Infinite dilution activity coefficients for oxygenate systems determined using a differential static cell

Pividal, Katherine A.; Birtigh, Andreas; Sandler, Stanley I.

doi:10.1021/je00008a025

Cited by 60 publications

(25 citation statements)

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“…To understand the influence of ethanol on K γ and, thus, on K x , the activity coefficients of the reactants and products as calculated by PC‐SAFT are shown as functions of the ethanol mole fraction at equilibrium in Figure . While the activity coefficients of the reactants (acetic acid and ethanol) are almost constant, the activity coefficients of the products (water and ethyl acetate) increase with increasing ethanol concentration, as is already known from the respective binary systems . According to Eq.…”

Section: Resultsmentioning

confidence: 80%

Solvent effects on esterification equilibria

et al. 2015

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Solvents are known to have strong impacts on the yields of equilibrium reactions. This work focuses on the thermodynamic investigation of these solvent effects on esterification reactions of acetic acid and propionic acid with ethanol. Esterification of acetic acid was performed in the solvents acetone, acetonitrile (ACN), dimethylformamide (DMF), and tetrahydrofurane as well as in mixtures thereof. ACN promotes the esterification of acetic acid, whereas it is strongly suppressed by DMF. The esterification of propionic acid was investigated with various reactant concentrations in acetone. The experimental equilibrium data in pure solvents and solvent mixtures were modeled using the thermodynamic equilibrium constant Ka and the reactant/product activity coefficients predicted by the perturbed chain‐statistical associating fluid theory (PC‐SAFT). For a given Ka, PC‐SAFT is able to predict the influence of the solvent and even solvent mixtures on the equilibrium concentrations of esterification in almost quantitative agreement with the experimental data. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3000–3011, 2015

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Section: Resultsmentioning

confidence: 80%

Solvent effects on esterification equilibria

et al. 2015

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“… a Covarrubias‐Cervantes et al ,35 Nongonierma et al ,8 Pividal et al ,36 Le Thanh et al ,17, 37, 38, 44, 50 Carelli et al ,26 Harvey et al ,27 Voilley and Bosset,39 Voilley and Sauvageot,40 Druaux et al ,41 Landy et al ,42 Fares et al ,43 Sancho et al ,28 Marinos and Saravacos,45 Philippe et al ,30 Nelson and Hoff,46 Sorrentino et al ,47 Baudot et al ,48 Kolb et al 49 …”

Section: Resultsmentioning

confidence: 99%

Retention of aroma compounds: an interlaboratory study on the effect of the composition of food matrices on thermodynamic parameters in comparison with water

Kopjar¹,

Andriot²,

Saint-Eve³

et al. 2010

J Sci Food Agric

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“…Second, the solvation free energy of H2O in 2PL was associated with a large negative value of −30.83 kJ•mol −1 , inconsistent with the solvation free energies of H2O in other small alcohols (e.g., −21.24 and −16.4 kJ• mol −1 for the solvation of H2O in ETL and BTL, respectively). Here, we estimated a new value of 5.60 for γ ∞,H2O:2PL ⊖ by extrapolating a value reported 180 at T = 288.15 K according to…”

Section: A2 Data-curation Proceduresmentioning

confidence: 99%

Evaluating Classical Force Fields against Experimental Cross-Solvation Free Energies

Kashefolgheta

Oliveira

Rieder

et al. 2020

J. Chem. Theory Comput.

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Experimental solvation free energies are nowadays commonly included as target properties in the validation and sometimes even in the calibration of condensed-phase force fields. However, this is often done in a nonsystematic fashion, by considering available solvation free energies involving an arbitrary collection of solutes in a limited set of solvents (e.g., water, octanol, chloroform, cyclohexane, or hexane). Here, this approach is made more systematic by introducing the concept of cross-solvation free energies Δ s G A:B ⊖ for a set of N molecules that are all in the liquid state under ambient conditions, namely the matrix of N 2 entries for Δ s G A:B ⊖ considering each of the N molecules either as a solute (A) or as a solvent (B). Relying on available experimental literature followed by careful data curation, a complete Δ s G A:B ⊖ matrix of 625 entries is constructed for 25 molecules with one to seven carbon atoms representative for alkanes, chloroalkanes, ethers, ketones, esters, alcohols, amines, and amides. This matrix is then used to compare the relative accuracies of four popular condensed-phase force fields: GROMOS-2016H66, OPLS-AA, AMBER-GAFF, and CHARMM-CGenFF. In broad terms, and in spite of very different force-field functional-form choices and parametrization strategies, the four force fields are found to perform similarly well. Relative to the experimental values, the root-mean-square errors range between 2.9 and 4.0 kJ·mol–1 (lowest value of 2.9 for GROMOS and OPLS), and the average errors range between −0.8 and +1.0 kJ·mol–1 (lowest magnitude of 0.2 for AMBER and CHARMM). These differences are statistically significant but not very pronounced, especially considering the influence of outliers, some of which possibly caused by inaccurate experimental data.

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Infinite dilution activity coefficients for oxygenate systems determined using a differential static cell

Cited by 60 publications

References 6 publications

Solvent effects on esterification equilibria

Solvent effects on esterification equilibria

Retention of aroma compounds: an interlaboratory study on the effect of the composition of food matrices on thermodynamic parameters in comparison with water

Evaluating Classical Force Fields against Experimental Cross-Solvation Free Energies

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