Thermodynamic prediction of the solvent effect on a transesterification reaction

Lemberg, Max; Schomäcker, Reinhard; Sadowski, Gabriele

doi:10.1016/j.ces.2017.10.033

Cited by 13 publications

(10 citation statements)

References 22 publications

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“…Thermodynamic Estimation of Reaction Rates. According to Lemberg et al, 21 the reaction rate r of an equilibrium reaction A + B ⇌ C + D is described in a thermodynamic-consistent way, as shown in eq 1.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Using thermodynamic activities instead of concentrations, the intrinsic reaction rate constants k 1 * and k −1 * no longer contain activity coefficients and thus are completely independent of the solvent as long as the transition state is not affected. 21 As at the start of the reaction (t = 0), the backward reaction can be neglected, eq 1 then simplifies to…”

Section: Theoretical Backgroundmentioning

confidence: 99%

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

Huxoll

Kampwerth

Seidensticker

et al. 2022

Ind. Eng. Chem. Res.

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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.

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Section: Theoretical Backgroundmentioning

confidence: 99%

Section: Theoretical Backgroundmentioning

confidence: 99%

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

Huxoll

Kampwerth

Seidensticker

et al. 2022

Ind. Eng. Chem. Res.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Since the solvent effects are already considered via the reactant activity coefficient, the forward rate constant k 1 can be regarded as independent of the solvent. 31 Thus, for the rate-determining enamine hydrogenation step, the reaction rate can be simplified to eq 1 r k a a…”

Section: ■ Experimental Detailsmentioning

confidence: 99%

“…At the beginning of the reaction ( t = 0), the rate constant of the reverse reaction k –1 is not determining the rate of the reaction and can be neglected. Since the solvent effects are already considered via the reactant activity coefficient, the forward rate constant k 1 can be regarded as independent of the solvent . Thus, for the rate-determining enamine hydrogenation step, the reaction rate can be simplified to eq …”

Section: Experimental Detailsmentioning

confidence: 99%

Solvent Selection in Homogeneous Catalysis—Optimization of Kinetics and Reaction Performance

et al. 2020

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Solvents have an enormous impact on yield and turnover of chemical reactions in complex media. There is, however, a lack of consistent model-based tools to a priori identify the appropriate solvent for homogeneously catalyzed reactions. Here, a thermodynamically consistent approach for a reductive amination reaction is presented. It combines solvent screening using a thermodynamic-activity model and quantum chemical calculations. The optimization of activity coefficient-based predicted kinetics gives a suitable list of candidate solvents. The results were confirmed by batch experiments in selected solvents. This approach allows reducing time and lab resources for solvent selection to a minimum.

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“…Overall, very promising results could be achieved. Moreover, esters were modeled using PC-SAFT in various other previous works. − Also, SAFT-γ Mie was applied to represent pure-component properties such as vapor pressures and various properties of binary mixtures for a broad range of esters. , …”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Systems Comprising Esters: Experimental Data and Modeling with PC-SAFT and SAFT-γ Mie

Haarmann

Siewert

Samarov

et al. 2019

Ind. Eng. Chem. Res.

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In this work, new experimental vapor-pressure data of 14 esters were obtained using the transpiration method. Besides dimethyl fumarate, dimethyl maleate, diethyl maleate, benzyl ethanoate, benzyl propanoate, and benzyl butanoate, eight representatives of the homologous series of ethyl alkanoates were investigated. The pure-component vapor pressures and liquid densities were modeled by means of Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) and SAFT-γ Mie. Satisfying modeling results could be achieved with both equations of state. Furthermore, the molar excess enthalpies of 12 binary mixtures benzyl ethanoate + n-alkane were modeled. Only one binary interaction parameter was fitted for PC-SAFT to quantitatively predict the molar excess enthalpies of all binary mixtures under study, while SAFT-γ Mie predicts these properties in qualitative agreement with the experimental data. Finally, the liquid–liquid equilibria of three binary mixtures ester (benzyl ethanoate, dimethyl maleate, and diethyl maleate) + water were investigated. These systems show a very low and almost temperature-independent solubility of the ester in the aqueous phase, whereas the moderate solubility of water in the organic phase is temperature-dependent. Promisingly, both PC-SAFT and SAFT-γ Mie predicted broad and unsymmetrical miscibility gaps for these mixtures, which is in qualitative agreement with the experimental data.

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Thermodynamic prediction of the solvent effect on a transesterification reaction

Cited by 13 publications

References 22 publications

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

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

Solvent Selection in Homogeneous Catalysis—Optimization of Kinetics and Reaction Performance

Thermodynamic Properties of Systems Comprising Esters: Experimental Data and Modeling with PC-SAFT and SAFT-γ Mie

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