Article pubs.acs.org/jced
The Critical Temperatures of a Number of (i) (Chloroalkane (C3−C4) + Hydrocarbon (C6−C7)) Binary Mixtures and (ii) (Aromatic Halocarbon (Chlorobenzene, Fluorobenzene, 1,2-Dichlorobenzene, or 1,3Dichlorobenzene) + Alkane (C8)) Binary Mixtures Colin L. Young,† Cam A. Tran,† and David W. Morton*,‡ †
Department of Chemistry, University of Melbourne, Parkville, Victoria 3052, Australia School of Pharmacy and Applied Science, La Trobe Institute for Molecular Sciences, La Trobe University, Edwards Rd, Bendigo, 3550, Australia
‡
ABSTRACT: In the last 30 years, little experimental work has been reported on the critical properties of (halogenated hydrocarbon + hydrocarbon) mixtures. Furthermore, the overall amount of reported critical property data for these types of mixtures is quite small. This work aims to extended the existing data set and presents data on the critical temperatures of (i) 14 different chloroalkane (C3−C4) + hydrocarbon mixtures (C6−C7) as a function of mole fraction and (ii) 10 different aromatic halocarbons (chlorobenzene, fluorobenzene, 1,2-dichlorbenzene, or 1,3-dichlorobenzene) + alkanes (C8) as a function of mole fraction. All of the (gas + liquid) critical lines were continuous. Therefore, all mixtures displayed either Type I or Type II behavior. n-alkane or alkane isomer).5 In 1991, Christou and co-workers reported critical temperature data for chlorobenzene (component 1) and C6−C10 alkane (component 2) mixtures.6
1. INTRODUCTION To be able to predict accurately the thermodynamic behavior of hydrocarbon mixtures is extremely important for many industrial processes in the chemical industry. In developing reliable predictive equations of state, and their associated mixing equations, it is important that there is a significant amount of experimentally determined data available to assist in both the development and testing of these predictive equations. However, there is little critical property data available for mixtures involving (halogenated alkanes/benzenes + alkanes) with most of the reported work over 30 years old. In 1975, Hicks and Young1 published a comprehensive review on previously reported experimental critical property data for a large number of binary mixtures. These mixtures consisted mainly of organic compounds but also included mixtures containing noble gases, hydrogen, nitrogen, oxygen, and carbon dioxide. There were also a number of mixtures reported that contained halogenated hydrocarbons. These were (perfluoroalkane (C1−C7) + alkane (C3−C9)) mixtures, (hexafluorobenzene + alkane (C5−C12)) mixtures, and a number of fluoro- and chloroalkane (C1−C2) mixtures. During 1985− 1991, Garcia-Sanchez and Trejo reported critical temperature and pressure data for a number of (chloroalkane + n-alkane) binary mixtures. These mixtures consisted of dichloromethane, 1,1- or 1,2-dichloroethane (component 1) with a C3−C9 nalkane (component 2).2−4 In 1989, Christou and co-workers also reported critical temperature data for a number of similar types of mixtures. They consisted of tetrachloromethane, 1,2dichloroethane, cis-1,2-dichloroethene, or trans-1,2-dichloroethene (component 1) with a C5−C16 alkane (component 2: an © 2017 American Chemical Society
2. EXPERIMENTAL SECTION Samples were placed into quartz tubes (1 mm inside diameter and 3 mm outside diameter), approximately 100 mm in length, previously sealed at one end. Before the other end of each tube was sealed, samples were degassed using successive freeze− thaw−pump cycles using liquid nitrogen to freeze the samples. Each mixture occupied one-third of the tube volume at room temperature. This sample volume ratio was employed to ensure that the liquid−vapor phase transition occurred at the critical point. The apparatus used to measure the critical temperatures is essentially the same as used by our group in previous work.7 It consists of a temperature-controlled aluminum furnace (30 cm × 16 cm) that has a hole drilled through its center, through which sample tubes are inserted into the furnace for critical temperature measurements. About half way along the furnace there is a viewing port for observing phase changes in the sample. The temperature of the furnace is measured using five chromel/alumel thermocouples arranged around the sample tube. The critical temperature of each sample was measured by heating the sample slightly above its critical point, then cooling Special Issue: Memorial Issue in Honor of Ken Marsh Received: February 19, 2017 Accepted: June 12, 2017 Published: June 23, 2017 2953
DOI: 10.1021/acs.jced.7b00191 J. Chem. Eng. Data 2017, 62, 2953−2958
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Dichloropropane + benzene) displayed an overall positive deviation over the whole mole fraction range. In this instance, the overall deviation was not very large with a maximum deviation of approximately +2 K observed at x1 ≈ 0.4. Figures 1−3 show that for each mixture there is an uninterrupted (gas + liquid) critical curve, which means that they display either Type I or Type II phase behavior.12 A closer examination of Figures 1−3 reveals that for (chlorocarbon + C6 hydrocarbon) mixtures Tc deviation from linearity generally becomes less negative when the hydrocarbon component changes from aliphatic alkane (hexane) to aliphatic ring (cyclohexane) to aromatic ring (benzene). Similar behavior has been previously observed by Banos and co-workers who measured excess molar enthalpy data for a number of (1,2dichloropropane + hydrocarbon) mixtures.13 For each group of (chlorocarbon + hydrocarbon) mixtures, maximum deviation from linearity was observed for mixtures (1,2-dichloropropane + hexane), (1,3-dichloropropane + heptane), and (1chlorobutane + hexane) mixtures, over a 0.4−0.5 mole fraction range. Note that for all three groups of mixtures (in Figures 1−3), the deviation from linearity versus mole fraction curve for mixtures containing branched alkanes (2,2-dimethylbutane, 2,2,4-trimethylpentane) generally lies between the curves for mixtures containing cyclohexane (larger deviation) and benzene (smaller deviation). Note that this does not apply for (1,3-dichloropropane + 2,2-dimethylbutane) mixtures rich in 1,3-dichorobutane (x1 > ∼0.6). In this region, the deviation from linearity becomes more positive than for the (1,3dichloropropane + benzene) mixture. Where there are large differences in the critical temperatures between mixture components, for instance, between (1,3-dichloropropane + cyclohexane) (|ΔTc| = 107.2 K) and (1,3-dichloropropane + 2,2-dimethylbutane) (|ΔTc| = 125.2 K), there is a tendency for a sigmoidal curve to form (Figure 2). For all the other mixtures reported in Figures 1−3, |ΔTc| is 0.999 0.995 >0.99 0.995 0.999 >0.99 >0.99 0.99 0.99 ≥0.990 ≥0.997 0.995 0.995 >0.99 0.998
3. RESULTS AND DISCUSSION Tables 2 and 3 give the critical temperature and mole fraction data for the mixtures studied. Almost all of the pure component critical temperatures measured in this work are in agreement (within experimental error) with currently accepted IUPAC critical temperature compilation data.10,11 However, there was significant difference between Tc for 1,2-dichlorobenzene reported here (698.8 K) and the recommended value of Marsh et al. (729 K).11 This recommended value is considerably higher value than our reported Tc. However, the recommended value reported by Marsh et al. is based on limited data, so further measurements are required to establish a more reliable “recommended” value for this compound. There was also significant difference between T c for fluorobenzene reported here (557.3 K) and the recommended value reported by Marsh et al. (560.1 K).11 3.1. Chloroalkane (C3−C4) + hydrocarbon (C6−C7) binary mixtures. The (gas + liquid) critical temperatures for the (chloroalkane (C3−C4) (component 1) + hydrocarbon (C6−C7) (component 2)) mixtures, as a function of mole fraction, are given in Table 2. Figures 1−3 plot the deviation from linearity versus chloroalkane mole fraction for the chloroalkane + hydrocarbon mixtures. The deviation of the critical temperature from linearity is deviation from linearity = Tc,m − (x1Tc,1 + x 2Tc,2)
(1)
where Tc,m is the measured critical temperature of the mixture, Tc,1 and Tc,2 are the critical temperature of the pure components and x1 and x2 are their mole fractions. The deviation from linearity critical curves for 1,2- and 1,3dichloropropane and 1-chlorobutane + hydrocarbon mixtures generally display negative deviations from linearity. However, there were a few notable exceptions. (1,3-Dichloropropane + 2,2-dimethylbutane) displayed a positive deviation from linearity for mixtures rich in 1,3-dichloropropane (when the mole fraction is slightly greater than 0.5) and a negative deviation for mixtures rich in 2,2-dimethylbutane. (1,32954
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Table 2. (Gas + Liquid) Critical Temperatures for the (Chloroalkane (C3−C4) (Component 1) + Hydrocarbon (C6−C7) (Component 2)) Mixtures as a Function of Mole Fractiona x1
Tc/K
(1,2-Dichloropropane + Benzene) 0.000 0.071 0.247 0.348 0.356 0.420 0.6646 0.702 1.000
562.2 563.4 566.1 567.4 567.5 568.5 572.4 572.9 578.515
(1,2-Dichloropropane + 2,2Dimethylbutane) 0.000 489.4 0.172 500.4 0.308 511.2 0.331 512.5 0.580 537.2 0.645 543.7 0.809 560.1 0.847 563.4 1.000 578.515 (1,2-Dichloropropane + Heptane) 0.000 540.6 0.129 541.9 0.195 542.8 0.290 544.4 0.347 546.0 0.570 553.2 0.669 557.7 0.737 561.2 0.816 565.7 1.000 578.515 (1,3-Dichloropropane + Cyclohexane) 0.000 0.099 0.180 0.473 0.617 0.821
553.616 556.5 559.4 576.5 586.4 602.4
x1
Tc/K
x1
(1,2-Dichloropropane + Cyclohexane) 0.000 553.616 0.135 554.5 0.140 554.3 0.177 554.8 0.341 556.2 0.442 558.6 0.562 561.2 0.655 564.4 0.730 567.2 0.853 571.8 1.000 578.515 (1,2-Dichloropropane + Hexane)
Tc/K
(1,3-Dichloropropane + Cyclohexane) 0.843 1.000 (1,3-Dichloropropane 0.000 0.187 0.259 0.295 0.361 0.577 0.687 0.931 1.000
0.000 507.4 0.205 515.0 0.252 515.3 0.427 526.4 0.716 550.1 0.739 551.7 0.843 560.8 0.890 565.9 1.000 578.515 (1,3-Dichloropropane + Benzene) 0.000 562.2 0.186 573.3 0.266 577.8 0.330 581.1 0.394 584.6 0.460 588.0 0.654 597.8 0.683 599.3 0.781 603.8 1.000 614.615 (1,3-Dichloropropane + 2,2Dimethylbutane) 0.000 489.4 0.120 501.6 0.156 505.4 0.219 513.3 0.292 520.5 0.569 562.0
604.0 614.615 + Hexane) 507.4 521.5 528.5 532.1 539.0 564.5 577.5 606.1 614.615
(1-Chlorobutane + Benzene) 0.000 562.2 0.191 557.4 0.260 555.6 0.341 553.4 0.532 548.9 0.729 544.3 0.873 541.3 1.000 539.215
(1-Chlorobutane + 2,2,4Trimethylpentane) 0.000 544.0 0.233 541.9 0.294 541.2 0.428 539.9 0.458 539.7 0.602 538.9 0.805 538.3 0.849 538.2 1.000 539.215
x1
Tc/K
(1,3-Dichloropropane + 2,2Dimethylbutane) 0.671 576.3 0.820 595.1 1.000 614.615 (1,3-Dichloropropane + Heptane) 0.000 540.6 0.180 546.5 0.183 546.7 0.295 552.1 0.421 559.9 0.543 567.2 0.753 586.9 0.770 587.9 0.850 595.8 1.000 614.615 (1-Chlorobutane + Cyclohexane) 0.000 553.616 0.082 552.0 0.092 551.8 0.160 549.7 0.211 548.8 0.435 544.5 0.535 543.1 0.644 542.0 0.708 541.4 0.811 540.2 1.000 539.215 (1-Chlorobutane + Hexane) 0.000 0.088 0.110 0.223 0.334 0.372 0.613 0.807 1.000
507.4 509.2 509.5 512.1 514.8 516.2 524.5 530.8 539.215
a Standard uncertainties are u(T) = 1.4 K and u(mole fraction) = 0.005.
dichlorobenzene (Figure 5) and octane + dichlorobenzene (Figure 6), the deviation from linearity is significantly different. For (cyclooctane + 1,2-dichlorobenzene) the maximum deviation observed is ≈ −7.5 K while for (cyclooctane + 1,3dichlorobenzene) the maximum deviation observed is ≈ −5 K. As previously mentioned, for (2,2,4-trimethylpentane + 1,2dichlorobenzene) the maximum deviation observed is ≈ −9.5 K while for (2,2,4-trimethylpentane + 1,3-dichlorobenzene) the maximum deviation observed is ≈ −10 K. There is even a greater difference in deviation from linearity observed for (octane + 1,2-dichlorobenzene) and (octane + 1,3-dichlorobenzene) mixtures (Figure 6). For (octane + 1,2-dichlorobenzene) the maximum deviation from linearity observed is ≈ −12 K while for (octane + 1,3-dichlorobenzene) the maximum deviation observed is ≈ −20 K. Note that the maximum deviation from linearity observed for (octane + 1,3-dichlor-
largest sigmoidal shaped curve. For this mixture, there is a maximum (negative) deviation at x1 ≈ 0.3, an inflection point at x1 ≈ 0.55, and a maximum (positive) deviation at x1 ≈ 0.7. That is, negative deviations occur for mixtures rich in fluorobenzene whereas positive deviations occur for mixtures rich in cyclooctane. When comparing deviation from linearity of mixtures of halocarbons with 2,2,4-trimethylpentane, least deviation is observed for fluorobenzene (maximum deviation ≈ −6 K), followed by chlorobenzene (maximum deviation ≈ −8.5 K), 1,2-dichlorobenzene (maximum deviation ≈ −9.5 K), and 1,3-dichlorobenzene (maximum deviation ≈ −10 K). Note that although the maximum deviation for chlorobenzene is similar to 1,2-dichlorobenzene, the overall deviation over the whole mole fraction range for 1,2-dichlorobenzene is greater. When comparing the (2,2,4-trimethylpentane + dichlorobenzene) mixtures (Figure 4) with those containing cyclooctane + 2955
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Table 3. (Gas + Liquid) Critical Temperatures for the (Alkane (C8) (Component 1) + Aromatic Halocarbon (Component 2)) Binary Mixtures as a Function of Mole Fractiona x1
Tc/K
(2,2,4-Trimethylpentane + Fluorobenzene) 0.000 557.3 0.091 553.6 0.152 552.4 0.307 547.3 0.430 545.9 0.636 544.1 0.695 543.7 0.819 542.9 1.000 544.0 (2,2,4-Trimethylpentane + 1,2Dichlorobenzene) 0.000 698.8 0.059 687.1 0.332 638.9 0.487 614.4 0.618 594.1 0.773 571.1 0.863 558.6 1.000 544.0 (Cyclooctane + Fluorobenzene) 0.000 557.3 0.081 563.6 0.209 574.0 0.300 581.5 0.467 597.7 0.668 619.1 0.879 637.5 1.000 647.516 (Cyclooctane + 1,2Dichlorobenzene) 0.000 698.8 0.098 694.2 0.158 687.9 0.335 674.5 0.576 663.1 0.629 661.4 0.844 653.1 1.000 647.516 (Octane + 1,2-Dichlorobenzene) 0.000 698.8 0.079 682.5 0.146 671.4 0.294 644.7 0.322 641.6 0.490 614.3 0.670 596.5 0.888 576.1 1.000 568.8
x1
Tc/K
(2,2,4-Trimethylpentane + Chlorobenzene) 0.000 633.415 0.057 627.7 0.136 618.8 0.425 586.7 0.561 575.5 0.738 561.7 0.794 556.4 1.000 544.0 (2,2,4-Trimethylpentane + 1,3Dichlorobenzene) 0.000 685.315 0.091 667.1 0.112 665.2 0.226 645.2 0.429 614.7 0.653 583.6 0.837 560.4 0.854 558.2 1.000 544.0 (Cyclooctane + Chlorobenzene) 0.000 633.415 0.097 632.6 0.131 632.5 0.254 633.9 0.448 637.1 0.530 639.7 0.795 644.7 0.873 646.4 1.000 647.516 (Cyclooctane + 1,3Dichlorobenzene) 0.000 685.315 0.123 678.5 0.229 673.4 0.282 670.1 0.454 663.3 0.613 658.1 0.796 653.3 1.000 647.516 (Octane + 1,3-Dichlorobenzene) 0.000 685.315 0.256 649.9 0.308 643.7 0.432 625.2 0.649 598.1 0.808 583.1 0.909 577.2 1.000 568.8
Figure 1. Plot of the deviation from linearity of (1,2-dichloropropane + hydrocarbon) mixtures versus mole fraction of 1,2-dichloropropane.
Figure 2. Plot of the deviation from linearity of (1,3-dichloropropane + hydrocarbon) mixtures versus mole fraction of 1,3-dichloropropane.
a Standard uncertainties are u(T) = 1.4 K and u(mole fraction) = 0.005.
Figure 3. Plot of the deviation from linearity of (1-chlorobutane + hydrocarbon) mixtures versus mole fraction of 1-chlorobutane.
obenzene) is the largest of all the mixtures studied. This is about twice as large as observed for (octane + 1,2dichlorobenzene). 2956
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Figure 6. Plot of the deviation from linearity of (octane + halobenzene) mixtures versus mole fraction of octane.
Figure 4. Plot of the deviation from linearity of (2,2,4trimethylpentane + halobenzene) mixtures versus mole fraction of octane. *Chlorobenzene mixture data from Christou et al.6
is only then that we will be able to better understand the behavior and properties of these types of mixtures.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
David W. Morton: 0000-0003-3620-5449 Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Hicks, C. P.; Young, C. L. The gas-liquid critical properties of binary mixtures. Chem. Rev. 1975, 75, 119−175. (2) Garcia-Sanchez, F.; Trejo, A. Critical Loci for binary chloroalkane-n-alkane mixtures. I. 1,2-dichloroethane with C3-C9 nalkanes. Fluid Phase Equilib. 1985, 24, 269−277. (3) Garcia-Sanchez, F.; Trejo, A. Critical loci for binary chloroalkanen-alkane mixtures. II. Dichloromethane with C3-C9 n-alkanes. Fluid Phase Equilib. 1986, 28, 191−197. (4) Garcia-Sanchez, F.; Trejo, A. Critical loci for binary chloroalkanen-alkane mixtures. III. 1, 1-Dichloroethane with C3-C9 n-alkanes. Fluid Phase Equilib. 1991, 62, 87−95. (5) Christou, G.; Sadus, R. J.; Young, C. L.; Svejda, P. Gas-liquid critical properties of binary mixtures of n-alkanes and 2,2,4trimethylpentane with the weakly polar halocarbons 1,2-dichloroethane, cis-1,2-dichloroethene trans-1,2-dichloroethene and tetrachloromethane. Ind. Eng. Chem. Res. 1989, 28, 481−484. (6) Christou, G.; Young, C. L.; Svejda, P. Gas-liquid critical temperatures of binary mixtures of polar compounds + hydrocarbons or + other polar compounds. Ber. Bunsen Ges. Phys. Chem. 1991, 95, 510−514. (7) Morton, D. W.; Lui, M. P. W.; Young, C. L. The (gas + liquid) critical properties and phase behaviour of some binary alkanol (C2− C5) + alkane (C5−C12) mixtures. J. Chem. Thermodyn. 2003, 35, 1737−1749. (8) Young, C. L. Experimental Methods for Studying Phase Behaviour of Mixtures at High Temperatures and Pressures. In Chemical Thermodynamics; McGlashan, M. L., Ed.; The Chemical Society: London, 1978; Vol. 2. (9) Ambrose, D.; Young, C. L. Vapor-liquid critical properties of elements and compounds. 1. An introductory survey. J. Chem. Eng. Data 1995, 40, 345−357.
Figure 5. Plot of the deviation from linearity of (cyclooctane + halobenzene) mixtures versus mole fraction of cyclooctane.
4. CONCLUSION For most of the mixtures, there was an overall negative deviation from linearity over the mole fraction range. The exceptions to this behavior were (i) the (1,3-dichloropropane + benzene) mixture, where there was an overall positive deviation; and (ii) the (1,3-dichloropropane + 2,2-dimethylbutane), (cyclooctane + fluorobenzene), and (cyclooctane + chlorobenzene) mixtures, where there was a sigmoidal distribution consisting of regions of both positive and negative deviation. The mixture with the largest deviation from linearity (≈ −21 K) was (octane + 1,2-dichlorobenzene). Note that although the mixtures (octane + 1,2-dichlorobenzene) and (octane + 1,3-dichlorobenzene) are very similar in nature, their deviation from linearity versus mole fraction curves are very different (Figure 6), indicating that the small differences in the placement of the chlorine atoms on the benzene ring has a significant effect on the interaction between the mixture components. As the critical property data set for these types of hydrocarbon binary mixtures is quite small, there is a need for further work in order to expand and develop this data set. It 2957
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(10) Ambrose, D.; Tsonopoulos, C.; Nikitin, E. D.; Morton, D. W.; Marsh, K. N. Vapor-liquid critical properties of elements and compounds. 12. Review of recent data for hydrocarbons and nonhydrocarbons. J. Chem. Eng. Data 2015, 60, 3444−3482. (11) Marsh, K. N.; Abramson, A.; Ambrose, D.; Morton, D. W.; Nikitin, E.; Tsonopoulos, C.; Young, C. L. Vapor-liquid critical properties of elements and compounds. 10. Organic compounds containing halogens. J. Chem. Eng. Data 2007, 52, 1509−1538. (12) Scott, R. L.; van Konynenburg, P. Static properties of solutions. Van der Waals and related models for hydrocarbon mixtures. Discuss. Faraday Soc. 1970, 49, 87−97. (13) Banos, I.; Valero, J.; Perez, P.; Gracia, M.; Losa, C. G. Excess molar enthalpies of mixtures containing 1,2-dichloropropane. J. Chem. Thermodyn. 1989, 21, 709−714. (14) Banos, I.; Valero, J.; Perez, P.; Gracia, M.; Losa, C. G. Excess molar volumes of mixtures containing 1,2-dichloropropane or 1,3dichloropropane. J. Chem. Thermodyn. 1990, 22, 431−437. (15) Morton, D. W.; Lui, M. P. W.; Tran, C. A.; Young, C. L. The gas-liquid critical temperature of some chlorinated alkanes and halogenated aromatic hydrocarbons. J. Chem. Eng. Data 2000, 45, 437−439. (16) Morton, D. W.; Lui, M. P. W.; Tran, C. A.; Young, C. L. Gasliquid critical temperatures of some alkenes, amines, and cyclic hydrocarbons. J. Chem. Eng. Data 2004, 49, 283−285.
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