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Title: Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H/sub 2/. -->. OH+H and O+D/sub 2/. -->. OD+D from measurements of O atoms in oxidation of H/sub 2/ and D/sub 2/ by N/sub 2/O

Abstract

Resonance absorption spectroscopy has been used to measure O atom concentration in shock treated H/sub 2/--N/sub 2/O--Ar and D/sub 2/--N/sub 2/O--Ar mixtures. Four compositions were studied over the temperature range 1919--2781 K for the H/sub 2/-containing mixtures and 2097--2481 K for those containing D/sub 2/. Only a few elementary reactions exerted any appreciable influence on the total oxidation process so that the rate coefficients of those reactions could be deduced. Primary sensitivity under all conditions was to the rate coefficients of the reactions directly responsible for the formation and removal of oxygen atoms. We find O+H/sub 2/..-->..OH+H, k = 2.3E14 exp(-57.5 kJ/RT) cm/sup 3/ mol/sup -1/ s/sup -1/ and O+D/sub 2/..-->..OD+D, k = 1.6E14 exp(-59.6 kJ/RT) cm/sup 3/ mol/sup -1/ s/sup -1/. Under our conditions the reaction of H or D atoms with N/sub 2/O was insignificant, in contrast to the observations of Dean at higher concentrations. The isotope effect for this reaction is close to 1.6 throughout our temperature range.

Authors:
;
Publication Date:
Research Org.:
Department of Chemistry, Wright State University, Dayton, Ohio 45435
OSTI Identifier:
5936001
Resource Type:
Journal Article
Journal Name:
J. Chem. Phys.; (United States)
Additional Journal Information:
Journal Volume: 76:1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ARGON; OXIDATION; NITROGEN OXIDES; HYDROGEN; DEUTERIUM; ABSORPTION; DISSOCIATION; ISOTOPE EFFECTS; MIXTURES; QUANTITY RATIO; SHOCK WAVES; SPECTROSCOPY; VERY HIGH TEMPERATURE; CHALCOGENIDES; CHEMICAL REACTIONS; DISPERSIONS; ELEMENTS; FLUIDS; GASES; HYDROGEN ISOTOPES; ISOTOPES; LIGHT NUCLEI; NITROGEN COMPOUNDS; NONMETALS; NUCLEI; ODD-ODD NUCLEI; OXIDES; OXYGEN COMPOUNDS; RARE GASES; STABLE ISOTOPES; 400102* - Chemical & Spectral Procedures

Citation Formats

Pamidimukkala, K.M., and Skinner, G.B. Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H/sub 2/. -->. OH+H and O+D/sub 2/. -->. OD+D from measurements of O atoms in oxidation of H/sub 2/ and D/sub 2/ by N/sub 2/O. United States: N. p., 1982. Web.
Pamidimukkala, K.M., & Skinner, G.B. Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H/sub 2/. -->. OH+H and O+D/sub 2/. -->. OD+D from measurements of O atoms in oxidation of H/sub 2/ and D/sub 2/ by N/sub 2/O. United States.
Pamidimukkala, K.M., and Skinner, G.B. Fri . "Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H/sub 2/. -->. OH+H and O+D/sub 2/. -->. OD+D from measurements of O atoms in oxidation of H/sub 2/ and D/sub 2/ by N/sub 2/O". United States.
@article{osti_5936001,
title = {Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H/sub 2/. -->. OH+H and O+D/sub 2/. -->. OD+D from measurements of O atoms in oxidation of H/sub 2/ and D/sub 2/ by N/sub 2/O},
author = {Pamidimukkala, K.M. and Skinner, G.B.},
abstractNote = {Resonance absorption spectroscopy has been used to measure O atom concentration in shock treated H/sub 2/--N/sub 2/O--Ar and D/sub 2/--N/sub 2/O--Ar mixtures. Four compositions were studied over the temperature range 1919--2781 K for the H/sub 2/-containing mixtures and 2097--2481 K for those containing D/sub 2/. Only a few elementary reactions exerted any appreciable influence on the total oxidation process so that the rate coefficients of those reactions could be deduced. Primary sensitivity under all conditions was to the rate coefficients of the reactions directly responsible for the formation and removal of oxygen atoms. We find O+H/sub 2/..-->..OH+H, k = 2.3E14 exp(-57.5 kJ/RT) cm/sup 3/ mol/sup -1/ s/sup -1/ and O+D/sub 2/..-->..OD+D, k = 1.6E14 exp(-59.6 kJ/RT) cm/sup 3/ mol/sup -1/ s/sup -1/. Under our conditions the reaction of H or D atoms with N/sub 2/O was insignificant, in contrast to the observations of Dean at higher concentrations. The isotope effect for this reaction is close to 1.6 throughout our temperature range.},
doi = {},
journal = {J. Chem. Phys.; (United States)},
number = ,
volume = 76:1,
place = {United States},
year = {1982},
month = {1}
}