DOI: 10.1002/kin.550141003. Experimental investigation of chamber‐dependent radical sources

Experimental investigation of chamber‐dependent radical sources

10.1002/kin.550141003

Crossref journal-article

Wiley

International Journal of Chemical Kinetics (311)

Abstract

AbstractWhile environmental chamber data have been widely used to generate and validate computer models of the chemistry occurring in polluted atmospheres, the effects of the chambers on the gas‐phase chemistry being studied have been poorly characterized. In order to investigate such chamber effects, a series of NOx—air irradiations, with trace levels of organics present to monitor OH radical concentrations, have been carried out in four different environmental chambers (ranging in volume from ∼100 to 40,000 L) at varying temperatures, humidities, pressures, and reaction conditions. In addition, a number of control experiments have been carried out to validate the technique for measuring OH radical levels in these irradiations. The data show that unknown sources of OH radicals are present in all of the chambers studied. The data are consistent with the presence of two distinct radical sources: (1) the photolysis of initially present HONO, whose importance increases with increasing NO2/NO concentration ratios, but which is a minor contributor to the overall radical flux after 30–60 min of irradiation, and (2) a constant (for these NOx—air irradiations) radical source which dominates beyond approximately the first 60 min of irradiation. The radical input rates, after the first ∽30–60 min of irradiation, are independent of the NO concentration, increase with increasing temperature, humidity, and NO2 concentration, are proportional to light intensity, and are dependent on the chamber employed. Although the exact nature of this radical source is still undetermined, results of experiments reported here allow a number of possible mechanisms to be ruled, out, and these are discussed.

Bibliography

Carter, W. P. L., Atkinson, R., Winer, A. M., & Pitts, J. N. (1982). Experimental investigation of chamberâdependent radical sources. International Journal of Chemical Kinetics, 14(10), 1071â1103. Portico.

Authors 4

W. P. L. Carter (first)
R. Atkinson (additional)
A. M. Winer (additional)
J. N. Pitts (additional)

References 32 Referenced 94

D. G.Hendry A. C.Baldwin J. R.Barker andD. M.Golden “Computer Modeling of Simulated Photochemical Smog ” EPA‐600/3‐78‐059 June1978.
10.1021/es60148a005
10.1002/kin.550110105
G. Z.Whitten H.Hogo M. J.Meldgin J. P.Killus andP. J.Bekowies “Modeling of Simulated Photochemical Smog with Kinetic Mechanisms ” vol. 1 Interim Rep. EPA‐600/3‐79‐001a Jan.1979.
G. Z.Whitten J. P.Killus andH.Hogo “Modeling of Simulated Photochemical Smog with Kinetic Mechanisms ” vol. 1 Final Rep. EPA‐600/3‐80‐028a Feb.1980.
10.1002/kin.550121102
10.1080/00139307209435458
10.1080/10934527609385765
10.1021/es60136a009
10.1002/kin.550130805
10.1021/j100515a001
{'key': 'e_1_2_1_13_2', 'first-page': '461', 'volume': '10', 'author': 'Winer A. M.', 'year': '1980', 'journal-title': 'Adv. Environ. Sci. Technol.'} / Adv. Environ. Sci. Technol. by Winer A. M. (1980)
10.1021/es60078a002
10.6028/NBS.SP.513 / Reactions Rate and Photochemical Data for Atmospheric Chemistry—1977 by Hampson R. F. (1978)
10.1021/es60124a006
J. N.PittsJr. K. R.Darnall W. P. L.Carter A. M.Winer andR.Atkinson “Mechanisms of Photochemical Reactions in Urban Air ” Final Rep. EPA‐600/3‐79‐110 Nov.1979.
10.1080/00022470.1981.10465221
J. N.PittsJr. A. M.Winer K. R.Darnall G. J.Doyle R. A.Graham andE. C.Tuazon “Chemical Consequences of Air Quality Standards and of Control Implementation Programs: Roles of Hydrocarbon Oxides of Nitrogen Oxides of Sulfur and Aged Smog in the Production of Photochemical Oxidant and Aerosol ” Rep. to California Air Resources Board Contract A6‐172‐30 June1979.
10.1021/es60128a006
J. P.KillusandG. Z.Whitten private communication to W. P. L. Carter Dec.1981.
10.1080/00022470.1974.10469926
10.1021/es60085a005
R.AtkinsonandA. C.Lloyd “Evaluation of Kinetic and Mechanistic Data for Modeling of Photochemical Smog ” Final Rep. to EPA Contract 68–02–3280 ERT Doc. P‐A040 July1980
J. Phys. Chem. Ref. Data in press (1982).
10.1063/1.555619
10.1002/9780470133415.ch5
10.1016/0047-2670(78)80019-7
G. W.Harris J. J.Treacy W. P. L.Carter R.Atkinson A. M.Winer andJ. N.PittsJr.paper presented at thePacific Coast Conference on Chemistry and Spectroscopy Anaheim CA October1981.
10.1029/GL006i012p00917
10.1021/j150607a022
10.1021/es60157a006
R. J.Countess G. T.Wolff andM. R.Whitbeck “The Effect of Temperature on Ozone Formation in the Propene/Nitrogen Dioxide/Air System ” General Motors Research Laboratories Rep. GMR‐3084 Oct.1979.

Dates

Type	When
Created	20 years, 8 months ago (Jan. 1, 2005, 9:51 p.m.)
Deposited	1 year, 10 months ago (Oct. 19, 2023, 11 a.m.)
Indexed	3 weeks, 3 days ago (Aug. 12, 2025, 6:27 p.m.)
Issued	42 years, 11 months ago (Oct. 1, 1982)
Published	42 years, 11 months ago (Oct. 1, 1982)
Published Online	20 years, 10 months ago (Oct. 19, 2004)
Published Print	42 years, 11 months ago (Oct. 1, 1982)

Funders 0

None

BibTeX

@article{Carter_1982, title={Experimental investigation of chamber‐dependent radical sources}, volume={14}, ISSN={1097-4601}, url={http://dx.doi.org/10.1002/kin.550141003}, DOI={10.1002/kin.550141003}, number={10}, journal={International Journal of Chemical Kinetics}, publisher={Wiley}, author={Carter, W. P. L. and Atkinson, R. and Winer, A. M. and Pitts, J. N.}, year={1982}, month=oct, pages={1071–1103} }

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