Kinetics and Mechanisms of the Tropospheric Reactions of Menthol, Borneol, Fenchol, Camphor, and Fenchone with Hydroxyl Radicals (OH) and Chlorine Atoms (Cl)

Relative kinetic techniques have been used to measure the rate coefficients for the reactions of oxygenated terpenes (menthol, borneol, fenchol, camphor, and fenchone) and cyclohexanol with hydroxyl radicals (OH) and chlorine atoms (Cl) at 298 ± 2 K and atmospheric pressure. The rate coefficients ob...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2012-04, Vol.116 (16), p.4097-4107
Main Authors: Ceacero-Vega, Antonio A, Ballesteros, Bernabé, Bejan, Iustinian, Barnes, Ian, Jiménez, Elena, Albaladejo, José
Format: Article
Language:English
Subjects:
Bornanes - chemistry
Camphor
Camphor - chemistry
Chlorine
Chlorine - chemistry
Cyclohexanols - chemistry
Fourier transforms
Gas Chromatography-Mass Spectrometry
Hydroxyl Radical - chemistry
Hydroxyl radicals
Infrared spectroscopy
Kinetics
Mass spectrometry
Menthol
Menthol - chemistry
Norbornanes - chemistry
Pressure
Reaction kinetics
Solid Phase Microextraction
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Summary:Relative kinetic techniques have been used to measure the rate coefficients for the reactions of oxygenated terpenes (menthol, borneol, fenchol, camphor, and fenchone) and cyclohexanol with hydroxyl radicals (OH) and chlorine atoms (Cl) at 298 ± 2 K and atmospheric pressure. The rate coefficients obtained for the reactions of the title compounds with OH are the following (in units of 10–11 cm3 molecule–1 s–1): (1.48 ± 0.31), (2.65 ± 0.32), (2.49 ± 0.30), (0.38 ± 0.08), (0.39 ± 0.09) for menthol, borneol, fenchol, camphor, and fenchone, respectively. For the corresponding reactions with Cl atoms the rate coefficients are as follows (in units of 10–10 cm3 molecule–1 s–1): (3.21 ± 0.26), (3.40 ± 0.28), (2.72 ± 0.13), (2.93 ± 0.17), (1.59 ± 0.10), and (1.86 ± 0.29) for cyclohexanol, menthol, borneol, fenchol, camphor, and fenchone, respectively. The reported error is twice the standard deviation. Product studies of the reactions were performed using multipass in situ FTIR (Fourier transform infrared spectroscopy) and solid-phase microextraction (SPME) with analysis by GC–MS (gas chromatography–mass spectrometry). A detailed mechanism is proposed to justify the observed reaction products.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp212076g