Atmospheric Chemistry of Toxic Contaminants. 2. Saturated Aliphatics: Acetaldehyde,Dioxane, Ethylene Glycol Ethers,Propylene Oxide

Detailed mechanisms are outlined for the chemical reactions that contribute to In-situ formation and atmospheric removal of the saturated aliphatic contaminants acetaldehyde, dioxane, ethylene glycol ethers (methyl, ethyl, n-butyl) and propylene oxide. In-situ formation Is of major Importance for acetaldehyde. In-situ removal Involves reaction with OH (all compounds) and, for acetaldehyde, photolysis and reaction with NO3. Acetaldehyde, dioxane, and the ethers are rapidly removed (half-lives of less than one day), leading to PAN (acetaldehyde) and to 2-oxodioxane and formaldehyde (dioxane). Reaction products of the glycol ethers include a large number of hydroxyesters, hydroxyacids, and hydroxycarbonyls. Propylene oxide reacts only slowly with OH, with an atmospheric half-life of 3-10 days, to yield formaldehyde, acetaldehyde, and PAN. Uncertainties in the reaction mechanisms for dioxane, the glycol ethers, and propylene oxide are discussed and include C-C vs C-0 bond scission in alkoxy radicals as well as alkoxy radical unimolecular decomposition vs reaction with oxygen.     

Atmospheric Chemistry of Toxic Contaminants. 5. Unsaturated Halogenated Aliphatics: Allyl Chloride,Chloroprene, Hexachlorocyclopentadiene,Vinylidene Chloride

Detailed mechanisms are outlined for the chemical reactions involved In the atmospheric removal of four unsaturated chlorinated aliphatic contaminants, allyl chloride, chloroprene, hexachlorocyclopentadiene and vlnylldene chloride. Rate constants estimated from structure-reactivity relationships Indicate rapid removal for all four compounds by reactions with OH (major), ozone, and NO₃, with half-lives of 2-16 hrs for removal by reaction with OH. Reaction products of allyl chloride (formaldehyde, chloroacetaldehyde, peroxychloroacetyl nitrate) and vinylidene chloride (formaldehyde, phosgene, chloroacetyl chloride) are consistent with OH addition-Initiated pathways that include Cl atom elimination. The chlorine atoms produced In the OH reaction sequence react rapidly with all four unsaturated compounds, but these reactions are of negligible Importance for atmospheric removal of the four toxic contaminants studied. Analogous mechanisms are discussed for chloroprene (leading to formaldehyde, CH₂ = CCICHO, and CICOCHO) and for hexachlorocyclopentadlene (leading to oxalyl chloride and CICOCCI₂COCI).     

Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol

Products of the gas-phase reactions of OH radicals (in the presence of NO) and O₃ with the biogenic organic compound 2-methyl-3-buten-2-ol have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography–mass spectrometry (GC-MS), gas chromatography with Fourier transform infrared detection (GC-FTIR), in situ FT-IR spectroscopy and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS/MS). Formaldehyde, 2-hydroxy-2-methylpropanal and acetone were identified from both the OH radical and O₃ reactions, glycolaldehyde and organic nitrate (s) were also observed from the OH radical reaction, and the OH radical formation yield from the O₃ reaction was measured. The formaldehyde, 2-hydroxy-2-methylpropanal, glycolaldehyde, acetone and organic nitrate yields from the OH radical reaction were 0.29±0.03, 0.19±0.07, 0.61±0.09, 0.58±0.04 and 0.05±0.02, respectively, and the formaldehyde, 2-hydroxy-2-methylpropanal and OH radical formation yields from the O₃ reaction were 0.29±0.03, 0.30±0.06 (0.47 from FT-IR measurements) and 0.19 (uncertain to a factor of 1.5), respectively. Acetone was also observed from the O₃ reaction, but appeared to be formed from secondary reactions. Reaction mechanisms are presented and discussed.     

Carbonyl products of the gas-phase reaction of ozone with 1-alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas-phase reaction of ozone with the 1-alkenes (RCH = CH 2) 3-methyl-l-butene (R = i-propyl), 4-methyl-l-pentene (R = i-butyl), 3-methyl-l-pentene (R= s-butyl), 3,3-dimethyl-l-butene (R = t-butyl) and styrene (R = C₆H₅) at ambient T and p = 1 atm of air. Sufficient cyclohexane was added to scavenge OH in order to minimize reactions of OH with the alkenes and with their carbonyl products. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃ + RCH = CH₂ → α(HCHO + RCHOO) + (1 - α) (H₂COO + RCHO), where formaldehyde and RCHO are the primary carbonyls and H₂COO and RCHOO are the biradicals. Measured sums of the primary carbonyl formation yields were 1.006 ± 0.053 (1 S.D.) for formaldehyde + methylpropanal from3-methyl-l-butene(α = 0.494 ± 0.049), 1.025 ± 0.017 for formaldehyde + 2-methylbutanal from 3-methyl-l-pentene (α = 0.384 ± 0.013),1.147 ± 0.050 for formaldehyde + 3-methylbutanal from 4-methyl-l-pentene (α = 0.384 ± 0.020), 0.986 ± 0.014 for formaldehyde + 2,2-dimethylpropanal from 3,3-dimethyl-l-butene (α = 0.320 ± 0.012) and 0.980 ± 0.086 for formaldehyde + benzaldehyde from styrene (α = 0.347 ± 0.059). Carbonyls other than the primary carbonyls were identified; formation pathways are proposed that involve subsequent reactions of the monosubstituted biradicals RCHOO. Similarities and differences between branched-chain 1-alkenes and n-alkyl-substituted 1-alkenes are discussed.     

Atmospheric degradation of alkylfurans with chlorine atoms: Product and mechanistic study

As part of a study on the oxidation mechanism of heterocyclic aromatic compounds, some aspects of the atmospheric chemistry of several alkyl derivatives of furan have been investigated. The aim of this work was to identify the products of the reactions of chlorine atoms with 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran. Experiments were performed in two different smog chambers at 296 ± 2 K and 1000 ± 20 mbar of synthetic air. The experimental investigation was carried out using in situ long-path FTIR absorption spectroscopy and both SPME-GC/FID-ECD and SPME-GC/MS as sampling and detection techniques. The major primary products from the addition reaction channel were 4-oxo-2-pentenoyl chloride and formaldehyde for the reactions of 2-methylfuran and 2,5-dimethylfuran; 4-oxo-2-hexenoyl chloride and acetaldehyde for the reaction of 2-ethylfuran and 5-chloro-2(5H)-furanone for the reactions of both 2-methylfuran and 2-ethylfuran. Other minor products were 4-oxo-2-pentenal, 4-oxo-2-hexenal and 3-hexene-2,5-dione for the 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran reactions, respectively. From the abstraction pathway, HCl, furfural, 2-acetylfuran, 5-methylfurfural, maleic anhydride and 5-hydroxy-2(5H)-furanone were detected. The formation of furfural, 2-acetylfuran and 5-methylfurfural confirmed the H-atom abstraction from the alkyl group of 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran, respectively. This mechanism was not observed in previous studies with OH and NO₃ radicals. A mechanism is proposed to explain the main reaction products observed. The observed products confirm that addition of Cl atoms to the double bond of the alkylfuran is the dominant reaction pathway.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Gas-phase rate coefficients for the reactions of NO3, OH and O3 with α,β-unsaturated esters and ketones: Structure−activity relations (SARs)

Gas-phase rate coefficients for the atmospherically important reactions of NO₃, OH and O₃ are predicted for 55 α,β-unsaturated esters and ketones. The rate coefficients were calculated using a correlation described previously [Pfrang, C., King, M.D., C. E. Canosa-Mas, C.E., Wayne, R.P., 2006. Atmospheric Environment 40, 1170–1179]. These rate coefficients were used to extend structure–activity relations for predicting the rate coefficients for the reactions of NO₃, OH or O₃ with alkenes to include α,β-unsaturated esters and ketones. Conjugation of an alkene with an α,β-keto or α,β-ester group will reduce the value of a rate coefficient by a factor of ∼110, ∼2.5 and ∼12 for reaction with NO₃, OH or O₃, respectively. The actual identity of the alkyl group, R, in −C(O)R or −C(O)OR has only a small influence. An assessment of the reliability of the SAR is given that demonstrates that it is useful for reactions involving NO₃ and OH, but less valuable for those of O₃ or peroxy nitrate esters.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

Characterization of products of ozonolysis of acrylonitrile in liquid phase

In order to elucidate the reaction mechanism of the ozonolysis of acrylonitrile in the liquid phase, characterization of reaction products has been attempted. One of the products, which was volatile, has been found to be formaldehyde by derivatizing with dimedone. The infrared and mass spectra of the derivative corresponded with that of alkylidene dimedone. Three other reaction products were isolated by TLC using silica gel, CHCl₃:MeOH (80:20). These have been tentatively identified as glyoxal, epoxide of acrylonitrile and acetamide from their mass spectra. Based on these findings a reaction pathway for the formation of formaldehyde is proposed to be that described by Criegee.     

Mechanism of OH-initiated atmospheric photooxidation of the organophosphorus insecticide (C2H5O)3PS

O,O,O-triethyl phosphorothioate ((C₂H₅O)₃PS, TEPT) is a widely used organophosphorus insecticide. TEPT may be released into the atmosphere where it can undergo transport and chemical transformations, which include reactions with OH radicals, NO₃ radicals and O₃. The mechanism of the atmospheric reactions of TEPT has not been fully understood due to the short-lifetime of its oxidized radical intermediates, and the extreme difficulty in detection of these species experimentally. In this work, we carried out molecular orbital theory calculations for the OH radical-initiated atmospheric photooxidation of TEPT. The profile of the potential energy surface was constructed, and the possible channels involved in the reaction are discussed. The theoretical study shows that OH addition to the PS bond and H abstractions from the CH₃CH₂O moiety are energetically favorable reaction pathways. The dominant products TEP and SO₂ arise from the secondary reactions, the reactions of OH-TEPT adducts with O₂. The experimentally uncertain dominant product with molecular weight 170 is mostly due to (C₂H₅O)₂P(S)OH and not (C₂H₅O)₂P(O)SH.     

Kinetics of Sulfur-Oxide Formation in Flames: II. Low Pressure H2S Flames

The microstructure of 1/10 and 1/20 atmosphere, lean H₂S—O₂—N₂ flames is developed using the mass-spectrometric flame-sampling technique. The flame mechanism developed is in agreement with that determined from an earlier study on 1-atm H₂S flames. The formation of SO₂ appears to be primarily related to the production of SH and the ensuing oxidation steps SH + O₂ = SO + OH and SO + O₂ = SO₂ + O. While there is some question whether SO₂ formation occurs via an SO or an S₂O intermediate, the present study does not give direct support to the role of S₂O in the oxidation mechanism. However, the presence of significant quantities of free sulfur in the pre-flame zone may be indicative of S₂O formation via SO + S → S₂O, and, possibly, via the disproportionation of SO, 3SO → S₂O + SO₂. Kinetic analyses of some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the decomposition of H₂S. The actual initiation process in the flame mechanism requires further examination. The specific rate for the reaction step H₂S + O = OH + SH is given by k ₆ = 1.45 × 10₁₅ exp ( – 6600/RT) cm³ mole^–1 sec^–1, and the specific rate for the oxidation of SO, SO + O₂ = SO₂ + O, is given by k ₅ = 5.2 × 10₁₄ exp (—19,300/RT) cm³ mole^–1 sec^–1.     

采用双氰胺甲醛缩聚物混凝去除水中酸性红B染料的研究

以双氰胺和甲醛为原料制备了聚合双氰胺甲醛,并对其进行红外光谱表征.采用聚合双氰胺甲醛与硫代硫酸钠共同作用对酸性红B染料溶液进行混凝脱色实验.对比了单独使用聚合双氰胺甲醛,以及聚合双氰胺甲醛与硫代硫酸钠共同作用的脱色效果.探讨了硫代硫酸钠和聚合双氰胺甲醛的用量以及pH值对脱色率的影响.结果表明,投加硫代硫酸钠可以明显地提高聚合双氰胺甲醛的脱色率,增大絮凝范围,使絮凝剂对pH值的变化有很强的适应性,pH值为7～12的范围内,脱色率均能维持在96%以上.此外,还对混凝脱色的机理进行了研究.     

Formation of 9,10-phenanthrenequinone by atmospheric gas-phase reactions of phenanthrene

Phenanthrene is a 3-ring polycyclic aromatic hydrocarbon which exists mainly in the gas-phase in the atmosphere. Recent concern over the presence of 9,10-phenanthrenequinone in ambient particles led us to study the products of the gas-phase reactions of phenanthrene with hydroxyl radicals, nitrate radicals and ozone. The formation yields of 9,10-phenanthrenequinone were measured to be ∼3%, 33±9%, and ∼2% from the OH radical, NO₃ radical and O₃ reactions, respectively. Calculations suggest that daytime OH radical-initiated and nighttime NO₃ radical-initiated reactions of gas-phase phenanthrene may be significant sources of 9,10-phenanthrenequinone in ambient atmospheres. In contrast, the ozone reaction with phenanthrene is unlikely to contribute significantly to ambient 9,10-phenanthrenequinone.     

Sources of hydrogen peroxide in cloudwater

Results of a theoretical investigation of H₂O₂ formation in cloud droplets arising from gaseous HO₂ radical scavenging are presented. It is shown that this process is pH dependent with the maximum rate of H₂O₂ production occurring below pH 3. This dependence arises as a result of the dissociation of HO₂ in water (pK_a = 4.9) and the subsequent disproportionation reaction of HO₂ and O₂⁻ to form hydrogen peroxide. O₂⁻ is also removed by reaction with O₃ to produce OH radicals and this process becomes more competitive as both the pH and $\text{O}{}_2{}^{\mathrm{-}}\text{HO}{}_2$ ratio increase. The presence of soluble organic species, such as aldehydes, in cloudwater counteracts the effect of ozone by converting OH back to HO₂. For low pHs (< 3) the net contribution of organic solutes of H₂O₂ production is predicted to be relatively small, being limited by the availability of OH radicals scavenged from the gas phase. Existing cloud chemistry models may overestimate the rate of aqueous oxidation of formaldehyde by OH radicals.Under conditions where scavenging of gas-phase free radicals by cloud droplets is efficient, uptake of HO₂ radicals may be reversible. The aqueous concentration of OH is unlikely to approach thermodynamic equilibrium with the gas phase (H ∼-30 M atm⁻¹ and can be treated as irreversible. In clouds with a small mean droplet radius, efficient scavenging of precursor OH radicals should result in a decrease in gas-phase HO₂ production with a reduction in the yield of aqueous H₂O₂, although this is offset by the presence of soluble organic species. A similar effect is predicted for clouds with a high liquid water content.The supply of HO₂ and OH radicals to cloud droplets is controlled by gas-phase ozone chemistry which is in turn dependent on the solar u.v. radiation intensity. The u.v. density in clouds may be higher than in clear air when the solar zenith angle is small, thus enhancing H₂O₂ production, but falls off markedly as the solar zenith angle becomes larger. Predicted rates of H₂O₂ formation in clouds based on midday conditions are likely to be considerably higher than the average daytime value, particularly in summer. Diurnal and seasonal effects on H₂O₂ generation are expected to be more marked in clouds than in clear air.     

Kinetics of the gas-phase reactions of alkylnaphthalenes with O3, N2O5 and OH radicals at 298 ± 2 K

Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N₂O₅ with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; for the reaction of N₂O₅ with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10⁻¹⁷, (4.2 ± 0.9) × 10⁻¹⁷ and (5.7 ± 1.9) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively. In addition, an upper limit to the rate constant of 1.3 × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ was measured for the reaction of O₃ with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.     

The effects of increasing atmospheric ozone on biogenic monoterpene profiles and the formation of secondary aerosols

Monoterpenes are biogenic volatile organic compounds (BVOCs) which play an important role in plant adaptation to stresses, atmospheric chemistry, plant–plant and plant–insect interactions. In this study, we determined whether ozonolysis can influence the monoterpenes in the headspace of cabbage. The monoterpenes were mixed with an air-flow enriched with 100, 200 or 400 ppbv of ozone (O₃) in a Teflon chamber. The changes in the monoterpene and O₃ concentrations, and the formation of secondary organic aerosols (SOA) were determined during ozonolysis. Furthermore, the monoterpene reactions with O₃ and OH were modelled using reaction kinetics equations. The results showed that all of the monoterpenes were unequally affected: α-thujene, sabinene and d-limonene were affected to the greatest extend, whereas the 1,8-cineole concentration did not change. In addition, plant monoterpene emissions reduced the O₃ concentration by 12–24%. The SOA formation was dependent on O₃ concentration. At 100 ppbv of O₃, virtually no new particles were formed but clear SOA formation was observed at the higher ozone concentrations. The modelled results showed rather good agreements for α-pinene and 1,8-cineole, whereas the measured concentrations were clearly lower compared to modelled values for sabinene and limonene. In summary, O₃-quenching by monoterpenes occurs beyond the boundary layer of leaves and results in a decreased O₃ concentration, altered monoterpene profiles and SOA formation.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

Aldehyde and Monocyclic Aromatic Hydrocarbon Mixing Ratios at an Urban Site in Las Vegas,Nevada

ABSTRACT

Linhong Jing completed a master's degree in chemistry at UNLV and is currently enrolled in the Ph.D. program at Purdue University. Her address is Department of Chemistry, Purdue University, West Lafayette, IN 47907. Dr. Spencer Steinberg is an associate professor of chemistry at UNLV. His address is UNLV Department of Chemistry, P.O. Box 454003, Las Vegas, NV 89154-4003. Dr. Brian Johnson is an associate professor of chemistry at UNLV. His address is UNLV Department of Chemistry, P.O. Box 454003, Las Vegas, NV 89154-4003.

Oxidation of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air, of significance due to, for example, the potential for O₃ formation, is believed to be initiated by OH attack on the ring (addition) or on the alkyl side chain (H abstraction). A series of ring-breaking reactions follows, with major products predicted to be a-dicarbonyls, simple aldehydes, and organic acids. To test this prediction, ambient air mixing ratios of aldehydes (formaldehyde, ac-etaldehyde, benzaldehyde, glyoxal, and pyruvaldehyde), along with some supporting BTEX data, were measured at an urban site in Las Vegas, NV. Samples were collected on sorbents and determined by chromatographic methods; mixing ratios were compared to ambient levels of CO, O₃, and NO_x. A meteorological analysis (temperature, wind speed, and wind direction) was also included. Statistically significant relationships were noted among the BTEX hydrocarbons (HCs) and among the photochemi-cally derived species (e.g., O₃, NO₂, and some of the aldehydes), although there was seasonal variation. The observations are consistent with a common primary source (i.e., vehicular exhaust or fuel evaporation) for the BTEX compounds and a common secondary source (e.g., OH attack) for glyoxal and pyruvaldehyde.     

FT-IR kinetic and product study of the Br-radical initiated oxidation of α, β-unsaturated organic carbonyl compounds

Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N₂+O₂) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm³ molecule⁻¹ s⁻¹): acrolein (3.21±0.11)×10⁻¹²; methacrolein (2.33±0.08)×10⁻¹¹; methyl vinyl ketone (1.87±0.06)×10⁻¹¹. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O₂. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.