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Title: A shock tube study of the CO + OH {yields} CO{sub 2} + H reaction

Abstract

The rate coefficient for the title reaction has been determined using mixtures of nitric acid (HNO{sub 3}), carbon monoxide (CO), and argon in incident shock wave experiments. Upon shock heating, the nitric acid rapidly decomposes into OH and NO{sub 2}. The OH subsequently reacts predominantly via the title reaction. Quantitative OH time histories were obtained by continuous-wave (cw) narrow-linewidth UV laser absorption of the R{sub 1}(5) line of the A{sup 2}{Sigma}{sup +} {l_arrow} X{sup 2}{Pi}{sub i} (0,0) transition at 32,606.56 cm{sup {minus}1} (vacuum). In some experiments, helium was added to the reactant mixture to examine CO vibrational excitation effects on the rate coefficient determination. It was found that the rate of excited CO (v = 1) with OH is less than the rate of ground-state CO (v = 0) with OH, which is in agreement with previous state-dependent work. The experiments were conducted over the temperature range 1,090--2,370 K and the pressure range 0.19--0.82 atm. The second-order rate coefficient was determined to be k{sub 1}(T) = 2.12 {times} 10{sup 12} exp[{minus}2630/T (K)] (cm{sup 3}/mol s) with overall uncertainties of + 16, {minus}12 % at high temperatures and + 19, {minus} 22 % at low temperatures. These results are in goodmore » agreement with recent studies of the reaction and are well fit by a chemically activated intermediate model. The current work also provides a link to previous low-temperature data.« less

Authors:
; ;  [1]
  1. Stanford Univ., CA (United States)
Publication Date:
OSTI Identifier:
93222
Report Number(s):
CONF-940711-
TRN: IM9537%%265
Resource Type:
Book
Resource Relation:
Conference: 25. international symposium on combustion, Irvine, CA (United States), 31 Jul - 5 Aug 1994; Other Information: PBD: 1994; Related Information: Is Part Of Twenty-fifth symposium (international) on combustion; PB: 1838 p.
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; CARBON MONOXIDE; CHEMICAL REACTIONS; HYDROXYL RADICALS; HYDROCARBONS; COMBUSTION KINETICS; NITRIC ACID; CARBON DIOXIDE; ABSORPTION SPECTRA; ACTIVATION ENERGY; MATHEMATICAL MODELS; AIR POLLUTION; EXPERIMENTAL DATA

Citation Formats

Wooldridge, M.S., Hanson, R.K., and Bowman, C.T. A shock tube study of the CO + OH {yields} CO{sub 2} + H reaction. United States: N. p., 1994. Web.
Wooldridge, M.S., Hanson, R.K., & Bowman, C.T. A shock tube study of the CO + OH {yields} CO{sub 2} + H reaction. United States.
Wooldridge, M.S., Hanson, R.K., and Bowman, C.T. Sat . "A shock tube study of the CO + OH {yields} CO{sub 2} + H reaction". United States. doi:.
@article{osti_93222,
title = {A shock tube study of the CO + OH {yields} CO{sub 2} + H reaction},
author = {Wooldridge, M.S. and Hanson, R.K. and Bowman, C.T.},
abstractNote = {The rate coefficient for the title reaction has been determined using mixtures of nitric acid (HNO{sub 3}), carbon monoxide (CO), and argon in incident shock wave experiments. Upon shock heating, the nitric acid rapidly decomposes into OH and NO{sub 2}. The OH subsequently reacts predominantly via the title reaction. Quantitative OH time histories were obtained by continuous-wave (cw) narrow-linewidth UV laser absorption of the R{sub 1}(5) line of the A{sup 2}{Sigma}{sup +} {l_arrow} X{sup 2}{Pi}{sub i} (0,0) transition at 32,606.56 cm{sup {minus}1} (vacuum). In some experiments, helium was added to the reactant mixture to examine CO vibrational excitation effects on the rate coefficient determination. It was found that the rate of excited CO (v = 1) with OH is less than the rate of ground-state CO (v = 0) with OH, which is in agreement with previous state-dependent work. The experiments were conducted over the temperature range 1,090--2,370 K and the pressure range 0.19--0.82 atm. The second-order rate coefficient was determined to be k{sub 1}(T) = 2.12 {times} 10{sup 12} exp[{minus}2630/T (K)] (cm{sup 3}/mol s) with overall uncertainties of + 16, {minus}12 % at high temperatures and + 19, {minus} 22 % at low temperatures. These results are in good agreement with recent studies of the reaction and are well fit by a chemically activated intermediate model. The current work also provides a link to previous low-temperature data.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sat Dec 31 00:00:00 EST 1994},
month = {Sat Dec 31 00:00:00 EST 1994}
}

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  • Rate constants for the reactions H + O{sub 2} {yields} OH + O (1) and H + O{sub 2} + M {yields} HO{sub 2} + M (2) were measured under pseudo-first-order conditions by the flash photolysis-shock tube technique that employs the atomic resonance absorption detection method to monitor (H){sub t}. Rate data for reaction 1 were obtained over the temperature range from 962 to 1705 K, and the results are well represented by the Arrhenius expression k{sub 1}(T) = (2.79 {plus minus} 0.32) {times} 10{sup {minus}10} exp(-16132 {plus minus} 276 cal mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Themore » mean deviation of the experimentally measured rate constants from those calculated by using this expression is {plus minus}16% over the stated temperature range. The recent shock tube data of Frank and Just (1693-2577 K) were combined with the present results for k{sub 1}(T) to obtain the following Arrhenius expression for the overall temperature span (962-2577 K); k{sub 1}(T) = (3.18 {plus minus} 0.24) {times} 10{sup {minus}10} exp(-16439 {plus minus} 186 cal mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The mean deviation of the experimentally measured rate constants from this expression is {plus minus}15% over the entire temperature range. Values for the rate constant for the reverse of reaction 1 were calculated from each of the experimentally measured K{sub 1}(T) values with expressions for the equilibrium constant derived by using the latest JANAF thermochemical data. These k{sub {minus}1}(T) values were also combined with similarly derived values from the Frank and Just data.« less
  • Mixtures of hydrogen and oxygen dilute in argon were heated by both incident and reflected shock waves to measure the rate coefficient of the H{sub 2}/O{sub 2} mechanism branching reaction H + O{sub 2} {yields} OH + O (2) in the temperature range 1,450-3,370 K. Time histories of OH(X{sup 2}II) were monitored by using narrow-line-width laser absorption at 306.7 nm. A detailed kinetic analysis of the data in rich mixtures yielded the following rate coefficient expression: k{sub 2} = (9.33 {plus minus} 0.40) {times} 10{sup 13} exp({minus}(14,800 {plus minus} 170) cal mol{sup {minus}1}/RT, K) cm{sup 3} mol{sup {minus}1} s{sup {minus}1}.
  • Mixtures of hydrogen and oxygen diluted in argon were studied behind reflected shock waves at temperatures from 1,050 to 2,700 K. The reaction progress was measured in situ by state-selective laser absorption of OH radicals. Solution mapping methodology was employed to interpret the experimental results, quantifying the effects of all active rate parameters. The rate coefficient expression for the key reaction in the system, H + O{sub 2} {yields} OH + O, derived was k{sub 1} = 1.59 {times} 10{sup 17}T{sup {minus}0.927}e{sup {minus}8,493/T} cm{sup 3} mol{sup {minus}1}s{sup {minus}1} with one standard deviation of 0.05 for log k{sub 1}. The analysismore » indicates that under no physically realistic conditions could the values of k{sub 1} reach those reported by Frank and Just (1985), ad that in most cases the k{sub 1} temperature-dependent expression is close to the results of Schott (1973).« less
  • Rate constants for the reaction, O + H{sub 2}O {yields} OH + OH, have been measured by the Flash Photolysis-Shock Tube (FP-ST) technique over the temperature range, 1500--2400 K. This technique combines stock heating with flash photolysis in the reflected shock wave regime, and the transient species, O-atoms in this case, are monitored by atomic resonance absorption spectroscopy (aras). Additional experiments were performed with N{sub 2}O as a thermal source of O-atoms, and the formation and depletion of (O) were followed by the aras technique. These results require that the decomposition rate behavior of N{sub 2}O be known. The resultsmore » obtained by this technique are compared to those obtained by the FP-ST technique and are found to be corroborative. Hence, the combined results are used to describe the rate constants for the title reaction. The experimental results are compared to earlier work, and rate constants for the title reaction are additionally calculated from published results for the reverse reaction, OH + OH, and the well known equilibrium constant. All results are combined, and the rate behavior for the title reaction is evaluated. Lastly, the results for both forward and reverse reactions are compared to the theoretical calculations presented recently by Harding and Wagner. It is concluded that theory and experiment are in agreement within experimental error.« less