A comprehensive experimental and kinetic modeling study of di-isobutylene isomers: Part 2

A wide variety of high temperature experimental data obtained in this study complement the data on the oxidation of the two di-isobutylene isomers presented in Part I and offers a basis for an extensive validation of the kinetic model developed in this study. Due to the increasing importance of unimolecular decomposition reactions in high-temperature combustion, we have investigated the di-isobutylene isomers in high dilution utilizing a pyrolysis microflow reactor and detected radical intermediates and stable products using vacuum ultraviolet (VUV) synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy. Additional speciation data at oxidative conditions were also recorded utilizing a plug flow reactor at atmospheric pressure in the temperature range 725-1150 K at equivalence ratios of 1.0 and 3.0 and at residence times of 0.35 s and 0.22 s, respectively. Combustion products were analyzed using gas chromatography (GC) and mass spectrometry (MS). Ignition delay time measurements for di-isobutylene were performed at pressures of 15 and 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in air in the temperature range 900-1400 K using a high-pressure shock-tube facility. New measurements of the laminar burning velocities of di-isobutylene/air flames are also presented. The experiments were performed using the heat flux method at atmospheric pressure and initial temperatures of 298-358 K. Moreover, data consistency was assessed with the help of analysis of the temperature and pressure dependencies of laminar burning velocity measurements, which was interpreted using an empirical power-law expression. Electronic structure calculations were performed to compute the energy barriers to the formation of many of the product species formed. The predictions of the present mechanism were found to be in adequate agreement with the wide variety of experimental measurements performed. (c) 2022 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/ )

Automated summary

A wide range of high temperature experimental data was obtained to complement the oxidation data of the two di-isobutylene isomers presented in Part I, providing a basis for validating the developed kinetic model. Utilizing a pyrolysis microflow reactor, radical intermediates and stable products were detected for the di-isobutylene isomers in high dilution. Additional speciation data under oxidative conditions were recorded using a plug flow reactor, and combustion products were analyzed using GC and MS. Ignition delay time measurements, laminar burning velocities, and electronic structure calculations were also performed, and the predictions of the present mechanism were found to be in good agreement with the experimental measurements.