Abstract
The construction of mechanistic models for the autoxidation of fatty acid or ester substrates found in oil paint binders is a challenging undertaking due to the complexity of the large crosslinked species that form, and the small molecules that volatilize. Building models that capture this product diversity are made possible by automating the process of network generation. This work presents a microkinetic model for the autoxidation of ethyl linoleate catalyzed by cobalt(II) 2-ethyl hexanoate. The mechanism size was controlled by using a rate-based criterion to include the most kinetically relevant reactions from among the millions of possible reactions generated. The resulting model was solved and compared to experimental metrics. Quantities such as hexanal production and the consumption of unsaturated moieties were in good agreement with experiment. Finally, the model was used to explore the effect of the catalyst concentration and temperature on key measurables.
Original language | English (US) |
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Pages (from-to) | 7413-7417 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 57 |
Issue number | 25 |
DOIs | |
State | Published - Jun 18 2018 |
Funding
Financial support for this work from the National Science Foundation Division of Materials Research (DMR-1241667) and the Northwestern University/Art Institute of Chicago Center for Scientific Studies in the Arts (NU-ACCESS) is gratefully acknowledged.
Keywords
- ethyl linoleate
- kinetics
- oil paint
- oxidation
- surface chemistry
ASJC Scopus subject areas
- Catalysis
- General Chemistry