Phase equilibrium properties of binary mixtures containing 2,5-dimethylfuran and furfuryl alcohol or methyl isobutyl ketone at several temperatures

J. Chem. Thermodynamics 70 (2014) 233–238

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Phase equilibrium properties of binary mixtures containing 2,5-dimethylfuran and furfuryl alcohol or methyl isobutyl ketone at several temperatures Latifa Negadi a,⇑, Ilham Mokbel b,c, Nouria Chiali-Baba-Ahmed a, Lamia Kara-Zaitri a a b c

LATA2M, Laboratoire de Thermodynamique Appliquée et Modélisation Moléculaire, University of Tlemcen, Post Office Box 119, Tlemcen 13000, Algeria UMR 5280, Institut des Sciences Analytiques, 5, rue de la Doua, 69100 Villeurbanne, France Université de Saint Etienne, Jean Monnet, Université de Lyon, F-42023 Saint Etienne, France

a r t i c l e

i n f o

Article history: Received 5 September 2013 Received in revised form 18 October 2013 Accepted 31 October 2013 Available online 9 November 2013 Keywords: (Vapor + liquid) equilibria 2,5-Dimethylfuran Furfuryl alcohol Methyl isobutyl ketone Models

a b s t r a c t The (vapor + liquid) equilibria of the pure components, furfuryl alcohol, and methyl isobutyl ketone along with the binary mixtures (2,5-dimethylfuran + furfuryl alcohol), or (2,5-dimethylfuran + methyl isobutyl ketone), were investigated experimentally by means of a static apparatus at temperatures between (313 and 393) K. The vapor pressures of the pure components were correlated with the Antoine equation. The experimental results for the mixtures were reduced by the Barker method using a third-order Redlich– Kister equation. The calculated values of the excess Gibbs free energy, GE, exhibit positive deviations for all investigated temperatures and over the whole composition range. The NRTL, UNIQUAC and Modified UNIFAC (Do) models have been applied to correlate the experimental VLE results. Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction The use of traditional solvents in the chemical industry produces well-known environmental problems from the consumption of unsustainable raw materials which cause the emergence of harmful derived chemical compounds that can be released to the environment. For these reasons, it is fundamental that new chemical processes be proposed, based on the green chemistry principles which minimize the environmental impact of industrial processes. One of the bases of green chemistry is the elimination or replacement of hazardous products and reagents, inefficient processes and unsustainable raw materials. For this reason, the research and use of so-called green solvents is increasing rapidly [1,2]. Among many energy alternatives, biofuels, hydrogen, natural gas and syngas may likely emerge as the four strategically important sustainable fuel sources in the foreseeable future. Within these four, biofuels are the most environment friendly energy source [3]. Hence, biofuels are being explored to replace fossil fuels. They are a favorable choice of fuel consumption due to their renewability, biodegradability and generating acceptable quality exhaust gases. Biofuels are referred to liquid, gas and solid fuels ⇑ Corresponding author. Tel./fax: +213 43286530. E-mail addresses: [email protected], [email protected] (L. Negadi). 0021-9614/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jct.2013.10.039

predominantly produced from biomass. A variety of fuels can be produced from biomass such as ethanol, methanol, biodiesel, Fischer–Tropsch diesel, hydrogen and methane [4]. The present work is a continuation of our systematic studies on thermodynamic properties of binary mixtures containing solvents derived from biomass [5]. In this paper, we report the experimental (vapor - liquid) equilibria (VLE) data of {2,5-dimethylfuran (CAS # 625-86-5) + furfuryl alcohol (CAS # 98-00-0)}, or {2,5-dimethylfuran (CAS # 625-86-5) + methyl isobutyl ketone (CAS # 108-10-1)} binary systems at several temperatures, which are necessary for the optimization of the separation step in the process. Additionally, the NRTL, UNIQUAC and Modified UNIFAC (Do) models are used to estimate and correlate the vapor pressures of pure and mixed liquids. A survey of the literature shows that no thermodynamic data are available for the investigated binary systems. Different sources report vapor pressures for pure methyl isobutyl ketone [6] and furfuryl alcohol [7–14].

2. Experimental 2.1. Materials In table 1 contains the purities stated by the supplier, Sigma–Aldrich, and those obtained by gas chromatography. The supplier’s values are confirmed. The substances were used without further

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L. Negadi et al. / J. Chem. Thermodynamics 70 (2014) 233–238 TABLE 1 Provenance, CAS number, and mass fraction purity of chemicals studied. Component

2,5-Dimethylfuran

Furfuryl alcohol

Methyl isobutyl ketone

CAS # Sigma–Aldrich purity GC purity

625-86-5 0.99 >0.99

98-00-0 P0.98 >0.99

108-10-1 P0.99 >0.99

purification. In any case, any volatile impurities were eliminated during the degassing operation. 2.2. VLE measurements The experimental VLE data comprising the total pressure p as a function of the temperature T for given mole fractions of the liquid phase xi (yielding (p  T  xi) data for the binary systems and vapor pressures for pure components) were obtained using the static apparatus shown in figure 1 and described in detail previously [5]. It is equipped with an absolute pressure gage from Keller, Model PAA-35X HTC 81090 (Switzerland). The estimated uncertainties of the pressure are 0.5% over the range (1.5 to 300) kPa and 2% within the range between (0.3 and 1.5) kPa. Temperature was measured with a copper–constantan thermocouple calibrated against a 25 X platinum resistance standard thermometer (accuracy of ±0.001 K claimed by the manufacturer in the IPTS 90 temperature scale) with a Leeds and Northrup bridge (±104 X). As the uncertainty of the voltmeter for the thermocouple reading is 0.1 lV, the precision of the temperature readings is about 0.01 K. The overall uncertainty on the measured temperatures is estimated to be ±0.02 K. Prior to VLE measurements, the sample is degassed. With this aim, the binary mixture is charged into the preparation bulb by weighing the components. The estimated uncertainty in the mole fraction composition xi is ±0.0005. The preparation bulb is then

connected to the apparatus, which is entirely submitted to vacuum during several hours. Later, the liquid is transferred to the degassing bulb by opening valve V1 (V2 is closed). The degassing process is carried out by boiling and submitting the liquid to vacuum for 1 s each 2 min during 30 min by means of the temporised electro-valve so the dissolved air is removed from the sample. The condenser, cooled down to 0 °C, limits the loss of the volatile compound. Once the sample is degassed, the liquid is slowly transferred to the measurement cell by opening V2. The cell is contained in an air bath and the mixture is stirred during the experiment. The total pressure of the liquid solution is recorded once the thermodynamic equilibrium is obtained (constant temperature and pressure). In the present study, the equilibrium pressures are measured between the temperatures (313 and 393) K; however, the apparatus could be used up to 573 K. At the end of the experiments, the composition of the samples is checked by gas chromatography. 3. Results and discussion 3.1. Pure components In table 2, the experimental vapor pressures of the pure compounds are presented. The data were fitted to the Antoine equation to check their consistency:

Mixture Preparation bulb

Temporized electrovalve Keller type pressure gage (heated) Condenser Magnetic stirrer

Glass Degassing Bulb

Measurement cell Heating cartridge

Purge valve

Air bath

Liquid N2+Pump

FIGURE 1. Static apparatus for vapor pressure measurements.

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L. Negadi et al. / J. Chem. Thermodynamics 70 (2014) 233–238 TABLE 2 Experimental vapor pressures of pure furfuryl alcohol, and methyl isobutyl ketone. T/Ka

T/Ka

pexp/Pa

pexp/Pa

Furfuryl alcohol 273.11 283.08 293.16 303.09 323.16 331.87 333.17 341.85 343.19

9 22 53 115 471 815 882 1479 1611

331.98 341.81 351.81 362.04 a

351.81 353.20 362.09 363.20 372.04 382.09 392.15 402.18 412.11

2577 2787 4368 4649 7065 11092 17099 25115 36527

Methyl isobutyl ketone 13853 372.03 20717 382.04 30285 392.07 43507

60558 82621 110739

u(T) = ±0.02 K.

TABLE 3 Coefficients A, B, C and overall mean relative deviation in pressure of the Antoine equation (equation (1)). Compound

Temperature/Ka

Furfuryl alcohol 273.11 to 412.11 Methyl isobutyl 331.98 to 392.07 ketone   P pcalc pexp 100dp=p ¼ N1 N . i¼1 100 pexp a u(T) = ±0.02 K.

log10 p=torr ¼ A 

A(rA)

B(rB)

C(rC)

100 dp/p

10.266 (0.043) 9.071 (0.017)

2035 (24) 1322 (10)

54.9 (1.6) 63.8 (1.1)

0.67 0.03

B : C þ t= C

ð1Þ

The objective function Q was the sum of the squared relative deviations in pressure:

TABLE 4 Values of the vapor pressure p, mole fraction of the vapor phase, activity coefficients c1 and c2 and excess molar Gibbs free energy GE for the binary system {2,5dimethylfuran (1) + furfuryl alcohol (2)}.

c2

GE/(J  mol1)

T = 313.15 K 5 9.3163 43 3.5050 57 2.4053 67 1.9059 69 1.5102 73 1.2071 70 1.0000

1.0000 1.0850 1.2253 1.4461 2.0302 3.8905 28.5106

0.0 742.2 1107.2 1320.8 1329.4 1076.7 0.0

475 12,333 16,407 19,398 20,527 21,658 21,541

T = 323.15 K 10 7.7956 62 3.2251 82 2.2478 97 1.7825 103 1.4336 108 1.1759 108 1.0000

1.0000 1.0773 1.2111 1.4282 1.9592 3.4787 19.1773

0.0 711.1 1061.6 1256.2 1246.8 996.4 0.0

890 17,305 23,250 27,512 29,639

T = 333.15 K 18 6.7198 87 3.0023 116 2.1219 138 1.6864 148 1.3742

1.0000 1.0709 1.1991 1.4116 1.8978

0.0 685.2 1023.3 1201.9 1177.7

x1

y1

pexp/Pa

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.9752 0.9825 0.9873 0.9887 0.9869 1.0000

242 8615 11,324 13,391 13,869 14,533 13,939

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.9662 0.9765 0.9829 0.9855 0.9849 1.0000

0.0000 0.1735 0.3292 0.5014 0.6676

0.0000 0.9551 0.9694 0.9779 0.9818

u(p)/Pa

c1

TABLE 4 (continued) GE/(J  mol1)

c1

c2

1.1514 1.0000

3.1655 13.8751

929.7 0.0

1597 23,836 32,286 38,275 41,845 44,737 46,744

T = 343.15 K 8 5.9357 119 2.8217 161 2.0197 191 1.6110 209 1.3280 224 1.1321 234 1.0000

1.0000 1.0658 1.1888 1.3957 1.8436 2.9225 10.6728

0.0 663.8 991.2 1156.5 1120.5 874.8 0.0

0.0000 0.9265 0.9512 0.9652 0.9728 0.9769 1.0000

2755 32,276 44,010 52,311 57,881 62,273 66,079

T = 353.15 K 14 5.3483 161 2.6724 220 1.9357 262 1.5514 289 1.2923 311 1.1171 330 1.0000

1.0000 1.0617 1.1798 1.3803 1.7950 2.7308 8.6427

0.0 646.0 964.2 1118.5 1073.6 830.5 0.0

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.9088 0.9400 0.9576 0.9676 0.9737 1.0000

4588 43,024 58,979 70,333 78,579 85,060 91,227

T = 363.15 K 23 4.8960 215 2.5466 295 1.8658 352 1.5043 393 1.2648 425 1.1057 456 1.0000

1.0000 1.0583 1.1718 1.3651 1.7507 2.5770 7.3076

0.0 631.0 941.1 1086.7 1035.5 795.3 0.0

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.8886 0.9275 0.9494 0.9621 0.9703 1.0000

7398 56,525 77,813 93,147 104,868 114,191 123,285

T = 373.15 K 37 4.5377 283 2.4385 389 1.8068 466 1.4670 524 1.2439 571 1.0972 616 1.0000

1.0000 1.0554 1.1645 1.3497 1.7095 2.4520 6.4068

0.0 618.2 921.1 1060.0 1005.1 768.2 0.0

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.8661 0.9136 0.9404 0.9562 0.9666 1.0000

11,588 73,271 101,191 121,647 137,768 150,880 163,427

T = 383.15 K 58 4.2446 366 2.3436 506 1.7566 608 1.4376 689 1.2285 754 1.0912 817 1.0000

1.0000 1.0530 1.1575 1.3340 1.6707 2.3488 5.7905

0.0 606.8 903.3 1037.5 981.2 748.1 0.0

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.8412 0.8985 0.9309 0.9501 0.9627 1.0000

17,675 93,799 129,851 156,822 178,388 196,455 212,881

T = 393.15 K 88 3.9958 469 2.2585 649 1.7133 784 1.4148 892 1.2176 982 1.0871 1064 1.0000

1.0000 1.0509 1.1505 1.3176 1.6335 2.2624 5.3687

0.0 596.1 886.9 1018.2 962.8 734.3 0.0

x1

y1

pexp/Pa

u(p)/Pa

0.8075 1.0000

0.9825 1.0000

31,482 32,204

157 161

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

0.0000 0.9419 0.9609 0.9719 0.9775 0.9798 1.0000

0.0000 0.1735 0.3292 0.5014 0.6676 0.8075 1.0000

u(T) = 0.02 K ; u(xi) = 0.0005 ; u(yi) = 0.005 ; u(GE) = 10 J  mol1.

Q¼

X pcalc  pexp pexp

!2 :

ð2Þ

The overall mean relative deviation in pressure is:

! dp 100 X pcalc  pexp ; %¼ p N pexp

ð3Þ

where N equals the total number of experimental values. The coefficients A, B, C of the Antoine equation and the overall mean relative deviation in pressure dp/p (%) for the pure components: furfuryl alcohol, and methyl isobutyl ketone are reported in table 3. For methyl isobutyl ketone, our experimental pressures agree to within 0.9% with those reported by Fuge et al. [6]. For furfuryl

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L. Negadi et al. / J. Chem. Thermodynamics 70 (2014) 233–238

TABLE 5 Values of the vapor pressure p, mole fraction of the vapor phase, activity coefficients c1 and c2 and excess molar Gibbs free energy GE for the binary system {2,5dimethylfuran (1) + methyl isobutyl ketone (2)}.

c2

GE/(J  mol1)

T = 313.15 K 29 4.1506 47 1.7162 54 1.3486 61 1.2671 68 1.2091 73 1.0878 70 1.0000

1.0000 1.0747 1.1574 1.2042 1.2921 1.8067 5.0780

0.0 400.6 508.4 549.9 552.7 446.1 0.0

9417 14,073 16,141 18,266 20,249 22,018 21,541

T = 323.15 K 47 3.4154 70 1.5815 81 1.2758 91 1.2055 101 1.1625 110 1.0697 108 1.0000

1.0000 1.0651 1.1380 1.1795 1.2456 1.6224 3.7204

0.0 355.0 445.0 472.8 467.2 373.4 0.0

0.0000 0.3904 0.5299 0.6888 0.8046 0.8854 1.0000

14561 20,745 23,684 26,699 29,584 32,172 32,204

T = 333.15 K 73 2.8644 104 1.4785 118 1.2242 133 1.1622 148 1.1283 161 1.0557 161 1.0000

1.0000 1.0558 1.1192 1.1567 1.2090 1.4935 2.9162

0.0 313.5 391.7 409.8 399.0 315.4 0.0

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.3703 0.5176 0.6803 0.8004 0.8881 1.0000

21,822 29,866 33,960 38,170 42,231 45,921 46,744

T = 343.15 K 109 2.4527 149 1.4008 170 1.1893 191 1.1332 211 1.1039 230 1.0452 234 1.0000

1.0000 1.0472 1.1017 1.1362 1.1811 1.4048 2.4236

0.0 276.8 346.4 360.5 347.2 271.2 0.0

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.3533 0.5078 0.6736 0.7966 0.8895 1.0000

31,802 42,084 47,682 53,475 59,025 64,165 66,079

T = 353.15 K 159 2.1466 210 1.3440 238 1.1675 267 1.1153 295 1.0874 321 1.0376 330 1.0000

1.0000 1.0395 1.0859 1.1185 1.1608 1.3463 2.1189

0.0 245.5 310.3 324.6 310.7 239.8 0.0

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.3391 0.5001 0.6684 0.7932 0.8897 1.0000

45,194 58,145 65,674 73,537 80,919 87,929 91,227

T = 363.15 K 226 1.9206 291 1.3043 328 1.1565 368 1.1063 405 1.0773 440 1.0324 456 1.0000

1.0000 1.0326 1.0721 1.1038 1.1471 1.3114 1.9354

0.0 220.3 283.7 301.5 288.8 220.3 0.0

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.3274 0.4940 0.6645 0.7901 0.8891 1.0000

62,784 78,901 88,872 99,411 108,991 118,370 123,285

T = 373.15 K 314 1.7561 395 1.2793 444 1.1546 497 1.1046 545 1.0725 592 1.0292 616 1.0000

1.0000 1.0268 1.0603 1.0920 1.1395 1.2955 1.8352

0.0 201.2 266.5 290.8 280.5 212.0 0.0

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.3177 0.4895 0.6616 0.7871 0.8876 1.0000

85,441 105,310 118,329 132,287 144,436 156,766 163,427

T = 383.15 K 427 1.6390 527 1.2670 592 1.1604 661 1.1090 722 1.0719 784 1.0277 817 1.0000

1.0000 1.0218 1.0505 1.0833 1.1374 1.2956 1.7966

0.0 188.5 258.7 292.1 284.9 213.8 0.0

0.0000 0.1748 0.3209 0.4986

0.0000 0.3099 0.4862 0.6595

114,119 138,430 155,213 173,494

T = 393.15 K 571 1.5591 692 1.2660 776 1.1731 867 1.1185

1.0000 1.0177 1.0427 1.0774

0.0 182.2 260.3 304.8

x1

y1

pexp/Pa

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.4419 0.5644 0.7130 0.8148 0.8745 1.0000

5882 9302 10,726 12,197 13,510 14,685 13,939

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

0.0000 0.4141 0.5454 0.6996 0.8094 0.8810 1.0000

0.0000 0.1748 0.3209 0.4986 0.6627 0.8281 1.0000

u(p)/Pa

c1

TABLE 5 (continued) x1

y1

pexp/Pa

u(p)/Pa

c1

c2

GE/(J  mol1)

0.6627 0.8281 1.0000

0.7844 0.8854 1.0000

188,569 204,522 212,881

943 1023 1064

1.0749 1.0276 1.0000

1.1405 1.3095 1.8066

301.4 225.1 0.0

u(T) = 0.02 K; u(xi) = 0.0005; u(yi) = 0.005; u(GE) = 10 J  mol1.

FIGURE 2. Plot of GE against x1 for the {2,5-dimethylfuran (1) + furfuryl alcohol (2)} system: , T = 313.15 K; d, 333.15 K; j, 353.15 K; N, 373.15 K; –, calculated values using equation (5).

FIGURE 3. Plot of GE against x1 for the {2,5-dimethylfuran (1) + methyl isobutyl ketone (2)} system: , T = 313.15 K; d, 333.15 K; j, 353.15 K; N, 373.15 K; –, calculated values using equation (5).

alcohol, our vapor pressure data are different by about 5% reported in the open literature [7–14] and are different by about 13% from those obtained by Lomba [2] using an ebulliometer. The 2,5-dimethylfuran vapor pressure data used in this work have been published in a previous paper [5]. 3.2. Binary systems Regarding the two binary mixtures, the data measured in the experiment consisted of the liquid composition, total pressure and temperature. The explored range lies between temperatures (313 and 393) K. Hence, to obtain the compositions of the vapor phase, the data were reduced according to the Barker method [15]. The values of the molar excess Gibbs free energy GE were estimated from a third-order Redlich–Kister equation: m X GE ¼ x1 ð1  x1 Þ RTGj ð2x1  1Þj1 : j¼1

ð4Þ

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L. Negadi et al. / J. Chem. Thermodynamics 70 (2014) 233–238 TABLE 6 NRTL, UNIQUAC parameters and sum of the squared relative deviations in pressure (SSQ), estimated via the experimental VLE data generated in this work. System

Model

2,5-Dimethylfuran + furfuryl alcohol 2,5-Dimethylfuran + methyl isobutyl ketone a b c

a

NRTL UNIQUACb NRTLa UNIQUACb

a12 (J  mol1)

a21 (J  mol1)

b12 (J  K1  mol1)

b21 (J  K1  mol1)

Alpha

SSQc

8202.40 1437.21 1395.19 125.62

778.24 2546.63 1487.42 125.76

41.05 4.25 6.31 1.15

0.69 9.12 23.31 0.82

0.3

0.94 0.96 0.02 0.09

0.3

aij ¼ C 0ij ; bij ¼ C Tij : aij ¼ ðuij  uii Þ0 ; bij ¼ ðuij  uii ÞT : P pexp pcalc 2 SSQ ¼ : p exp

FIGURE 4. Comparison between experimental and calculated P  x(y) using NRTL (–), UNIQUAC (——) and Modified UNIFAC (Do) (———) models of the system {2,5dimethylfuran (1) + furfuryl alcohol (2)} at different temperatures , 313.15 K; d, 333.15 K; j, 353.15 K; N, 373.15 K.

ponent i, and xi is the activity coefficient of component i in the liquid phase. The liquid and vapor phase compositions for the mixtures (2,5dimethylfuran + furfuryl alcohol), and (2,5-dimethylfuran + methyl isobutyl ketone), along with the activity coefficients x1 and x2, and the values of the excess molar Gibbs functions GE calculated by Barker’s method are reported in tables 4 and 5. No literature data were found to be compared with the present study. The two investigated systems show azeotropic behavior: The azeotropic coordinates are (T = 313.15 and 323.15 K; xaz  0.7) for (2,5-dimethylfuran + furfuryl alcohol) and (T = 313.15 and 323.15 K; xaz  0.2) for (2,5-dimethylfuran + methyl isobutyl ketone). As seen in figures 2 and 3, the GE values for the two binary systems are positive throughout the concentration range and decrease when the temperature increases. The NRTL [18] and UNIQUAC [19] equations were also applied to correlate the experimental VLE data and to estimate the liquid phase activity coefficients. The Simulis thermodynamic software developed by Prosim (France) was used to correlate the data and to fit the parameters. The non-random parameter (alpha) in the NRTL equation has been fixed to 0.3 for all cases. The fitting parameters (aij and bij) are given in table 6. Figures 4 and 5 show the results of correlation using NRTL and UNIQUAC models at four different temperatures for the two investigated mixtures. The NRTL and UNIQUAC models fit the experimental results of the systems very well. Additionally, prediction of VLE for the systems studied has been carried out by the Modified UNIFAC (Do) group contribution method [20] using the same software. It is observed that the descriptions of the systems by the Modified UNIFAC (Do) method are very good at all temperatures (cf. Figures 4 and 5).

4. Conclusions FIGURE 5. Comparison between experimental and calculated P  x(y) using NRTL (–), UNIQUAC (——) and Modified UNIFAC (Do) (—) models of the system {2,5dimethylfuran (1) + methyl isobutyl ketone (2)} at different temperatures , 313.15 K; d, 333.15 K; j, 353.15 K; N, 373.15 K.

The coefficients Gj were determined by regression through minimization of the sum of deviations in vapor pressures. Vapor phase deviations were accounted for in terms of the second molar virial coefficients, estimated by the method of Tsonopoulos [16,17]. The vapor phase compositions are calculated from:

yi ¼

xi ci pi ; p

The VLE data have been determined for the pure compounds (furfuryl alcohol, methyl isobutyl ketone) and two binary systems {2,5-dimethylfuran (1) + furfuryl alcohol (2)}, or {2,5-dimethylfuran (1) + methyl isobutyl ketone (2)} from T = (313 to 393) K. The experimental vapor pressures for the pure compounds are in good agreement with those reported in the literature. The binary systems have not been previously reported in the literature. Additionally, the experimental results generated for the two mixtures were successfully correlated with the NRTL and UNIQUAC models. Moreover experimental values were compared to those predicted by the Modified UNIFAC (Do) group contribution method.

ð5Þ

where p is the total equilibrium pressure, Pi is the vapor pressure of pure component i, xi is the mole fraction in the liquid phase of com-

Acknowledgement This work has been done in the framework of the international project PHC Tassili (Ref. 09 MDU 761).

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L. Negadi et al. / J. Chem. Thermodynamics 70 (2014) 233–238

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JCT 13-508