Multiphase Ozonolysis of Aqueous α-Terpineol. 2016

Dani H Leviss, and Daryl A Van Ry, and Ryan Z Hinrichs
Department of Chemistry, Drew University , Madison, New Jersey 07940, United States.

Multiphase ozonolysis of aqueous organics presents a potential pathway for the formation of aqueous secondary organic aerosol (aqSOA). We investigated the multiphase ozonolysis of α-terpineol, an oxygenated derivative of limonene, and found that the reaction products and kinetics differ from the gas-phase ozonolysis of α-terpineol. One- and two-dimensional NMR spectroscopies along with GC-MS identified the aqueous ozonolysis reaction products as trans- and cis-lactols [4-(5-hydroxy-2,2-dimethyltetrahydrofuran-3-yl)butan-2-one] and a lactone [4-hydroxy-4-methyl-3-(3-oxobutyl)-valeric acid gamma-lactone], which accounted for 46%, 27%, and 20% of the observed products, respectively. Hydrogen peroxide was also formed in 10% yield consistent with a mechanism involving decomposition of hydroxyl hydroperoxide intermediates followed by hemiacetal ring closure. Multiphase reaction kinetics at gaseous ozone concentrations of 131, 480, and 965 parts-per-billion were analyzed using a resistance model of net ozone uptake and found the second-order rate coefficient for the aqueous reaction of α-terpineol + O3 to be 9.9(±3.3) × 106 M-1 s-1. Multiphase ozonolysis will therefore be competitive with multiphase oxidation by hydroxyl radicals (OH) and ozonolysis of gaseous α-terpineol. We also measured product yields for the heterogeneous ozonolysis of α-terpineol adsorbed on glass, NaCl, and kaolinite, and identified the same three major products but with an increasing lactone yield of 33, 49, and 55% on these substrates, respectively.

UI MeSH Term Description Entries
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D010126 Ozone The unstable triatomic form of oxygen, O3. It is a powerful oxidant that is produced for various chemical and industrial uses. Its production is also catalyzed in the ATMOSPHERE by ULTRAVIOLET RAY irradiation of oxygen or other ozone precursors such as VOLATILE ORGANIC COMPOUNDS and NITROGEN OXIDES. About 90% of the ozone in the atmosphere exists in the stratosphere (STRATOSPHERIC OZONE). Ground Level Ozone,Low Level Ozone,Tropospheric Ozone,Level Ozone, Ground,Level Ozone, Low,Ozone, Ground Level,Ozone, Low Level,Ozone, Tropospheric
D000336 Aerosols Colloids with a gaseous dispersing phase and either liquid (fog) or solid (smoke) dispersed phase; used in fumigation or in inhalation therapy; may contain propellant agents. Aerosol
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide
D017665 Hydroxyl Radical The univalent radical OH. Hydroxyl radical is a potent oxidizing agent.

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