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Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products
Author(s) -
Braure Tristan,
Riffault Véronique,
Tomas Alexandre,
Olariu Romeo Iulian,
Arsene Cecilia,
Bedjanian Yuri,
Coddeville Patrice
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20934
Subject(s) - ozonolysis , chemistry , alkene , ozone , laminar flow reactor , yield (engineering) , analytical chemistry (journal) , chromatography , organic chemistry , catalysis , physics , turbulence , thermodynamics , materials science , metallurgy , open channel flow
ABSTRACT The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10 −17 for 22dM3H and (2.71 ± 0.26) × 10 −17 for 25dM3H, both in cm 3 molecule −1 s −1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor.