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In this work the isobaric vapor-liquid equilibrium (VLE) data for hexane + 1-decene and octane + 1-decene
systems have been measured at 101.33 kPa. The results were correlated using the Margules, Van Laar,
Wilson, and UNIQUAC equations for the liquid phase activity coefficients. The average deviations fall
within the same range for all models and agree well with experimental VLE data obtained in this work.
Also, the experimental results were compared with the predictions of the modified UNIFAC group contribution
method, which suggests that UNIFAC works well for unbranched alkane + 1-alkene systems.
[ ]
sampling valve; 10, condenser.
Bii(P - Pis) + (1 - yi)2Pij
i ) exp (3)
RT
wrapped by a thermal insulating jacket (not shown in Figure 1)
to prevent loss of heat from the system to the surroundings. where i is the activity coefficient of component i; xi and yi are
The equilibrium temperature was measured with a Lutron the equilibrium mole fractions of component i in the liquid and
model TM-917 digital thermometer with a 0.01 K resolution vapor phases; P is the total pressure; Pis is the saturated vapor
using a Pt-100 sensor positioned at the Cottrell pump shown in pressure of component i; R is the gas constant; T is the absolute
Figure 1. The pressure of the system was measured and temperature; and Bii and Bij are the pure-component and cross
controlled by the setup shown in Figure 2. In each experiment, second virial coefficients, respectively, which have been cal-
the pressure was fixed to 101.33 kPa and was read to ( 0.06 culated using the Pitzer and Curl equations with the corrections
kPa. For this purpose, at first the apparatus was evacuated with proposed by Tsonopoulos19 and mixing rules of Prausnitz.20 The
a vacuum pump, and then about 175 mL of the liquid mixture, binary interaction parameter, k12, was estimated by the relation-
which was initially placed under nitrogen atmosphere in a sealed ship proposed by Chueh and Prausnitz21 for nonpolar pairs being
bottle, was transferred to the still via a sample inlet valve. The 0.00884 for hexane + 1-decene and 0.00140 for octane +
liquid was heated to boiling, and the pressure of the system 1-decene systems, respectively.
was adjusted to 101.33 kPa by introducing nitrogen gas through The Antoine equation was used to calculate the vapor
the drying vessel (5) in Figure 2. The still was operated under pressures of the pure compounds, the parameters of which were
constant pressure until equilibrium was reached normally after obtained by fitting the Antoine equation to experimental vapor
about 30 min. Heating of the mixture was regulated to achieve pressure data14 and are summarized in Table 4.
a mean speed of 25 to 30 drops per min. Equilibrium conditions After obtaining the activity coefficients from the experimental
were assumed when constant temperature and pressure were VLE data (eqs 1 and 2), several models were used for
obtained for 30 min. Samples of 0.5 mL were taken simulta- correlation. Equations based on classic models (Margules22 and
neously from the liquid and condensed vapor, and their Van Laar23) and two models based on the local composition
compositions were analyzed with a calibrated Bellingham & concept (Wilson24 and UNIQUAC25) were applied. To obtain
400 Journal of Chemical & Engineering Data, Vol. 53, No. 2, 2008
Figure 2. System for the determination of vaporliquid equilibria: 1, temperature read-out device; 2, modified Scott-ebulliometer; 3, mercury manometer;
4, 5 L ballast bulb for pressure control; 5, drying vessel (CaCl2); 6, trap; 7, vacuum pump.
Table 7. Average Absolute Deviations between Experimental (12) Castells, C. B.; Carr, P. W.; Eikens, D. I.; Bush, D.; Eckert, C. A.
Equilibrium y and T Data and Data Obtained by Using the Comparative study of semitheoretical models for predicting infinite
UNIFAC Method dilution activity coefficients of alkanes in organic solvents. Ind. Eng.
Chem. Res. 1999, 38, 41044109.
mixture y1 T/K (13) Strukul, G.; Michelin, R. O. Catalytic epoxidation of 1-octene with
hexane (1) + 1-decene (2) 0.0034 0.525 diluted hydrogen peroxide. On the basic role of hydroxo complexes
octane (1) + 1-decene (2) 0.0032 0.049 of platinum(II) and related species. J. Am. Chem. Soc. 1985, 107,
75637569.
(14) CRC Handbook of Chemistry and Physics, 84th ed.; Lide, D. R., Ed.;
CRC Press: Boca Raton, FL, 20032004.
confirm the VLE data values generated by the predictive (15) Dean, J. A. Langes Handbook of Chemistry, 15th ed.; McGraw-Hill:
UNIFAC group contribution method. This suggests that for New York, 1999.
engineering purposes the UNIFAC method may be used for any (16) Yaws, C. L. Chemical Properties Handbook; McGraw-Hill: New York,
1999.
other unbranched alkane + alkene system in the C5 to C11 (17) Arce, A.; Blanco, A.; Soto, A.; Tojo, J. Isobaric vapor-liquid equilibria
range when experimental data do not exist. of methanol + 1-octanol and ethanol + 1-octanol mixtures. J. Chem.
Eng. Data 1995, 40, 10111014.
(18) Spencer, C. F.; Danner, R. P. Improved equation for prediction of
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(10) Kudryavtseva, L. S.; Toome, M.; Osta, E. EestiNSV Tead. Akad. Toim, Received for review August 5, 2007. Accepted December 16, 2007. We
Keem., Geol. 1981, 30, 147. In NIST/TRC Floppy Book on Vapor- are thankful to the research council of the Research Institute of
Liquid Equilibrium, Binary and Ternary Data, Version 2004. Petroleum Industry and also to the Research and Development of the
(11) Mihkelson, V.; Kirss, H.; Kudryavtseva, L. S.; Eisen, O. Vapor-liquid National Iranian Oil Company for their support of this work.
equilibrium T-x measurements by a new semi-micro method. Fluid
Phase Equilib. 1977, 1, 201209. JE700445Y