Solubilities of sulfuryl fluoride in propylene carbonate, tributyl phosphate and N-methylpyrrolidone

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Highlights

  • Solubility data of SO2F2 in propylene carbonate, tributyl phosphate and N-methylpyrrolidone were provided.

  • Henry’s law constants of SO2F2 were obtained, contributing to recovery of SO2F2 after fumigation.

  • Thermodynamic properties of SO2F2 dissolution in selected three solvents were calculated.

Abstract

The solubilities of sulfuryl fluoride (SO2F2) in propylene carbonate (PC), tributyl phosphate (TBP) and N-methylpyrrolidone (NMP) was measured by isochoric saturation method at the pressure of up to 600 kPa and temperatures ranging from (293.15 to 313.15) K. Results showed that SO2F2 solubility increased with increasing pressure and decreased with increasing temperature in the three solvents, and the dissolution of SO2F2 in the solvents was a physical process. Moreover, Henry’s law constants and thermodynamic properties such as standard Gibbs free energy, enthalpy, and entropy changes of SO2F2 solvation were further calculated according to the experimental solubility data. The solubility of SO2F2 in these three solvents followed the order of TBP > PC > NMP. The results illustrated that TBP possessed the potentiality to capture SO2F2 among the present absorbents due to the relatively large solubility and low absorption enthalpy for SO2F2.

Introduction

As the methyl bromide was phased out under the Montreal Protocol, sulfuryl fluoride (SO2F2) is used increasingly as a replacement to fumigate the timber, construction materials, soils, buildings, foods, etc.[1], [2], [3], [4], owing to its striking characteristics including zero ozone depletion, rapid penetration, and easy dispersal [5]. However, SO2F2 gas emitted from fumigation can intensify the greenhouse effect and cause health problems [6], [7], [8]. Therefore, it is increasingly important to find a reasonable way to effectively remove SO2F2 after fumigation.

Up to date, several methods have been proposed for the treatment of SO2F2 after fumigation, such as plasma, chemical absorption, and plasma coupled with chemical absorption [9], [10], [11]. However, there still exist some obvious disadvantages including complex process, secondary pollution and intensive energy consumption. Additionally, these methods are also inconsistent with the sustainable development because of wasting the valuable S and F resources. Thus, developing green, economical and reversible absorbent for SO2F2 is highly desirable.

Many physical solvents are now in commercial use, among which propylene carbonate (PC), N-methylpyrrolidone (NMP) and tributyl phosphate (TBP) were reported as absorbents for acid exhaust gases such as CO2, H2S and SO2 [12], [13], [14], [15]. Murrieta-Guevara et al. presented experimental data on the solubilities of CO2 and H2S in PC and NMP [16]. Chen et al. provided thermodynamic parameters of SO2 dissolution in TBP at 295–323 K [17]. Huang et al. compared the solubilities of SO2 in PC and NMP with those in other three solvents including sulfolane, ethylene glycol and n-methylimidazole [18]. Similar to acid gases, the central atom of SO2F2 molecule is lacking of electrons. Therefore, PC, TBP and NMP could be extended to remove SO2F2. However, there are no reports on SO2F2 removal by PC, TBP and NMP. Meanwhile, the data on SO2F2 solubility in physical solvents is lacked.

In this work, we used PC, TBP and NMP as the physical solvents for SO2F2 removal. Therefore, new solubility data of SO2F2 in PC, TBP and NMP were determined at temperatures ranging from (293.15 to 313.15) K and pressures ranging from (0 to 600) kPa. Henry’s law constants were obtained by experimental data regression. The thermodynamic properties including standard dissolution Gibbs free energy, dissolution enthalpy and dissolution entropy were further determined.

Section snippets

Chemicals

CO2. (124-38-9: carbon dioxide) was supplied by Jingong Special Gas Co., Ltd. (Hangzhou, China). SO2F2 (2699-79-8: sulfuryl fluoride) was supplied by Maoyu Co., Ltd. (Hangzhou, China). Propylene carbonate (108-32-7: 1,2-propanediol carbonate), Tributyl phosphate (126-73-8: n-butyl phosphate) and N-methylpyrrolidone (872-50-4: 1-Methyl-2-pyrrolidinone) were obtained from Aladdin Industrial Co., Ltd. (Shanghai, China). SO2F2 is almost insoluble in water [19]. Furthermore, experimental results

Solubilities

Solubility experiments were carried out with PC, TBP and NMP at the pressure of up to 600 kPa and temperatures ranging from (293.15 to 313.15) K. The solubility data of SO2F2 are listed in Table 4, Table 5, Table 6.

Moreover, the SO2F2 solubility profiles (expressed as mole fraction) in PC, TBP and NMP at various temperatures are shown in Fig. 3, Fig. 4, Fig. 5, respectively. It can be seen from Fig. 3, Fig. 4, Fig. 5 that SO2F2 solubility increased with increasing pressure and decreased with

Conclusion

In the present study, solubilities of SO2F2 in PC, TBP and NMP were measured at temperatures of (293.15–313.15) K and pressures of (0–600) kPa using an isochoric saturation method. Meanwhile, Henry’s law constants and thermodynamic properties were calculated based on the solubility data. The solubilities in the three solvents followed the order of TBP > PC > NMP. The dissolution enthalpies were negative at all conditions. Compared with water, PC, TBP and NMP showed potential application for SO2F

Acknowledgments

The financial support from the National Natural Science Foundation of China (NSFC) [Grant No. 51107118], the Science and Technology Plan of General Administration of Quality Supervision of the P.R.C. [Grant No. 201010256651.9], and the Excellent Postdoctoral Science Foundation of Zhejiang Province are gratefully acknowledged.

Author disclosure statement

No competing financial interest exists.

References (23)

  • R. Rajasingam et al.

    J. Supercrit. Fluids

    (2004)
  • Z. Zhao et al.

    Int. J. Greenouse Gas Control

    (2017)
  • F. Murrieta-Guevara et al.

    Fluid Phase Equilib.

    (1988)
  • X. Liang et al.

    J. Chem. Thermodyn.

    (2016)
  • J. Jacquemin et al.

    J. Chem. Thermodyn.

    (2006)
  • K.A. Kurnia et al.

    J. Chem. Thermodyn.

    (2009)
  • R. Jagadeesan et al.

    Pest Manage. Sci.

    (2016)
  • F. Şen et al.

    Acta Hortic.

    (2016)
  • G.P. Opit et al.

    J. Econ. Entomol.

    (2016)
  • A. Cao et al.

    Pest Manage. Sci.

    (2014)
  • W.T. Tsai

    J. Environ. Sci. Health. C. Environ. Carcinog. Ecotoxicol. Rev.

    (2010)
  • Cited by (0)

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