It is well known that solvents influence reaction kinetics. The classical concentration-based kinetic modeling is unable to describe these effects. In this work, the reaction kinetics was studied for the esterifications of acetic acid and propionic acid with ethanol at 303.15 K. It was found that the reactant ratio as well as the applied solvents (acetonitrile, tetrahydrofurane, dimethylformamide) significantly affect the reaction rate. The thermodynamic model PC-SAFT was applied to account for the interactions between the reacting species and the solvents via activity coefficients. This allowed the identification of solvent-independent kinetic constants and the prediction of the solvent effect on reaction kinetics in almost quantitative agreement with experimental data. The presented approach shows the importance of taking into account thermodynamic non-idealities and significantly reduces experimental effort for finding the best solvent candidate for a given target reaction.

This paper investigates phase equilibria of interest for the hydroesterification of 10-undecenoic acid methyl ester with methanol and carbon monoxide to dodecanedioic acid dimethyl ester in a solvent system composed of methanol and ndodecane. Carbon monoxide solubilities were measured in 10-undecenoic acid methyl ester, dodecanedioic acid dimethyl ester, and a mixture of methanol/dodecanedioic acid dimethyl ester at 363 and 393 K and at pressures up to 15 MPa. Vapor−liquid equilibrium measurements in the systems methanol/10-undecenoic acid methyl ester, methanol/dodecanedioic acid dimethyl ester, n-dodecane/10-undecenoic acid methyl ester, n-dodecane/dodecanedioic acid dimethyl ester, and 10-undecenoic acid methyl ester/dodecanedioic acid dimethyl ester were performed at temperatures between 342 and 437 K and at pressures of 2 or 80 kPa. The measured data were accurately modeled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT).

This work investigates solvent effects on the reaction equilibrium of the 1-dodecene hydroformylation in a decane/N,N-dimethylformamide solvent system. The reaction was performed at different decane/N,N-dimethylformamide ratios and at temperatures between 368 K and 388 K. The equilibrium concentrations of all reactants and products were determined experimentally. The enthalpy and Gibbs energy of this reaction at the ideal-gas standard state were determined by quantum-chemical calculations in good agreement with literature data. Moreover, quantum-chemically calculated standard Gibbs energies of reaction at infinite dilution in liquid decane/DMF-solvent mixtures allowed a qualitative prediction of the solvent effect on the equilibrium concentrations. Based on the standard Gibbs energy of reaction at the ideal-gas standard state and on fugacity coefficients calculated using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), the equilibrium concentrations of reactants and products for the 1-dodecene hydroformylation performed in decane/N,N-dimethylformamide mixtures of different compositions could be predicted in very good agreement with experimental data.

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