화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.122, No.43, 8674-8685, 2018
Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor
Ethylene oxidation initiated by ozone addition (ozonolysis) is carried out in a jet-stirred reactor from 300 to 1000 K to explore the kinetic pathways relevant to low-temperature oxidation. The temperature dependencies of species' mole fractions are quantified using molecular-beam mass spectrometry with electron ionization and single-photon ionization employing tunable synchrotron-generated vacuum-ultraviolet radiation. Upon ozone addition, significant ethylene oxidation is found in the low-temperature regime from 300 to 600 K. Here, we provide new insights into the ethylene ozonolysis reaction network via identification and quantification of previously elusive intermediates by combining experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Specifically, the C2H4 + O-3 adduct C2H4O3 is identified as a keto-hydroperoxide (hydroperoxy-acetaldehyde, HOOCH2CHO) based on the calculated and experimentally observed ionization energy of 9.80 (+/- 0.05) eV. Quantification using a photoionization cross-section of 5 Mb at 10.5 eV results in 5 ppm at atmospheric conditions, which decreases monotonically with temperature until 550 K. Other hydroperoxide species that contribute in larger amounts to the low-temperature oxidation of C2H4, like H2O2, CH3OOH, and C2H5OOH, are identified and their temperature-dependent mole fractions are reported. The experimental evidence for additional oxygenated species such as methanol, ketene, acetaldehyde, and hydroxy-acetaldehyde suggest multiple active oxidation routes. This experimental investigation closes the gap between ozonolysis at atmospheric and elevated temperature conditions and provides a database for future modeling.