Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT

Abstract

Solvents may significantly affect the phase behavior and kinetics of chemical reactions. Especially for complex reactions performed in mixtures of different solvents, it requires a high experimental effort to quantify these effects. This work focuses on a novel thermodynamic approach to predict solvent effects on both reaction rates and phase behavior. We applied this method to the homogeneously catalyzed hydroaminomethylation of 1-decene in a thermomorphic multiphase system of methanol and n-dodecane. For that purpose, the thermodynamic activities of the reactants and the liquid–liquid equilibrium of the multicomponent reaction system were successfully modeled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). An increasing concentration of n-dodecane in the solvent mixture was predicted not only to limit the working space for the reaction due to unwanted phase separation but also to massively reduce the reaction rate. These results were in good agreement with batch experiments and homogeneity tests performed in this work. The approach is applicable to a wide variety of liquid-phase reactions and thus is a valuable tool for reducing the experimental effort to a minimum.

Influence of Solvents and Salts on CO2 Solubility and the Impact on an Esterification Reaction

“…Moreover, the activity coefficient of HAc did not play a crucial role in both kinetics and equilibrium. This finding is new since previous works by Huxoll et al 3 and Pabsch et al 4 found that the solvent influence on the activity coefficient of the acid was the main driving force for slower/faster kinetics. We now see that this is not the case for the addition of CO 2 addition.…”

“…This gives rise to the importance of developing thermodynamic models to predict gas solubility in electrolyte solutions as well as to predict the kinetics and equilibria of chemical or biochemical reactions. Several equations of state (EOS) were developed in the last decades, providing a robust modeling framework for calculating the gas solubility in electrolyte solutions and predicting kinetics and equilibria of chemical or biochemical reactions. − Moreover, methods were developed to describe the simultaneous occurrence of chemical reactions and phase equilibria …”

Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

“…As it is known from literature [14,26,27] an additional solvent usually decreases kinetics of esterification reactions and reduces the equilibrium concentration of a reaction product. In this work, the activities of reacting agents $${a}$$ i at reaction equilibrium were predicted using ePC‐SAFT advanced for different conditions.…”

Fitting Error vs Parameter Performance─How to Choose Reliable PC-SAFT Pure-Component Parameters by Physics-Informed Machine Learning

“…The possible contributions (hard-chain repulsion, dispersion interaction, association, ionic interaction) calculate for the total residual Helmholtz energy by summation. Detailed information about applications can be found in the literature for, e.g., polymer systems, ,, pharmaceuticals, , ionic liquids, ,, solubility modeling, , or reaction modeling. , …”