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Kinetic Modeling of Maleic Acid Isomerization to Fumaric Acid Catalyzed by Thiourea Determined by Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy
journal contribution
posted on 2020-05-22, 21:03 authored by Victor Tozatto Verissimo Lobo, Ronald Wbeimar Pacheco Ortiz, Vinicius Ottonio
O. Gonçalves, João Cajaiba, Vinicius KartnallerFumaric
acid (FA) is an important commodity in the food and polymer industries;
its main route of production is the chemical synthesis from maleic
acid (MA). In this work, the isomerization of MA to FA catalyzed by
thiourea was investigated. The experiments were performed in an automated
reactor with temperature and stirring control, using methanol as the
solvent to ensure a homogeneous system and to avoid a possible parallel
hydration reaction to malic acid. The reaction kinetics was monitored
in real time by attenuated total reflectance Fourier-transform infrared
spectroscopy (ATR/FT-IR). Studies on the influence of the catalyst
concentration (1–20% of the initial molar concentration of
MA) and the temperature (20–60 °C) were carried out in
reaction times between 2 and 5 h. The kinetics of the reaction was
modeled using an integral method over the infrared data, assuming
a reaction mechanism that yielded a partial order of 1.41 for the
MA concentration and a 0.99 order for the thiourea. These orders were
similar to the ones found by the proposed mechanism for the acid-catalyzed
isomerization, in which monomaleate is a nucleophilic reagent to react
with the protonated MA. This may present a path for further studies
regarding the correct reaction mechanism. The kinetic model provided
an excellent correlation with the experimental data, and the observed
activation energy of the reaction was calculated to be 43.1 kJ mol–1. At higher temperatures, such as 60 °C, and
with a thiourea concentration of 10% mol/mol (0.0502 mol L–1), the isomerization conversion was around 90% in 60 min. Accordingly,
thiourea proved to be an appropriate catalyst for FA synthesis, and
ATF/FT-IR proved to be a reliable technique for the kinetic study.