This work was undertaken to obtain new thermochemical data for 5-hydroxymethylfurfural (HMF) and parent compounds. The standard molar enthalpy of formation in the gaseous state of HMF was obtained from combustion calorimetry, differential scanning calorimetry (DSC), and measurements of the temperature dependence of the vapor pressure by the transpiration method. To verify the experimental data, ab initio calculations of all compounds were performed. Enthalpies of formation derived from the G3MP2 method are in an excellent agreement with the experimental results. A weak hydrogen bond in HMF was revealed using ab initio methods. Thermodynamic analysis of the transformation of HMF to the bulk intermediates according to hydrogenation and oxidation pathways has revealed a very high feasibility of these reactions, with equilibrium constants that are completely shifted to the desired reaction products even at 298 K.
Within the last decade the Carbonate Based Ionic liquid Synthesis (CBILS®) has developed towards a widely applicable, greener and halogen free process for the industrial production of ionic liquids. A large number of diverse starting materials have been screened experimentally, to explore the structural limits of the core reaction step, which is the quaternization of nitrogen, phosphor or sulfur based nucleophiles with carbonic acid dialkyl or diaryl esters to the corresponding quaternary alkyl- or arylcarbonates. In order to overcome the large experimental effort of empirical screening, a practical method based on quantum-chemical calculation has been developed for an assessment of feasibility of chemical reactions. This method has been successfully tested with 16 typical CBILS® reactions by calculation of their thermodynamic functions. Thermodynamic equilibrium constants as a measure for the practical yield of the CBILS® reactions at 298 K and 393 K have been determined for both the gaseous state and the liquid state. The method has been evaluated by comparison of the theoretical results with experimental data and it can be considered as the powerful tool to reduce "trial and failure" for the industrial application of the CBILS® process.
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