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Direct studies of the thermal decomposition of N{sub 2}O and CO{sub 2} and of the reaction of CO with O{sub 2}

Conference ·
OSTI ID:10118669
The thermal decompositions of N{sub 2}O and CO{sub 2} was investigated by monitoring the kinetics of formation of O({sup 3}P) atoms in the reflected shock regime using atomic resonance absorption spectrophotometry (A.R.A.S.). The temperature range was 1805K to 2379K for N{sub 2}O and 2332K to 2869K for CO{sub 2}. Total densities were 3--4 {times} 10{sup 18} molecules cm{sup {minus}3} and hence the reported rate constants are at or near the low pressure limit for unimolecular decomposition. The results were expressed by the following Arrhenius equations: CO{sub 2} k(T) = (1.63 {plus_minus} 1.96) {times} 10{sup {minus}8} exp({minus}122565 {plus_minus} 5183/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} N{sub 2}O k(T) = (6.02 {plus_minus} 2.81) {times} 10{sup 10} exp({minus}53397 {plus_minus} 1865/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Uncertainties in the Arrhenius expressions are given at the one standard deviation level and the mean deviations of the experimental data from the respective expression are {plus_minus} 18.6% and {plus_minus} 30.7%. Corresponding values for the reverse reaction, k{sub rev}(CO{sub 2}) were computed from the expression k{sub for}/k{sub rev} = K{sub c}. The value obtained for k{sub rev}(CO{sub 2}) was (2.18 {plus_minus} 0.83) {times} 10{sup {minus}34} cm{sup 6} molecule{sup {minus}2} s{sup {minus}1}, independent of temperature from 2332K to 2869K. Preliminary results are also reported for the direct determination of the rate constant for the reaction, CO + O{sub 2} {yields} CO{sub 2} + O, from measurements of the initial rate of formation of O({sup 3}P) atoms. 35 refs., 9 figs., 4 tabs.
Research Organization:
Brookhaven National Lab., Upton, NY (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
AC02-76CH00016
OSTI ID:
10118669
Report Number(s):
BNL--46985; CONF-920707--17; ON: DE92007183
Country of Publication:
United States
Language:
English