ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A kinetic study has been made of the 3130-Å photolysis of CH2O (8 torr) in O2-containing mixtures (0.02-8 torr) and in the presence of added CO2 (0-300 torr) at 25°C. Quantum yields of formation of H2, CO, and CO2 and the loss of O2 were measured. ΦH2 and ΦCO were much above unity. In an explanation of these unexpected results, a new H-atom-forming chain mechanism was postulated involving HO2 and HO addition to CH2O: CH2O + hν → H + HCO (1) H + CH2O → H2 + HCO (3) H + O2 + M → HO2 + M (6) HCO + O2 → HO2 + CO (8) HO2 + CH2O → (HO2CH2O) → HO + HCO2H (15) HO + CH2O → H2O + HCO† (16); HCO† → H + CO (19) HO + CH2O → H2O + HCO (17) and HO + CH2O → HCO2H + H (18). When the results are rationalized in terms of this mechanism, the data suggest k16 ≫ k17 and k16/k18 ≅ 0.5. The data require that a reassessment of the relative rates of reactions (7) and (8) be made, since in the previous work HCO2H formation was used as a monitor of the rate of reaction (7) HCO + O2 + M → HCOO2 + M (7). The present data from experiments at PCH2O = 8 torr and PO2 = 1-4 torr give k7[M]/(k7[M] + k8) ≥ 0.049 ± 0.017. These data coupled with the k8 estimates of Washida and coworkers give k7 ≥ (4.4 ± 1.6) × 1011 l2/mol2·sec for M = CH2O. The reaction sequence proposed here is consistent with the observed deterimental effect of O2 addition on the laser-induced isotope enrichment in HDCO. In additional studies of CH2O-O2-isobutene mixtures it was found that ΦH2 was equal to φ2 as estimated in O2-free CH2O-isobutene mixtures. These results suggest that the increase in CO (ν = 1) product observed with O2 addition in CH2O photolysis does not result from perturbations in the fragmentation pattern of the excited CH2O, but it is likely that it originates in the occurrence of the exothermic reaction HCO + O2 → HO2 + CO (ν = 1).
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550101102
