Measurement and Correlation of Isobaric VaporâLiquid Equilibrium for

Article pubs.acs.org/jced

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

Measurement and Correlation of Isobaric Vapor−Liquid Equilibrium for Camphene, (+)-3-Carene, and (±)-Limonene Systems Jinzhi Wu,† Linlin Wang,*,†,‡ Xiaopeng Chen,*,†,‡ Xiaojie Wei,†,‡ Jiezhen Liang,†,‡ and Zhangfa Tong†,‡ †

School of Chemistry and Chemical Engineering, Guangxi University, Nanning, 530004, P. R. China Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Nanning, 530004, P. R. China

Downloaded via MACQUARIE UNIV on February 12, 2019 at 10:39:00 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) experimental data for camphene + (±)-limonene, camphene + (+)-3-carene, (±)-limonene + (+)-3carene, and camphene + (+)-3-carene + (±)-limonene were determined in an improved Ellis still. Furthermore, saturated vapor pressure measurements for camphene across a temperature range of 357.01 to 432.16 K were reported. Additionally, the vapor pressure data, obtained also using an improved Ellis equilibrium still, were fitted by the Antoine equation. The thermodynamic consistency of the VLE values was confirmed by the Herington area and van Ness tests. The VLE data were correlated using the nonrandom two-liquid (NRTL), Wilson, and universal quasichemical (UNIQUAC) activity coefficient models with the measurements demonstrating good correlation. Moreover, the corresponding binary interaction parameters of the three models were regressed. The maximum average absolute deviation of temperature (AAD(T)) and maximum average absolute deviation of vapor-phase mole fraction (AAD(y)) are 0.0855 and 0.0013 for the camphene + (±)-limonene system, 0.0112 and 0.0003 for the camphene + (+)-3-carene system, and 0.0128 and 0.0002 for the (±)-limonene + (+)-3-carene system, respectively. These models were also used to predict the ternary system VLE data. The predictive results suggested that the NRTL model had the best prediction.

1. INTRODUCTION Wood turpentine oil, a natural essential oil obtained by steamdistillation of pine oleoresin from various species of coniferous trees, is one of the most widely used and least expensive plant byproducts.1 The main constituents include multiple monoterpenes, such as camphene (2,2-dimethyl-3-methylene-bicycloheptane, CASRN 79-92-5), (+)-3-carene (3,7,7-trimethylbicyclo-hept-3-ene, CASRN 498-15-7), (±)-limonene (1-methyl4-methylethenyl-cyclohexene, CASRN 138-86-3), α-pinene (2,6,6-trimethylbicyclo-2-heptene, CASRN 80-56-8) and βpinene (6,6-dimethyl-2-methylenebicyclo-heptane, CASRN 127-91-3). Turpentine oil is commonly used in the synthesis of a wide variety of fine chemicals such as synthetic resins and terpenic surfactants, and in the pharmaceutical and cosmetic industries.2,3 The monoterpenes that comprise turpentine oil play a dominant role in industry, especially in the fragrance, drugs, and flavor sectors. Camphene, (+)-3-carene, and (±)-limonene are important components of turpentine and are the raw materials for the synthesis of a certain industrial important chemicals. Camphene is a key compound among industrially used terpenes,4 and is mainly used for the preparation of mint and certain spice flavors.5 Camphene is a bicyclic monoterpene that can be isolated from essential oils produced by turpentine. Furthermore, camphene is known to show biological activity as an anticancer, anti-inflammatory, antifungal, and antigastric ulcer agent.6 Alternative uses of © XXXX American Chemical Society

camphene are as an adjuvant and to treat cardiovascular diseases.7 Furthermore, camphene is commonly employed as an insecticide.8,9 (+)-3-Carene is one of the few naturally occurring chiral compounds possessing a ternary ring structure that displays biological activity.10 Additionally, this compound is commonly used to alter the profile of a variety of edible flavors,11 and can be adopted as a pesticide or as an active pharmaceutical ingredient.12 Furthermore, certain plasticizers and nontoxic solvents employ (+)-3-carene as an important commodity.13 (±)-Limonene is principally employed as a fragrance and flavor additive in food, cosmetic products, and pharmaceuticals.14 These monoterpenes, which are separated or purified based on phase equilibrium data, are of great significance for the aforementioned applications. The design and optimization of the distillation process requires input from saturated vapor pressure and vapor−liquid equilibrium (VLE) data. Thus, it is necessary to study their thermodynamic properties in detail. There is a wealth of interdependent research published in the open literature that presents VLE data for wood turpentine oil systems containing monoterpenes. Bernardo-Gil and Ribeiro et al.15,16 presented isobaric binary VLE data related to α-pinene + p-cymene systems at atmospheric pressure, which were Received: July 30, 2018 Accepted: January 28, 2019

A

DOI: 10.1021/acs.jced.8b00672 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

determined using an Othmer equilibrium still. Xu et al.17 measured the α-pinene + p-cymene binary system VLE data by use of the Ellis equilibrium still. Tong et al.18 measured isobaric binary VLE systems comprising α-pinene, (S)-(−)-limonene and p-cymene by modifying the heat insulation section of an Ellis equilibrium still. Sun et al.19 presented VLE results for a βpinene + p-cymene + (S)-(−)-limonene system at 100.7 kPa. Furthermore, Xu et al.17 studied the VLE data for a ternary mixture comprising α-pinene + β-pinene + p-cymene at 100.7 kPa. However, there are no previously reported VLE data for the camphene + (±)-limonene, camphene + (+)-3-carene, (±)-limonene + (+)-3-carene, binary systems and camphene + (+)-3-carene + (±)-limonene ternary system. Herein, a modified Ellis equilibrium still20,21 was used to determine the isobaric VLE values for the camphene + (±)-limonene, camphene + (+)-3-carene, (±)-limonene + (+)-3-carene, and camphene + (+)-3-carene + (±)-limonene systems at 101.3 kPa, and the vapor pressure of camphene was studied to further progress the development of distillation technology to purify camphene. Additionally, the Herington22 and van Ness23 thermodynamic tests were adopted to verify the VLE data. The VLE data were correlated by the nonrandom two-liquid (NRTL),24 Wilson,25 and universal quasichemical (UNIQUAC)26 models, and the energy interaction parameters were obtained by the model. The models were also used to predict VLE data of the ternary system of camphene + (+)-3-carene + (±)-limonene.

2.2. Apparatus and Procedure. In this work, the VLE experiments and the saturated vapor pressure measurements were conducted in a modified Ellis equilibrium still. A detailed description of the operation and veracity of the apparatus in measuring the VLE and vapor pressure has previously been reported.20,21 The experimental apparatus is shown in Figure 2. The apparatus comprises a liquid-phase sampling port, a vaporphase sampling port, a magnetic whisk, an equilibrium chamber (250 mL), a measurement system, a heating system, an insulation system, and a vacuum control system. To determine the saturated vapor pressure of a pure substance at different temperatures, the pressure was regulated by a pressure control system, including one vacuum pump, one WT3000 intelligent absolute pressure transmitter (Shanghai Welltech Automation Co., Ltd.) with an accuracy of 0.001 kPa, and a U-shape mercury manometer having an accuracy of 0.5 mmHg, giving an uncertainty of 0.3 kPa. Temperatures were measured using a precision mercury-in-glass thermometer with an accuracy of 0.1 K; the uncertainty is 0.15 K. For VLE and the saturated vapor pressure measurements, solutions were prepared gravimetrically using an electronic weighing balance and a graduated cylinder with an accuracy of 0.0001 g and ±0.01 mL, respectively. The cooling rate was appropriate to ensure no vapor loss (i.e., ∼2−3 drops/second). Once the equilibrium temperature and condensation rate were in steady state, in excess of 2 h, which indicates attainment of VLE, both liquid and vapor samples were collected from two different sampling points and analyzed for their composition by GC. Herein, small sample aliquots (0.993 was obtained. All chemical reagents were of analytical pure grade and confirmed by GC (Agilent 7890B Co., Ltd.). Chemical structures and chemical specifications of these molecules are listed in Figure 1 and Table 1, respectively.

Figure 1. Chemical structures of these molecules.

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The isobaric VLE and activity coefficient values for the binary systems of camphene +

Table 1. Specifications of Used Chemical Compounds chemical name

CAS

source

initial mole fraction purity

final mole fraction purity

purification method

analysis method

camphene (+)-3-carene (±)-limonene

79-92-5 498-15-7 138-86-3

Sigma-aldrich TCI TCI

0.9768 0.9769 0.9752

>0.993 >0.993 >0.993

distillation distillation distillation

GCa GCa GCa

a

Gas chromatograph. B



Article

Figure 2. Schematic diagram of the modified Ellis equilibrium still for VLE measurement. (1) thermal insulation wood case; (2) reflux condenser; (3) liquid phase thermometer; (4) vapor phase thermometer; (5) vapor-phase sampling port; (6) heating chamber; (7) liquid-phase sampling port; (8) magneton; (9) magnetic whisk; (10) thermal insulation material; (11) gas chromatograph (GC, Agilent 7890B); (12) buffer bottle (Erlenmeyer flask); (13) mercury U-shaped differential manometer; (14) vacuum pump; (15) intelligent pressure transmitter; (16) data acquisition system.

Table 2. Isobaric Experimental VLE Data of Temperature T, Mole Fraction of Liquid-Phase x, and Mole Fraction of VaporPhase y, Activity Coefficient γi, Relative Volatility α12, for the Three Binary Systems at 101.33 kPaa T/K

x1

449.33 448.15 446.86 445.81 444.23 443.14 442.28 441.81 441.10 440.15 439.53 438.08 437.70 436.55 435.89 435.58 435.13 434.78 434.30 433.99 433.89 433.45 432.89 432.58

0.0000 0.0380 0.0740 0.1073 0.1583 0.1973 0.2368 0.2565 0.2891 0.3290 0.3612 0.4419 0.4728 0.5472 0.5991 0.6269 0.6703 0.7086 0.7582 0.7895 0.8096 0.8613 0.9425 1.0000

442.62 441.90 441.24 440.73 440.34 440.06 439.04 438.61 438.02 437.52

0.0000 0.0491 0.0988 0.1402 0.1721 0.1951 0.2841 0.3241 0.3804 0.4299

y1

γ1

Camphene + (±)-Limonene 0.0000 0.0730 1.3141 0.1339 1.2787 0.1856 1.2554 0.2573 1.2285 0.3071 1.2103 0.3536 1.1873 0.3758 1.1790 0.4096 1.1614 0.4510 1.1520 0.4819 1.1396 0.5546 1.1139 0.5810 1.1015 0.6427 1.0854 0.6833 1.0729 0.7041 1.0653 0.7383 1.0574 0.7674 1.0495 0.8055 1.0428 0.8299 1.0403 0.8454 1.0364 0.8868 1.0341 0.9528 1.0308 1.0000 1.0000 Camphene + (+)-3-Carene 0.0000 0.0661 1.1214 0.1290 1.1065 0.1783 1.0922 0.2160 1.0889 0.2425 1.0863 0.3413 1.0785 0.3838 1.0752 0.4419 1.0713 0.4917 1.0689

γ2

α12

1.0000 1.0353 1.0247 1.0316 1.0478 1.0471 1.0530 1.0555 1.0616 1.0590 1.0780 1.1103 1.1168 1.1387 1.1553 1.1722 1.1796 1.1919 1.2110 1.2189 1.2382 1.2716 1.2901

1.9938 1.9345 1.8957 1.8418 1.8034 1.7634 1.7450 1.7057 1.6754 1.6450 1.5729 1.5461 1.4880 1.4442 1.4164 1.3878 1.3570 1.3207 1.3001 1.2862 1.2619 1.2318

1.0000 1.0493 1.0497 1.0512 1.0518 1.0526 1.0558 1.0576 1.0606 1.0632

1.3707 1.3509 1.3307 1.3254 1.3207 1.3057 1.2989 1.2897 1.2828

T/K

(±)-limonene, camphene + (+)-3-carene, and (±)-limonene +

x1

436.90 436.28 435.69 435.09 434.78 434.19 433.72 433.25 432.92 432.72

0.4934 0.5600 0.6271 0.6970 0.7347 0.8079 0.8681 0.9299 0.9733 1.0000

442.56 442.79 443.01 443.45 443.75 444.15 444.35 444.63 444.85 445.15 445.35 445.88 446.33 446.43 446.65 447.08 447.63 447.82 448.15 448.55 449.01 449.32 449.57

0.0000 0.0395 0.0815 0.1704 0.2312 0.2986 0.3338 0.3819 0.4168 0.4633 0.4948 0.5670 0.6279 0.6420 0.6693 0.7249 0.7880 0.8112 0.8467 0.8920 0.9405 0.9711 1.0000

y1

γ1

Camphene + (+)-3-Carene 0.5537 1.0661 0.6167 1.0636 0.6788 1.0620 0.7416 1.0608 0.7751 1.0608 0.8388 1.0606 0.8902 1.0609 0.9420 1.0613 0.9780 1.0621 1.0000 1.0000 (±)-Limonene + (+)-3-Carene 0.0000 0.0351 1.0807 0.0725 1.0708 0.1518 1.0654 0.2065 1.0591 0.2678 1.0594 0.3009 1.0533 0.3447 1.0511 0.3775 1.0483 0.4216 1.0469 0.4519 1.0429 0.5227 1.0404 0.5839 1.0401 0.5983 1.0390 0.6264 1.0377 0.6848 1.0356 0.7530 1.0354 0.7787 1.0344 0.8185 1.0341 0.8705 1.0336 0.9276 1.0330 0.9645 1.0338 1.0000 1.0000

γ2

α12

1.0672 1.0722 1.0763 1.0821 1.0844 1.0899 1.0945 1.1011 1.1059

1.2738 1.2642 1.2567 1.2476 1.2445 1.2373 1.2319 1.2243 1.2195

1.0000 1.0499 1.0360 1.0376 1.0398 1.0414 1.0417 1.0453 1.0468 1.0492 1.0511 1.0544 1.0580 1.0591 1.0605 1.0644 1.0682 1.0701 1.0722 1.0758 1.0793 1.0814

0.8853 0.8807 0.8714 0.8654 0.8590 0.8591 0.8514 0.8484 0.8444 0.8418 0.8361 0.8315 0.8304 0.8284 0.8245 0.8202 0.8187 0.8164 0.8135 0.8106 0.8087

the equilibrium relationship between the vapor and liquid phases and is used to calculate the activity coefficient:27

(+)-3-carene were listed in Table 2, while the data for the ternary

γi = Pyi /Pisxi

system camphene + (+)-3-carene + (±)-limonene were presented in Table 3. At atmospheric pressure, the vapor

(1)

where xi and yi are the liquid and vapor phase mole fractions, respectively, of pure component i; γi is its activity coefficient; P

phase could be considered as the ideal gas. Equation 1 expresses C



Article

Table 3. Isobaric Experimental VLE Data of Temperature T, Mole Fraction of Liquid-Phase x, and Mole Fraction of Vapor-Phase y, Maximum Absolute Deviations and Mean Absolute Deviations for the Ternary System at 101.33 kPaa camphene +3-carene + (±)-limonene T/K

x1

x2

434.15 0.8035 0.1121 434.66 0.7453 0.1635 435.36 0.6705 0.2029 435.91 0.6172 0.2293 436.39 0.5721 0.2665 436.69 0.5490 0.2404 437.37 0.4954 0.2445 438.10 0.4421 0.2514 438.77 0.3949 0.2761 439.55 0.3421 0.3126 440.09 0.3137 0.2951 440.83 0.2609 0.3681 441.40 0.2349 0.3491 442.65 0.1685 0.3810 443.03 0.1456 0.4077 445.69 0.0739 0.2312 443.03 0.0954 0.6121 440.85 0.2808 0.2317 443.21 0.0586 0.7137 442.71 0.1961 0.2031 442.74 0.1331 0.5199 443.23 0.1299 0.4367 445.08 0.1129 0.1294 446.52 0.0655 0.1197 445.22 0.0257 0.5179 444.00 0.0814 0.4986 442.64 0.0353 0.8817 442.39 0.0714 0.8017 443.17 0.0347 0.8009 443.62 0.0264 0.7592 444.20 0.0514 0.5817 447.23 0.0554 0.0485 445.63 0.1071 0.0334 maximal absolute deviation average absolute deviation

calculated by NRTL

calculated by Wilson

calculated by UNIQUAC

y1

y2

ΔTb

Δy1c

Δy2c

ΔTb

Δy1c

Δy2c

ΔTb

Δy1c

Δy2c

0.8383 0.7901 0.7284 0.6838 0.6439 0.6272 0.5817 0.5346 0.4893 0.4352 0.4085 0.3463 0.3193 0.2387 0.2082 0.1200 0.1332 0.3803 0.0817 0.2869 0.1857 0.1863 0.1837 0.1128 0.0389 0.1188 0.0481 0.0966 0.0481 0.0372 0.0747 0.1000 0.1827

0.0914 0.1347 0.1685 0.1919 0.2257 0.2030 0.2085 0.2173 0.2429 0.2813 0.2681 0.3439 0.3301 0.3737 0.4050 0.2443 0.6156 0.2125 0.7230 0.1953 0.5167 0.4373 0.1326 0.1284 0.5502 0.5118 0.8820 0.7968 0.8114 0.7776 0.6024 0.0528 0.0344

0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.02 0.00 0.02 0.00 0.00 0.02 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.04 0.04 0.01

0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000

0.02 0.01 0.01 0.02 0.04 0.05 0.07 0.10 0.13 0.17 0.18 0.23 0.25 0.31 0.34 0.32 0.33 0.17 0.29 0.20 0.33 0.35 0.17 0.19 0.45 0.39 0.12 0.18 0.23 0.29 0.40 0.07 0.01 0.45 0.19

0.0007 0.0014 0.0023 0.0030 0.0033 0.0038 0.0045 0.0049 0.0052 0.0053 0.0054 0.0050 0.0049 0.0041 0.0037 0.0025 0.0019 0.0052 0.0009 0.0046 0.0029 0.0033 0.0032 0.0022 0.0008 0.0021 0.0002 0.0006 0.0004 0.0004 0.0012 0.0017 0.0025 0.0054 0.0029

0.0009 0.0012 0.0017 0.0021 0.0023 0.0028 0.0033 0.0038 0.0040 0.0039 0.0043 0.0034 0.0038 0.0033 0.0027 0.0059 0.0020 0.0052 0.0036 0.0056 0.0000 0.0020 0.0053 0.0052 0.0007 0.0002 0.0027 0.0031 0.0040 0.0043 0.0019 0.0028 0.0020 0.0059 0.0030

0.05 0.04 0.04 0.04 0.02 0.05 0.06 0.07 0.06 0.04 0.06 0.03 0.06 0.11 0.12 0.26 0.14 0.13 0.18 0.19 0.10 0.14 0.24 0.23 0.39 0.22 0.10 0.09 0.18 0.24 0.28 0.18 0.24 0.39 0.13

0.0003 0.0003 0.0007 0.0008 0.0009 0.0006 0.0001 0.0008 0.0015 0.0027 0.0032 0.0047 0.0051 0.0062 0.0065 0.0028 0.0059 0.0029 0.0040 0.0029 0.0067 0.0066 0.0006 0.0002 0.0026 0.0058 0.0012 0.0030 0.0021 0.0020 0.0044 0.0015 0.0028 0.0067 0.0028

0.0010 0.0014 0.0019 0.0021 0.0020 0.0024 0.0025 0.0024 0.0021 0.0014 0.0013 0.0001 0.0000 0.0011 0.0015 0.0032 0.0013 0.0013 0.0004 0.0001 0.0018 0.0017 0.0017 0.0029 0.0003 0.0015 0.0013 0.0001 0.0019 0.0026 0.0002 0.0017 0.0007 0.0032 0.0015

Standard uncertainties u are u(T) = 0.15 K, u(P) = 0.3 kPa and u(x) = u(y) = 0.002. bΔTi = |Ti,exp − Ti,cal|. cΔyi = |Ti,exp − yi,cal|.

a

Table 4. Experimental Saturated Vapor Pressure Data and Relative Derivations (Δ) from eq 3 for Camphene at Different Temperaturesa no.

Tb/(K)exp

P/(kPa)exp

Δb

no.

Tb/(K)exp

P/(kPa)exp

Δb

1 2 3 4 5

432.16 430.74 425.03 422.41 413.19

99.87 94.89 80.81 75.01 58.03

0.0119 0.0005 0.0029 0.0034 0.0078

6 7 8 9 10

407.39 399.98 390.11 378.08 357.01

48.91 38.82 28.37 18.33 8.36

0.0114 0.0108 0.0175 0.0062 0.0015

Standard uncertainties (u), u(T) = 0.15 K, and u(P) = 0.3 kPa. bΔ = (Pcal − Pexp)/Pexp.

a

denotes the total pressure; and Psi is the saturated vapor pressure of component i at VLE temperature T, which is calculated by Antoine eq 2. All activity coefficients are marginally greater than 1.0 indicating a positive deviation from Raoult’s law for all binary systems. log(Pis/kPa) = Ai + Bi /(T /K + Ci)

αij =

yi xi

yj xj

(3)

where αij is the relative volatility; x and y are the liquid and vapor mole fractions, respectively; the subscripts i and j are the components i and j, respectively. For the camphene + (±)-limonene and camphene + (+)-3carene systems, the relative volatility α12 is >1.2 across the entire concentration range, as shown in Table 2, indicating that these two binary systems are easy to separate by conventional

(2)

where Ai, Bi, and Ci are the Antoine parameters. Table 2 also presents the relative volatilities28,29 of the binary systems, which can be calculated by eq 3: D



Article

Table 5. Regressed Constants for Antoine Equationf Antoine parameters

temp range

compounds

A

B

C

AADa/K

ARDb/%

R2c

K

camphene (+)-3-carened (±)-limonenee

7.226 5.8919 5.779

2340.8673 1423.9794 1369.68

13.4387 −78.1690 −88.5047

0.24

0.06

0.9998 0.9982 0.9997

432.16−357.01 356.07−444.44 346.96−420.21

a

AAD caculated as n

AAD =

∑ i=1

1 ·|Texp − Tcalc|i n

ARD calculated as ÄÅ ÉÑ n |Texp − Tcalc| ÑÑÑ 1 ÅÅÅÅ ÑÑ ARD = ∑ ·ÅÅÅ100· ÑÑ ÑÑ n ÅÅÅ Texp i=1 ÑÖ Ç

b

c 2

R is coefficient of determination. dFrom reference.30 eFrom reference.31 fAntoine equation: log(P/kPa) = Ai - Bi/(T/K + Ci).

Table 7. Results of Thermodynamic Consistency Test of Van Ness Testa for the Binary Systems system

NRTL

Δy1 Δy2 Δy1 Δy2 Δy1 Δy2 Δy1 Δy2 Δy3 a

Figure 3. P vs T diagram for the camphene saturated vapor pressure (●, experimental data; dash line, literature data;32−42 dot line, estimated data;43,44 solid line, curve fitting).

Wilson

UNIQUAC

Camphene + (±)-Limonene 0.1252 0.1306 0.0681 0.0466 0.0384 0.0366 Camphene + (+)-3-Carene 0.0280 0.0281 0.0196 0.0500 0.0216 0.0205 (±)-Limonene + (+)-3-Carene 0.0178 0.0186 0.0184 0.0187 0.0187 0.0200 Camphene + (+)-3-Carene + (±)-Limonene 0.0029 0.2860 0.2809 0.0023 0.3029 0.1451 0.0019 0.1834 0.3257

results pass pass pass pass pass pass pass pass pass

Calculated as Δyi =

1 N

N

∑ 100|yiexp − yicalc | i=1

Table 6. Results of Thermodynamic Consistency Test of Herington Area Test for The Binary Systems Heringtona system

D

J

D−J

results

camphene + (±)-limonene camphene + (+)-3-carene (±)-limonene + (+)-3-carene

5.8250 3.8748 11.8277

5.8082 3.4318 2.3759

0.01677 0.4430 9.5518

pass pass pass

Consistency test tolerance: |D −J| < 10.

a

distillation. Particularly, for the (±)-limonene + (+)-3-carene system, when the composition of liquid phase x1 < 0.23, 0.86 < a12 < 1.00 (1 < a21 < 1.15), which is difficult for a conventional distillate separation, when x1 > 0.23, 0.80 < a12 < 0.86 (1.15 < a21 < 1.25), which is relatively easy for a conventional distillate separation. All results demonstrate the absence of any azeotrope. The experimental results of camphene vapor pressure are listed in Table 4, and the corresponding Antoine parameters are listed in Table 5. The Antoine parameters for (+)-3-carene and (±)-limonene are also listed in Table 5.30,31 Furthermore, a comparison between the experimental data and the literature data32−42 of camphene saturated vapor pressure derived from

Figure 4. ln(γ1/γ2) vs x1 diagram: ●, camphene + (+)-limonene; ▲, camphene + (+)-3-carene; ■, (±)-limonene + (+)-3-carene; solid line, fitted with cubic polynomial.

the NIST ThermoData Engine (TDE)43,44 database is presented in Figure 3. E



Article

Table 8. Binary Interaction Parameters, Root Mean Square Deviation (RMSD), and the Average Absolute Deviations (AAD) for the Vapor Phase Mole Fraction (y1) and the Equilibrium Temperature (T) of the NRTL, Wilson, and UNIQUAC Activity Coefficient Models binary interaction parameters model

aij

aji

NRTL Wilson UNIQUAC

2.0457 −0.9723 −0.2862

−0.3452 −0.4207 0.09762

NRTL Wilson UNIQUAC

−4.0359 −5.5916 2.4969

5.4328 3.9472 −3.7661

NRTL Wilson UNIQUAC

−1.9765 −3.5732 −0.0698

2.0206 3.2582 0.1213

bij/K

RMSD α a ij

bji/K

Camphene + (±)-Limonene −714.0372 109.7527 0.3 422.5280 48.8875 142.8520 −56.6848 Camphene + (+)-3-Carene 1604.5907 −2164.9753 0.3 2283.4841 −1612.9762 −918.7255 1441.8694 (±)-Limonene + (+)-3-Carene 824.7475 −817.9191 0.3 1528.7574 −1414.6375 42.5209 −67.0455

AAD δ (y1)

y1b

c T/K

d

0.0015 0.0015 0.0010

0.0931 0.0855 0.0966

0.0013 0.0013 0.0007

0.0799 0.0855 0.0843

0.0004 0.0004 0.0003

0.0151 0.0151 0.0150

0.0003 0.0003 0.0002

0.0112 0.0112 0.0110

0.0002 0.0002 0.0002

0.0171 0.0171 0.0171

0.0002 0.0002 0.0002

0.0128 0.0128 0.0128

In NRTL model, the parameter α is set to 0.3 when the mixture containing polar component. bRMSD(y) =

a c

RMSD(T ) =

N

∑i = 1 (Tical − Tiexp)2 /N . dδ(y1) =

1 n

n

∑1 |y1cal − y2exp |. eδ(T ) =

1 n

e δ (T)

N

∑i = 1 (yical − yiexp )2 /N .

n

∑1 |T1cal − T1exp|.

Table 9. Van Der Waals Volume (r) and Surface Area (q) of the Components for the UNIQUAC Equationa component

r

q

camphene (+)-3-carene (±)-limonene

6.0560 6.0541 6.2782

4.7600 4.7560 5.2080

a

Taken from Aspen property databank.30

Figure 6. T vs x1, y1 diagram for the camphene + (+)-3-carene system at 101.3 kPa: ●, experimental data; dash line, calculated data with NRTL model; solid line, calculated data with Wilson model; dot line, calculated data with UNIQUAC model.

The Herington area test, based on the analysis of Wisniak,45 considered the VLE data to be thermodynamically consistent only when the calculated result of |D − J| < 10. The D and J values are calculated by eqs 4 and 5:46,47

Figure 5. T vs x1, y1 diagram for the camphene + (±)-limonene system at 101.3 kPa: ●, experimental data; dash line, calculated data with NRTL model; solid line, calculated data with Wilson model; dot line, calculated data with UNIQUAC model.

D=

The relative deviations of camphene are shown in Table 5, and average ∼0.06%. The experimental results of camphene vapor pressure are in good agreement with the literature. The excellent correlation supports the reliability of the modified Ellis equilibrium still to determine the saturated vapor pressure of the pure substance. Therefore, there is confidence to use the camphene Antoine constants to correlate VLE data for the binary systems. 3.2. Thermodynamic Consistency Tests of Binary Systems. Herington area22 and van Ness23 tests were employed to determine thermodynamic consistency for all experimental data.

|I | 100 ∑

J = 150

(4)

θ Tmin

∫ 10ln(γ1/γ2) dx1,

(5)

where I = ∑= dx1, θ = Tmax − Tmin. The Tmin and Tmax are the lowest and the highest boiling temperature in the experiment, respectively (K). The van Ness test, a point consistency method reported by Fredenslund et al.,48 verifies the reliability of the experimental data.49 If Δyi is < 1, the VLE data can be confirmed to be thermodynamically consistent. The criterion of the point test method is described by eq 6:50 F

∫ 10|ln(γ1/γ2)|



Article

Figure 9. Relative volatilities of camphene + (+)-3-carene system at 101.33 kPa: ●, experimental data; −, NRTL, UNIQUAC, and Wilson model; ---, ±2% deviations from the calculated relative volatilities.

Figure 7. T vs x1, y1 diagram for the (±)-limonene + (+)-3-carene system at 101.3 kPa: ●, experimental data; dash line, calculated data with NRTL model; solid line, calculated data with Wilson model; dot line, calculated data with UNIQUAC model.

Figure 10. Relative volatilities of (±)-limonene + (+)-3-carene system at 101.33 kPa: ●, experimental data; −, NRTL, UNIQUAC, and Wilson model; ---, ±2% deviations from the calculated relative volatilities.

Figure 8. Relative volatilities of camphene + (±)-limonene system at 101.33 kPa: ●, experimental data; −, NRTL, UNIQUAC, and Wilson model; ---, ±5% deviations from the calculated relative volatilities.

Δyi =

1 N

N

∑ 100|yiexp − yical | i=1

carene, and (±)-limonene + (+)-3-carene binary systems at 101.33 kPa. Those models were defined as follows:

(6)

In which N is the number of experimental data points; yi represents the vapor phase mole fractions of pure component i and the indices “exp” and “cal” represent the experimental and calculated values by NRTL, Wilson, and UNIQUAC models, respectively. The results of the thermodynamic consistency tests are presented in Tables 6, 7, and Figure 4. The results demonstrate that all experimental data are considered to be thermodynamically consistent. 3.3. VLE Experimental Data Correlation. The NRTL,24 Wilson,25 and UNIQUAC26 activity coefficient models (Aspen Plus V8.7), adopting the maximum-likelihood method, were chosen to correlate the isobaric experimental VLE measurements for the camphene + (±)-limonene camphene + (+)-3-

NRTL: ln γi =

∑ j

xjτjiGji ∑k xkGki

+

∑ j

ij y jjτ − ∑m xmτmjGmj zzz jj ij z ∑k xkGkj zz ∑k x k Gkj j k { xjGij

(7)

where τij = aij + bij/T; Gij = exp(−αijτij). Wilson: ij yz j z ln γi = 1 − lnjjj∑ Aij xjzzz − jj zz k j {

∑ Ajixj/∑ Ajk xk j

k

(8)

where ln Aij = aij + bij/T G



Article

Figure 11. Deviations of the experimental data, Texp, and yexp from the calculated results of models, Tcal and ycal, for camphene + (±)-limonene system.

Figure 12. Deviations of the experimental data, Texp, and yexp from the calculated results of models, Tcal and ycal, for camphene + (+)-3-carene system.

Figure 13. Deviations of the experimental data, Texp, and yexp from the calculated results of models, Tcal and ycal, for (±)-limonene + (+)-3-carene system.

where τij = exp(aij + bij /T );

UNIQUAC: ln γi = ln

ϕi xi

+

+ qit −

θ Z qi ln i − qit ln tit − 2 ϕi ϕi xi

∑j θjtτij t qi t jt

θi =

+ li

qixi ∑j qjxj

;

ϕi =

Z

li = 2 (ri − qi) − (ri − 1); T h e rx i i ∑j rjxj

objective function for a binary system is expressed as follows:51

∑ xjlj j

(9) H



Article

Figure 14. VLE experimental data for the ternary system camphene + (+)-3-carene + (±)-limonene at 101.3 kPa: ●, experimental liquid phase composition; ○, experimental vapor phase composition. Figure 17. Percentage errors of the relative volatilities ((+)-3-carene to (±)-limonene) predicted by NRTL, Wilson, and UNIQUAC models in comparison to the ternary VLE data of this work for the camphene + (+)-3-carene + (±)-limonene system at 101.3 kPa.

ÄÅ 2 ÅÅ 2 2 ÅÅji Ti ,c − Ti ,e zy jij xi ,c − xi ,e zyz jij Pi ,c − Pi ,e zyz Å j z OF = ∑ ÅÅjj zz zzz + jjj zzz + jj ÅÅj σT j z σx i=1 Å { k σP { k { ÅÇk É 2Ñ Ñ ji yi ,c − yi ,e zyz ÑÑÑÑ zz ÑÑ + jjjj j σy zz ÑÑÑ k { ÑÖ (10) N

where σX =

1 N−1

N

∑ (Xi ,e − X̅i ,e)2 i=1

and X = {T, P, x, y}. N represents the number of experiments; σ is standard deviation; T, P, x, and y represent equilibrium temperature, pressure, liquid phase mole fraction, and vapor phase mole fraction, respectively; and the subscripts of e and c are the experimental and calculated values, respectively. Using Aspen Plus, three optimized binary interaction parameters can be derived from the experimental data. Concomitantly, the activity coefficient models can be used to calculate bubble point temperatures and vapor-phase compositions by using the aforementioned parameters. The parameters aij, aji, bij, bji, αij, the root-mean-square deviations and the average absolute deviations (AAD) for the vapor-phase mole fraction (y1) and the equilibrium temperature (T) of the three systems were obtained (Table 8). As recommended by Renon and Prausnitz,52 the nonrandomness parameter (αij) in the NRTL model was set at 0.3. The structural parameters r (van der Waals molecular volume) and q (van der Waals molecular surface area) values used as an input parameter for the UNIQUAC model are listed in Table 9. The comparison between the experimental data and the regression results of the models are shown in Figures 5−7. The results correlated by the NRTL, Wilson, and UNIQUAC models are in good agreement with the experimental results. The experimental relative volatilities of camphene + (±)-limonene, camphene + (+)-3-carene, and (±)-limonene + (+)-3-carene system are compared with results calculated28,53 using model parameters in Table 8, plotted in Figures 8, 9, and

Figure 15. Percentage errors of the relative volatilities (camphene to (±)-limonene) predicted by NRTL, Wilson, and UNIQUAC models in comparison to the ternary VLE data of this work for the camphene + (+)-3-carene + (±)-limonene system at 101.3 kPa.

Figure 16. Percentage errors of the relative volatilities (camphene to (+)-3-carene) predicted by NRTL, Wilson, and UNIQUAC models in comparison to the ternary VLE data of this work for the camphene + (+)-3-carene + (±)-limonene system at 101.3 kPa.

I



Article

and the maximum absolute deviations of temperature and vapor mole fraction are 0.04 K and 0.0001, respectively. Therefore, we recommend the NRTL model for predicting the ternary system.

10, which clearly demonstrate that the relative standard uncertainty of the model for the relative volatility of these systems are better than 0.05, 0.02, and 0.02, respectively. This demonstrates that the experimental data are in agreement with calculated results. Figures 11−13 depict the relative and standard deviations for temperature and vapor phase mole fractions of the experimental data from the calculated data of models for camphene + (±)-limonene, camphene + (+)-3-carene, and (±)-limonene + (+)-3-carene, respectively. From Figures 11−13, we can see that the relative and standard deviations are random around the zero axis, which indicates the three models could correlate the experimental data of this work very well for these systems. 3.4. Predication of the Ternary VLE. With the obtained interaction parameters involved in these models, the ternary VLE of camphene + (+)-3-carene + (±)-limonene were predicted and were compared with the measured ternary VLE data given in Table 3. The maximum absolute deviation and mean absolute deviation of boiling temperature and vapor composition were also listed in Table 3. Also the VLE experimental data are displayed in Figure 14. The results show that the binary data allowed a good prediction of the ternary system. The NRTL model gives the smallest mean absolute deviations compared with the Wilson and UNIQUAC models. Furthermore, Figures 15−17 show that the α12 values predicted by models agree well with the experimental data, and the error points were evenly distributed around the zero line. Compared with Wilson and UNIQUAC models, the α12 values predicted by the NRTL model has the smallest relative volatility percentage error. Therefore, we recommend the NRTL model for predicting VLE of the system of camphene + (+)-3-carene + (±)-limonene.

■

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Tel.: +86 771 3272702. Fax: +86 771 3233718. ORCID

Jinzhi Wu: 0000-0002-9927-8269 Xiaopeng Chen: 0000-0002-7496-3497 Funding

We acknowledge the financial support for this work from the National Natural Science Foundation of China (Grant Nos. 21878056, 31560241, and 21566002), Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (Grant No. 2016Z002). Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Gómez-Pozuelo, G.; Cabello, C. P.; Opanasenko, M. Superior Activity of Isomorphously Substituted MOFs with MIL-100 (M= Al, Cr, Fe, In, Sc, V) Structure in the Prins Reaction: Impact of Metal Type. ChemPlusChem 2017, 82, 152−159. (2) Liao, D. K.; Chen, X. P.; Tong, Z. F.; Liu, X. M.; Lu, B. C.-Y. In Frontiers on Separation Science and Technology (ICSST’04); Tong, Z. F., Kim, S. H., Eds.; World Scientific Publishing Co.: Singapore, 2004; pp 112−116. (3) Tong, Z. F.; Wang, K.; Sun, L. X.; Liao, D. K.; Wei, T. Y.; Chen, X. P. J. Chem. Eng. Chin. Univ. (China) 2011, 25, 734−738. (4) Ebmeyer, F. Theoretical investigations towards an understanding of the α-pinene/camphene rearrangement. J. Mol. Struct.: THEOCHEM 2002, 582, 251−255. (5) BIPM Joint Committee for Guides in Metrology. Evaluation of measurement dataGuide to the expression of uncertainty in measurement JCGM 100:2008 (GUM 1995 with minor corrections). BIPM: Paris, France, 2008; Vol. JCGM 100:2008. (6) Okuniewski, M.; Paduszynski, K.; Domanska, U. Thermodynamic Study of Molecular Interactions in Eutectic Mixtures Containing Camphene. J. Phys. Chem. B 2016, 120, 12928−12936. (7) Li, J. F.; Liang, N.; Sun, Z.; Du, R. J.; Shi, B.; Hou, X. H. Simulataneous Determination of Isoquinoline, Caryophyllene Oxide, Hexadecane in Essential Oils from Juglandis Mandshuricae Cortex by Vapour−Vapour Extaction Combined with Gas Chromatograph Analysis. Asian J. Tradit. Med. 2012, 7, 246−252. (8) Benelli, G.; Govindarajan, M.; Rajeswary, M. Insecticidal activity of camphene, zerumbone and α-humulene from Cheilocostus speciosus rhizome essential oil against the Old-World bollworm, Helicoverpa armigera. Ecotoxicol. Environ. Saf. 2018, 148, 781−786. (9) Benelli, G.; Govindarajan, M.; Rajeswary, M.; Vaseeharan, B.; Alyahya, S. A.; Alharbi, N. S.; Kadaikunnan, S.; KhaLED, J. M.; mAGGI, ̂ F. Insecticidal activity of camphene, zerumbone and I±-humulene from Cheilocostus speciosus rhizome essential oil against the Old-World bollworm, Helicoverpa armigera. Ecotoxicol. Environ. Saf. 2018, 148, 781−786. (10) Banina, O. A.; Sudarikov, D. V.; Nigmatov, A. G.; Frolova, L. L. Carane amino alcohols as organocatalysts in asymmetric aldol reaction of isatin with acetone. Russ. Chem. Bull. 2017, 66, 293−296. (11) Torregiani, E.; Lorier, S.; Sagratini, G. Comparative analysis of the volatile profile of 20 commercial samples of truffles, truffle sauces, and truffle-flavored oils by using HS-SPME-GC-MS. Food Anal. Methods 2017, 10, 1857−1869. (12) Lee, H. R.; Lee, S. C.; Lee, D. H. Identification of the aggregationsex pheromone produced by male Monochamus saltuarius, a major

4. CONCLUSIONS The isobaric VLE of the camphene + (±)-limonene, camphene + (+)-3-carene, (±)-limonene + (+)-3-carene, and camphene + (+)-3-carene + (±)-limonene systems were determined by use of a modified Ellis equilibrium still. All binary systems display the absence of any azeotropes. The thermodynamic consistency of the binary systems experimental VLE values were confirmed by the Herington area and van Ness tests. Furthermore, the NRTL, Wilson, and UNIQUAC models were used to correlate the VLE data, and concomitantly, to obtain the corresponding binary interaction parameters. The maximum AAD of temperature and vapor-phase mole fraction are 0.0855 and 0.0013 for the camphene + (±)-limonene system, 0.0112 and 0.0003 for the camphene + (+)-3-carene system, and 0.0128 and 0.0002 for the (±)-limonene + (+)-3-carene system, respectively. The correlated results are in good agreement with the experimental data. Additionally, camphene saturated vapor pressures were measured across a temperature range of 357.01 to 432.16 K also using a modified Ellis equilibrium still and the Antoine constants obtained. The camphene temperature average relative deviation is ∼0.06%. The results indicate that the camphene Antoine constants are suitable to correlate VLE data for the binary systems, and the binary interaction parameters obtained can be used to optimize and design the separation process. The NRTL, Wilson, and UNIQUAC models were used to predict VLE data of the ternary system of camphene + (+)-3carene + (±)-limonene. The values predicted by these models were reasonably in agreement with the experimental results, the NRTL model is the best model for the ternary VLE prediction, J



Article

insect vector of the pine wood nematode. J. Chem. Ecol. 2017, 43, 670− 678. (13) Alparslan, Y.; Baygar, T. Effect of chitosan film coating combined with orange peel essential oil on the shelf life of Deepwater pink shrimp. Food Bioprocess Technol. 2017, 10, 842−853. (14) Corma, A.; Iborra, S.; Velty, A. Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 2007, 107, 2411− 2502. (15) Bernardo-Gil, M. G.; Ribeiro, M. A. Vapor-liquid equilibria of binary system based on pine resin. Fluid Phase Equilib. 1989, 53, 15−22. (16) Rodrigues, M. F.; Bernardo-Gil, M. G. Vapor− Liquid Equilibrium Data of α-Pinene+ β-Pinene+ Limonene at 80 and 101 kPa. J. Chem. Eng. Data 1996, 41, 581−585. (17) Xu, X.; Liao, D.; Li, L. S.; Chen, X. P.; Tong, Z. F. Determination and correlation of atmospheric VLE data of alpha-pinene+ beta-pinene + p-cymene. J. Chem. Ind. Eng. 2007, 58, 2970−2974. (18) Tong, Z. F.; Yang, Z. Y.; Liao, D. K.; Wei, T. Y.; Chen, X. P. Measurement and correlation of VLE data for α-pinene+ limonene and p-cymene+ limonene systems under atmospheric pressure. J. Chem. Ind. Eng. 2009, 60, 1877−1882. (19) Sun, L. X.; Wang, K.; Liao, D. K.; Wei, T. Y.; Chen, X. P.; Tong, Z. F. Measurement and Correlation of Vapor− Liquid Equilibrium Data for β-Pinene+ p-Cymene+(S)-(−)-Limonene at Atmospheric Pressure. J. Chem. Eng. Data 2009, 56, 1378−1382. (20) Walas, S. M.; Phase Equilibria in Chemical Engineering; Butterworth-Heinemann: London, 1985. (21) Sun, L.; Liao, D.; Yang, Z. Measurement and correlation of (vapor+ liquid) equilibrium data for {α-pinene+p-cymene+ (S)(−)-limonene} ternary system at atmospheric pressure. J. Chem. Thermodyn. 2013, 58, 416−421. (22) Herington, E. F. G. Tests for the consistency of experimental isobaric vapour-liquid equilibrium data. J. Inst. Petrol. 1951, 37, 457− 470. (23) Van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapour-liquid equilibrium: Part I. An appraisal of data reduction methods. AIChE J. 1973, 19, 238−244. (24) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135− 144. (25) Wilson, G. M. Vapour-liquid equilibrium. XI. A new expression for the excess free energy of mixing. J. Am. Chem. Soc. 1964, 86, 127− 130. (26) Abrams, D. S.; Prausnitz, J. M. Statistical thermodynamics of liquid mixtures: a new expression for the excess Gibbs energy of partly or completely miscible systems. AIChE J. 1975, 21, 116−128. (27) Van Ness, H. C.; Abbott, M. M. Classical Thermodynamics of Nonelectrolyte Solutions; McGraw-Hill: New York, 1982. (28) Mathias, P. M. Guidelines for the Analysis of Vapor-Liquid Equilibrium Data. J. Chem. Eng. Data 2017, 62, 2231−2233. (29) Mathias, P. M. Effect of VLE Uncertainties on the Design of Separation Sequences by Distillation-Study of the Benzene-Chloroform- Acetone System. Fluid Phase Equilib. 2016, 408, 265−272. (30) Aspen Plus Software, version 8.7; Aspen Technology Inc.: Burlington, MA, 2014. (31) Wang, Y.; Huang, N.; Xu, B.; Wang, B.; Bai, Z. Measurement and Correlation of the Vapor Pressure of a Series of α-Pinene. Derivatives. J. Chem. Eng. Data 2014, 59, 494−498. (32) Lecat, M. Nouveaux aze′otropes binaires: 2nd list. Recl. Trav. Chim. Pays-Bas 1926, 45, 620−627. (33) Smith, H. A.; Fuzek, J. F.; Meriwether, H. T. The Catalytic Hydrogenation of Terpenes. J. Am. Chem. Soc. 1949, 71, 3765−3769. (34) Stull, D. R. Vapor Pressure of Pure Substances Organic and Inorganic Compounds. Ind. Eng. Chem. 1947, 39, 517−540. (35) Lecat, M. New binary azeotropes: second list. Ann. Soc. Sci. Bruxelles, Ser. B 1926, 45, 94−284. (36) Lecat, M. New binary azeotropes: 6th list. Ann. Soc. Sci. Bruxelles, Ser. B 1927, 47, 14−108. (37) Pariselle, M. C. R. Hebd. Seances Acad. Sci. 1923, 176, 1901.

(38) Lecat, M. New binary azeotropes: 3rd list. Ann. Soc. Sci. Bruxelles, Ser. B 1926, 45, 620−627. (39) Lecat, M. New binary azeotropes: 7th list. Ann. Soc. Sci. Bruxelles, Ser. B 1927, 47, 14−108. (40) Lecat, M. C. R. Azeotropes of Ethyl Urethane and other Azeotropes. Hebd. Seances Acad. Sci. 1943, 217, 273. (41) Lecat, M. Orthobaric Azeotropes of Sulfides. Bull. Cl. Sci., Acad. R. Belg. 1947, 33, 82−160. (42) Stull, D. R. Vapor Pressure of Pure Substances Organic Compounds. Ind. Eng. Chem. 1947, 39, 517. (43) The NIST Bank, National Institute of Standards and Technology: Gaithersburg, MD, 1994. (44) Frenkel, M.; Chirico, R. D.; Diky, V. ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. J. Chem. Inf. Model. 2005, 45, 816−838. (45) Wisniak, J.; Pérez-Correa, J. R.; Mejía, A. Comments on ‘‘experimental measurements of vapour-liquid equilibrium data for the binary systems of methanol + 2-butyl acetate, 2-butyl alcohol + 2-butyl acetate, and methyl acetate + 2-butyl acetate at 101.33 kPa. J. Chem. Eng. Data 2013, 58, 3563−3566. (46) Ma, P. S. Chemical Engineering Thermodynamics; Chemical Industry Pess: Beijing, 2009. (47) Wisniak, J.; Apelblat, A.; Segura, H. An assessment of thermodynamic consistency tests for vapor-liquid equilibrium data. Phys. Chem. Liq. 1997, 35, 1−58. (48) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-liquid Equilibria Using UNIFAC: A Group Contribution Method; Elsevier: Amsterdam, 1977. (49) Jackson, P. L.; Wilsak, R. A. Thermodynamic consistency tests based on the Gibbs- Duhem equation applied to isothermal, binary vapor-liquid equilibrium data: data evaluation and model testing. Fluid Phase Equilib. 1995, 103, 155−197. (50) Kang, J. W.; Diky, V.; Chirico, R. D. Algorithmic framework for quality assessment of phase equilibrium data. J. Chem. Eng. Data 2014, 59, 2283−2293. (51) Zhang, L. Z.; Xu, D. M.; Gao, J. Measurements and correlations of density, viscosity, and vapour-liquid equilibrium for fluoro alcohols. J. Chem. Thermodyn. 2016, 102, 155−163. (52) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135− 144. (53) Wang, J.; Ou, J.; Sun, X.; Tong, X.; Gao, B.; Huang, C.; Leng, Y. Experimental and Predicted Vapor−Liquid Equilibrium for Diisopropanolamine with m-Cresol and 2, 6-Dimethylphenol at 20.0 kPa. J. Chem. Eng. Data 2018, 63, 1220−1227.

K


Measurement and Correlation of Isobaric VaporâLiquid Equilibrium for

Recommend Documents

Measurement and Correlation of Isobaric VaporâLiquid Equilibrium for