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

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.