Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes. Issue 2 (30th September 2020)

• Record Type: Journal Article
• Authors: Barraza‐Botet, Cesar L.; Liu, Changpeng; Kim, John H.; Wagnon, Scott W.; Wooldridge, Margaret S.
• Is Part Of: International journal of chemical kinetics. Volume 53:Issue 2(2021)
• Page Start: 287
• Page End: 298
• Publication Date: 2020-09-30
• Subjects: cis and trans isomers -- hexene isomers -- ignition and species measurements; Chemical kinetics -- Periodicals; 541.394
• DOI: 10.1002/kin.21442
• Languages: English
• ISSNs: 0538-8066

Abstract

Abstract: The current work presents new experimental autoignition and speciation data on the two cis ‐hexene isomers: cis ‐2‐hexene and cis ‐3‐hexene. The new data provide insights on the effects of carbon‐carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure‐time histories. Stoichiometric (ϕ = 1.0) mixtures at dilution levels of inert gas to O2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted at T = 900 K for the two cis ‐hexene isomers, where fast‐gas sampling and gas chromatography were used to identify and quantify the two cis ‐hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon‐carbon double bond and the stereoisomeric structure (cis‐trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2‐hexene showed strong selectivity to propene, acetaldehyde, and 1, 3‐butadiene, and 3‐hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. There was generally good agreement for the model predictions of the species data for 2‐hexene; however, the mechanism overpredicted some of the small aldehyde (C2 ‐C4 ) species for 3‐hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H‐atom abstraction reactions at the conditions studied ( P = 11 atm, T > 900 K), and not by C3 ‐C4 scission as observed in high‐temperature (>1300 K) hexene ignition studies. Improved estimates for 3‐hexene + OH reactions may improve model predictions for the species measured in this work.