scholarly journals A Time Resolved IR Laser Photolysis-Laser Induced Fluorescence Study of the OH/Methanol Reaction

1995 ◽  
Vol 16 (2) ◽  
pp. 53-61
Author(s):  
José M. Riveros ◽  
Luis Gilberto Barreta
Keyword(s):  
Isotope Effects ◽  
Laser Induced Fluorescence ◽  
Bulk Temperature ◽  
Buffer Gas ◽  
Fluorescence Study ◽  
Time Resolved ◽  
Ir Laser ◽  
Multiphoton Dissociation ◽  
Photolysis Laser ◽  
Good Agreement

The reaction of hydroxyl radicals (OH and OD) generated by infrared multiphoton dissociation of different isotopomers of methanol were studied in the presence of variable amounts of Ar buffer gas. The disappearance of the OH, or OD, radicals in the presence of the parent methanol was followed by laser induced fluorescence at 310 nm. Comparison of the rate constants obtained from these experiments reveal good agreement with observed isotope effects observed by other authors but suggest that the reactions occurs at higher temperatures than the macroscopic bulk temperature of the sample.

Time-Resolved Laser-Induced Fluorescence Study of Photoinduced Electron Transfer at the Water/1,2-Dichloroethane Interface

1997 ◽  
Vol 101 (14) ◽  
pp. 2519-2524 ◽  
Author(s):  
Robert A. W. Dryfe ◽  
Zhifeng Ding ◽  
R. Geoffrey Wellington ◽  
Pierre F. Brevet ◽  
Alexander M. Kuznetzov ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Laser Induced Fluorescence ◽  
Fluorescence Study ◽  
Time Resolved

Time-resolved laser-induced fluorescence study of NO removal plasma technology in N2/NO mixtures

2000 ◽  
Vol 33 (11) ◽  
pp. 1315-1322 ◽  
Author(s):  
F Fresnet ◽  
G Baravian ◽  
S Pasquiers ◽  
C Postel ◽  
V Puech ◽  
...  
Keyword(s):  
Laser Induced Fluorescence ◽  
Plasma Technology ◽  
Fluorescence Study ◽  
Time Resolved ◽  
No Removal

Temperature Dependent Kinetics of the OH/HO2/O3Chain Reaction by Time-Resolved IR Laser Absorption Spectroscopy

2000 ◽  
Vol 104 (17) ◽  
pp. 3964-3973 ◽  
Author(s):  
Sergey A. Nizkorodov ◽  
Warren W. Harper ◽  
Bradley W. Blackmon ◽  
David J. Nesbitt
Keyword(s):  
Absorption Spectroscopy ◽  
Laser Absorption Spectroscopy ◽  
Temperature Dependent ◽  
Time Resolved ◽  
Laser Absorption ◽  
Ir Laser ◽  
Kinetics Of

scholarly journals Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2

2020 ◽  
Vol 234 (7-9) ◽  
pp. 1233-1250 ◽  
Author(s):  
Arrke J. Eskola ◽  
Mark A. Blitz ◽  
Michael J. Pilling ◽  
Paul W. Seakins ◽  
Robin J. Shannon
Keyword(s):  
Energy Transfer ◽  
Master Equation ◽  
Rate Coefficient ◽  
Zero Point ◽  
Buffer Gas ◽  
Unimolecular Decomposition ◽  
Time Resolved ◽  
Point Energy ◽  
Wide Range ◽  
Transfer Parameters

AbstractThe rate coefficient for the unimolecular decomposition of CH3OCH2, k1, has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)2, in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k1(T,p) was measured over the ranges: 573–673 K and 0.1–4.3 × 1018 molecule cm−3 with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, ΔE0,1, and the energy transfer parameters, ⟨ΔEdown⟩ × Tn, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem.1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned ΔE0,1 = (112.3 ± 0.6) kJ mol−1, and leads to $k_{1}^{\infty}(T)=2.9\times{10^{12}}$ (T/300)2.5 exp(−106.8 kJ mol−1/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N2 was the buffer gas, to generate k1(T,p) over a wide range of conditions: 300–1000 K and N2 = 1012–1025 molecule cm−3. The resulting k1(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k1(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N2.

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