A chemiluminescence study of the decomposition of methyl linoleate hydroperoxides on active substrates |
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| Institution: | 1. Physico-Chemical Fundamentals of Combustion, RWTH Aachen University, 52056 Aachen, Germany;2. Chair of Technical Thermodynamics, RWTH Aachen University, 52056 Aachen, Germany;3. Institute for Combustion Technology, RWTH Aachen University, 52056 Aachen, Germany;4. Laboratory of Physical Chemistry, Department of Chemistry, University of Helsinki, A.I. Virtasen Aukio 1, FI-00560 Helsinki, Finland;5. Combustion Chemistry Centre, School of Chemistry & Ryan Institute, National University of Ireland Galway, H91 TK33 Galway, Ireland;1. Clean Combustion Research Centre, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia;2. Key Laboratory for Power Machinery and Engineering of MOE, Shanghai Jiao Tong University, Shanghai 200240, China;1. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, PR China;2. State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026, PR China;3. King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal 23955-6900, Saudi Arabia;4. Laboratoire Réactions et Génie des Procédés, CNRS – Université de Lorraine, ENSIC, 1 rue Grandville 54001 Nancy, France;5. Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551, United States |
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| Abstract: | Chemiluminescence (CL) from the decomposition of the hydroperoxides of methyl linoleate (ML) was studied between 70°C and 106°C in an inert atmosphere in the bulk, on neutral, acidic, and basic alumina, and on silica gel. The decomposition of the hydroperoxides in the bulk followed first order kinetics and showed the slowest decomposition rates. The largest signals and the fastest decays occurred on neutral alumina. The rate data indicated bimolecular decomposition of the hydroperoxides adsorbed on adjacent active sites. From sorption data it appeared that the majority of the hydroperoxides were bound by the ester group perpendicular to the surface while the remainder were believed to lie flat, being attached by the hydroperoxide group. The hydroperoxide is susceptible to acid catalysed decomposition on an acidic alumina substrate and this may account for the lower emission intensity observed on this substrate. |
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