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

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....

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Detalles Bibliográficos
Autores: López-Porfiri, Pablo, Gorgojo, Patricia, González-Miquel, María
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/330070
Acceso en línea:http://hdl.handle.net/10261/330070
Access Level:acceso abierto
Palabra clave:Organic acid
Green solvent
Solubility
Solution energy
COSMO-RS
Descripción
Sumario: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.