Elsevier

Thermochimica Acta

Volume 679, September 2019, 178318
Thermochimica Acta

Measurement and correlation of vapor–liquid equilibrium data for binary systems composed of camphene, (+)-3-carene, (-)-β-caryophyllene, p-cymene, and α-pinene at 101.33 kPa

https://doi.org/10.1016/j.tca.2019.178318Get rights and content

Highlights

  • VLE of binary systems of camphene + (-)-β-caryophyllene/p-cymene/ α-pinene and α-pinene + (+)3-carene/(-)-β-caryophyllene.

  • VLE data were measured by a modified Ellis equilibrium still for high boiling-points and high viscosities.

  • The VLE experimental data were correlated by the NRTL, Wilson, and UNIQUAC models.

  • Comparisons between the experimental data and calculated values were performed.

Abstract

Isobaric vapor-liquid equilibrium (VLE) data have been measured in a modified Ellis still for the following binary systems: camphene + p-cymene, camphene + α-pinene, (+)-3-carene + α-pinene, α-pinene + (-)-β-caryophyllene, and camphene + (-)-β-caryophyllene, at 101.33 kPa. The pressure was controlled by a U-shape mercury manometer and a WT3000 intelligent absolute pressure transmitter. The thermodynamic consistency of the VLE experimental data was checked using the Herington area test and Van Ness test. Afterwards, the VLE data were correlated by the nonrandom two-liquid (NRTL), Wilson and universal quasichemical (UNIQUAC) activity coefficient models, with the corresponding binary interaction parameters being regressed. The root mean square deviations of temperature (RMSD(T)) and vapor-phase mole fraction (RMSD(y)) are all less than 0.61 K and 0.0076, respectively. Additionally, the average absolute deviations of temperature (AAD(T)) and vapor-phase mole fraction (AAD(y)) are all less than 0.54 K and 0.0061, respectively. Hence, all of the aforementioned models are deemed to be suitable to calculate the VLE data of the binary systems. In addition, for camphene + (-)-β-caryophyllene system, NRTL shows the best fit. Across all the binary systems studied no azeotropic behavior was observed.

Introduction

Camphene, (+)-3-carene, (-)-β-caryophyllene, p-cymene and α-pinene are important terpenes constituting the main components in many essential oils, and play an important role in the drug and fragrance & flavor industries. Camphene, a bicyclic monoterpene, is a key compound among industrially used terpenes [1], which has biological benefits of the anticancer, anti-inflammatory, antifungal and antigastriculcer [2]. (+)-3-Carene is one of the few naturally occurring chiral compounds having a unique ternary ring structure, which displays biological activity [3] and can be used in pesticide and pharmaceutical applications [4]. (-)-β-Caryophyllene is a naturally occurring bicyclic sesquiterpene-type compound [5], which has been used as a fragrance chemical [6]. p-Cymene, a mono-ring monoterpene, is an important organic synthesis intermediate [7], which can be used as an additive in musk fragrances and perfumes [8], and has been reported to have an increasing effect on the environment [9]. α-Pinene is also an important bicyclic terpenoid, widely used in the fragrance industry and in the synthesis of a variety of chemicals [10].

Accurately measured VLE data of terpenes are critical factor to consider during the separation process of essential oils. Some of the VLE data of the aforementioned monoterpenes have already been reported. Bernardo-Gil and Ribeiro [11,12] obtained VLE data for α-pinene + β-pinene, α-pinene + (S)-(-)-limonene, and α-pinene + p-cymene binary systems at atmospheric pressure, and determined the VLE experimental data for β-pinene + (S)-(-)-limonene and β-pinene + p-cymene binary systems, at 101.3 kPa. The VLE data for the α-pinene + (S)-(-)-limonene binary system, at 40.0, 66.7, and 101.3 kPa, were reported by Nadais and Bernardo-Gil [13]. Additionally, the VLE data for α-pinene + β-pinene, at 80.0 and 53.3 kPa, were determined by Bernardo-Gil and Barreiros [14]. Tong et al. [15] reported VLE data for the binary systems of α-pinene + (S)-(-)-limonene and p-cymene + (S)-(-)-limonene} in a modified Ellis still. Xu et al. [16] determined VLE data for the α-pinene + p-cymene binary system in an Ellis equilibrium still. And Yao et al. [17] reported VLE data for the binary and ternary systems composed of (-)-β-caryophyllene, p-cymene and 3-carene at 101.33 kPa. However, there are no reports providing VLE data of binary systems containing camphene, and in addition, there are limited reports detailing VLE data relating to sesquiterpene component such as β-caryophyllene.

(-)-β-Caryophyllene is a heavy turpentine with high boiling point (527.15˜530.15 K [18], 528.15 K [19]) and high viscosity (>92 mPa.s [20]). It is difficult to obtain the VLE data containing (-)-β-caryophyllene in an ordinary Ellis equilibrium still [17]. Herein, a modified Ellis double-circulating equilibrium still [17,21] composed of an insulating layer and a magnetic stirring component was used to investigate the vapor-liquid phase behavior of mixtures comprising components having high boiling points and viscosities. Experimental VLE data for the binary systems of: camphene + p-cymene, camphene + α-pinene, (+)-3-carene + α-pinene, α-pinene + (-)-β-caryophyllene, and camphene + (-)-β-caryophyllene were acquired, at 101.3 kPa. Additionally, both the Herington [22] and van Ness [23] thermodynamic tests were adopted to verify the consistency of the VLE data, which were then correlated using the nonrandom two-liquid (NRTL) [24], Wilson [25] and universal quasichemical (UNIQUAC) [26] activity coefficient (γi) models to obtain the energy interaction parameters.

Section snippets

Materials

The chemicals used in this work included camphene provided by Sigma Aldrich Co., Ltd., (+)-3-carene, (-)-β-caryophyllene, p-cymene, and α-pinene supplied by Tokyo Chemical Industry Co., Ltd. These reagents were purified by distillation under high purity nitrogen. The purity of all reagents was confirmed by GC (Agilent 7890B Co., Ltd.). Chemical structure and detailed information of the reagents were shown in Fig. 1 and Table 1. The boiling temperature data of these reagents are summarized in

Experimental results

The experimental VLE data of the camphene + p-cymene, camphene + α-pinene, (+)-3-carene + α-pinene, α-pinene + (-)-β-caryophyllene, and camphene + (-)-β-caryophyllene systems are listed in Table 4, Table 5, Table 6, Table 7, Table 8 and depicted in Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6. The equilibrium relationship between the liquid and vapour phase can be expressed as follows:φˆiyip=xiγiφispisexpViL(ppis)RT,(i=1,2,,N)

In which P is the total pressure and Pis is the saturated vapor

Conclusion

New sets of isobaric VLE data were obtained for the camphene + p-cymene, camphene + α-pinene, (+)-3-carene + α-pinene, α-pinene + (-)-β-caryophyllene, and camphene + (-)-β-caryophyllene binary systems. The measurements were performed using a modified Ellis still. All of the binary systems studied displayed no azeotropic behavior. All experimental data demonstrated thermodynamic consistency when subjected to the Herington area test and Van Ness test. Excellent correlation were observed between

Acknowledgement

We acknowledge the financial support for this work from the National Natural Science Foundation of China (Grant Nos. 21878056, 31560241, 21566002), Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (Grant No. 2016Z002).

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