Fluid Phase Equilibria 235 (2005) 211214

Activity coefcients in binary mixtures formed by cyclohexanone with a variety of compounds at 94.7 kPa
T.E. Vittal Prasad a , K. Venugopalachary b , B.V. Sudhindra b , G. Veerendra b , A. Vallinatha Sarma b , D.H.L. Prasad a,
a Properties Group, Chemical Engineering Laboratory, Indian Institute of Chemical Technology, Hyderabad 500007, India b JNTU College of Engineering, Anantapur 515002, India

Received 18 May 2005; accepted 20 June 2005

Abstract Bubble temperatures at 94.7 kPa, over the entire composition range, are measured for the binary mixtures formed by cyclohexanone with acrylonitrile, carbontetrachloride, 2-cyanopyrazine, cyclohexane and 2-methylpyrazine. A Swietoslawski-type ebulliometer is used for the measurements. The liquid phase mole fractionbubble temperature data are found to be well represented the Wilson model. Activity coefcients calculated from the model are presented. 2005 Published by Elsevier B.V.
Keywords: Wilson model; Activity coefcients; Cyclohexanone; Acrylonitrile; Pyrazines; Cyclohexane; Carbontetrachloride

1. Introduction This investigation of the bubble temperatures of the binary mixtures of cyclohexanone with acrylonitrile, carbontetrachloride, 2-cyanopyrazine, chclohexane and 2-methylpyrazine is in continuation of our recent studies on the phase equilibria of the binary mixtures containing hydrocarbons and alcohols [13]. The measurements have been carried out at 94.7 kPa. Cyclohexane(1) + cyclohexane(2) system has been investigated at 323.25 and 348.15 K by Boublik and Lu [4] while Castells et al. [5] measured the innite dilution activity coefcient for the same system at 298.15 K. We could not locate any literature vapor liquid equilibrium data on the other systems chosen for the present work.

2. Experimental 2.1. Method A Swietoslawski-type ebulliometer, very similar to the one described by Hala et al. [6] is used for this study. Connection of the ebulliometer to a good vacuum system, through an in-line mercury manometer, facilitated the creation and the maintenance of the chosen pressure with in 0.1 kPa. The equilibrium temperatures are measured to an accuracy of 0.05 K, by means of a platinum resistance thermometer, carefully calibrated by point-to-point comparison with a standard platinum resistance thermometer (IPTS-68). The liquid mixtures were prepared gravimetrically making use of an electronic balance precise to 0.0001 g, They were stirred well before being placed in the ebulliometer. The heating rate is adjusted to yield the desired condensate drop rate of 30 drops/min, in accordance with the suggestion of Hala et al. [6]. The equilibrium temperature was measured after a steady drop rate and a constant temperature were maintained for at

Corresponding author. Tel.: +91 40 27193142; fax: +91 40 27193626. E-mail addresses: dasika@iict.ap.nic.in, dasika@iict.res.in (D.H.L. Prasad). 0378-3812/$ see front matter 2005 Published by Elsevier B.V. doi:10.1016/j.uid.2005.06.022

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Table 1 Comparison of the molar volume (V) and refractive-index (nD ) of the pure substances used in this study with literature data Substance T (K) V (cm3 mol1 ) This work Cyclohexanone Acrylonitrile Carbontetrachloride 2-Cyanopyrazine Chclohexane 2-Methylpyrazine 293.15 298.15 298.15 293.15 298.15 293.15 103.840 66.292 97.084 89.520 108.748 91.379 Literature [reference] 103.840 [5] 66.292 [5] 97.086 [5] 89.520 [6] 108.749 [5] 91.379 [6] nD This work 1.4510 1.3888 1.4574 1.5340 1.4235 1.5050 Literature [reference] 1.45097 [5] 1.38880 [5] 1.45739 [5] 1.53400 [6] 1.42354 [5] 1.50500 [6]

least 30 min. The constancy of the liquid phase composition during each experiment was ensured by injecting a sample of the liquid phase to a gas chromatogram at the beginning and the end of each phase equilibrium experiment. Each measurement is repeated several times, till at least two consecutive observations were within the stated limits of the experimental error of 0.05 K in temperature, 0.1 kPa in pressure and 0.0001 in the liquid phase mole fraction. 2.2. Materials The AR grade chemicals used in this study were further puried by drying followed by fractional distillation. The purity of the chemicals was veried by measuring their density and refractive index, which compare favorably with the literature data [7,8] as shown in Table 1.

3. Results and discussion The experimental liquid phase composition mole fraction (x1 ) versus temperature (T) data, summarized in Table 2, were tted to the Wilson equation [9] in the form ln 1 = ln(x1 + 12 x2 ) + x2 21 x2 + 21 x1 21 x2 + 21 x1 (2) 12 x1 + 12 x2 (1)

ln 2 = ln(x2 + 21 x1 ) + x1 12 x1 + 12 x2

Table 2 Bubble temperatures and activity coefcients for the selected mixtures at 94.7 kPa Acrylonitrile(1) + cyclohexanone(2) x1 0.0000 0.1002 0.2079 0.3003 0.3962 0.5002 0.6116 0.7002 0.7902 0.9002 1.0000 T (K) 426.35 410.55 397.25 388.05 379.95 372.45 365.55 360.75 356.45 351.95 348.55 1 0.8140 0.8277 0.8458 0.8638 0.8841 0.9079 0.9343 0.9550 0.9744 0.9930 1.0000 2 1.0000 0.9985 0.9929 0.9836 0.9684 0.9439 0.9056 0.8641 0.8098 0.7235 0.6239 Carbontetrachloride(1) + cyclohexanone(2) x1 0.0000 0.1002 0.2106 0.3002 0.4157 0.5002 0.6115 0.7001 0.9002 1.0000 T (K) 426.35 397.15 385.25 378.65 371.65 367.15 361.95 358.15 350.95 347.85 1 2.4315 1.6214 1.2745 1.1478 1.0663 1.0356 1.0143 1.0061 1.0003 1.0000 2 1.0000 1.0211 1.0656 1.1030 1.1460 1.1719 1.1984 1.2134 1.2297 1.2303 Cyclohexanone(1) + 2-cyanopyrazine(2) x1 0.0000 0.1662 0.2850 0.4436 0.6019 0.7514 0.9236 1.0000 T (K) 476.05 467.85 461.95 453.95 445.65 437.95 429.45 426.35 1 0.6656 0.7097 0.7456 0.8001 0.8620 0.9252 0.9889 1.0000 2 1.0000 0.9930 0.9766 0.9324 0.8499 0.7198 0.4863 0.3561

Cyclohexane(1) + cyclohexanone(2) 0.0000 0.1001 0.1934 0.3002 0.3900 0.5001 0.6092 0.7002 0.8060 0.9002 1.0000 426.35 397.65 384.95 376.85 371.65 366.95 363.15 360.35 357.25 354.55 351.85 2.0310 1.7790 1.5673 1.3820 1.2666 1.1635 1.0926 1.0517 1.0205 1.0052 1.0000 1.0000 1.0095 1.0351 1.0823 1.1361 1.2198 1.3229 1.4258 1.5670 1.7150 1.8982

2-Methylpyrazine(1) + cyclohexanone(2) 0.0000 0.1394 0.2882 0.4475 0.6135 0.7605 0.8881 1.0000 426.85 416.55 412.85 409.15 405.25 401.65 398.95 396.65 7.4334 1.3476 1.0582 1.0006 0.9932 0.9963 0.9991 1.0000 1.0000 1.0790 1.1428 1.1733 1.1754 1.1601 1.1384 1.1152

T.E.V. Prasad et al. / Fluid Phase Equilibria 235 (2005) 211214 Table 3 Antoine constants for the equation ln P (kPa) = A B/[T (K) + C] Substance Cyclohexanone Acrylonitrile Carbontetrachloride 2-Cyanopyrazine Cyclohexane 2-Methylpyrazine Table 4 Representation of the measurements by Wilson model System Acrylonitrile(1) + cyclohexanone(2) Carbontetrachloride(1) + cyclohexanone(2) Cyclohexanone(1) + 2-cyanopyrizine(2) Cyclohexane(1) + cyclohexanone(2) 2-Methylpyrazine(1) + cyclohexanone(2) (12 11 )/R (K) 235.72 706.33 430.97 302.73 1415.78 (12 22 )/R (K) 212.09 261.81 390.72 1.8371 382.98 A 14.7481 13.9089 13.8568 11.2459 13.7352 6.9322 B 3949.28 2782.21 2808.19 1970.03 2766.64 216.92 C

213

38.97 51.55 45.99 181.66 50.50 305.47

S.D. in T (K) 0.04 0.02 0.04 0.03 0.04

where 12 = 21 =
L V2 L V1

exp

12 11 RT

(3)

L V1 12 22 exp L RT V2

(4)

the van Laar and NRTL models yielded worse representation. The results of representation of the phase equilibrium data by the Wilson [7] equation, summarized in Table 4, indicate that the data and the representation are quite good and are likely to be useful for engineering design purposes. The values of the activity coefcients as a function of composition, calculated from the model are also given in Table 2. List of symbols Pcal calculated pressure (kPa) Pexpt experimental pressure (kPa) R universal gas constant T absolute temperature L V1 liquid molar volume of component 1 (kg m1 ) L V2 liquid molar volume of component 2 (kg m1 ) mole fraction of component 1 x1 x2 mole fraction of component 2 Greek letters 12 parameter dened by Eq. (3) 21 parameter dened by Eq. (4) objective function dened by Eq. (5) 1 activity coefcient of component 1 2 activity coefcient of component 2 energy of interaction between the molecular species 11 11 12 energy of interaction between the molecular species 12 22 energy of interaction between molecular species 22

L L V1 and V2 are the pure liquid molar volumes, and [(12 11 )/R] and [(12 22 )/R] are the Wilson parameters with giving the energies of interaction between the molecules denoted by the subscripts. The optimum Wilson parameters are obtained by minimizing the objective function dened as

Pcal 1 Pexpt

(5)

where Pcal and Pexpt are the calculated and experimental total pressures. The Nelder-Mead optimization technique described by Kuester and Mize [10] was used. Vapor pressures of the pure substances are calculated from the Antoine equation with the constants noted in Table 3, for ready reference. Prior to use, the Antoine equation with the constants noted in Table 3, has been tested for its applicability. It is examined whether the Antoine equation can predict the available literature experimental vapor pressure data to with in the claimed accuracy of the particular set of data or within an average absolute deviation of 0.5%. The equation was also used to calculate the vapor pressure of each pure liquid used in the present study at the boiling point observed in the present study and compared with the observed value of 94.7 kPa. In all cases the departures are within the experimental accuracy of the set of measurements or an average absolute deviation of 0.5%. Hence, the Antoine vapor pressure equation for the six liquids under study is used employing the constants given in Table 3. The molar volumes of the pure liquids measured in this study (recorded in Table 1) are used as the input to obtain the optimum Wilson parameters. Attempts to t the data to

References
[1] T.E. Vittal Prasad, G. Kumari Vallabhaneni, M. Krishna Sameera, V. Praveena Bose, D.H.L. Prasad, J. Chem. Eng. Data 43 (1998) 555557. [2] T.E. Vittal Prasad, K. Chandrika, M. Haritha, N.B. Geetha, D.H.L. Prasad, Fluid Phase Equilib. 149 (1998) 121125.

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T.E.V. Prasad et al. / Fluid Phase Equilibria 235 (2005) 211214 [7] J.A. Riddick, W.S. Bunger, T.K. Sakano, Organic Solvents: Physical Properties and Methods of Purication, vol. 2, fourth ed., Wiley/Interscience, New York, 1986. [8] G.K. Roberts, J.A. Medwin, CRC Handbook of Data on Organic Compounds, vol. I and II, CRC Press, Boca Raton, FL, 1985. [9] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127130. [10] R.T. Kuester, J.H. Mize, Optimization Techniques with Fortran, McGraw-Hill, New York, 1973.

[3] T.E. Vittal Prasad, P. Satyakishore, G.V. Ramserish, D.H.L. Prasad, J. Chem. Eng. Data 46 (2001) 12661268. [4] T. Boublik, B.C.Y. Lu, J. Chem. Eng. Data 22 (1977) 331 333. [5] C.B. Castells, D.I. Eikens, P.W. Carr, J. Chem. Eng. Data 45 (2000) 369375. [6] E. Hala, J. Pick, V. Fried, O. Villim, Vapor Liquid Equilibrium, Pergamon Press, Oxford, 1958.