Thermodynamic Analysis of α‐Pinene and Limonene Allylic Oxidation over a FePcCl16‐NH2‐SiO2 Catalyst

Abstract

AbstractFrom oxidation over a FePcCl16‐NH2‐SiO2 catalyst and tert‐butyl hydroperoxide (TBHP) as oxidant, verbenone, α‐pinene epoxide, and verbenol were obtained from α‐pinene while carvone, limonene 1,2‐epoxide and carveol were produced from limonene. TBHP decomposes into O2, tert‐butanol, and di‐tert‐butyl peroxide (DTBP). With the aim to perform a batch‐reactor conceptual design, α‐pinene and limonene oxidation was thermodynamically analyzed. Standard enthalpy and entropy of formation, liquid heat capacity, enthalpy of reaction and vaporization, and Gibbs free energy were determined by group contribution methods using Aspen Plus® simulation. Although the results depend on the method, it was found that α‐pinene and limonene oxidations were exothermic and spontaneous at the selected reaction temperature. However, TBHP decomposition into O2, tert‐butanol, and DTBP was an endothermic reaction.