Prediction of pH in multiphase multicomponent systems with ePC-SAFT advanced

Ascani, Moreno; Pabsch, Daniel; Klinksiek, Marcel; Gajardo‐Parra, Nicolás F.; Sadowski, Gabriele; Held, Christoph

doi:10.1039/d2cc02943j

Cited by 10 publications

(7 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this section, our implementation of the algorithm to perform numerical calculation of the CPE is presented. Although the implementation is general, i.e., not limited to a single key reaction and neutral components (see, for instance, our previous work [ 93 , 94 ]), its scope in this work is to calculate the coupled reaction equilibrium and LLE of the two investigated esterification systems. Thus, only systems containing four molecular (i.e., non-charged) components and described by one key reaction are considered.…”

Section: Algorithmic Approachmentioning

confidence: 99%

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

2023

Self Cite

View full text Add to dashboard Cite

The study of chemical reactions in multiple liquid phase systems is becoming more and more relevant in industry and academia. The ability to predict combined chemical and phase equilibria is interesting from a scientific point of view but is also crucial to design innovative separation processes. In this work, an algorithm to perform the combined chemical and liquid–liquid phase equilibrium calculation was implemented in the PC-SAFT framework in order to predict the thermodynamic equilibrium behavior of two multicomponent esterification systems. Esterification reactions involve hydrophobic reacting agents and water, which might cause liquid–liquid phase separation along the reaction coordinate, especially if long-chain alcoholic reactants are used. As test systems, the two quaternary esterification systems starting from the reactants acetic acid + 1-pentanol and from the reactants acetic acid + 1-hexanol were chosen. It is known that both quaternary systems exhibit composition regions of overlapped chemical and liquid–liquid equilibrium. To the best of our knowledge, this is the first time that PC-SAFT was used to calculate simultaneous chemical and liquid–liquid equilibria. All the binary subsystems were studied prior to evaluating the predictive capability of PC-SAFT toward the simultaneous chemical equilibria and phase equilibria. Overall, PC-SAFT proved its excellent capabilities toward predicting chemical equilibrium composition in the homogeneous composition range of the investigated systems as well as liquid–liquid phase behavior. This study highlights the potential of a physical sound model to perform thermodynamic-based modeling of chemical reacting systems undergoing liquid–liquid phase separation.

show abstract

Section: Algorithmic Approachmentioning

confidence: 99%

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…ePC-SAFT advanced enables modeling these interactions in organic media by utilizing a modified Born term to consider electrostatic interactions of ionic compounds with their surrounding medium. In addition to that, Ascani et al [25] successfully predicted pH values in multiphase multicomponent systems with ePC-SAFT advanced. Thus, we used this approach to calculate the activity coefficients of each ion in the reaction mixture and the ion influence on the activity coefficients of reacting agents.…”

Section: Kinetic Model II -Ion Effects On Reactantsmentioning

confidence: 99%

“…ePC‐SAFT advanced enables modeling these interactions in organic media by utilizing a modified Born term to consider electrostatic interactions of ionic compounds with their surrounding medium. In addition to that, Ascani et al [25] . successfully predicted pH values in multiphase multicomponent systems with ePC‐SAFT advanced.…”

Section: Introductionmentioning

confidence: 99%

Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

et al. 2022

Self Cite

View full text Add to dashboard Cite

The solvent is of prime importance in biomass conversion as it influences dissolution, reaction kinetics, catalyst activity and thermodynamic equilibrium of the reaction system. So far, activity-based models were developed to predict kinetics and equilibria, but the influence of the catalyst could not be predicted by thermodynamic models. Thus, in this work, the thermodynamic model ePC-SAFT advanced was used to predict the activities of the reactants and of the catalyst at various conditions (temperature, reactant concentrations, γ-valerolactone GVL cosolvent addition, catalyst concentration) for the homogeneously acid-catalyzed esterification of levulinic acid (LA) with ethanol. Different kinetic models were applied, and it was found that the catalyst influence on kinetics could be predicted correctly by simultaneously solving the dissociation equilibrium of H2SO4 catalyst along the reaction coordinate and the relating reaction kinetics to proton activity. ePC-SAFT advanced model parameters were only fitted to reaction-independent phase equilibrium data, but the key reaction properties were determined by one experimental kinetic curve for a set of temperatures, yielding the reaction enthalpy at standard state ∆ 𝑅 𝐻 0 = 11.48 𝑘𝐽 𝑚𝑜𝑙 −1 , activation energy 𝐸 𝐴 = 30.28 𝑘𝐽 𝑚𝑜𝑙 −1 and the intrinsic reaction rate constant k = 0.011 s -1 at 323 K, which is independent of catalyst concentration. The new procedure allowed an a-priori identification of the effects of catalyst, solvent and reactant concentration on LA esterification.

show abstract

“…Sadowski et al used the advanced ePC-SAFT thermodynamic equation of state to predict pH in a multiphase multicomponent system. Proton activity is used to predict pH in multiphase systems, and the developed framework considers reaction and phase equilibria ( Gabriele et al, 2022 ). Macedo et al used the PDH (Pitzer–Debye–Hückel equation) + unique model to determine the degree of dissociation of ionic liquids in water ( Eugenia et al, 2022 ).…”

Section: Introductionmentioning

confidence: 99%

Study on vapor–liquid equilibrium and microscopic properties of DL-proline, L-glutamic acid, and L-serine aqueous solutions

Liu

Zhou

2022

Front. Chem.

View full text Add to dashboard Cite

The vapor–liquid equilibrium (VLE) in aqueous amino acid solutions is essential in chemical production, such as purification, isolation, or crystallization of amino acid intermediates. In this work, VLE of DL-proline, L-glutamic acid, and L-serine aqueous solutions was measured at pressures ranging from 4.82 to 102.58 kPa. The developed model was successfully applied to correlate experimental data with temperatures in the range of 298.15–382.75 K. Model parameters (h, τw,i(0), τw,i(1), τi,w(0), and τi,w(1) ) were given. Moreover, the amino acid aqueous solution was investigated by Fourier transform infrared spectroscopy (FTIR). By analyzing infrared spectra, the strength of intermolecular interactions was obtained, and the structure–activity relationship between the microscopic interactions and the VLE was established.

show abstract

Prediction of pH in multiphase multicomponent systems with ePC-SAFT advanced

Abstract: Proton activity, which is usually expressed as pH value, is among the most important properties in the design of chemical and biochemical processes as it determines the dissociation of species...

Cited by 10 publications

References 24 publications

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

Activity‐Based Models to Predict Kinetics of Levulinic Acid Esterification

Study on vapor–liquid equilibrium and microscopic properties of DL-proline, L-glutamic acid, and L-serine aqueous solutions

Contact Info

Product

Resources

About