Hochgreb, S., and Dryer, F.L. (1992)
A Comprehensive Study on CH2O Oxidation Kinetics
Combust. Flame 1992, 91, 257.
Abstract
Results of calculations based on detailed chemical mechanism for the oxidation of
formaldehyde are compared with data from a variety of experimental conditions:
flow reactor, shock tube, static reactor, and a lean flame. The range of
conditions spans temperatures from 773 to 2500 K, equivalence ratios from pure
pyrolysis to very fuel-lean and pressures from 0.3 to 1.5 atm. New experimental
results from the oxidation of formaldehyde in flow reactors at 1095 K are
reported. The original model, based on reaction rate constants obtained in the
literature, was modified based on comparisons of calculated and experimental
results. Recommended changes were guided by extensive sensitivity and flux
analysis for each case, as well as on the current knowledge of uncertainties in
reaction rate constant values. The comprehensive mechanistic features of
formaldehyde oxidation at low and high temperatures are discussed. The results of
the analysis reveal the key role of HO2 radicals up to temperatures around 1100
K, through the cycle (168), (121) and (-85). Shock tube data are revisited
using more recent reaction rate constants to verify the model. Finally, the
competition between formyl radical reactions (167) and (168), which determines the rate of
production of H radicals, was found to be primary controlling factor in the
evolution of lean formaldehyde flames. A matrix of influences of the most
important reaction rates on the calculated parameters for the different
experimental conditions summarizes the conclusions.
REACTION RATE COEFFICIENTS SUGGESTED IN THIS WORK:
GRI-Mech Number ('-' sign means reverse) |
Reaction |
Rate Coefficient A T^n exp(-E/RT) |
Temperature Range (K) |
A (mol,cm3,s) |
n (T in K) |
E (cal/mol) |
-54 |
CH2O + M -> H + HCO + M |
4.21E+23 |
-1.66 |
92170 |
700-2500 |
58 |
H + CH2O -> HCO + H2 |
5.18E+7 |
1.66 |
1834 |
700-2500 |
121 |
HO2 + CH2O -> HCO + H2O2 |
1.47E+13 |
|
15200 |
700-2000 |