共查询到16条相似文献,搜索用时 0 毫秒
1.
Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k
HO+C2H4}=8.1×10-12 cm3 molecule-1 s-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10-12 cm3 molecule-1: CH3ONO2, 0.37±0.09; C2H5ONO2, 0.48±0.20; n-C3H7ONO2, 0.70±0.22; C2H5OH, 3.6±0.4; CH3COCH3, 0.26±0.08; CH3CO2
i-C3H7, 3.0±0.8; CH3CO2
n-C3H7, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules. 相似文献
2.
Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique.The following rate coefficients (in units of 10-12 cm3 molecule-1 s-1) were obtained: 1,2-propandiol dinitrate, <0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; -nitrooxyacetone, <0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50.The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered. 相似文献
3.
Difunctional organic nitrates are important products of the atmospheric reaction of NO3 radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH3CH(ONO2)CH2(ONO2); 1,2-butandiol dinitrate, CH3CH2CH(ONO2)CH2(ONO2); 2,3-butandiol dinitrate, CH3CH(ONO2)CH(ONO2)CH3;cis 1,4-dinitrooxy-2-butene, CH2(ONO2)CH=CHCH2(ONO2); 3,4-dinitrooxy-1-butene, CH2(ONO2CH(ONO2)CH=CH2; -nitrooxy acetone, CH3COCH2(ONO2); 1-nitrooxy-2-butanone, CH3CH2COCH2(ONO2); 3-nitrooxy-2-butanone, CH3CH(ONO2)COCH3.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO2 is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO
y
in the atmosphere, especially during the night, is briefly discussed. 相似文献
4.
Rate coefficients have been measured for the reactions of hydroxyl radicals with a range of aliphatic ethers by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, isobutene and an ether were photolyzed in a Teflon-bag smog chamber. From the rates of depletion of the ether and of the isobutene, and based on the value of the rate coefficient k(OH+i-C4H8)=5.26×10-11 cm3 molecule-1 s-1, the following rate coefficients were obtained for the hydroxyl radical reactions at 750 Torr and at 294±2K in units of 10-12 cm3 molecule-1 s-1: diethylether = 12.0±1.1, di-n-propylether = 15.3±1.6, di-n-butylether=17.1±0.9, ethyl n-butylether = 13.5±0.4, ethyl t-butyl-ether = 5.6±0.5, and di-isobutylether = 26.1±1.6. The quoted error limits correspond to 2 standard deviations but do not include any contribution from k(OH+i-C4H8) for which the error limits are estimated to be about ±10%. The results are discussed in relation to the available literature data and considered in terms of the structure-activity relation for hydroxyl radical reactions with organic molecules. 相似文献
5.
Rate coefficients have been measured for the reactions of hydroxyl radicals with five aliphatic ethers over the temperature range 242–328 K. Competitive studies were carried out in an atmospheric flow reactor in which the hydroxyl radicals were generated by the photolysis of methyl nitrite in the presence of air containing nitric oxide. The reaction of OH with 2,3-dimethyl-butane was used as the reference reaction and the following Arrhenius parameters have been obtained for the reactions: OH+RORproducts:
相似文献
ROR | E/kJ mol–1 | 1012 A/cm3 molecule–1 s–1 |
---|---|---|
dethyl ether | –2.8±0.4 | 3.5±0.6 |
di-n-propyl ether | –1.2±0.6 | 11.5±2.7 |
methylt-butyl ether | 0.85±0.59 | 4.0±1.3 |
ethyln-butyl ether | –1.3±0.5 | 8.7±1.7 |
ethylt-butyl ether | –1.2±0.6 | 3.0±0.8 |
6.
Rate constants have been measured for the gas-phase reactions of hydroxyl radical with partly halogenated alkanes using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units 10–13 cm3 molecule–1 s–1): (8.1
–1.2
+1.5
) exp{–(1516±53)/T} for CHF2Cl (HCFC-22); (10.3
–1.5
+1.8
) exp{–(1588±52)/T} for CH2FCF3 (HFC-134a); (11.3
–1.6
+2.1
) exp{–(918±52)/T} for CHCl2CF2Cl (HCFC-122); (9.2
–2.0
+2.5
) exp{–(1281±85)/T} for CHFClCF2Cl (HCFC-123a).The atmospheric lifetimes for the substances have been estimated to be 12.6, 12.9, 1.05, and 4.8 years, respectively, and the accuracy of the estimates is discussed. 相似文献
7.
Hannele Hakola Janet Arey Sara M. Aschmann Roger Atkinson 《Journal of Atmospheric Chemistry》1994,18(1):75-102
The formation yields of nine carbonyl products are reported from the gas-phase OH radical-initiated reactions (in the presence of NO
x
) and the O3 reactions with seven monoterpenes. The products were identified using GC/MS and GC-FTIR and quantified by GC-FID analyses of samples collected on Tenax solid adsorbent cartridges. The identities of products from camphene, limonene and -pinene were confirmed by comparison with authentic standards. Sufficient quantities of products from the 3-carene, limonene, -pinene, sabinene and terpinolene reactions were isolated to allow structural confirmation by proton NMR spectroscopy. The measured total carbonyl formation yields ranged from non-detectable for the OH radical reaction with camphene and the O3 reactions with 3-carene and limonene to 0.5 for the OH radical reaction with limonene and the O3 reaction with sabinene. 相似文献
8.
Rate constants have been measured for the gas-phase reactions of hydroxyl radical with two halons and three of their proposed substitutes and also with CHClBr-CF3 using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units are 10–13 cm3 molecule–1 s–1): (9.3
–0.9
+1.0
) exp{–(1326±33)/T} for CHF2Br; (7.2
–0.6
+0.7
) exp{–(1111±32)/T} for CHFBrCF3; (8.5
–0.8
+0.9
) exp{–(1113±35)/T} for CH2BrCF3; (12.8
–1.2
+1.5
) exp{–(995±38)/T} for CHClBrCF3. The rate constants at 298 K have been estimated to be <2×10–17 cm3 molecule–1 s–1 for CF3Br and CF2Br—CF2Br. The atmospheric lifetimes due to hydroxyl attack have been estimated to be 5.5, 3.3, 2.8, and 1.2 years for CHF2Br, CHFBr—CF3, CH2Br—CF3 and CHClBr—CF3, respectively. 相似文献
9.
Ingvar Wängberg 《Journal of Atmospheric Chemistry》1993,17(3):229-247
The NO3 radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N2O5-NO2-N2-O2-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO, -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed. 相似文献
10.
The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO
x
/alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10–12 cm3 s–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10–17 cm3 s–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard. 相似文献
11.
A statistically relevant correlation between the reaction rate coefficient, k
OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E
i,v, reveals two classes of compounds: aromatics where –log(k
OH/cm3s-1)3/2E
i,v(eV)–2 and aliphatics where –log(k
OH/cm3s-1)4/5E
i,v(eV)+3. The prediction of the rate coefficient, k
OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×105 cm3, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated. 相似文献
12.
Formation of methoxy (CH3O) radicals in the reaction (1) CH3O2+NOCH3O+NO2 at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH3O2 and CH3ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k
1 is (7±2) 10-12 cm3/molecule · s in good agreement with previous results. 相似文献
13.
The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O2 of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O2 versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(Hdecomposition–HO
2
reaction), between these two reactions pathways. For (H)[22–0.5(HO
2
reaction)], alkoxy radical decomposition dominates over the reaction with O2 at room temperature and atmospheric pressure of air, while for (H)[25-0.5(HO
2
reaction)], the O2 reaction dominates over decomposition (where the units of H are in kcal mol–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed. 相似文献
14.
M. Karl H.-P. Dorn F. Holland R. Koppmann D. Poppe L. Rupp A. Schaub A. Wahner 《Journal of Atmospheric Chemistry》2006,55(2):167-187
Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower. 相似文献
15.
The following temperature-dependent rate coefficients (k/cm3 molecule–1 s–1) of the reactions of hydroxyl radicals with aliphatic ethers have been determined over the temperature range 247–373 K by a competitive flow technique: diethyl ether,k
OH=5.2×10–12 exp[(262±150)/T]; methyln-butyl ether,k
OH=5.4×10–12 exp[(309±150)/T]; ethyln-butyl ether,k
OH=7.3×10–12 exp[(335±150)/T]; di-n-butyl ether,k
OH=5.5×10–12 exp[(502±150)/T] and di-n-pentyl ether,k
OH=8.5×10–12 exp[(417±150)/T]. The data have been measured relative to the rate coefficientk(OH + 2,3-dimethylbutane)=6.2×10–12 cm3 molecule–1 s–1 independent of temperature.Previous discrepancies in the room-temperature rate coefficients for the OH reactions with ethyln-butyl ether and di-n-butyl ether, obtained in the flow and static experiments of Bennett and Kerr (J. Atmos. Chem.
8, 87–94, 1989;10, 29–38, 1990) compared with those of Wallingtonet al. (Int. J. Chem. Kinet.
20, 541–547, 1988;21, 993–1001, 1989) and of Nelsonet al. (Int. J. Chem. Kinet.
22, 1111–1126, 1990) have been resolved. The results are considered in relation to the available literature data and evaluated rate expressions are deduced where possible. The data are also discussed in terms of structure-activity relationships. 相似文献
16.
R. Iannone R. S. Anderson A. Vogel J. Rudolph P. Eby M. J. Whiticar 《Journal of Atmospheric Chemistry》2004,47(2):191-208
The hydrogen kinetic isotope effects (KIEs) of the reactions of 15 non-methane hydrocarbons (NMHCs) with the OH radical were measured at 298 ± 2 K. The measurements were made using NMHCs without artificial isotopic labeling or enrichment. The following average hydrogen KIE values, in per mil (), were obtained: 29.8 ± 2.1 (toluene),51.6 ± 2.1 (n-butane), 97.3± 12.5 (i-butane), 63.2 ± 5.9 (cyclopentane), 10.5 (p-xylene), 26.8 ± 3.5 (ethylbenzene), 65.9± 7.0 (n-pentane), 79.5 ± 9.6 (cyclohexane), 52.8 ± 5.0(n-hexane), 38.9 ± 7.8 (n-heptane), 33.4 ± 3.1 (n-octane), 29.6 ± 1.6(n-nonane), and 29.0 ± 5.3 (n-decane). The KIEs for reactions of two alkenes (cyclohexene and 1-heptene) could not be determined accurately due to interference from reaction with ozone, but nevertheless the results clearly show that the KIEs for reaction of alkenes with OH are significantly lower than those for saturated hydrocarbons. The KIEs for reaction of alkanes are smaller than isotope effects reported in literature for the reactions of NMHCs artificially labeled with deuterium. The main reason for this difference is the reduced probability for reaction at a labeled site for compounds with close to natural deuterium abundance, although some impact of secondary isotope effects cannot be ruled out. Still, the KIEs for NMHCs with natural or close to natural abundance of deuterium are of sufficient magnitude to allow determination of the extent of chemical processing of hydrocarbons in the atmosphere using methods analogous to stable carbon KIE studies. Furthermore, it is shown that combining stable hydrogen and stable carbon isotope ratio data has the potential to also provide valuable information regarding the stable isotope ratios of emissions, and specifically to test one of the key assumptions of the stable isotope hydrocarbon clock, the absence of significant variations of the stable isotope ratio for the emitted NMHCs. 相似文献