Journal ArticleDOI
The decomposition of nitrous oxide at 1.5 ⩽ P ⩽ 10.5 atm and 1103 ⩽ T ⩽ 1173 K
TLDR
In this article, Baulch et al. proposed a new rate constant for N2O + OH HO2 + N2 with an upper limit of 5.5 s. This is considerably smaller than presently reported in the literature.Abstract:
Reaction experiments on mixtures of N2O/H2O/N2 were performed in a variable pressure flow reactor over temperature, pressure, and residence time ranges of 1103–1173 K, 1.5–10.5 atm, and 0.2–0.8 s, respectively. Mixtures of approximately 1% N2O in N2 were studied with the addition of varying amounts of water vapor, from background to 3580 ppm. Experimentally measured profiles of N2O, O2, NO, NO2, H2O, and temperature were compared with predictions from detailed kinetic modeling calculations to assess the validity of a reaction mechanism developed from currently available literature thermochemical and rate constant parameters. Sensitivity and reaction flux analyses were performed to determine key elementary reaction path processes and rates.
Reaction rate constants for the uni-molecular reaction, N2O N2 + O, were determined at various pressures in order to match overall experimental and numerical decomposition rates of N2O. The numerical model included a newly determined rate constant for N2O + OH HO2 + N2 with an upper limit of 5.66 × 108 cm3 mol−1 sec−1 at 1123 K. This is considerably smaller than presently reported in the literature. The experimentally observed rate of N2O decomposition was found to be slightly dependent on added water concentration. The rate constant determined for the elementary decomposition is strongly dependent on the choice of rate constants for the N2O + O N2 + O2 and N2O + O NO + NO reactions. In the absence of accurate data at the temperatures of this work, and based on these and other experiments in this laboratory, we presently recommend rate constants from the review of Baulch et al. The basis for this recommendation is discussed, including the impact on the rate constants derived for elementary nitrous oxide decomposition. The uncertainties in the rate constants as reported here are ±30%.
The present mechanism was applied to previously reported high-pressure shock tube data and yields a high-pressure limit rate constant a factor of three larger than previously reported at these temperatures. The following expressions for the elementary decomposition reaction are recommended: k = 9.13 × 1014 exp (−57, 690/RT) cm3 mol−1 s−1 and k∞ = 7.91 × 1010 exp(−56020/RT) s−1. Simple Lindemann fits utilizing these parameters reproduce the pressure dependent rate constants measured here within ±25%. © 1995 John Wiley & Sons, Inc.read more
Citations
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Journal ArticleDOI
The reaction kinetics of dimethyl ether. I: High‐temperature pyrolysis and oxidation in flow reactors
TL;DR: Dimethyl ether reaction kinetics at high temperature were studied in two different flow reactors under highly dilute conditions, with the equivalence ratio varying from 0.32 ≤ ϕ ≤ 3.4 as discussed by the authors.
Journal ArticleDOI
Experimental measurements and kinetic modeling of CO/H2/O2/NOx conversion at high pressure
TL;DR: In this paper, experimental measurements and kinetic modeling of CO/H₂/O/O₆/NO conversion at high pressure were used to investigate the effect of high pressure on CO 2.
Journal ArticleDOI
Kinetic modeling of the CO/H2O/O2/NO/SO2 system: Implications for high-pressure fall-off in the SO2 + O(+M) = SO3(+M) reaction
TL;DR: In this article, a detailed chemical kinetic reaction mechanism was developed and validated for the spin-forbidden dissociation-recombination reaction between SO2 and O-atoms in the falloff regime at pressures above 1 atm.
Journal ArticleDOI
High pressure studies of moist carbon monoxide/nitrous oxide kinetics
TL;DR: In this article, a detailed kinetic model was developed to predict the measured species profiles over the entire range of conditions studied here, and is consistent with previously and concurrently studied mechanisms for N{sub 2}O decomposition and reacting H{sub 1 O decomposition.
Journal ArticleDOI
Modern chemistry of nitrous oxide
TL;DR: In this paper, the effect of N2O on the environment and the possibility of its utilisation are considered, focusing on the processes in which the oxidising potential of nitrous oxide can be employed.
References
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Journal ArticleDOI
Mechanism and modeling of nitrogen chemistry in combustion
James A. Miller,Craig T. Bowman +1 more
TL;DR: In this article, the mechanisms and rate parameters for the gas-phase reactions of nitrogen compounds that are applicable to combustion-generated air pollution are discussed and illustrated by comparison of results from detailed kinetics calculations with experimental data.
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Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds
W. Tsang,R. F. Hampson +1 more
TL;DR: In this paper, the authors evaluated data on the kinetics and thermodynamic properties of species that are of importance in methanepyrolysis and combustion, including H, H2, O, O2, OH, HO2, CH2O, CH4, C2H6, HCHO, CO2, CO, HCO, CH3, CH5, CH6, CH7, CH8, CH9, CH10, CH11, CH12, CH13, CH14, CH15, CH16, CH17, CH
Journal ArticleDOI
Chemical Kinetic Data Base for Propellant Combustion I. Reactions Involving NO, NO2, HNO, HNO2, HCN and N2O
Wing Tsang,John T. Herron +1 more
TL;DR: In this article, the authors evaluated chemical kinetic data on a number of single step elementary reactions involving small polyatomic molecules which are of importance in propellant combustion, and the results of the first years effort lead to coverage of all pertinent reactions of the following species; H, H 2, H2O, O, OH, OCHO, CHO, CO, NO, NO2, HCN, and N2O.
Journal ArticleDOI
A Comprehensive Reaction Mechanism For Carbon Monoxide/Hydrogen/Oxygen Kinetics
TL;DR: In this article, a comprehensive reaction mechanism for the oxidation of carbon monoxide in the presence of hydrogen is described, and model predictions are compared with experimental data over wide ranges of physical conditions.
Journal ArticleDOI
Improved Sensitivity of Infrared Spectroscopy by the Application of Least Squares Methods
TL;DR: In this paper, the spectral least squares (SLS) method was applied to the spectra of CO, N2O, and CO2 in dry air and the results showed that the SLS method was more reliable for the gases studied.
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