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Author(s):   DeSain, J.D.; Klippenstein, S.J.; Taatjes, C.A.; Hurley, M.D.; Wallington, T.J.
Title:   Product Formation in the Cl-Initiated Oxidation of Cyclopropane
Journal:   J. Phys. Chem. A
Volume:   107
Page(s):   1992 - 2002
Year:   2003
Reference type:   Journal article
Squib:   2003DES/KLI1992-2002

Reaction:   Cyclopropyl + O2Oxirane + HCO
Reaction order:   2
Temperature:   298 K
Pressure:  0.93 bar
Rate expression:   3.8x10-13 [cm3/molecule s]
Bath gas:   N2
Category:  Experiment
Data type:   Derived from fitting to a complex mechanism
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Other (IR)
Comments:   Combined experimental and ab initio quantum study. Energetics of reaction pathways computed using QCISD(T)/6-311++G(3df,2pd) and QCISD(T)/cc-pVnZ/CBS(D,T,Q). Paper contains some new estimates for heats of formation of a number of species from ab initio calculations. Reaction of Cyclopropyl+O2 was monitored by detecting OH and HO2 as a function of temperature 300-700 K. Based on observed concentrations a model was constructed with rate constants consistent with data. These rate constants for the branching ratios for different channels for Cyclopropyl + O2 were indirectly derived from this model.

Relative rate constants of Cyclopropyl+O2 and Cyclopropyl+Cl2 were also measured at different pressures. A rate constant for Cycloropane+Cl was derived from HO2 production being a rate limiting step for further reactions of cyclopropyl.

Cyclopropyl produced via Cyclopropane+Cl where Cl produced by 355 nm laser photolysis of Cl2. OH and HO2 detected using CW IR frequency modulation and FTIR absorption. In the HO2 and OH production experiments typically used total pressure of about 8.5E17 cm-3 He, Cyclopropane of 8-50E15 cm-3, O2 6.4E16 cm-3, and Cl2 2E15 cm-3. In UV Smog chamber FTIR experiments typically 10-700 torr N2 at 296 K, with 100-200 mtorr Cyclopropane, 1.0 torr Cl2, and 0.05-10 torr O2.

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