Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

doi:10.1016/j.fluid.2011.02.002

Fluid Phase Equilibria

Volume 303, Issue 2, 25 April 2011, Pages 205-216

https://doi.org/10.1016/j.fluid.2011.02.002 Get rights and content

Abstract

Recommended vapor pressure data for important industrial solvents, thiophene (CAS RN: 110-02-1), sulfolane (CAS RN: 126-33-0), and dimethyl sulfoxide (CAS RN: 67-68-5), were developed by the simultaneous correlation of vapor pressure and related thermal data (heat capacities of condensed phases, ideal gas heat capacities and calorimetrically determined enthalpies of vaporization). For sulfolane and dimethyl sulfoxide, new vapor pressure data were obtained using the static method in the temperature interval from 273 to 308 K. Liquid heat capacities and calorimetric enthalpies of vaporization were taken from the literature and/or determined by Calvet calorimetry. The thermodynamic properties in the ideal gaseous state were calculated using the methods of statistical thermodynamics based on experimental as well as calculated fundamental vibrational frequencies and molecular structure data. Comparisons with literature values are shown for all measured and derived properties.

Research highlights

► Thiophene, sulfolane, and dimethyl sulfoxide were studied. ► Vapor pressures and liquid heat capacities were determined. ► Thermodynamic properties in the ideal gas state were calculated. ► Recommended vapor pressure equations were developed.

Introduction

Thiophene, sulfolane, and dimethyl sulfoxide are important industrial solvents produced on a large scale. Despite of this fact, their vapor pressures at ambient temperatures are not known with sufficient accuracy. Reliable vapor pressure data are indispensible for processes involving phase equilibria and for phase equilibrium studies on systems containing these compounds.

In this work, we first assessed all available literature vapor pressure data and examined their consistency with calorimetrically determined vaporization enthalpies and heat capacities of condensed phases and ideal gas. Literature review and consistency tests revealed that new vapor pressure data in the low pressure region for sulfolane and dimethyl sulfoxide and new liquid heat capacities for sulfolane were needed. These data were experimentally determined in this work. Also, heat capacities of ideal gas and thermodynamic properties in the ideal gaseous state for all the studied compounds were calculated using the methods of statistical thermodynamics. We employed both the experimental and calculated fundamental vibrational frequencies and compared the obtained results as part of our effort to assess the reliability of the calculations based purely on ab initio data. Consequently, recommended vapor pressure data for thiophene, sulfolane, and dimethyl sulfoxide were developed by the simultaneous correlation of selected vapor pressure and related thermal data [1].

Section snippets

Simultaneous treatment of vapor pressures and related thermal data (SimCor method)

Vapor pressure p, enthalpy of vaporization $Δ_{ℓ}^{g} H_{m}$ and the difference between ideal gas heat capacity and heat capacity of liquid $Δ_{ℓ}^{g} C_{p, m}^{0} = C_{p, m}^{g 0} - C_{p, m}^{ℓ}$ are linked by exact thermodynamic relationships $R T^{2} {(\frac{d \ln p}{d T})}_{s a t} = \frac{Δ_{ℓ}^{g} H_{m}}{Δ_{ℓ}^{g} z} = Δ H^{'}$ ${(\frac{d Δ H^{'}}{d T})}_{s a t} = R {\{\frac{d [T^{2} (d \ln p / d T)]}{d T}\}}_{s a t} = Δ C^{'} = Δ_{ℓ}^{g} C_{p, m}^{0} + p V T correction$ where subscript ‘sat’ denotes a derivative along the saturation line, R is the molar gas constant (R = 8.314472 J K⁻¹ mol⁻¹ [2], [3]), $Δ_{ℓ}^{g} z$ stands for the difference between the compressibility factors of the coexisting

Materials

Sulfolane was obtained from Novasol Belgium. The mass fraction purity (determined by gas gromatography (GC)) and mass fraction of water (determined by Coulometric titration, UOP 481) were w = 0.9985 and w(H₂O) = 3 × 10⁻⁴, respectively, as stated in the certificates of analysis provided by the supplier. The sample was stored over 4 Å molecular sieves for approximately 2 weeks. The mass fraction of water determined prior to taking vapor pressure and heat capacity measurements was w(H₂O) = 6.5 × 10⁻⁵

Vapor pressures

The vapor pressure measurements of sulfolane and dimethyl sulfoxide were performed in the temperature interval from 253 to 308 K by varying the temperature at random to detect systematic errors caused by insufficient degassing of the sample. The experiments were carried out repeatedly at selected temperatures. When the pressure did not change with the number of measuring cycles, the sample was considered completely degassed, and the final set of data was recorded. At least two experimental

Conclusions

Recommended vapor pressure equation for thiophene, sulfolane, and dimethyl sulfoxide was developed by a multi-property fit of selected experimental vapor pressure data, calorimetrically measured enthalpies of vaporization and differences in heat capacities of condensed phases and ideal gas. New vapor pressure data for sulfolane and dimethyl sulfoxide, and liquid heat capacities for sulfolane were determined in this work. The thermodynamic properties in the ideal gaseous state for all the

List of symbols

integrated values of differential heat flow

A₀, A₁, A₂, A₃

parameters of Cox equation, Eq. (3)

specific heat capacity

C_{p, m}^{g 0}

molar ideal gas heat capacity at constant pressure

C_{p, m}^{g}

molar heat capacity of saturated vapor at constant pressure

C_{p, m}^{c d}

molar heat capacity of condensed phases (crystalline or liquid phase) at constant pressure

C_{p, m}^{c r}

molar heat of crystalline phase at constant pressure

C_{p, m}^{ℓ}

molar liquid heat capacity at constant pressure

Δ_{ℓ}^{g} C_{p, m}^{0}

difference between ideal gas heat capacity and

Acknowledgements

We thank Vladimir Diky and Ala Bazyleva for providing the program StatTD and for valuable and helpful discussions on statistical thermodynamic calculations of ideal gas properties, Pavel Morávek for help with the sample degassing prior to vapor pressure determinations, and Novasol Belgium for providing us free of charge with anhydrous sample of sulfolane. This work is supported by the Ministry of Education of the Czech Republic under grant MSM 604 613 7307 and the Czech science foundation

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View full text

Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

Abstract

Research highlights

Introduction

Section snippets

Simultaneous treatment of vapor pressures and related thermal data (SimCor method)

Materials

Vapor pressures

Conclusions

List of symbols

Acknowledgements

Fluid Phase Equilib.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Phys. B

Fluid Phase Equilib.

J. Chem. Thermodyn.

Thermochim. Acta

J. Chin. Inst. Chem. Eng.

J. Mol. Spectrosc.

J. Mol. Struct.

J. Mol. Struct.

Spectrosc. Acta A: Mol. Biomol. Spectrom.

Spectrochim. Acta

J. Mol. Spectrosc.

Spectrosc. A: Mol. Biomol. Spectrom.

Spectrochim. Acta

J. Mol. Struct.

J. Mol. Struct.

J. Chem. Thermodyn.

AIChE J.

Rev. Modern Phys.

J. Phys. Chem. Ref. Data

Ind. Eng. Chem.

Fluid Phase Equilib.

Thermochim. Acta

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

Heat Capacity of Liquids. Critical Review and Recommended Values

J. Therm. Anal. Calorim.

J. Phys. Chem.

J. Chem. Phys.

J. Am. Chem. Soc.

J. Phys. Chem. Ref. Data