Isothermal phase (vapour + liquid) equilibrium data for binary mixtures of propene (R1270) with either 1,1,2,3,3,3-hexafluoro-1-propene (R1216) or 2,2,3-trifluoro-3-(trifluoromethyl)oxirane in the temperature range of (279 to 318) K

doi:10.1016/j.jct.2015.06.017

The Journal of Chemical Thermodynamics

Volume 90, November 2015, Pages 100-105

https://doi.org/10.1016/j.jct.2015.06.017 Get rights and content

Highlights

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Phase equilibrium data for propene and hexafluoropropylene.
•
Phase equilibrium data for propene and hexafluoropropylene oxide.
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Systems exhibit pressure-maximum azeotropes.
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Data well correlated by Peng–Robinson equation of state with the Wong–Sandler mixing rule.

Abstract

Isothermal (vapour + liquid) equilibrium data (P–x–y) are presented for the 1-propene 1,1,2,3,3,3-hexafluoro-1-propene and the 1-propene + 2,2,3-trifluoro-3-(trifluoromethyl)oxirane binary systems. Both binary systems were studied at five temperatures, ranging from (279.36 to 318.09) K, at pressures up to 2 MPa. The experimental (vapour + liquid) equilibrium data were measured using an apparatus based on the “(static + analytic)” method incorporating a single movable Rapid On-Line Sampler-Injector to sample the liquid and vapour phases at equilibrium. The expanded uncertainties are approximated on average as T = 0.07 K, 0.008 MPa, and 0.007 and 0.009 for the temperature, pressure, and the liquid and vapour mole fractions, respectively. A homogenous maximum-pressure azeotrope was observed for both binary systems at all temperatures studied. The experimental data were correlated with the Peng–Robinson equation of state using the Mathias–Copeman alpha function, paired with the Wong–Sandler mixing rule and the Non-Random Two Liquid activity coefficient model. The model provided satisfactory representation of the phase equilibrium data measured.

Graphical abstract

Introduction

This study is part of an on-going research programme investigating the thermodynamic properties of fluorocarbons and their mixtures [1], [2], [3], [4], [5], [6], and more specifically isothermal phase behaviour for binary mixtures involving either 1,1,2,3,3,3-hexafluoro-1-propene or 2,2,3-trifluoro-3-(trifluoromethyl)oxirane [6], [7], [8], [9], [10], [11], [12]. (Vapour + liquid) equilibrium (VLE) data play an integral part in the design process of numerous unit operations and chemical processes. Furthermore, VLE data is a core necessity for the development and validation of correlative and predictive thermodynamic models. Accordingly, accurate VLE data are required for the calculation of interaction energies between functional groups for group contribution methods such as PSRK [13].

VLE data were measured for the binary systems of propene (R1270) + 1,1,2,3,3,3-hexafluoro-1-propene (R1216), and R1270 + trifluoro-3-(trifluoromethyl)oxirane. Trifluoro-3-(trifluoromethyl)oxirane is more commonly known as hexafluoropropylene oxide (HFPO). To the best of our knowledge no VLE data have been published for the R1270 + HFPO binary system, and thus, all data presented herein for this system are new data. Concerning the R1270 + R1216 binary system, isothermal VLE data have been measured by Coquelet et al. [6] in the temperature range from (263.17 to 353.14) K. The data corresponding to this work were measured within the same temperature range, but at different isothermal conditions. Consequently, they may be considered as useful complementary data. These two binary systems exhibit homogenous pressure-maximum (positive) azeotropes within the investigated temperature range. The new experimental data were correlated with the Peng–Robinson (PR) [14] equation of state (EoS) integrating the Mathias–Copeman (MC) alpha function [15], the Wong–Sandler (WS) mixing rule [16] and the Non-Random Two Liquid (NRTL) activity coefficient model [17].

Section snippets

Materials

Propene was supplied by Air Products (South Africa) with a certified purity greater than 0.9995 in volume fraction. 1,1,2,3,3,3-Hexafluoro-1-propene and 2,2,3-trifluoro-3-(trifluoromethyl)oxirane were supplied by Pelchem (South Africa) with a certified purity greater than 0.999 in volume fraction. Apart from degassing via periodic vapour withdrawal, no further purification was undertaken. Gas chromatographic (GC) analysis is a classical method to validate the purities of each component.

Results and discussion

Experimental vapour pressure data for R1270 are reported in table 3. The P–T data were modelled using the PR equation of state with the MC alpha function. The deviations of the data correlated by the model from experimental data are listed in table 3. The model accurately represents the vapour pressure data for R1270. The experimental vapour pressure data for R1270 were also compared to reference values from REFPROP [25], the resulting average absolute deviation for pressure is 0.33%.

P–x–y data

Conclusion

P-x-y data are reported for binary mixtures of propene with either 1,1,2,3,3,3-hexafluoro-1-propene or 2,2,3-trifluoro-3-(trifluoromethyl)oxirane at temperatures ranging from (279.36 to 318.09) K. The two binary systems exhibit a pressure-maximum azeotrope at all measured temperatures. The data are well correlated using a single set of binary interaction parameters across the entire temperature range for each system using the Peng–Robinson equation of state including the Mathias–Copeman alpha

Acknowledgements

This work is based upon research supported by the National Research Foundation of South Africa under the South African Research Chair Initiative of the Department of Science and Technology.

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Compared to pure refrigerants, mixed refrigerants can effectively fulfill the demands of high efficiency, safety, and environmental preservation. An efficient mixture can be created by combining environmentally safe and non-combustible refrigerants with low global warming potential (GWP) and high latent heat hydrofluorocarbons (HFCs) in precise ratios. For this investigation, an experimental apparatus was built to obtain vapor–liquid equilibrium (VLE) data for the R152a + R1216 mixture within temperatures of 283.15 to 313.15 K. To depict the VLE characteristics of the binary systems, the Peng-Robinson (PR) equation of state (EoS) was utilized with the van der Waals (vdW) mixing rule. And to compare, the Huron and Vidal first-order (HV) and the Wong-Sandler (WS) mixing rules were utilized alongside the PR EoS and the non-random two-liquid (NRTL) activity coefficient model to correlate the acquired data. The findings indicated that the models showed strong concurrence with the empirical data. The binary mixture displays a near-azeotropic phenomenon when the mole fraction of R152a is below 0.65. The azeotropic point is fall within the experimental temperature range when the R152a liquid-phase has a mole fraction between 0.3069 and 0.4104.
High-pressure fluid-phase equilibria: Experimental methods, developments and systems investigated (2013–2016)
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With this article we extend our review series on high-pressure (above 1 MPa) phase equilibrium data to articles published between 2013 and 2016, including a compilation of systems investigated, recent developments, and trends. We considered phase equilibria of vapor, liquid, and solid phases, hydrates, critical points, solubility of high-boiling substances in supercritical fluids, solubility of gases in liquids, and solubility (sorption) of volatile components in ionic liquids and in polymers. In total, we found 1400 relevant articles in the four-year period 2013–2016 which means a 40 % increase as compared to the previous review period 2009–2012. This can be explained by a more elaborated search strategy, new publication strategies of the authors, and by the ongoing scientific interest in high-pressure phase equilibria. We summarize scientific areas that drive the measurement of high-pressure phase equilibria, and we give examples of review articles, which focus on a specific topic related to experimental high-pressure phase equilibrium data.
Apart from 14 systematically searched journals, we observed a tremendous increase in the number of articles found in other journals, rising from 59 articles (2009–2012) to 473 articles (2013–2016). Until the late 1990s, the average number of authors per article was approximately 3. From then on, it has been increasing almost linearly and has reached a value of 4.7 in 2016. More than one third of the articles contain data on only one system. While the average number of systems per article is close to 3, the median value is 2.
For more than 4000 systems, the reference, the temperature and pressure range of the data, and the experimental method used for the measurements is given in 41 tables. Information on hydrate systems and systems containing ionic liquids are given in 6 additional tables. 47.1 % of all systems of the review period 2013–2016 contain CO₂ as one of the components. Other frequently measured components are water (32 %), methane (12.3 %), nitrogen (5.1 %), propane (3.7 %), ethane (3 %), hydrogen (2.7 %), and ethanol (2.2 %). In the period 2013–2016, 18 % of the data sets involve hydrate equilibria, 15.4 % of the systems include an ionic liquid, and 7.7 % contain a refrigerant. In the period from 1988 to 2016, we observed a clear shift in the investigated systems from chlorofluorocarbon to hydrofluorocarbon and then to hydrofluoroolefin refrigerants.
The number of investigations at very high temperatures and pressures has increased, since a higher number of data sets from the Earth and planetary sciences have been found and included in the period of this review. The average internal volume of all cells used for measurements in the review period is 141 mL. Many different methods for the measurements of high-pressure phase equilibrium data exist. We discuss the main advantages and challenges of the methods and give examples of their use in the period 2013–2016. The percentage of the use of synthetic methods constantly rose from 29 % in the first period (1988–1993) to 62 % in the fourth period (2005–2008). Since then, it has stayed almost constant. Analytical–isobaric–isothermal (flow) methods have been used less and less, from 22 % (1988–1993) to 5 % (2013–2016). Synthetic-nonvisual methods are used more and more often, rising from 3 % (1988–1993) to 23 % (2013–2016).
Measurement of vapor-liquid equilibrium for the binary system propene (R1270) + trans-1,3,3,3‑tetrafluoropropene (R1234ze(E)) at temperatures from 288.18 K to 318.18 K
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The search for alternative refrigerants that are environmentally friendly and highly efficient has become one of the most urgent and important issues facing the refrigeration industry. R1270 has excellent thermodynamic properties, but its high flammability limits its range of applications. R1234ze(E) is an environmentally friendly refrigerant with negligible flammability though it has the drawback of poor heat transfer performance. R1270 can be blended with R1234ze(E) as a new mixture refrigerant. vapor–liquid equilibrium (VLE) is the basic physical property of mixtures. The vapor–liquid equilibrium data have been measured for the binary system R1270/ R1234ze(E) based on the liquid-phase cycling method at four temperatures (288.15 K, 298.15 K, 308.15 K, 318.15 K). All the experimental data were regressed by the Peng-Robinson (PR) equation of state (EoS) with the Huron–Vidal (HV) mixing rule involving the non-random two-liquid (NTRL) activity coefficient model, and the PR EoS relating to the van der Waals (vdWs) mixing rule. The results show that the predicted values by the two models are in good agreement with the experimental data, and the prediction accuracy of the PR + HV + NTRL model was higher than that of the PR + vdWs model. In addition, azeotropic behaviors of the binary mixture have been found in the measured temperature range.
Modeling binary vapor–liquid equilibrium data containing perfluorocarbons using the Peng–Robinson and the PC-SAFT equations of state
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Citation Excerpt :
Therefore, it is necessary to know fluid-phase behavior of such mixtures (Qian et al., 2017). In the literature, several different thermodynamic methods for modeling the experimental VLE data of perfluorocarbon-containing binary systems using cubic equations of state were proposed such as the PR EoS, the PR EoS with the Wong–Sandler (WS) mixing rule, the SRK EoS with the Wong–Sandler (WS) mixing rule, the PR EoS with the Huron–Vidal first-order (MHV1) mixing rule (Bengesai et al., 2016; Coquelet et al., 2010a; El Ahmar et al., 2011; Nelson et al., 2015, 2016a, 2016b; Subramoney et al., 2010, 2012, 2013a, 2013b, 2013c, 2015a, 2015b, 2015c; Tebbal et al., 2016; Tshibangu et al., 2013; Valtz et al., 2011) and the E-PPR78 model (Qian et al., 2017). Also, the Mathias–Copeman alpha function was used in the PR EoS and the non-random two liquid (NRTL) excess Gibbs energy model was proposed for the WS mixing rule.
In this communication, thermodynamic modeling of twenty four binary systems containing perfluorocarbon compounds is studied using the Peng–Robinson and the PC-SAFT equations of state. Interaction parameters of binary systems were estimated through fitting to experimental equilibrium pressures and vapor phase compositions. Very good results were obtained through using temperature-independent interaction parameter for both equations of state. According to the results, percent deviations in pressure were varying between 0.5 and 7.7 for the PR EoS and 0.2 and 6.5 for the PC-SAFT EoS. Also, percent deviations in vapor phase composition were varying between 0.1 and 6.6 for the PR EoS and 0.1 and 7.4 for the PC-SAFT EoS. Furthermore, when binary system has critical point, phase equilibrium calculations using the PR EoS do not converge through common methods. For solving this problem, a solution is suggested that was absolutely effective on all the studied systems.
Phase equilibrium and critical point data for ethylene and chlorodifluoromethane binary mixtures using a new “static-analytic” apparatus
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Citation Excerpt :
Firstly, a low-volume sapphire cell (capacity of approximately 17 cm3) has been utilized for measurement of phase equilibrium data involving high-value and hazardous components [10–12]. Secondly, an equilibrium cell of moderate volume (60 cm3), limited to pressures of 200 bar, originating from the work of Muhlbauer and Raal [13] has also been extensively used for phase equilibrium measurement [14–18]. In this work, a new apparatus following the “static-analytic” method utilizing a sapphire cell was designed and tested.
An apparatus based on the “static-analytic” method was designed and commissioned. The apparatus was tested by measuring vapour-liquid equilibrium data for the binary system of carbon dioxide + chlorodifluoromethane at 273.15 K. There is excellent agreement between the experimental data and previous measurements reported in the literature. New experimental vapour-liquid equilibrium data were also measured for the binary systems of ethylene + chlorodifluoromethane at five temperatures, viz. (273.15, 293.15, 313.15, 333.15, and 353.15) K. At the same temperatures (excluding 273.15 K) the critical points of the binary mixtures were also experimentally determined. The experimental data for this binary system were accurately correlated using the Peng–Robinson Equation of State utilizing the Wong–Sandler mixing rule coupled with the Non-Random Two-Liquid (NRTL) activity coefficient model.
High-Pressure Fluid-Phase Equilibria: Experimental Methods, Developments and Systems Investigated (2013–2016)
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Isothermal phase (vapour + liquid) equilibrium data for binary mixtures of propene (R1270) with either 1,1,2,3,3,3-hexafluoro-1-propene (R1216) or 2,2,3-trifluoro-3-(trifluoromethyl)oxirane in the temperature range of (279 to 318) K

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Results and discussion

Conclusion

Acknowledgements

J. Chem. Thermodyn.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Eng. Data

Ind. Eng. Chem. Res.

J. Chem. Eng. Data

Fluid Phase Equilib.

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data