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Oxidation of ethyl ether on borate glass: chemiluminescence, mechanism, and development of a sensitive gas sensor
Jing Hu1, Kailai Xu, Yunzhen Jia
1Key Laboratory of Green Chemistry & Technology of MOE at College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China.
Abstract:
A gas sensor was developed by using the chemiluminescence (CL) emission from the oxidation of ethyl ether by oxygen in the air on the surface of borate glass. Theoretical calculation, together with experimental investigation, revealed the main CL reactions: ethyl ether is first oxidized to acetaldehyde and then to acetic acid, during which main luminous intermediates such as CH 3CO (*) are generated and emit light with a peak at 493 nm. At a reaction temperature of 245 degrees C, the overall maximal emission was found at around 460 nm, and the linear range of the CL intensity versus the concentration of ethyl ether was 0.12-51.7 microg mL (-1) ( R = 0.999, n = 7) with a limit of detection (3sigma) of 0.04 microg mL (-1). Interference from foreign substances including alcohol (methanol, ethanol and isopropanol), acetone, ethyl acetate, n-hexane, cyclohexane, dichloromethane, or ether ( n-butyl ether, tetrahydrofuran, propylene oxide, isopropyl ether and methyl tert-butyl ether) was not significant except a minimal signal from n-butyl ether (<2%). It is a simple, sensitive and selective gas sensor for the determination of trace ethyl ether.
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Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
