Fourier Transform Infrared-Probed O(3P) Microreactor: Demonstration with Ethylene Reactions in Argon Matrix

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Abstract:

To demonstrate the development of an oxygen atom microreactor in the form of liquid-helium-cooled solid argon matrix deposited on an infrared (IR) window, the oxidation of ethylene by mobile O atoms has been investigated. O atom diffusion through the argon matrix is confirmed and used to examine ethylene–oxygen atom reactions. In a bench-scale matrix isolation system probed with a Fourier transform infrared (FT-IR) spectrometer, matrices of solid Ar at 8–10 K doped with NO2 and ethylene have been prepared on a ZnSe window within an evacuated cryostat. The matrices have been photolyzed using 350–450 nm photons, and the reaction products resulting from the reaction of O(3P), one of the photolysis products of NO2, with ethylene have been identified using FT-IR and a Gaussian 98W simulation program. These products include oxirane, acetaldehyde, ethyl nitrite radical, and ketene. The temperature effect in the range of 10–30 K on the products formed has also been investigated. The reaction mechanisms are discussed and the viability of the solid Ar matrix being a low temperature microreactor to examine reaction mechanisms of mobile oxygen atoms is elaborated.

Keywords: AR MATRIX; ETHYLENE; FOURIER TRANSFORM INFRARED; FT-IR; MARM; MATRIX ATOM/RADICAL MICROREACTOR; MATRIX ISOLATION SPECTROSCOPY; NO2; OXYGEN ATOM MICROREACTOR; PHOTOLYSIS

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/0003702042336127

Affiliations: Department of Chemical Engineering, Lamar University, Beaumont, Texas 77710

Publication date: October 1, 2004

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