Timonen, R.S., Ratajczak, E., Gutman, D., and Wagner, A.F. (1987)
The Addition and Dissociation Reaction H + CO = HCO. 2.
Experimental Studies and Comparison with Theory
J. Phys. Chem. 1987, 91, 5325.
Abstract
Directly measured low-pressure thermal HCO dissociation rate constants and isotope effects are presented
for the first time. The temperature range of the measurements is 637-832 K. A theoretical model
developed in the preceding paper (Wagner and Bowman
(1987)) is found to be highly consistent with these results and with all available H + CO thermal
addition rate constant measurements. The calculations are used to extend the measured dissociation rate
constant to combustion temperatures. The calculated low-pressure dissociation rate constant k(167) in
various buffer gases is accurately represented from 300 to 3000 K by k(167)(Ar)=3.09E-7 T^(-1)
exp(-17.0/RT), k(167)(He)=3.80E-7 T^(-1) exp(-17.1/RT), k(167)(N2)=3.07E-7 T^(-1) exp(-17.0/RT),
and k(167)(H2)=5.79E-7 T^(-1) exp(-17.0/RT), where k(167) is in cm3/molecule s and R is in kcal/mol K.
The calculations suggest that dEtot, the average energy transfer between metastable HCO* and the
buffer gas, varies between -40 and -50 cm-1 for buffer gases N2, H2, He, and Ar.
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) |
| 167* |
HCO + M -> H + CO + M |
1.86E+17 |
-1.0 |
17000 |
300-3000 |
* M = Ar