%0 Journal Article
%A Taatjes, Craig A.
%A Liu, Fang
%A Rotavera, Brandon
%A Kumar, Manoj
%A Caravan, Rebecca
%A Osborn, David L.
%A Thompson, Ward H.
%A Lester, Marsha I.
%D 2016
%T Hydroxyacetone Production From C3 Criegee Intermediates
%U https://acs.figshare.com/articles/journal_contribution/Hydroxyacetone_Production_From_C_sub_3_sub_Criegee_Intermediates/4506350
%R 10.1021/acs.jpca.6b07712.s001
%2 https://ndownloader.figshare.com/files/7284284
%K reaction times
%K OH
%K multiplexed photoionization mass spectrometer detection
%K C 3 Criegee Intermediates Hydroxyacetone
%K CH
%K hydroxyacetone end product
%K 2 COO Criegee
%K Criegee intermediates
%K hydrogen atom transfer
%X Hydroxyacetone
(CH3C(O)CH2OH) is observed as a stable end product
from reactions of the (CH3)2COO Criegee intermediate,
acetone oxide, in a flow tube coupled with multiplexed photoionization
mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different
photoionization spectra and reaction times. Hydroxyacetone is observed
as a persistent signal at longer reaction times at a higher photoionization
threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison
with the known photoionization spectrum. Complementary electronic structure
calculations reveal multiple possible reaction pathways for hydroxyacetone
formation, including unimolecular isomerization via hydrogen atom
transfer and −OH group migration as well as self-reaction of
Criegee intermediates. Varying the concentration of Criegee intermediates
suggests contributions from both unimolecular and self-reaction pathways
to hydroxyacetone. The hydroxyacetone end product can provide an effective,
stable marker for the production of transient Criegee intermediates
in future studies of alkene ozonolysis.
%I ACS Publications