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Kinetics and mechanism of the atmospheric oxidation of Ethyl tertiary butyl ether
Author(s) -
Smith D. F.,
Kleindienst T. E.,
Hudgens E. E.,
McIver C. D.,
Bufalini J. J.
Publication year - 1992
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550240208
Subject(s) - chemistry , radical , acetaldehyde , reaction rate constant , kinetics , ethyl formate , acetone , ethyl acetate , formaldehyde , ether , butyl acetate , reaction mechanism , inorganic chemistry , organic chemistry , medicinal chemistry , solvent , ethanol , physics , quantum mechanics , catalysis
Ethyl tertiary butyl ether (ETBE) is being proposed as an additive for use in reformulated gasolines. In this study, experiments were performed to examine the kinetics and mechanism of the atmospheric removal of ETBE. The kinetics of the reaction of ETBE with OH radicals were examined by using a relative rate technique with the photolysis of methyl nitrite to generate OH radicals. With n ‐hexane as the reference compound, a value of (9.73 ± 0.33) × 10 −12 cm 3 molecule −1 s −1 was obtained for the rate constant. The OH rate constant for t ‐butyl acetate, a product of the oxidation of ETBE, was (4.4 ± 0.4) × 10 −13 cm 3 molecule −1 s −1 at 298 K. The primary products and molar yields for the OH reaction with ETBE in the presence of NO x were t ‐butyl formate (0.64 ± 0.03), t ‐butyl acetate (0.13 ± 0.01), ethyl acetate (0.043 ± 0.003), acetaldehyde (0.16 ± 0.01), acetone (0.019 ± 0.002), and formaldehyde (0.53 ± 0.04). Under the described reaction conditions, the formation of t ‐butyl nitrite was also observed. From these molar yields, approximately 98% of the reacted ETBE could be accounted for by paths leading to these products. Chemical mechanisms to explain the formation of these products are presented.