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11.
文章研究了臭氧及臭氧类高级氧化技术(AOPs-O3)在不同pH条件下降解甲基对硫磷(MP)的效能。结果表明,在pH 3~10的条件下(反应过程控制pH),单独臭氧化5min即可完全降解MP,但不同pH下化学耗氧量(COD)和有机磷的释放率差异明显。在pH为3.3,7.5和9.4的条件下单独臭氧30min后COD的去除率分别为55.17%,89.64%和93.10%,有机磷的释放率分别为16.33%,95.00%和99.99%。考虑酸性条件下可以规避碳酸盐的负面影响(特别是高浓度废水),利用O3/H2O2/Ti(IV)在pH 3.3条件下处理MP溶液,COD去除率和有机磷释放率分别达到89.64%和81.57%。相对法计算求得MP与O3和羟基自由基(·OH)的速率常数分别为31.98L·(mol·s)-1和7.488×109 L·(mol·s)-1。活性污泥法的测试结果表明,MP经O3/Ti(IV)/H2O2(pH=3.3)和O3(pH=9.4)可提升含MP废水的可生化性,但与培养液体系相比仍具有一定的毒性。 相似文献
12.
This paper employs the highly accurate valence internally contracted multireference configuration interaction method to investigate the potential energy curves (PECs) for the ground state (X1Σ+) and two low-lying excited states (A1Π and D1Δ of phosphorus nitride (PN) radical with the correlation-consistent basis set, aug-cc-pV6Z, in the valence range. Relativistic effects are considered in these calculations. The spectroscopic constants of the X1Σ+ and A1Π states are calculated based on the PECs, and the results are in good accord with the available experimental data. The first 30 vibrational states for the A1Π state and the first 40 vibrational states for the A1Π state are determined when J=0. For each vibrational state, molecular constants G(υ), B(υ) and D(υ) are also attained. 相似文献
13.
Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10-12 cm3 s-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10-12 cm3 s-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions. 相似文献
14.
Information from a variety of sources, including an airborne field expedition in November 1985, is used to produce estimates of the annual emissions of some hydrocarbons from bushfires, and isoprene from trees, in tropical Australia. For the continent north of 23° S the annual bushfires (biomass burning) input was estimated, in units of Tg carbon, to be 2 TgC (uncertainty range 0.8–5 TgC), emitted predominantly during the May to October dryseason. Isoprene emissions during this period were estimated also to be 2 TgC (uncertainty range 0.5–8 TgC), but were estimated to be an order of magnitude higher during the November to April wet season, at a level of 23 TgC (uncertainty range 6–100 TgC).The large annual emission of isoprene over the tropical part of the Australian continent yields ppbv levels of isoprene measured at the surface in summertime. Isoprene reactivity with hydroxyl radical is such that at these concentrations isoprene must be a dominant factor in controlling the concentration of OH radical in the convective boundary layer. Simple arguments based on the convective velocity scale suggest that the shape of the isoprene vertical profile in November 1985 would be consistent with available data on the OH-isoprene reaction rate if OH concentration in the boundary layer averaged about 2.5×106 cm-3 over the middle part of the day.Temporarily at the International Meteorological Institute, Stockholm University, S-106 91, Stockholm, Sweden. 相似文献
15.
16.
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
17.
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
18.
Products and mechanisms for the gas-phase reactions of NO3 radicals with CH2=CHCl, CH2=CCl2, CHCl=CCl2,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO3 was generated by the thermal dissociation of N2O5. Experiments with15NO3 and CD2CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO2. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH2=CCl2 and CHCl=CCl2 are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO3 addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10–16 cm3 molecule–1 s–1 for CH2=CHCl, CH2=CCl2, CHCl=CCl2 andcis-CHCl=CHCl, respectively. 相似文献
19.
The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10–20 cm2 molecule–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH2OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10–11 and (1.1± 0.3)×10–11 cm3 molecule–1 s–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies. 相似文献
20.