Oxidation of C₅ esters: Influence of the position of the ester function

Abstract

The oxidation of esters has been extensively studied over the past 15 years, mainly focusing on methyl‐ and ethyl‐esters. Recently, the oxidation of esters produced from higher alcohols has received more and more attention. In this work, we report experiments and modeling on the oxidation of a series of four esters with five carbon atoms, namely, methyl butanoate, ethyl propanoate, propyl acetate, and butyl formate. The oxidation of these esters was performed in a jet‐stirred reactor under the same experimental conditions (τ = 700 ms, p = 10 atm, φ = 1, and Xfuel, initial = 1000 ppm). The mole fraction profiles obtained from these experiments were used to develop a unique detailed kinetic mechanism for the oxidation of these four esters, which performs well against our experimental data and on data from the literature. Although these esters are isomers, this work highlights the influence of the position of the ester function in terms of global reactivity and product distribution. In particular, this comparison shows the strong impact of the nature of the products (i.e., acid + alkene) formed by the different molecular decomposition reactions during the oxidation process of these esters.