Ozonolysis of alpha-pinene and beta-pinene: kinetics and mechanism. Academic Article

abstract

• A combined quantum-chemical and RRKM/ME (ME--master equation) approach is employed to investigate the structures, energetics, and kinetics of intermediate and stable species, and the yields of stabilized carbonyl oxides and OH radicals from the alpha-pinene and beta-pinene ozonolysis reactions. The cycloaddition of O(3) is highly exothermic, with the reaction energies of 55.1 and 51.1 kcal mol(-1) for alpha- and beta-pinenes, respectively. Cleavage of primary ozonides yields carbonyl oxides with the barrier height of 12.2-17.5 kcal mol(-1). For the prompt reactions of carbonyl oxides from alpha- and beta-pinene ozonolysis, H migration to hydroperoxides represents the dominant pathway over ring closure to dioxiranes. The kinetic calculations indicate a significant portion of stabilization for alpha- and beta-carbonyl oxides. The yields of stabilized carbonyl oxides are estimated to be 0.34 for alpha-pinene and 0.22 for beta-pinene. The applicability of theoretical methods for investigation of oxidation reactions of large hydrocarbon molecules is demonstrated.

authors

• Zhang, Renyi

published proceedings

• J Chem Phys

author list (cited authors)

• Zhang, D., & Zhang, R.

citation count

• 91

complete list of authors

• Zhang, Dan||Zhang, Renyi

publication date

• March 2005

publisher

• AIP Publishing  Publisher

published in

• Journal of Chemical Physics  Journal

keywords

• Bicyclic Monoterpenes
• Bridged Bicyclo Compounds
• Computer Simulation
• Kinetics
• Models, Chemical
• Models, Molecular
• Molecular Conformation
• Monoterpenes
• Ozone
• Quantum Theory

PubMed Central ID

• 15836216

Digital Object Identifier (DOI)

• 10.1063/1.1862616

start page

• 114308

end page

• 114308

volume

• 122

issue

• 11

URL

• http%3A%2F%2Fdx.doi.org%2F10.1063%2F1.1862616