Structural effects on the chemiluminescence from the reaction of ozone with selected organic compounds

Hansen, Deren; Atkinson, Roger; Pitts, James N.

doi:10.1016/0047-2670(77)80021-x

Cited by 16 publications

(9 citation statements)

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“…A similar scheme has been taken into consideration for 2-butene ozonolysis by Hansen et al [47], for propene and 2-methyl-1-propene by Herron & Huie [lo] and for ethylene by Herron & Huie [9]. In the latter case the existence of dioxirane (VII) has been proven directly by MW.…”

Section: VIImentioning

confidence: 89%

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Kühne¹,

Förster²,

Hulliger³

et al. 1980

Helvetica Chimica Acta

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SummaryInvestigation of the formation of complex products in the gas-phase ozonolysis of cis-2-butene by linear-reactor-infrared-matrix and linear-reactor-microwave spectroscopy is reported. The following species have been unequivocally detected: secondary 2-butene ozonide, acetic acid, peracetic acid, glycolaldehyde, dimethyl ketene, the simple and mixed anhydrides of formic and acetic acid, 2,3-epoxybutane and 2-butanone, besides polyatomic products already known. In contrast, the primary ozonide has been detectable neither by LR.-MW. nor by LR.-IR. Observation of both stereoisomeric epoxides and kinetic modelling are used to support the intermediate formation of the O'Neal-Blumstein radical CH3CH (02)CH (0)CH3 and the existence of a reaction channel in which the two carbon atoms of the C , C double bond of the olefin remain connected. As the dominant reaction path a mechanism with a Criegee type split into methyldioxirane (ethylidene peroxide) and acetaldehyde is considered and subsequently proposed to explain formation of many complex products by either unimolecular or bimolecular processes of the peroxide. For the reactions considered, thermochemical estimates of reaction enthalpies and activation data are included. Kinetic modelling for a partial reaction mechanism involving at least two different paths of decay of the O'Neal-Blumstein biradical into Criegee-type intermediates and the 2,3-epoxybutanes is discussed.

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Section: VIImentioning

confidence: 89%

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Kühne¹,

Förster²,

Hulliger³

et al. 1980

Helvetica Chimica Acta

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“…Finlayson et al, 1974). While the long-pass filters used in chemiluminescence NO x monitors should preclude emissions from electronically excited species, vibrationally excited OH produced through the hydroperoxide mechanism is known to emit in the 700-1100 nm wavelength range (Finlayson et al, 1974;Schurath et al, 1976;Hansen et al, 1977;Toby, 1984) and would be detected as NO 2 . Specifications of the long-pass filters used in the chemiluminescence NO x monitors in this study are not reported in their respective user manuals but typically block light below ca.…”

Section: Speciesmentioning

confidence: 99%

“…Atmospheric trace composition comprises many thousands of different chemical components (Goldstein and Galbally, 2007). Consequently, specific measurement approaches have been developed to measure key atmospheric species within the specific conditions (analyte abundance; presence of other constituents) anticipated (Heard, 2008). This paper reports a systematic study of the interference arising in measurements of nitrogen oxides from the presence of alkenes in sampled air when using their most widespread air quality monitoring technique of chemiluminescence detection.…”

mentioning

confidence: 99%

“…Techniques used for the measurement of atmospheric NO x include laser-induced fluorescence (LIF) spectroscopy for both NO and NO 2 ; absorption spectroscopy (e.g. long path differential optical absorption spectroscopy -LP-DOAS; cavity-enhanced differential optical absorption spectroscopy -CE-DOAS; cavity attenuated phase shift spectroscopy -CAPS; cavity ring-down spectroscopy -CRDS; passive diffusion tubes, primarily for NO 2 ), chemical ionisation mass spectrometry (CIMS) and both on-and offline wet chemical methods, for example, a long path absorption photometer (LOPAP;Heard, 2008;Sandholm et al, 1990;Kasyutich et al, 2003;Kebabian et al, 2005;Cape, 2009;Fuchs et al, 2009;Thalman and Volkamer, 2010;Villena et al, 2011). However, the most commonly employed technique for the measurement of NO x species, including for statu-tory air quality monitoring purposes, is the detection of the chemiluminescence arising from electronically excited NO 2 (NO * 2 ) formed from the reaction between NO and O 3 (via reaction R1) as follows:…”

mentioning

confidence: 99%

“…The photolytic conversion technique can have greater specificity than the heated Mo catalyst, as the photolysis wave- lengths may be selected to match the NO 2 photolysis action spectrum, while potential NO z interferents for an NO 2 measurement are thermally unstable and may convert to NO 2 when exposed to heat in the latter approach (Heard, 2008). Despite this, the chemiluminescent analyser with the heated Mo catalyst is the most widely used technique for air quality monitoring of NO and NO 2 worldwide.…”

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confidence: 99%

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Interference from alkenes in chemiluminescent NO<sub><i>x</i></sub> measurements

et al. 2020

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Abstract. Nitrogen oxides (NOx=NO+NO2) are critical intermediates in atmospheric chemistry and air pollution. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3 and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atmospheric pollutants, and NO2 is commonly included in air quality objectives and regulations. NOx levels also affect the production of the nitrate component of secondary aerosol particles and other pollutants, such as the lachrymator peroxyacetyl nitrate (PAN). The accurate measurement of NO and NO2 is therefore crucial for air quality monitoring and understanding atmospheric composition. The most commonly used approach for the measurement of NO is the chemiluminescent detection of electronically excited NO2 (NO2∗) formed from the NO + O3 reaction within the NOx analyser. Alkenes, ubiquitous in the atmosphere from biogenic and anthropogenic sources, also react with ozone to produce chemiluminescence and thus may contribute to the measured NOx signal. Their ozonolysis reaction may also be sufficiently rapid that their abundance in conventional instrument background cycles, which also utilises the reaction with ozone, differs from that in the measurement cycle such that the background subtraction is incomplete, and an interference effect results. This interference has been noted previously, and indeed, the effect has been used to measure both alkenes and ozone in the atmosphere. Here we report the results of a systematic investigation of the response of a selection of commercial NOx monitors to a series of alkenes. These NOx monitors range from systems used for routine air quality monitoring to atmospheric research instrumentation. The species-investigated range was from short-chain alkenes, such as ethene, to the biogenic monoterpenes. Experiments were performed in the European PHOtoREactor (EUPHORE) to ensure common calibration and samples for the monitors and to unequivocally confirm the alkene levels present (via Fourier transform infrared spectroscopy – FTIR). The instrument interference responses ranged from negligible levels up to 11 %, depending upon the alkene present and conditions used (e.g. the presence of co-reactants and differing humidity). Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high VOC, low NOx environments such as forests or indoor environments where alkene abundance from personal care and cleaning products may be significant.

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Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

Carter

Lloyd

Sprung

et al. 1979

Int J of Chemical Kinetics

162

153

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A detailed mechanism is presented far reactions occurring during irradiation of part-permillion concentrations of propene and/or n-butane and oxides of nitrogen in air. Data from an extensive series of well-characterized smog chamber experiments carried out in our 5800-liter evacuable chamber-solar simulator facility designed for providing data suitable for quantitative model validation were used to elucidate several unknown or uncertain kinetic parameters and details of the reaction mechanism.The mechanism was then tested against the data base from the smog chamber runs. In general, most calculated concentration-time profiles agreed with experiments to within the experimental uncertainties. Fits were usually attained to within f20% or better for ozone, NO, propene, and n-butane, to within -+30% or better for NOz, PAN, methyl ethyl ketone, 2-butyl nitrate, butyraldehyde, and (in runs not containing propene) methyl nitrate, to within --f50% or better for the minor products 1-butyl nitrate and propene oxide, and to within a factor of 2 for methyl nitrate in propene-containing runs. Propionaldehyde was consistently underpredicted in all runs; it is probably a chamber contaminant. For formaldehyde and acetaldehyde, the major products in both systems, fits to within -420% were often obtained, yet for a number of experiments, significantly greater discrepancies were observed, probably as a result of experimental and/or analytical problems.The good fits to experimental data were attained only after adjusting several rate constants or rate constant ratios related to uncertainties concerning chamber effects or the chemical mechanism. The largest uncertainty concerns the necessity to include in the mechanism a significant rate of radical input from unknown sources in the smog chamber. Other areas where fundamental kinetic and mechanistic data are most needed before a predictive, detailed propene + n-butane-NO,-air smog model can be completely validated concern other chamber effects, the 03 + propene mechanism, decomposition rates of substituted alkoxy radicals, CARTER E T AL.primary quantum yields for radical production as a function of wavelength for aldehyde and ketone photolyses, and the mechanisms and rates of reactions of peroxy radicals with NO and NOz.

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Structural effects on the chemiluminescence from the reaction of ozone with selected organic compounds

Cited by 16 publications

References 50 publications

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Interference from alkenes in chemiluminescent NO<sub><i>x</i></sub> measurements

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

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Structural effects on the chemiluminescence from the reaction of ozone with selected organic compounds

Cited by 16 publications

References 50 publications

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

Interference from alkenes in chemiluminescent NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; measurements

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

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Interference from alkenes in chemiluminescent NO<sub><i>x</i></sub> measurements