Title

Branching fractions of the CN + C3H6 reaction using synchrotron photoionization mass spectrometry: evidence for the 3-cyanopropene product

RIS ID

43978

Publication Details

Trevitt, A. J., Soorkia, S., Savee, J. D., Selby, T. S., Osborn, D. L., Taatjes, C. A. & Leone, S. R. (2011). Branching fractions of the CN + C3H6 reaction using synchrotron photoionization mass spectrometry: evidence for the 3-cyanopropene product. Journal of Physical Chemistry A, 115 (46), 13467-13473.

Abstract

The gas-phase CN + propene reaction is investigated using synchrotron photoionization mass spectrometry (SPIMS) over the 9.8 - 11.5 eV photon energy range. Experiments are conducted at room temperature in 4 Torr of He buffer gas. The CN + propene addition reaction produces two distinct product mass channels, C3H3N and C4H5N, corresponding to CH3 and H elimination, respectively. The CH3 and H elimination channels are measured to have branching fractions of 0.59 + 0.15 and 0.41 + 0.10, respectively. The absolute photoionization cross sections between 9.8 and 11.5 eV are measured for the three considered H-elimination coproducts: 1-, 2-, and 3-cyanopropene. Based on fits using the experimentally measured photoionization spectra for the C4H 5N mass channel and contrary to the previous study (Int. J. Mass. Spectrom.2009, 280, 113 - 118), where it was concluded that 3-cyanopropene was not a significant product, the new data suggests 3-cyanopropene is produced in significant quantity along with 1-cyanopropene, with isomer branching fractions from this mass channel of 0.50 + 0.12 and 0.50 + 0.24, respectively. However, similarities between the 1-, 2-, and 3-cyanopropene photoionization spectra make an unequivocal assignment difficult based solely on photoionization spectra. The CN + CH2CHCD3 reaction is studied and shows, in addition to the H-elimination product signal, a D-elimination product channel (m/z 69, consistent with CH2CHCD 2CN), providing further evidence for the formation of the 3-cyanopropene reaction product. Copyright 2011 American Chemical Society.

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Link to publisher version (DOI)

http://dx.doi.org/10.1021/jp208496r