Solubility study and thermodynamic modelling of succinic acid and fumaric acid in bio-based solvents

https://doi.org/10.1016/j.molliq.2022.120836Get rights and content
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Highlights

  • Solubilities of two important organic acids for the bio-refinery industry have been measured in several bio-based green solvents and correlated.

  • Activity coefficients and excess energies at the saturation concentration were estimated from the solid–liquid equilibria computed by the COSMO-RS method.

  • Systems molecular interactions were analyzed throughout the excess enthalpy contributions: electrostatic, hydrogen bonding, and van der Waals forces interactions.

  • The free Gibbs energy, enthalpy, and entropy of solution of all systems were estimated at the experimental harmonic mean temperature.

Abstract

The solubility and involved energies of organic acids in green solvents are relevant to the design of sustainable biorefinery downstream processes. In this work, the solubility of two important bio-based organic acids such as succinic acid and fumaric acid, in water and four bio-based solvents (i.e., ethyl acetate, 1,8-cineole, cyclopentyl methyl ether, and 2-methyl tetrahydrofuran) were measured within a temperature range of [283 – 313] K. A gravimetric methodology was adopted, previously validated using the organic acid aqueous solubilities available in the literature. The reported data present an average estimated uncertainty of measurement, with a level of confidence of 95%, of 5.2·10-4 mol·mol−1. Experimental results were correlated with the van’t Hoff equation, and the Buchowski–Ksiazaczak λh model, where the root mean squared deviations were <3.9·10-4 for all systems. From the experimental data and the COSMO-RS molecular simulation method, the solid–liquid equilibria were modelled to estimate the excess energies and the solute activity coefficients of the saturated solutions. Excess enthalpy contribution analysis shows that attractive hydrogen-bonding interactions between the organic acids and the green solvents drive the dissolution phenomena. The magnitude of the hydrogen-bonding interactions increases with temperature for all systems, agreeing with the observed solubility trends. The organic acid energies of solution were estimated from the van’t Hoff equation, demonstrating an enthalpy–entropy compensation effect. The energetic analysis shows that the dissolution phenomenon is an enthalpy-driven process for fumaric acid, whereas no predominant effect is observed for succinic acid.

Graphical abstract

Solubilities of succinic and fumaric acids in water and bio-based solvents were experimentally measured and correlated, and thermodynamically assessed.

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Keywords

Organic acid
Green solvent
Solubility
COSMO-RS
Solution energy

Data availability

Data will be made available on request.

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