Cyclic alkylene carbonates. Experiment and first principle calculations for prediction of thermochemical properties

https://doi.org/10.1016/j.jct.2008.05.001Get rights and content

Abstract

The standard molar enthalpies of formation of ethylene carbonate, propylene carbonate, and butylene carbonate were measured using combustion calorimetry. Ab initio calculations of molar enthalpies of formation of alkylene carbonates were performed using the G3MP2 method. The calculated values are in excellent agreement with available experimental data. Ring strain corrections were quantified for the refinement of the group-contribution method for prediction of enthalpies of formation and vaporization of alkylene carbonates.

Introduction

The alkylene carbonates (or 1,2-glycol carbonates, or cyclic acid esters) have become increasingly attractive not only for their unique physico-chemical properties but also for the relative simplicity of their manufacturing [1]. They are long-term commercially available solvents used in many industrial applications such as cleaning, degreasing, paint stripping, gas treating, and textile dyeing [2]. Cyclic alkylene carbonates, such as ethylene carbonate, propylene carbonate, and their linear analogue, dimethyl carbonate, as well as their mixtures are widely used as solvents of electrolytes in lithium-ion batteries [3]. Our recent research has revealed specific features of propylene carbonate towards asymmetric hydrogenation with self-assembling catalysts [4] and for palladium-catalyzed substitution reactions [5]. Alkylene carbonates are biodegradable and non-toxic, thus they could be considered as possible “green” solvents. There is great interest in the computation of heat balances, equilibrium yields and feasibilities of processes, using the thermodynamic properties of organic compounds. Despite the practical importance of carbonates, relevant thermodynamic information is rather limited [6], [7], [8], [9], [10]. The aim of this work was an experimental and computational study of the enthalpies of formation for a series of alkylene carbonates (figure 1). This paper extends our previous experimental research of organic carbonates [11], [12], [13], [14].

Section snippets

Materials

Samples of alkylene carbonates of commercial purity were obtained from Huntsman Corporation and were further purified by fractional distillation at reduced pressures. The purity analyses were performed using a gas chromatograph (GC) with a flame ionization detector. A HP-5 capillary column (stationary phase crosslinked 5% PH ME silicone) was used in all our experiments. The column was 30 m long, 0.32 mm inside diameter, and had a film thickness of 0.25 μm. The flow rate of the carrier gas

Enthalpies of formation from combustion calorimetry

Results of combustion experiments for alkylene carbonates are summarized in TABLE 2, TABLE 3, TABLE 4. Values of the standard specific energies of combustion Δcu, together with their mean, are also given in table 2. To derive ΔfHm (l or cr) from ΔcHm, molar enthalpies of formation of H2O (l): −(285.830 ± 0.042) kJ · mol−1 and CO2 (g): −(393.51 ± 0.13) kJ · mol−1 were taken, as assigned by CODATA [21]. Table 5 lists the derived standard molar enthalpies of combustion, and standard molar enthalpies of

Conclusions

The group-additivity methods serve as a valuable tool for many scientists and engineers whose work involves thermodynamic characterization of elementary and overall reaction processes. New experimental thermochemical results for alkylene carbonates have been determined and extended available data for this chemical family. The use of the modern first principle calculations allowed the validation of the mutual consistency of the experimental data. Strain corrections derived in this work are

Acknowledgement

This work has been supported by Research Training Group “New Methods for Sustainability in Catalysis and Technique” (DFG).

References (31)

  • B. Schäffner et al.

    Tetrahedron Lett.

    (2008)
  • S.A. Kozlova et al.

    J. Chem. Thermodyn.

    (2008)
  • D. Kulikov et al.

    Fluid Phase Equilibr.

    (2001)
  • S.K. Kushare et al.

    J. Chem. Thermodyn.

    (2008)
  • W.J. Peppel

    Ind. Eng. Chem.

    (1958)
  • J.H. Clements

    J. Ind. Eng. Chem. Res.

    (2003)
  • M. Wakihara et al.

    Lithium Ion Batteries Fundamentals and Performance

    (1998)
  • B. Schäffner et al.

    Chem. Sus. Chem.

    (2008)
  • L. Vogdanis et al.

    Makromol. Chem.

    (1990)
  • J.K. Choi et al.

    J. Chem. Eng. Data

    (1971)
  • G. Silvestro et al.

    J. Phys. Chem.

    (1961)
  • T.F. Vasil’eva et al.

    Russ. J. Phys. Chem. [Engl. Transl.]

    (1972)
  • W.L. Calhoun

    J. Chem. Eng. Data

    (1983)
  • S.P. Verevkin, A. Toktonov, Y. Chernyak, B. Schäffner, A. Börner, Fluid Phase Equilibr. (in...
  • S.P. Verevkin, V.N. Emel’yanenko, S.A. Kozlova, J. Phys. Chem. A (in...
  • Cited by (32)

    • Kinetic modelling of the synthesis of diethyl carbonate and propylene carbonate from ethanol and 1,2-propanediol associated with CO<inf>2</inf>

      2020, Chemical Engineering Research and Design
      Citation Excerpt :

      The uncertainties surrounding these data are high, and this has an important impact on the calculation of the Gibbs free energy. In a more recent publication, Verevkin et al. confirm the formation enthalpy of PC (Verevkin et al., 2008). The value found was −614.1 ± 0.8 kJ/mol, which is near to that of Vasil’eva et al. (1972).

    • Heats of formation for boron compounds based on quantum chemical calculations

      2010, Journal of Theoretical and Computational Chemistry
    View all citing articles on Scopus
    View full text