Isomer-specific product detection of CN radical reactions with ethene and propene by tunable VUV photoionization mass spectrometry

Abstract

Product detection studies of CN reactions with ethene and propene are conducted at room temperature (4 Torr, 533.3 Pa) using multiplexed time-resolved mass spectrometry with tunable synchrotron photoionization. Photoionization efficiency curves, i.e., the ion signal as a function of photon energy, are used to determine the products and distinguish isomers. Both reactions proceed predominantly via CN addition to the π orbital of the olefin. For CN + ethene, cyanoethene (C 2H 3CN) is detected as the sole product in agreement with recent studies on this reaction. Multiple products are identified for the CN + propene reaction with 75(±15)% of the detected products in the form of cyanoethene from a CH 3 elimination channel and 25(±15)% forming different isomers of C 4H 5N via H elimination. The C 4H 5N comprises 57(±15)% 1-cyanopropene, 43(±15)% 2-cyanopropene and <15% 3-cyanopropene. No evidence of direct H abstraction or indirect HCN formation is detected for either reaction. The results have relevance to the molecular weight growth chemistry on Saturn's largest moon Titan, where the formation of small unsaturated nitriles are proposed to be key steps in the early chemical stages of haze formation.