7

837.7

837.6

837.3

837.2

837.2

837.4

837.4

837.3

837.3

837.3

836.5

836.3

836.4

836.4

836.4

836.3

836.5

837.0

836.4

836.5

836.5

836.6

837.3

837.3

0.811

0.862

0.870

0.909

0.910

0.837

0.895

0.860

0.871

0.871

0.877

0.883

0.837

0.917

0.887

0.863

0.823

0.866

0.852

0.830

0.832

0.854

0.841

0.832

0.810

0.815

0.816

0.848

0.829

0.812

0.818

0.858

0.821

1.051

1.060

0.993

1.017

1.027

1.036

1.012

1.014

1.010

1.037

1.027

0.983

1.049

1.034

1.027

1.059

1.030

1.048

1.033

0.990

0.980

0.992

0.994

0.997

0.998

1.003

1.003

0.992

0.992

0.996

0.991

0.998

1.004

0.58

0.55

0.40

0.41

0.45

0.52

0.46

0.47

0.39

0.45

0.46

0.37

0.58

0.55

0.51

0.58

0.52

0.56

0.54

0.53

0.52

0.55

0.56

0.56

0.58

0.58

0.49

0.58

0.53

0.58

0.53

0.42

0.44

0.009

0.041

0.038

0.039

0.045

0.046

0.036

0.038

0.038

0.032

0.038

0.041

0.039

0.040

0.033

0.037

0.017

0.034

0.079

0.077

0.080

0.076

0.079

0.075

0.071

0.070

0.073

0.072

0.071

0.072

0.073

0.074

0.074

w1

0.024

0.023

0.024

0.023

0.021

0.020

0.014

0.015

0.016

0.010

0.011

0.010

0.005

0.005

0.005

0.024

0.024

0.024

0.018

0.018

0.018

0.012

0.012

0.012

0.006

0.006

0.006

w4

0.550

0.639

0.623

0.629

0.646

0.648

0.654

0.654

0.637

0.638

0.660

0.661

0.652

0.678

0.673

0.664

0.659

0.651

0.687

0.685

0.680

0.691

0.688

0.686

0.697

0.694

0.693

0.695

0.704

0.706

0.706

0.707

0.712

w6

0.441

0.296

0.315

0.308

0.286

0.285

0.289

0.294

0.310

0.314

0.292

0.288

0.299

0.277

0.289

0.294

0.323

0.315

0.210

0.214

0.215

0.214

0.215

0.221

0.219

0.224

0.221

0.228

0.220

0.216

0.221

0.218

0.215

w7 847.3

888.2

865.3

867.5

866.5

863.0

862.9

862.6

864.8

866.4

866.5

862.5

862.2

863.6

862.1

862.5

866.5

865.8

864.7

846.6

846.6

846.6

846.6

846.5

846.4

847.2

847.4

846.3

846.1

846.1

846.3

847.2

847.2

2.196

2.025

2.027

2.025

1.942

1.952

1.913

1.983

1.996

2.000

1.892

1.893

1.904

1.879

2.126

1.922

1.941

1.986

1.713

1.717

1.723

1.716

1.716

1.716

1.713

1.708

1.694

1.685

1.686

1.695

1.698

1.694

1.717

η/ mPa s

ρ/ kg m−3

w7

VE/ cm3 mol−1

solvent-rich phase (SP) ν/ mm2 s−1

ρ/ kg m−3

η/ mPa s

terpene-rich phase (TP)

2.387

2.319

2.378

2.357

2.292

2.284

2.277

2.280

2.338

2.336

2.269

2.259

2.295

2.199

2.234

2.251

2.285

2.312

1.982

2.006

2.013

1.992

1.993

2.029

2.002

2.027

2.016

2.037

1.992

1.973

1.984

1.967

1.947

ν/ mm2 s−1

2.4 2.4 2.4 2.1 2.1 2.0 2.1 2.1 2.1

−3.83 −3.56 −3.25 −3.27 −3.29 −3.85 −4.00 −3.64

4.6

2.5 −3.86

−6.61

2.5

1.7

−0.50

−3.23

1.7

−0.54

−3.18

1.7

−0.55

2.5

1.8

−0.53

2.8

2.0

−0.52

−3.41

2.0

−0.56

2.8

2.2

−0.64

−3.10

2.1

−0.71

2.9

2.1

−0.54

−3.22

2.3

−0.55

−3.75

2.2

−0.47

3.2

2.3

3.3

2.4 −0.46

−3.78

2.3 −0.63

−3.61

2.2 −0.60

π/ mN m−1

−0.60

VE/ cm3 mol−1

Table 3. Liquid−Liquid Equilibrium Data for Orange Essential Oil Model Systems Composed of Limonene (1), Linalool (4), Ethanol (6), and Water (7) in Mass Fractions (w), Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Excess Volume (VE) of the Phases and Interfacial Tension (π) at T = 298.2 K and p = 1 × 105 Paa

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

I

0.305

0.005

0.005

0.010

0.010

0.010

0.015

0.015

0.016

0.026

0.025

0.025

0.035

0.035

0.035

0.495

0.494

0.490

0.490

0.490

0.485

0.485

0.485

0.474

0.472

0.470

0.465

0.464

0.460

0.302

0.295

0.295

0.298

0.287

0.286

0.294

0.286

0.286

0.295

0.289

0.290

0.295

0.295

0.286

0.005

w6

0.477

w4

0.500

w1

0.203

0.206

0.205

0.208

0.215

0.214

0.205

0.214

0.214

0.205

0.211

0.210

0.205

0.205

0.213

0.214

w7

0.912

0.902

0.904

0.929

0.931

0.931

0.949

0.952

0.953

0.965

0.958

0.965

0.973

0.973

0.978

0.981

w1

0.050

0.047

0.047

0.033

0.034

0.033

0.021

0.019

0.019

0.013

0.014

0.013

0.006

0.006

0.006

w4

0.035

0.047

0.045

0.036

0.032

0.032

0.029

0.027

0.025

0.020

0.026

0.020

0.019

0.019

0.014

0.017

w6

0.004

0.005

0.004

0.003

0.004

0.003

0.002

0.003

0.003

0.002

0.003

0.002

0.002

0.001

0.002

0.002

w7

838.2

837.8

837.9

837.4

837.5

837.4

837.4

837.4

837.4

838.4

837.8

838.0

838.2

837.9

837.8

837.8

ρ/ kg m−3

0.909

0.858

0.863

0.843

0.859

0.843

0.835

0.835

0.826

0.732

0.868

0.830

0.875

0.816

0.819

0.821

η/ mPa s

terpene-rich phase (TP)

1.053

1.024

1.026

1.018

1.049

1.043

1.024

1.042

1.050

1.050

1.039

1.047

1.054

1.043

1.071

1.048

ν/ mm2 s−1

0.42

0.37

0.37

0.48

0.53

0.54

0.51

0.54

0.56

0.42

0.46

0.48

0.44

0.49

0.57

0.51

V/ cm3 mol−1

E

0.013

0.012

0.013

0.012

0.013

0.011

0.012

0.012

0.013

0.010

0.012

0.012

0.011

0.011

0.011

0.011

w1

0.020

0.020

0.021

0.014

0.016

0.014

0.010

0.010

0.010

0.006

0.007

0.008

0.003

0.004

0.004

w4

0.560

0.551

0.549

0.565

0.537

0.547

0.575

0.560

0.549

0.576

0.562

0.562

0.580

0.587

0.592

0.568

w6

0.407

0.417

0.417

0.409

0.435

0.429

0.404

0.418

0.428

0.408

0.420

0.418

0.406

0.399

0.393

0.421

w7

892.1

891.5

891.4

892.6

892.6

892.7

892.1

892.1

892.2

890.8

889.0

888.9

890.5

890.0

889.8

892.0

ρ/ kg m−3

2.214

2.184

2.187

2.211

2.211

2.211

2.177

2.177

2.193

2.148

2.148

2.146

2.136

2.168

2.176

2.170

η/ mPa s

solvent-rich phase (SP)

2.413

2.423

2.430

2.393

2.434

2.408

2.379

2.398

2.415

2.368

2.399

2.405

2.365

2.356

2.349

2.371

ν/ mm2 s−1

π/ mN m−1 4.6 3.8 3.7 3.8 3.6 3.5 3.4 3.5 3.5 3.5 3.0 3.0 3.0 2.5 2.5 2.5

VE/ cm3 mol−1 −6.99 −6.75 −6.77 −6.83 −6.67 −6.68 −6.87 −7.01 −7.00 −7.00 −7.07 −7.06 −7.06 −6.94 −6.94 −7.01

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(w) = 0.001, u(ρ) = 0.9 kg m−3, u(η) = 0.007 mPa s, u(ν) = 0.007 mm2 s−1, and u(π) = 0.1 mN m−1. bWater mass fraction in the solvent followed by the standard uncertainty.

a

w7,Sb

overall composition (OC)

Table 3. continued

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

w1

w2

w3

J

845.2 843.4

0.320 0.076 0.069 0.040 0.144 0.608 0.140 0.132 0.059 0.057

0.320 0.076 0.069 0.040 0.145 0.613 0.147 0.133 0.059 0.044

843.0 842.6 843.6 843.6 843.7 843.5 843.3 843.4 844.6 844.6 844.6

0.333 0.082 0.073 0.010 0.201 0.647 0.161 0.145 0.017 0.028

0.335 0.082 0.074 0.010 0.201 0.644 0.160 0.143 0.016 0.035

0.322 0.079 0.070 0.020 0.205 0.634 0.158 0.140 0.036 0.031

0.320 0.076 0.067 0.020 0.210 0.644 0.155 0.135 0.036 0.027

0.317 0.081 0.070 0.020 0.208 0.634 0.159 0.139 0.037 0.029

0.316 0.077 0.069 0.030 0.207 0.611 0.152 0.136 0.049 0.047

0.320 0.078 0.070 0.031 0.201 0.606 0.151 0.135 0.047 0.056

0.321 0.079 0.071 0.030 0.201 0.610 0.151 0.136 0.051 0.047

0.315 0.081 0.069 0.040 0.201 0.598 0.155 0.133 0.071 0.041

0.317 0.081 0.067 0.040 0.201 0.602 0.156 0.129 0.068 0.044

0.315 0.081 0.068 0.040 0.201 0.598 0.158 0.132 0.070 0.040

842.6 843.0

0.024

0.323 0.079 0.071 0.010 0.207 0.649 0.162 0.145 0.017 0.026

0.202 0.663 0.165 0.148

0.340 0.083 0.075

842.8 842.6

0.201 0.664 0.163 0.147

0.340 0.083 0.075

0.024 0.023

0.201 0.665 0.162 0.147

0.426 ± 0.005 0.342 0.084 0.075

843.9

843.0

0.320 0.079 0.071 0.030 0.147 0.616 0.153 0.136 0.044 0.048

0.308 0.076 0.067 0.050 0.150 0.589 0.144 0.130 0.078 0.057

843.1

0.319 0.078 0.070 0.030 0.154 0.612 0.149 0.135 0.048 0.052

843.8

842.9

0.320 0.083 0.072 0.020 0.147 0.619 0.161 0.141 0.025 0.051

0.306 0.075 0.067 0.051 0.153 0.586 0.143 0.130 0.079 0.057

842.9

0.322 0.079 0.072 0.020 0.148 0.629 0.154 0.140 0.026 0.049

843.7

842.8

0.324 0.079 0.072 0.020 0.147 0.628 0.153 0.141 0.025 0.051

843.2

842.4

0.332 0.081 0.073 0.010 0.156 0.647 0.158 0.143 0.014 0.036

0.306 0.075 0.067 0.051 0.151 0.588 0.143 0.130 0.079 0.056

842.4

0.335 0.082 0.073 0.010 0.155 0.646 0.158 0.143 0.014 0.037

0.318 0.076 0.069 0.039 0.145 0.607 0.145 0.132 0.058 0.054

842.4

842.1

842.1

0.988

0.997

1.065

0.951

0.973

0.931

1.003

0.986

0.961

0.944

0.951

0.909

0.893

0.890

0.901

0.953

0.995

0.965

0.980

0.997

0.986

0.946

0.939

0.954

0.966

0.955

0.923

0.927

0.926

0.867

0.866

0.875

1.170

1.180

1.261

1.127

1.154

1.104

1.188

1.168

1.139

1.120

1.129

1.078

1.060

1.057

1.069

1.129

1.179

1.143

1.163

1.182

1.166

1.122

1.114

1.132

1.146

1.133

1.095

1.100

1.100

1.029

1.029

1.039

2.31

2.25

2.29

2.36

2.19

2.31

2.53

2.62

2.51

2.53

2.58

2.62

2.69

2.67

2.63

2.20

2.23

2.24

2.29

2.44

1.92

2.37

2.30

2.20

2.27

2.24

2.54

2.53

2.55

2.61

2.63

2.62

ρ/ η/ ν/ VE/ kg m−3 mPa s mm2 s−1 cm3 mol−1

0.334 0.082 0.073 0.010 0.153 0.647 0.158 0.143 0.014 0.036

0.030

0.031

w6

842.2

w5

terpene-rich phase (TP)c

0.031

0.155 0.660 0.161 0.146

w6 0.152 0.662 0.162 0.145

w5

0.340 0.084 0.074

w3

0.338 0.083 0.074

w2 0.153 0.661 0.162 0.145

w1

0.311 ± 0.003 0.340 0.084 0.075

w7,Sb

overall composition (OC)c w2

w3

w5

0.667

0.675

0.670

w6

0.589

0.588

0.587

0.004 0.002 0.002 0.012 0.566

0.004 0.001 0.001 0.013 0.565

0.005 0.001 0.001 0.013 0.560

0.006 0.001 0.001 0.011 0.574

0.007 0.002 0.002 0.011 0.574

0.007 0.001 0.002 0.011 0.572

0.004 0.001 0.001 0.005 0.579

0.004 0.001 0.001 0.005 0.578

0.004 0.001 0.001 0.005 0.583

0.006 0.001 0.001 0.004 0.578

0.006 0.001 0.001 0.004 0.590

0.006 0.001 0.001 0.004 0.586

0.005 0.001 0.001

0.005 0.001 0.001

0.005 0.001 0.001

0.017 0.004 0.004 0.027 0.649

0.017 0.004 0.004 0.027 0.638

0.017 0.004 0.004 0.027 0.645

0.033 0.006 0.004 0.019 0.654

0.019 0.004 0.004 0.019 0.671

0.024 0.005 0.005 0.020 0.662

0.013 0.003 0.003 0.014 0.680

0.013 0.003 0.003 0.015 0.658

0.018 0.004 0.004 0.014 0.672

0.018 0.004 0.004 0.015 0.667

0.019 0.004 0.004 0.015 0.678

0.014 0.003 0.003 0.005 0.665

0.013 0.003 0.003 0.005 0.665

0.015 0.003 0.003 0.005 0.666

0.013 0.003 0.003

0.014 0.003 0.003

0.014 0.003 0.003

w1

895.0

895.1

895.5

889.0

889.0

888.9

894.9

893.5

894.8

888.6

888.2

888.1

888.0

888.0

888.1

867.6

867.6

867.1

863.1

863.6

863.6

866.8

866.7

863.0

863.3

863.1

866.3

866.5

866.5

876.8

876.8

866.5

2.387

2.383

2.382

2.197

2.200

2.197

2.390

2.399

2.384

2.202

2.188

2.179

2.180

2.184

2.187

2.004

1.987

2.000

2.091

2.089

2.120

1.987

1.986

2.072

2.070

2.071

1.985

1.995

1.987

1.947

1.920

1.918

2.667

2.662

2.660

2.472

2.474

2.472

2.671

2.685

2.664

2.478

2.463

2.454

2.455

2.459

2.463

2.310

2.290

2.307

2.423

2.420

2.455

2.292

2.291

2.401

2.398

2.399

2.291

2.302

2.293

2.220

2.190

2.213

2.6 2.5 2.5 2.2 2.2

−1.04 −1.02 −1.23 −1.05 −1.09

4.2 4.3 4.3 3.9 3.9 3.8 3.9 4.0 3.9 3.3 3.3 3.3 3.3 3.4 3.4

−1.05 −1.06 −1.06 −1.06 −1.10 −1.02 −1.27 −1.18 −1.23 −1.02 −1.05 −1.03 −1.15 −1.17 −1.17

2.1

2.6

−1.01

2.1

2.6

−1.12

−1.07

2.9

−1.02

2.1

3.0

−1.03

−0.97

3.0

−1.05

2.2

3.2

−1.43

−1.03

3.3

−1.53

−1.01

3.3

−1.04

ρ/ η/ ν/ V E/ π/ kg m−3 mPa s mm2 s−1 cm3 mol−1 mN m−1

solvent-rich phase (SP)c

Table 4. Liquid−Liquid Equilibrium Data for Lemon/Lime Model Systems Composed of Limonene (1), γ-Terpinene (2), β-Pinene (3), Citral (5), Ethanol (6), and Water (7) in Mass Fractions (w), Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Excess Volume (VE) of the Phases and Interfacial Tension (π) at T = 298.2 K and p = 1 × 105 Paa

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

w2

w3

w6

843.0

K

843.5 843.5 844.2 844.2 844.2 844.7 844.8 844.4 845.1 845.1 845.1 845.4 845.6 845.6

0.328 0.081 0.073 0.010 0.256 0.651 0.162 0.146 0.019 0.021

0.333 0.082 0.074 0.010 0.252 0.652 0.161 0.145 0.019 0.020

0.328 0.080 0.076 0.020 0.250 0.631 0.156 0.148 0.038 0.025

0.331 0.081 0.073 0.020 0.250 0.637 0.158 0.141 0.038 0.025

0.330 0.081 0.073 0.020 0.250 0.636 0.158 0.141 0.038 0.025

0.324 0.080 0.071 0.029 0.250 0.621 0.154 0.136 0.058 0.028

0.323 0.079 0.074 0.029 0.249 0.618 0.153 0.142 0.054 0.030

0.329 0.080 0.071 0.030 0.247 0.621 0.152 0.140 0.055 0.030

0.323 0.080 0.072 0.039 0.245 0.606 0.153 0.135 0.074 0.030

0.323 0.080 0.071 0.039 0.246 0.606 0.151 0.133 0.076 0.031

0.324 0.080 0.071 0.039 0.245 0.605 0.152 0.134 0.076 0.031

0.328 0.075 0.068 0.048 0.242 0.604 0.141 0.127 0.087 0.038

0.319 0.078 0.071 0.049 0.244 0.596 0.149 0.133 0.082 0.036

0.321 0.079 0.071 0.049 0.242 0.597 0.149 0.133 0.085 0.032

0.914

1.116

0.962

0.974

0.989

0.989

0.984

0.943

0.972

0.962

0.949

0.936

0.913

0.912

0.918

0.925

0.916

0.913

1.320

1.138

1.152

1.170

1.170

1.165

1.117

1.151

1.139

1.124

1.109

1.081

1.081

1.088

1.097

1.086

1.083

1.084

1.205

1.188

1.199

2.35

2.26

2.34

2.43

2.43

2.42

2.46

2.39

2.48

2.51

2.54

2.50

2.65

2.63

2.65

2.71

2.74

2.73

2.23

2.29

2.24

w2

w3

w5

w6

0.491 0.488

0.490

0.001 0.000 0.000 0.007 0.474

0.001 0.000 0.000 0.008 0.478

0.001 0.000 0.000 0.006 0.472

0.001 0.000 0.000 0.006 0.479

0.001 0.000 0.000 0.005 0.468

0.001 0.000 0.000 0.004 0.478

0.002 0.000 0.000 0.005 0.478

0.001 0.000 0.000 0.004 0.482

0.001 0.000 0.000 0.004 0.477

0.001 0.000 0.000 0.003 0.480

0.001 0.000 0.000 0.004 0.488

0.001 0.000 0.000 0.003 0.485

0.001 0.000 0.000 0.002 0.487

0.001 0.000 0.000 0.002 0.487

0.001 0.000 0.000 0.002 0.485

0.001 0.000 0.000

0.001 0.000 0.000

0.001 0.000 0.000

0.004 0.001 0.001 0.013 0.563

0.005 0.001 0.001 0.012 0.568

0.004 0.001 0.001 0.013 0.567

w1

913.4

913.0

913.5

913.1

913.6

913.5

912.7

913.1

913.4

912.8

912.5

912.6

911.3

911.9

912.3

912.1

911.9

911.8

895.8

895.6

895.5

2.369

2.366

2.367

2.488

2.448

2.490

2.368

2.370

2.368

2.374

2.388

2.373

2.364

2.697

2.368

2.373

2.363

2.365

2.403

2.414

2.305

2.594

2.592

2.591

2.724

2.680

2.726

2.595

2.596

2.592

2.601

2.617

2.600

2.595

2.957

2.595

2.601

2.592

2.594

2.683

2.695

2.574

5.7 5.8 5.7 5.4 5.4 5.4 5.0 5.0 4.8 4.6 4.4 4.6 4.3 4.4 4.3 4.2 4.1 4.1

−1.00 −0.99 −1.00 −0.98 −1.01 −1.03 −0.98 −0.97 −1.00 −0.96 −0.99 −0.91 −0.98 −0.95 −0.99 −0.96

3.2

−1.17 −1.01

3.2

−1.21 −1.02

3.2

−1.20

ρ/ η/ ν/ V E/ π/ kg m−3 mPa s mm2 s−1 cm3 mol−1 mN m−1

solvent-rich phase (SP)c

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(w) = 0.001, u(ρ) = 0.9 kg m−3, u(η) = 0.007 mPa s, u(ν) = 0.007 mm2 s−1, and u(π) = 0.1 mN m−1. bWater mass fraction in the solvent followed by the standard uncertainty. cw7 = 1 − (w1 + w2 + w3 + w5 + w6).

843.5

0.334 0.083 0.073 0.010 0.252 0.652 0.163 0.144 0.019 0.021

842.9 842.9

0.255 0.667 0.165 0.147

0.338 0.083 0.074

0.017 0.017

1.019

1.004

1.014

ρ/ η/ ν/ VE/ kg m−3 mPa s mm2 s−1 cm3 mol−1

0.018

0.256 0.668 0.166 0.147 0.255 0.669 0.166 0.146

0.338 0.083 0.074

a

w5

845.3

w1

0.311 0.078 0.070 0.050 0.199 0.591 0.149 0.128 0.086 0.043

w6 845.2

w5 845.1

w3

0.311 0.078 0.070 0.049 0.200 0.587 0.151 0.131 0.088 0.040

w2

terpene-rich phase (TP)c

0.311 0.078 0.070 0.049 0.200 0.588 0.151 0.134 0.083 0.042

w1

0.508 ± 0.002 0.336 0.083 0.074

w7,Sb

overall composition (OC)c

Table 4. continued

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

L

0.005 0.005 0.005 0.005 0.005 0.007 0.007 0.007 0.010 0.009 0.011 0.011 0.011 0.012 0.011 0.005 0.005 0.007 0.007 0.009 0.009 0.011 0.011 0.011 0.011 0.011

wO

0.470 0.470 0.467 0.471 0.470 0.354 0.352 0.350 0.236 0.233 0.176 0.175 0.140 0.141 0.140 0.382 0.392 0.288 0.292 0.195 0.194 0.145 0.146 0.146 0.117 0.118

w6 0.197 0.197 0.196 0.197 0.197 0.148 0.148 0.150 0.099 0.100 0.075 0.075 0.060 0.059 0.060 0.283 0.274 0.211 0.208 0.141 0.139 0.106 0.105 0.105 0.084 0.082

w7 0.960 0.960 0.959 0.960 0.965 0.956 0.956 0.955 0.953 0.953 0.953 0.952 0.953 0.953 0.952 0.965 0.965 0.961 0.963 0.960 0.961 0.957 0.961 0.961 0.961 0.961

wT 0.007 0.007 0.007 0.006 0.009 0.009 0.009 0.009 0.011 0.011 0.012 0.012 0.013 0.013 0.013 0.010 0.009 0.012 0.011 0.012 0.012 0.013 0.013 0.013 0.013 0.013

wO 0.031 0.031 0.031 0.032 0.024 0.033 0.033 0.034 0.034 0.034 0.033 0.034 0.032 0.032 0.034 0.023 0.024 0.025 0.025 0.025 0.025 0.026 0.025 0.025 0.024 0.024

w6 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.003 0.002 0.001 0.003 0.002 0.003 0.001 0.001 0.002 0.001

w7 837.6 837.8 837.6 837.8 837.7 838.4 838.0 837.8 838.0 838.1 838.2 838.2 838.3 838.2 838.2 838.4 838.2 838.5 838.8 838.8 838.7 838.9 838.9 838.8 838.5 839.2

ρ/ kg m−3

terpene-rich phase (TP)

0.892 0.912 0.911 0.870 0.917 0.915 0.915 0.910 0.915 0.911 0.904 0.914 0.901 0.900 0.874 0.853 0.861 0.866 0.862 0.869 0.856 0.863 0.866 0.854 0.864 0.864

η/ mPa s 1.065 1.088 1.087 1.039 1.095 1.091 1.092 1.087 1.092 1.086 1.079 1.090 1.075 1.074 1.043 1.018 1.027 1.033 1.027 1.036 1.021 1.029 1.032 1.018 1.031 1.029

ν/mm2 s−1 0.45 0.40 0.46 0.41 0.52 0.30 0.38 0.39 0.36 0.33 0.34 0.32 0.32 0.34 0.33 0.40 0.44 0.35 0.30 0.33 0.33 0.30 0.29 0.31 0.36 0.25

VE/ cm3 mol−1 0.029 0.032 0.029 0.033 0.012 0.028 0.030 0.030 0.026 0.027 0.024 0.024 0.026 0.027 0.024 0.008 0.009 0.007 0.008 0.008 0.008 0.007 0.007 0.008 0.007 0.006

wT 0.004 0.003 0.003 0.004 0.003 0.005 0.005 0.005 0.006 0.006 0.007 0.006 0.007 0.007 0.006 0.002 0.002 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003

wO 0.676 0.671 0.678 0.679 0.691 0.672 0.673 0.667 0.664 0.649 0.652 0.647 0.635 0.647 0.636 0.563 0.578 0.558 0.573 0.553 0.553 0.538 0.541 0.544 0.534 0.539

w6 0.292 0.294 0.290 0.284 0.294 0.295 0.291 0.297 0.304 0.317 0.317 0.323 0.332 0.320 0.334 0.427 0.411 0.432 0.416 0.436 0.436 0.453 0.449 0.445 0.457 0.452

w7 863.0 862.6 863.1 863.3 863.7 865.0 915.9 864.5 868.0 868.8 871.3 871.3 874.3 874.4 911.8 893.7 893.4 895.3 895.4 898.0 898.3 901.0 901.4 901.0 903.8 903.8

ρ/ kg m−3 1.964 1.964 1.968 1.891 1.989 1.960 2.035 1.993 2.035 2.046 2.082 2.092 2.105 2.106 2.109 2.143 2.154 2.162 2.139 2.184 2.190 2.212 2.210 2.212 2.226 2.235

η/ mPa s

solvent-rich phase (SP)

2.276 2.277 2.280 2.191 2.303 2.266 2.222 2.305 2.344 2.355 2.390 2.401 2.407 2.408 2.313 2.398 2.411 2.415 2.389 2.432 2.438 2.455 2.451 2.455 2.463 2.472

ν/mm2 s−1

−1.07 −1.02 −1.09 −1.14 −1.11 −1.11 −3.21 −1.07 −1.15 −1.06 −1.16 −1.12 −1.14 −1.26 −2.57 −1.06 −1.19 −1.07 −1.21 −1.13 −1.14 −1.09 −1.14 −1.15 −1.15 −1.19

VE/cm3 mol−1

3.6 3.7 3.5 3.5 3.1 3.2 3.2 3.1 3.0

2.7 2.7 2.7 2.7 2.6 2.7 2.6

2.7 2.8 2.8 2.7

π/ mN m−1

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(w) = 0.001, u(ρ) = 0.9 kg m−3, u(η) = 0.007 mPa s, u(ν) = 0.007 mm2 s−1, and u(π) = 0.1 mN m−1. bWater mass fraction in the solvent followed by the standard uncertainty.

a

0.329 0.328 0.332 0.327 0.329 0.490 0.493 0.493 0.656 0.657 0.738 0.739 0.789 0.788 0.788 0.330 0.329 0.493 0.493 0.655 0.657 0.739 0.739 0.739 0.788 0.788

0.311 ± 0.003

0.426 ± 0.005

wT

w7,Sb

overall composition (OC)

Table 5. Liquid−Liquid Equilibrium Data for Systems Composed of Crude Orange Essential Oil [Represented by Terpenes (T) and Oxygenated Compounds (O)], Ethanol (6), and Water (7) in Mass Fractions (w), Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Excess Volume (VE) of the Phases and Interfacial Tension (π) at T = 298.2 K and p = 1 × 105 Paa

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

M

0.426 ± 0.005

0.311 ± 0.003

0.247 ± 0.001

0.035

0.465

0.037

0.023

0.059

0.059

0.774

0.772

0.312

0.057

0.059

0.742

0.774

0.053

0.057

0.696

0.741

0.056

0.055

0.692

0.695

0.047

0.054

0.617

0.047

0.616

0.693

0.035

0.047

0.465

0.619

0.036

0.035

0.468

0.465

0.033

0.035

0.463

0.461

0.023

0.032

0.312

0.464

0.023

0.463

0.311

0.037

0.037

0.463

0.463

0.025

0.025

0.308

0.317

0.025

0.035

0.465

0.329

0.024

0.035

0.310

0.463

0.024

0.024

0.310

0.206 ± 0.008

wO

0.310

wT

w7,Sb

0.382

0.117

0.115

0.115

0.138

0.140

0.173

0.173

0.173

0.174

0.232

0.233

0.227

0.345

0.344

0.342

0.347

0.347

0.347

0.456

0.459

0.377

0.377

0.377

0.498

0.504

0.488

0.400

0.401

0.402

0.530

0.529

0.528

w6

0.283

0.053

0.052

0.052

0.062

0.062

0.078

0.077

0.079

0.079

0.104

0.105

0.107

0.155

0.155

0.154

0.157

0.157

0.157

0.209

0.207

0.123

0.123

0.123

0.161

0.163

0.158

0.100

0.099

0.100

0.137

0.137

0.138

w7

overall composition (OC)

0.917

0.870

0.866

0.873

0.873

0.871

0.875

0.870

0.870

0.874

0.870

0.873

0.870

0.883

0.883

0.871

0.887

0.894

0.894

0.900

0.897

0.869

0.878

0.878

0.894

0.859

0.878

0.849

0.849

0.852

0.877

0.881

0.880

wT

0.047

0.064

0.064

0.065

0.062

0.064

0.062

0.063

0.065

0.063

0.059

0.059

0.059

0.050

0.050

0.052

0.050

0.048

0.046

0.039

0.040

0.050

0.050

0.050

0.039

0.038

0.039

0.044

0.044

0.043

0.036

0.036

0.036

wO

0.032

0.059

0.064

0.057

0.059

0.060

0.055

0.062

0.060

0.058

0.066

0.061

0.065

0.063

0.062

0.073

0.058

0.054

0.056

0.056

0.059

0.073

0.066

0.064

0.060

0.093

0.076

0.100

0.100

0.099

0.081

0.077

0.078

w6 0.006

0.004

0.006

0.006

0.005

0.005

0.005

0.007

0.005

0.005

0.004

0.005

0.007

0.006

0.004

0.005

0.005

0.005

0.005

0.005

0.004

0.004

0.008

0.006

0.008

0.007

0.010

0.006

0.007

0.006

0.006

0.006

0.006

851.8

857.1

859.5

859.6

859.6

859.2

859.3

858.9

858.5

858.5

858.7

857.6

857.7

857.7

856.4

856.1

856.3

856.3

855.8

855.4

855.5

855.0

856.2

856.1

856.1

854.7

853.7

855.0

853.8

853.9

854.2

851.8

851.8

1.104

1.145

1.198

1.193

1.181

1.182

1.199

1.215

1.185

1.183

1.176

1.178

1.184

1.165

1.167

1.153

1.166

1.141

1.172

1.153

1.127

1.142

1.152

1.164

1.158

1.146

1.137

1.129

1.133

1.136

1.144

1.122

1.117

1.336

1.393

1.388

1.373

1.375

1.395

1.414

1.380

1.378

1.370

1.373

1.380

1.358

1.362

1.347

1.361

1.333

1.370

1.348

1.317

1.336

1.346

1.360

1.353

1.341

1.332

1.321

1.327

1.331

1.339

1.317

1.312

1.296

ν/ mm2 s−1

0.089

−1.99

0.055

0.009

0.021 0.016

−2.57 −2.52 −2.12

0.021 0.016

−2.54 −2.57

0.018 0.019

−2.40 −2.55

0.026 0.027

−2.42 −2.44

0.028 0.027

−2.33

0.028

−2.27 −2.47

0.030 0.027

−2.19 −2.32

0.029 0.030

−2.22 −2.11

0.033 0.032

−2.02 −2.13

0.032 0.033

−2.04 −1.97

0.031

−2.12 −1.97

0.052 0.058

−2.03 −2.12

0.057 0.063

−1.84 −1.86

0.068

0.090

−2.01 −2.04

0.075 0.095

−1.60 −2.06

0.077 0.075

−1.56

wT

−1.56

VE/ cm3 mol−1

0.011

0.015

0.017

0.016

0.018

0.017

0.018

0.022

0.020

0.021

0.020

0.021

0.019

0.020

0.020

0.018

0.019

0.017

0.017

0.014

0.014

0.024

0.024

0.024

0.019

0.018

0.019

0.027

0.027

0.028

0.019

0.019

0.018

wO

0.558

0.565

0.559

0.565

0.587

0.590

0.619

0.616

0.599

0.614

0.628

0.635

0.610

0.637

0.640

0.644

0.647

0.647

0.651

0.645

0.650

0.682

0.678

0.687

0.690

0.692

0.683

0.693

0.693

0.688

0.715

0.716

0.711

w6

0.422

0.404

0.404

0.403

0.374

0.374

0.346

0.335

0.355

0.338

0.324

0.316

0.344

0.313

0.310

0.310

0.302

0.302

0.298

0.309

0.305

0.238

0.240

0.238

0.228

0.233

0.231

0.191

0.190

0.189

0.192

0.190

0.193

w7 846.0

893.2

891.1

891.9

892.0

887.0

886.7

882.8

881.9

881.9

881.6

876.6

878.0

876.8

871.3

871.2

871.6

871.0

869.9

869.0

867.9

868.2

859.6

859.2

859.1

856.0

855.7

856.5

849.7

849.7

849.7

846.2

846.2

2.164

2.220

2.225

2.202

2.156

2.205

2.139

2.160

2.113

2.110

2.071

2.095

2.053

2.033

2.014

2.037

1.994

1.987

1.983

1.954

1.955

1.892

1.869

1.854

1.807

1.815

1.803

1.714

1.718

1.722

1.692

1.782

1.797

η/ mPa s

ρ/ kg m−3

η/ mPa s

ρ/ kg m−3

w7

solvent-rich phase (SP)

terpene-rich phase (TP)

2.423

2.491

2.494

2.469

2.430

2.486

2.423

2.450

2.396

2.393

2.362

2.386

2.341

2.333

2.311

2.337

2.289

2.284

2.282

2.251

2.251

2.201

2.175

2.158

2.111

2.121

2.105

2.018

2.022

2.027

1.999

2.106

2.124

ν/ mm2 s−1

−1.05

−1.11

−1.13

−1.15

−1.21

−1.20

−1.32

−1.35

−1.17

−1.31

−1.26

−1.38

−1.07

−1.14

−1.16

−1.19

−1.23

−1.18

−1.19

−1.05

−1.11

−1.31

−1.28

−1.31

−1.26

−1.21

−1.24

−1.26

−1.28

−1.27

−1.15

−1.16

−1.12

VE/ cm3 mol−1

1.9

1.4

1.4

1.4

1.4

1.4

1.5

1.6

1.5

1.8

1.7

1.9

1.8

1.5

1.2

1.4

1.1

1.0

1.1

π/ mN m−1

Table 6. Liquid−Liquid Equilibrium Data for Systems Composed of Crude Acid Lime Essential Oil [Represented by Terpenes (T) and Oxygenated Compounds (O)], Ethanol (3), and Water (4) in Mass Fractions (w), Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Excess Volume (VE) of the Phases and Interfacial Tension (π) at T = 298.2 K and p = 1 × 105 Paa

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

N

0.047

0.053

0.053

0.614

0.696

0.697

0.047

0.047

0.620

0.036

0.467

0.620

0.035

0.036

0.465

0.053

0.051

0.693

0.675

0.468

0.047

0.053

0.614

0.696

0.047

0.047

0.620

0.621

0.041

0.047

0.532

0.620

0.042

0.043

0.555

0.558

0.036

0.035

0.463

0.458

0.028

0.036

0.372

0.028

0.370

0.467

0.026

0.026

0.306

0.310

wO

wT

0.121

0.124

0.165

0.161

0.165

0.246

0.246

0.248

0.158

0.146

0.149

0.195

0.190

0.193

0.194

0.243

0.229

0.237

0.293

0.288

0.293

0.350

0.354

0.381

0.383

w6

0.129

0.127

0.175

0.171

0.168

0.251

0.250

0.252

0.115

0.109

0.101

0.144

0.141

0.140

0.139

0.183

0.170

0.166

0.213

0.214

0.205

0.250

0.249

0.283

0.284

w7

0.901

0.903

0.901

0.908

0.899

0.906

0.909

0.900

0.885

0.896

0.885

0.902

0.903

0.900

0.886

0.903

0.896

0.888

0.903

0.910

0.892

0.897

0.897

0.905

0.913

wT

0.067

0.068

0.065

0.067

0.066

0.064

0.064

0.062

0.064

0.065

0.065

0.063

0.063

0.063

0.063

0.062

0.061

0.061

0.059

0.060

0.058

0.054

0.055

0.056

0.056

wO

0.029

0.025

0.030

0.021

0.031

0.027

0.023

0.034

0.046

0.035

0.046

0.031

0.029

0.033

0.047

0.031

0.040

0.048

0.034

0.027

0.046

0.045

0.044

0.035

0.028

w6

0.003

0.004

0.004

0.004

0.004

0.003

0.004

0.004

0.005

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.004

0.003

w7

861.3

861.2

860.7

860.7

860.6

860.0

859.8

859.7

860.0

860.0

860.2

859.6

862.9

859.6

859.5

859.0

859.2

858.9

858.5

858.4

858.4

857.7

857.7

857.3

857.4

ρ/ kg m−3

1.212

1.213

1.209

1.202

1.185

1.202

1.204

1.172

1.194

1.185

1.185

1.200

1.191

1.178

1.176

1.187

1.197

1.166

1.193

1.156

1.162

1.152

1.162

1.173

1.188

η/ mPa s

terpene-rich phase (TP)

1.408

1.408

1.405

1.396

1.376

1.398

1.401

1.363

1.388

1.378

1.377

1.396

1.380

1.371

1.369

1.382

1.393

1.357

1.389

1.346

1.354

1.343

1.355

1.368

1.385

ν/ mm2 s−1

0.002 0.003 0.002

−2.65 −2.66 −2.72

0.002 0.003

−2.59

0.002

−2.51 −2.53

0.004 0.004

−2.51

0.005 0.007

−2.54 −2.59 −2.42

0.009 0.007

−2.43 −2.65

0.009 0.007

−2.47 −2.99

0.010 0.009

−2.35 −2.54

0.009 0.010

−2.47 −2.46

0.011 0.010

−2.23 −2.31

0.010 0.011

−2.28

0.010

−2.28 −2.39

0.007 0.007

−2.11 −2.14

wT

V/ cm3 mol−1

E

0.005

0.005

0.006

0.007

0.006

0.006

0.006

0.006

0.011

0.012

0.010

0.014

0.013

0.012

0.011

0.013

0.013

0.011

0.012

0.011

0.011

0.010

0.010

0.011

0.011

wO

0.437

0.457

0.455

0.460

0.458

0.472

0.478

0.476

0.520

0.517

0.521

0.519

0.541

0.540

0.535

0.539

0.539

0.549

0.557

0.552

0.557

0.559

0.561

0.561

0.563

w6

0.557

0.536

0.536

0.530

0.534

0.519

0.511

0.514

0.462

0.466

0.461

0.459

0.439

0.439

0.445

0.438

0.438

0.430

0.422

0.426

0.421

0.420

0.419

0.420

0.419

w7

924.0

924.1

918.9

919.4

918.9

914.6

914.5

914.3

905.7

906.3

906.0

901.7

902.0

901.3

901.4

898.3

899.1

898.6

896.2

895.9

896.0

894.1

894.1

894.0

893.3

ρ/ kg m−3

2.298

2.301

2.283

2.303

2.299

2.272

2.272

2.279

2.300

2.169

2.290

2.240

2.242

2.237

2.233

2.226

2.230

2.218

2.193

2.193

2.198

2.176

2.177

2.174

2.159

η/ mPa s

solvent-rich phase (SP)

2.487

2.491

2.484

2.505

2.502

2.484

2.485

2.493

2.540

2.393

2.527

2.485

2.485

2.482

2.477

2.478

2.480

2.468

2.447

2.448

2.453

2.434

2.435

2.432

2.417

ν/ mm2 s−1

−0.98

−1.15

−0.99

−1.04

−1.01

−0.99

−1.04

−1.02

−1.14

−1.13

−1.16

−1.02

−1.21

−1.19

−1.14

−1.08

−1.11

−1.17

−1.16

−1.11

−1.16

−1.10

−1.11

−1.10

−1.09

VE/ cm3 mol−1

1.3

1.3

1.4

1.4

1.4

1.7

1.7

1.7

1.4

1.3

1.4

1.5

1.6

1.5

1.6

1.6

1.6

1.6

1.8

1.7

1.8

1.8

2.0

2.0

π/ mN m−1

a

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 × 103 Pa, u(w) = 0.001, u(ρ) = 0.9 kg m−3, u(η) = 0.007 mPa s, u(ν) = 0.007 mm2 s−1, and u(π) = 0.1 mN m−1. bWater mass fraction in the solvent followed by the standard uncertainty.

0.508 ± 0.002

w7,Sb

overall composition (OC)

Table 6. continued

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

O

0.27 0.24 0.26

5.66 4.26 2.89 4.25

1.27 1.39 1.57 1.58 1.67 1.54 1.60

0.311 ± 0.003 0.426 ± 0.005 Δ/%

0.311 ± 0.003 0.426 ± 0.005 0.508 ± 0.002 Δ/%

0.206 ± 0.008 0.247 ± 0.001 0.311 ± 0.003 0.426 ± 0.005 0.508 ± 0.002 Δ/% Δ(global)/%d

1.80 2.02 2.09 2.18 2.23 2.10 1.99

1.79 2.10 2.01 1.97

2.45 2.24 2.36

1.21 1.50 1.85 1.53

1.65 1.50 1.77 1.67 1.63 1.68 0.55

0.10 0.11 0.09 0.10

0.13 0.15 0.14

0.27 0.30 0.31 0.29

2.77 3.01 3.37 3.18 2.66 3.11 3.36

3.62 3.35 3.00 3.32

3.30 3.09 3.21

3.78 3.94 3.62 3.79

SP

SMR, in x

TP

3.37 4.08 6.57 6.52 7.43 6.08

2.38 2.07 2.33 2.26

6.31 0.98 4.06

2.30 3.63 4.60 3.56

8.49 4.02 2.30 6.50 3.28 4.56

2.93 2.48 1.81 2.40

3.12 3.56 3.30

1.35 2.18 2.13 1.91

SP

GN, in w TP

6.85 8.46 16.5 11.9 12.7 12.7

7.10 3.66 5.83 5.50

2.14 7.18 4.27

2.51 4.06 7.54 4.87

SP

GN, in w TP

TP

SP

GN, in x

Δν/%

Orange Essential Oil Model System 4.92 2.25 1.37 2.67 5.41 3.17 3.56 2.43 4.31 3.66 7.77 4.37 0.96 7.53 6.85 5.28 3.44 1.60 5.02 5.27 Orange Essential Oil Real System 2.78 6.16 1.67 2.03 2.89 1.93 0.91 5.58 7.65 12.4 2.42 3.94 3.32 4.41 6.91 Lemon/Lime Essential Oil Model System 10.2 2.34 3.09 5.23 8.86 8.44 2.09 2.31 2.59 6.38 10.6 2.19 1.83 3.62 12.7 9.75 2.21 2.40 3.78 9.33 Acid Lime Essential Oil Real System 22.8 1.92 8.25 14.0 16.8 28.0 2.56 3.69 19.8 15.0 8.37 5.24 2.35 15.7 5.46 6.76 5.72 6.50 11.0 11.4 20.1 6.59 3.34 11.8 23.5 13.0 4.95 4.53 14.0 11.9

SP

GN, in x TP

Δη/%

34.3 31.5 27.8 19.9 15.9 24.8 27.8

41.9 38.2 36.4 38.8

17.2 20.9 18.8

28.6 22.0 26.3 25.5

TP

13.6 11.1 4.34 1.15 3.78 4.93 5.02

2.38 2.44 2.40 2.41

1.92 2.31 2.08

12.4 4.10 3.20 5.86

SP

UNIFAC-VISCO

41.9 11.9 32.8 106 194 90.8

7.50 6.07 3.75 5.74

5.68 13.4 9.15

1.97 2.49 3.38 2.67

linear adjustment in w

Δπ/%

31.3 20.5 30.6 97.8 170 82.4

13.0 8.75 7.38 9.66

1.95 6.46 3.98

8.80 11.5 11.8 10.3

linear adjustment in x

20.8 25.0 31.0 50.3 64.4 43.7 17.2

5.73 6.00 4.90 5.54

6.31 16.0 10.7

6.78 11.0 8.10 8.70

BD

a SMR, simple mixing rule; GN, Grunberg−Nissan model;17 DB, Bahramian−Danesh model;20 TP, terpene-rich phase; SP, solvent-rich phase. bWater mass fraction in the solvent followed by the standard uncertainty. cAverage relative deviation for the phase (for density and viscosity) or system (for interfacial tension) calculated by eq 10. dGlobal relative deviation of the prediction procedure calculated by eq 10.

0.38 0.34 0.34 0.36

0.235 ± 0.002 0.311 ± 0.003 0.426 ± 0.005 Δ/%c

SP

SMR, in w

TP

w7,Sb

Δρ/%

Table 7. Average Relative Deviations (Δ) between the Experimental and Calculated Density (ρ), Dynamic Viscosity (η), Kinematic Viscosity (ν), and Interfacial Tension (π)a

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.8b00086 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Figure 1. Physical properties of the phases from the liquid−liquid equilibrium of the orange model system with respect to the mass percentage of linalool in the terpene-rich phase (100w4,TP) at T = (298.2 ± 0.1) K. Experimental values: △/▽, kinematic viscosity (ν, in mm2 s−1); ▲/▼, density (ρ, in kg m−3); ●, interfacial tension (π, in mN m−1). △/▲, terpene-rich phase (TP); ▽/▼, solvent-rich phase (SP). Calculated values: ·····, approach in molar fraction (x); - - -, approach in mass fraction (w), for both simple mixing rule or the Grunberg−Nissan model.17 Water mass fraction in the solvent: (a) 0.235 ± 0.002, (b) 0.311 ± 0.003, and (c) 0.426 ± 0.005.

Figure 2. Physical properties of the phases from the liquid−liquid equilibrium of the lemon/lime model system with respect to the mass percentage of citral in the terpene-rich phase (100w5,TP) at T = (298.2 ± 0.1) K. Experimental values: △/▽, kinematic viscosity (ν, in mm2·s−1); ▲/▼, density (ρ, in kg m−3); ●, interfacial tension (π, in mN m−1). △/▲, terpene-rich phase (TP); ▽/▼, solvent-rich phase (SP). Calculated values: ·····, approach in molar fraction (x); - - -, approach in mass fraction (w), for both simple mixing rule or the Grunberg−Nissan model;17 -·-·-, Bahramian−Danesh model.20 Water mass fraction in the solvent: (a) 0.311 ± 0.003, (b) 0.426 ± 0.005, and (c) 0.508 ± 0.002. P

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Figure 3. Physical properties of the phases from the liquid−liquid equilibrium of the orange real system with respect to the mass percentage of oxygenated compounds in the terpene-rich phase (100wO,TP) at T = (298.2 ± 0.1) K. Experimental values: △/▽, kinematic viscosity (ν, in mm2 s−1); ▲/▼, density (ρ, in kg m−3); ●, interfacial tension (π, in mN m−1). △/▲, terpene-rich phase (TP); ▽/▼, solvent-rich phase (SP). Calculated values: ·····, approach in molar fraction (x); - - -, approach in mass fraction (w), for both simple mixing rule or the Grunberg−Nissan model;17 ··−··, UNIFAC-VISCO model.18,19 Water mass fraction in the solvent: (a) 0.311 ± 0.003, (b) 0.426 ± 0.005, and (c) 0.508 ± 0.002.

Figure 4. Physical properties of the phases from the liquid−liquid equilibrium of the acid lime real system with respect to the mass percentage of oxygenated compounds in the terpene-rich phase (100wO,TP) at T = (298.2 ± 0.1) K. Experimental values: △/▽, kinematic viscosity (ν, in mm2 s−1); ▲/▼, density (ρ, in kg m−3); ●, interfacial tension (π, in mN m−1). △/▲, terpene-rich phase (TP); ▽/▼, solvent-rich phase (SP). Calculated values: ······, approach in molar fraction (x); - - -, approach in mass fraction (w), for both simple mixing rule or the Grunberg−Nissan model.17 Water mass fraction in the solvent: (a) 0.206 ± 0.008, (b) 0.247 ± 0.001, (c) 0.311 ± 0.003, (d) 0.426 ± 0.005, and (e) 0.508 ± 0.002. Q

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Viscosity. The parameters of the Grunberg−Nissan model17 adjusted for the model systems for both dynamic and kinematic viscosities, using the compositions in mass and molar fractions, are shown in Table 8. The relative deviations between the

efficient on the prediction of the terpene-rich phases’ kinematic viscosities (Δ = 18.8−38.8%). In this case, the parameters of the Grunberg−Nissan in mass basis revealed better results (Δ = 2.21−4.95%). Interfacial Tension. The linear adjustment for the interfacial tensions of the orange model system is shown in eq 11 for mass fraction (w) and in eq 12 for molar fraction (x). The adjustment of the lemon/lime model system is shown in eq 13 for mass fraction and in eq 14 for molar fraction. Note that better adjustments were reached using the compositions in mass fraction (higher R values).

Table 8. Grunberg−Nissan Parameters for Model Systems at T = (298.2 ± 0.1) K dynamic viscosity (η) parameter

w

a

b

x

kinematic viscosity (ν) wa

xb

Orange Essential Oil Model System −1.86 28.2 −1.84 28.4 −8.4 2.47 −8.15 2.44 31.9 −27.5 31.2 −27.1 −1.05 −268 −1.13 −271 4.89 271 5.04 274 6.1 6.32 5.93 6.6 Lemon/Lime Essential Oil Model System G12 27.5 −16 28.2 −17 G13 −32 −71.8 −31 −70.1 G15 −12.7 −6 −13.7 −7 G16 143 262 135 261 G17 −233 −1166 −216 −1164 G23 187 160 183 150 G25 −9.3 −1331 −12.5 −1335 G26 −843 −1005 −817 −999 G27 1478 10233 1426 10246 G35 73.5 1548 81.4 1558 G36 307 −32 313 −35 G37 −804 −6211 −833 −6234 G56 1.6 −41 2.5 −41 G57 17.5 −6 16.4 −4 G67 7.4 9 7.2 9 Lemon/Lime Essential Oil Model System (Used for the Real System) G15 1.12 8.05 1.1 7.97 G16 −0.26 1.26 −0.4 1.09 G17 −16.9 −12.9 −17.7 −12.6 G56 6.93 −25.9 8.18 −25.4 G57 7.21 −83.8 5.36 −83 G67 7.29 8.21 7.07 8.44 G14 G16 G17 G46 G47 G67

π calc = −1.1093 − 1.4768· ln(w1,SP + w4,SP + w6,TP + w7,TP),

R = 0.9226

(11)

π calc = −2.0889 − 2.1747· ln(x1, SP + x4, SP + x6, TP + x 7, TP) ,

R = 0.8675

(12)

π calc = −2.2514 − 2.1008· ln(w1,SP + w2,SP + w3,SP + w5,SP + w6,TP + w7,TP),

R = 0.9718

(13)

π calc = −2.6536 − 2.9132· ln(x1,SP + x 2,SP + x3,SP + x5,SP + x6,TP + x 7,TP),

R = 0.9148

(14)

where the subscripts are limonene (1), γ-terpinene (2), β-pinene (3), linalool (4), citral (5), ethanol (6), water (7), terpene-rich phase (TP), and solvent-rich phase (SP). The parameters adjusted to the model system were used to predict the interfacial tension values of the real systems. The deviations for the adjustment and the prediction are shown in Table 7, where it is possible to observe that, for the orange real system, the approach using the composition in molar fraction (eq 11) provided better results (Δ = 3.98%). For the acid lime real systems, both eqs 12 and 13 were not effective on the calculation of the interfacial tensions. This property is much more complex than the others because several factors affect its value, such as the solubility of the phases and the differences between the densities and viscosities of the phases. Moreover, differences between the experimental interfacial tensions of the model and the real systems were observed, which may be related to the nonvolatile compounds present in the system, as discussed previously. Regarding the values estimated by the Bahramian−Danesh model,10 in Table 7 it is possible to observe that good results were achieved for both orange model and real systems, as well for the lemon/lime model system, which exhibited better results (Δ = 5.54%). As for the linear adjustment, higher deviations were calculated for acid lime real systems. Therefore, these estimated values are not exhibited in Figure 4.

a

Composition in mass fraction. bComposition in molar fraction.

calculated and experimental values are exposed in Table 7. For the orange model system, better adjustments were reached for kinematic viscosity (ν) for both terpene-rich (Δ = 3.44%) and solvent-rich phases (Δ = 1.60%) using the compositions in mass fraction (w). The adjusted Grunberg−Nissan parameters provided satisfactory results on the prediction of the phase kinematic viscosity values from the orange real systems using the composition in mass fraction (Δ = 3.94% for the terpenerich phase, and Δ = 3.32% for the solvent-rich phase). Regarding the acid lime model systems, both dynamic and kinematic viscosities exhibited a good adjustment (Δ = 2.21− 2.40%) using the Grunberg−Nissan model17 and the phase composition in mass fraction. For the acid lime real system, better predicted values were calculated using the Grunberg− Nissan parameters for kinematic viscosity and the phases compositions in mass fraction (Δ = 4.53% for the solvent-rich phase and Δ = 4.95% for the terpene-rich phase). Kinematic viscosities of the solvent-rich phases, estimated by both the UNIFAC-VISCO and Grunberg−Nissan in mass basis, exhibited low average relative deviations (Δ = 1.60− 5.86%). However, the UNIFAC-VISCO model18,19 was not

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CONCLUSIONS In general, increased water content in the solvent led to higher values of density, dynamic viscosity, surface tension, and interfacial tension. Increased amount of oxygenated compounds also resulted in higher values of density and dynamic viscosity but attenuated interfacial tension. The GCVOL model provided suitable performance in the estimation of density values of the pure components. The simple mixing rule was also efficient for the estimation of density values of the phases from the liquid−liquid equilibrium. R

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(6) Gonçalves, D.; Teschke, M. E. E.; Koshima, C. C.; Gonçalves, C. B.; Oliveira, A. L.; Rodrigues, C. E. C. Fractionation of Orange Essential Oil Using Liquid−liquid Extraction: Equilibrium Data for Model and Real Systems at 298.2 K. Fluid Phase Equilib. 2015, 399 (6), 87−97. (7) Florido, P. M.; Andrade, I. M. G.; Capellini, M. C.; Carvalho, F. H.; Aracava, K. K.; Koshima, C. C.; Rodrigues, C. E. C.; Gonçalves, C. B. Viscosities and Densities of Systems Involved in the Deterpenation of Essential Oils by Liquid-Liquid Extraction: New UNIFAC-VISCO Parameters. J. Chem. Thermodyn. 2014, 72, 152−160. (8) Koshima, C. C.; Nakamoto, K. T.; Aracava, K. K.; Oliveira, A. L.; Rodrigues, C. E. C. Fractionation of Bergamot and Lavandin Crude Essential Oils by Solvent Extraction: Phase Equilibrium at 298.2 K. J. Chem. Eng. Data 2015, 60 (1), 37−46. (9) Koshima, C. C.; Capellini, M. C.; Geremias, I. M.; Aracava, K. K.; Gonçalves, C. B.; Rodrigues, C. E. C. Fractionation of Lemon Essential Oil by Solvent Extraction: Phase Equilibrium for Model Systems at T = 298.2 K. J. Chem. Thermodyn. 2012, 54, 316−321. (10) Gonçalves, D.; Costa, P.; Rodrigues, C. E. C.; Rodrigues, A. E. Effect of Citrus Sinensis Essential Oil Deterpenation on the Aroma Profile of the Phases Obtained by Solvent Extraction. J. Chem. Thermodyn. 2018, 116 (49−50), 166−175. (11) Gonçalves, D.; Paludetti, M. F.; Gonçalves, C. B.; Rodrigues, C. E. C. Extraction of Oxygenated Compounds from Crude Citrus Latifolia Peel Oil Using Ethanol/Water Mixtures as Solvents: Phase Equilibrium and Continuous Equipment Operation. Sep. Purif. Technol. 2018, 199, 271−281. (12) Franceschi, E.; Grings, M. B.; Frizzo, C. D.; Oliveira, J. V.; Dariva, C. Phase Behavior of Lemon and Bergamot Peel Oils in Supercritical CO2. Fluid Phase Equilib. 2004, 226, 1−8. (13) Gonçalves, D.; Koshima, C. C.; Nakamoto, K. T.; Umeda, T. K.; Aracava, K. K.; Gonçalves, C. B.; Rodrigues, C. E. da C. Deterpenation of Eucalyptus Essential Oil by Liquid+liquid Extraction: Phase Equilibrium and Physical Properties for Model Systems at T = 298.2 K. J. Chem. Thermodyn. 2014, 69, 66−72. (14) Capellini, M. C.; Carvalho, F. H.; Koshima, C. C.; Aracava, K. K.; Gonçalves, C. B.; Rodrigues, C. E. C. Phase Equilibrium Data for Systems Composed of Oregano Essential Oil Compounds and Hydroalcoholic Solvents at T = 298.2 K. J. Chem. Thermodyn. 2015, 88, 61−71. (15) Oliveira, C. M.; Koshima, C. C.; Capellini, M. C.; Carvalho, F. H.; Aracava, K. K.; Gonçalves, C. B.; Rodrigues, C. E. C. Liquid− liquid Equilibrium Data for the System Limonene+carvone+ethanol +water at 298.2 K. Fluid Phase Equilib. 2013, 360, 233−238. (16) Giraldo-Zuniga, A. D.; Coimbra, J. S. R.; Arquete, D. A.; Minim, L. A.; Silva, L. H. M.; Maffia, M. C. Interfacial Tension and Viscosity for Poly(Ethylene Glycol) + Maltodextrin Aqueous TwoPhase Systems. J. Chem. Eng. Data 2006, 51 (3), 1144−1147. (17) GRUNBERG, L.; NISSAN, A. H. Mixture Law for Viscosity. Nature 1949, 164, 799−800. (18) Chevalier, J. L.; Petrino, P.; Gaston-Bonhomme, Y. Estimation Method for the Kinematic Viscosity of a Liquid-Phase Mixture. Chem. Eng. Sci. 1988, 43 (6), 1303−1309. (19) Gaston-Bonhomme, Y.; Petrino, P.; Chevalier, J. L. UNIFAC VISCO Group Contribution Method for Predicting Kinematic Viscosity: Extension and Temperature Dependence. Chem. Eng. Sci. 1994, 49 (11), 1799−1806. (20) Bahramian, A.; Danesh, A. Prediction of Liquid−liquid Interfacial Tension in Multi-Component Systems. Fluid Phase Equilib. 2004, 221 (1−2), 197−205. (21) Sousa, A. T.; Castro, C. A. N. Density of α-Pinene, β-Pinene, Limonene, and Essence of Turpentine. Int. J. Thermophys. 1992, 13 (2), 295−301. (22) Djojoputro, H.; Ismadji, S. Density and Viscosity of Several Aldehydes Fragrance Compounds in Their Binary Mixtures with Ethanol at (298.15 K, 308.15 K, and 318.15 K). J. Chem. Eng. Data 2005, 50 (6), 2003−2007. (23) Dilmohamud, B. A.; Seeneevassen, J.; Rughooputh, S. D. D. V; Ramasami, P. Surface Tension and Related Thermodynamic

The parameters of the Grunberg−Nissan model, adjusted for the model systems, exhibited satisfactory results on the calculation of viscosity values of the phases. The parameters of the UNIFACVISCO model provided good results on the calculation of viscosity of the solvent-rich phases. The linear equation adjusted for the orange model system presented a good description of the interfacial tensions of the real systems, whereas the Bahramian−Danesh thermodynamic model exhibited satisfactory results on the estimation of the interfacial tension of both orange and lemon/lime model systems as well for the orange real system. However, the same was not observed for the acid lime real systems. Overall, it is possible to observe that the proposed models can easily be applied to the estimation of important physical properties values of the phases from the citrus systems evaluated in this study.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00086. Equations of the UNIFAC-VISCO thermodynamic model (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected]. ORCID

Daniel Gonçalves: 0000-0002-2581-7207 Cintia B. Gonçalves: 0000-0001-9306-9776 Christianne E. C. Rodrigues: 0000-0002-5456-9708 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors would like to acknowledge FAPESP (Fundaçaõ de Amparo à Pesquisa do Estado de São Paulo, 13/11150-3, 14/ 22272-5), CNPq (Conselho Nacional de Desenvolvimento ́ Cientifico e Tecnológico, 303797/2016-9, 308615/2016-6), FINEP (Inovaçaõ e Pesquisa, 01/11/0140/00), and CAPES ́ (Coordenação de Aperfeiçoamento de Pessoal de Nivel Superior) for the financial support and Louis Dreyfus Company (Mr. Antonio Carlos Gonçalves) for the crude orange and acid lime essential oils donation.

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REFERENCES

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T

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