ePC-SAFT advanced - Part I: Physical meaning of including a concentration-dependent dielectric constant in the born term and in the Debye-Hückel theory

Bülow, Mark; Ascani, Moreno; Held, Christoph

doi:10.1016/j.fluid.2021.112967

Cited by 59 publications

(74 citation statements)

References 35 publications

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“…The most recent version is called 'ePC-SAFT advanced', and it contains the Born term altered by a concentration-dependent dielectric constant. [43] The theory is briefly discussed in the following.…”

Section: Thermodynamic Frameworkmentioning

confidence: 99%

“…Later, PC-SAFT was extended to include electrostatic interionic interactions [59] and to account for the change of the dielectric constant at different concentrations. [34] Recently, an altered Born term was introduced within ePC-SAFT, [43] which accounts for electrostatic interactions between charged components and their surrounding medium. The resulting residual Helmholtz energy is given as the sum of all contributions according to Eq.…”

Section: Thermodynamic Frameworkmentioning

confidence: 99%

“…Modeling the phase behavior of electrolyte systems has been performed by different groups; these already included the Born theory into thermodynamic models e. g., the electrolyte Cubic-Plus-Association (eCPA), [22][23][24] Peng-Robinson [25,26] and Soave-Redlich-Kwong [22] models and electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] as well as the most recent version, 'ePC-SAFT advanced'. [43] In that work the Born term was altered by a concentration-dependent dielectric constant. This allowed for a more predictive treatment of binary data (activity and osmotic coefficients) and for calculation of transfer properties (Gibbs free energies of solvation and transfer) [43] .…”

Section: Introductionmentioning

confidence: 99%

“…[43] In that work the Born term was altered by a concentration-dependent dielectric constant. This allowed for a more predictive treatment of binary data (activity and osmotic coefficients) and for calculation of transfer properties (Gibbs free energies of solvation and transfer) [43] .…”

Section: Introductionmentioning

confidence: 99%

“…In the present work, 'ePC-SAFT advanced' which includes an altered Born term [43] was further investigated for predicting LLE of mixed solvents containing dissolved electrolytes. Furthermore, the role of an appropriate expression of the dielectric constant as function of the system composition was studied with respect to the impact on the quality of the predicted LLE.…”

Section: Introductionmentioning

confidence: 99%

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Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Ascani

Held

2021

Zeitschrift anorg allge chemie

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We dedicate this to honor the 60 th birthday of Prof. Christoph Janiak for outstanding networking activities and great research.Knowledge on phase equilibria is of crucial importance in designing industrial processes. However, modeling phase equilibria in liquid-liquid two-phase systems (LLTPS) containing electrolytes is still a challenge for electrolyte thermodynamic models and modeling still requires a lot of experimental input data. Further, modeling electrolyte solutions requires accounting for different physical effects in the electrolyte theory, especially the change of the dielectric properties of the medium at different compositions and the related change of solvation free energy of the dissolved ions. In a previous work, the Born term was altered by combining it with a concentration-dependent dielectric constant within the framework of electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT), and hence called 'ePC-SAFT advanced'. In the present work, ePC-SAFT advanced was validated against liquid-liquid equilibria (LLE) of LLTPS water + organic solvents + alkali halides as well as aqueous two-phase systems containing the phase formers poly (propylene glycol) and an ionic liquid. All the ePC-SAFT parameters were used as published in the literature, and each binary interaction parameter between ion-solvent was set to zero. ePC-SAFT advanced allowed quantitatively predicting the salt effect on LLTPS without adjusting binary interaction parameters, while classical ePC-SAFT or meaningless mixing rules for the dielectric constant term failed in predicting the phase behavior of the LLTPS.

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Section: Thermodynamic Frameworkmentioning

confidence: 99%

Section: Thermodynamic Frameworkmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Ascani

Held

2021

Zeitschrift anorg allge chemie

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Salzabfall‐freie Carboxylierung von Acetylen: Grüne Synthese von C₄‐Chemikalien durch einen CO₂‐Druck‐induzierten Aciditätsswitch

et al. 2023

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Die Vermeidung der Bildung equimolarer Mengen an Salzabfällen ist eine der größten Herausforderungen zur Nutzung von CO 2 als C 1 Baustein in C-H-Carboxylierungsreaktionen. Zur Lösung dieses Problems wurde ein zyklischer Prozess entwickelt, in welchem die industrielle Basischemikalie Dimethylsuccinat aus CO 2 und Acetylen synthetisiert wird. Bei moderatem CO 2 -Druck kann Acetylen mit Cäsiumcarbonat zweifach carboxyliert und das intermediäre Salz durch Hydrierung der C-C-Dreifachbindung stabilisiert werden. Bei 70 bar CO 2 wird das Reaktionsmedium reversibel angesäuert, was die Veresterung des Carboxylatsalzes mit dem Lösemittel Methanol ermöglicht. Die Cäsiumbase und der Hydrierkatalysator können regeneriert und wiederverwendet werden. Dieses Reaktionskonzept eröffnet einen neuen Weg zur Umsetzung von Biogas (CH 4 /CO 2 ) zu industriell relevanten C 4 Basischemikalien. Der reversible Aziditätsswitch, die Rolle der Cäsiumbase so wie die des Lösungsmittelgemisches wurden durch thermodynamische Modellierung aufgeklärt.

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Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch

et al. 2023

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The inherent formation of salt waste in C−H carboxylations is a key obstacle precluding the utilization of CO2 as C1 building block in the industrial synthesis of base chemicals. This challenge is addressed in a circular process for the production of the C4 base chemical dimethyl succinate from CO2 and acetylene. At moderate CO2 pressures, acetylene is doubly carboxylated in the presence of cesium carbonate. Hydrogenation of the C−C triple bond stabilizes the product against decarboxylation. By increasing the CO2 pressure to 70 bar, the medium is reversibly acidified, allowing an esterification of the succinate salt with methanol. The cesium base and the hydrogenation catalyst are regenerated and can be reused. This provides the proof of concept for a salt‐free route to C4 chemicals from biogas (CH4/CO2). The origin of this reversible acidity switch and the critical roles of the cesium base and the NMP/MeOH solvents were elucidated by thermodynamic modeling.

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ePC-SAFT advanced - Part I: Physical meaning of including a concentration-dependent dielectric constant in the born term and in the Debye-Hückel theory

Cited by 59 publications

References 35 publications

Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Salzabfall‐freie Carboxylierung von Acetylen: Grüne Synthese von C₄‐Chemikalien durch einen CO₂‐Druck‐induzierten Aciditätsswitch

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch

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ePC-SAFT advanced - Part I: Physical meaning of including a concentration-dependent dielectric constant in the born term and in the Debye-Hückel theory

Cited by 59 publications

References 35 publications

Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Prediction of salting‐out in liquid‐liquid two‐phase systems with ePC‐SAFT: Effect of the Born term and of a concentration‐dependent dielectric constant

Salzabfall‐freie Carboxylierung von Acetylen: Grüne Synthese von C4‐Chemikalien durch einen CO2‐Druck‐induzierten Aciditätsswitch

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C4 Chemicals Enabled by a CO2‐Pressure Induced Acidity Switch

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Product

Resources

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Salzabfall‐freie Carboxylierung von Acetylen: Grüne Synthese von C₄‐Chemikalien durch einen CO₂‐Druck‐induzierten Aciditätsswitch

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C₄ Chemicals Enabled by a CO₂‐Pressure Induced Acidity Switch