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1.
Using a single drop experiment, the uptake of NO3 radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10− 3 were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10−3 depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of αNO3 = (4.2− 1.7+2.2)⋅ 10−3. The product H(Dl kCl−II)0.5 for the NO3 radical was determined to be (1.9 ± 0.2) M atm− 1 cm s−0.5 M−0.5 s−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO3 radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO3 radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO3 concentration was found indicating a conversion of gas-phase NO3 radicals to gas-phase HNO3 on the moist reactor walls.  相似文献   

2.
A combined study of the OH gas phase reaction and uptake on aqueous surfacesof two carbonates, dimethyl and diethyl carbonate has been carried out todetermine the atmospheric lifetimes of these compounds. Rate coefficients havebeen measured for gas phase reactions of OH radicals with dimethyl and diethylcarbonate. The experiments were carried out using pulsed laser photolysis– laser induced fluorescence over the temperature range 263–372K and the kinetic data were used to derive the following Arrhenius expressions(in units of cm3 molecule–1 s–1):for dimethyl carbonate, k1 = (0.83±0.27)×10–12 exp [–(247± 98)/T] and fordiethyl carbonate, k2 = (0.46±0.15)×10–12 exp [(503± 203)/T]. At 298 K, therate coefficients obtained (in units of 10–12 cm3molecule–1 s–1) are: k1 =(0.35± 0.04) and k2 = (2.31± 0.29). The results arediscussed in terms of structure-activity relationships.The uptake coefficients of both carbonates on aqueous surfaces were measuredas a function of temperature and composition of the liquid phase, using thedroplet train technique coupled to a mass spectrometric detection. Dimethyland diethyl carbonate show very similar results. For both carbonates, themeasured uptake kinetics were found to be independent of the aqueous phasecomposition (pure water, NaOH solutions) but dependent on gas-liquid contacttime which characterises a surface saturation effect. The uptake coefficientvalues show a slight negative temperature dependence for both carbonates.These values vary from 1.4×10–2 to0.6×10–2 in the temperature range of 265–279 Kfor dimethyl carbonate, from 2.4×10–2 to0.9×10–2 in the temperature range of 270–279 Kfor diethyl carbonate. From the kinetic data, the following Henry's lawconstants were derived between 279 and 265 K: dimethyl carbonate,H1 = 20–106 M atm–1; and diethyl carbonate,H2 = 30–98 M atm–1. The reported data showthat the OH reaction is the major atmospheric loss process of these twocarbonates with lifetimes of 33 and 5 days, respectively, while the wetdeposition is a negligible process.  相似文献   

3.
We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of exp=(6.0±0.8)×10–2 at 298 K and with a total pressure of 38 Torr for SO2, (5.0±1.0)×10–2 at 297 K and total pressure of 52 Torr for HNO3, (1.5±0.6)×10–3 at 298 K and total pressure of 50 Torr for NO2, (2.4±1.0)×10–2 at 290 K and total pressure of 70 Torr for NH3.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10–1 (298 K) for SO2, (1.1±0.1)×10–1 (298 K) for HNO3, (9.7±0.9)×10–2 (290 K) for NH3, (1.5±0.8)×10–3 (298 K) for NO2 but this last value should not be considered as the true value of for NO2 because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.  相似文献   

4.
A simple and inexpensive procedure is presented for the measurement of gaseous accommodation coefficients upon liquid or solid surfaces. The gas of interest is passed in laminar flow through an annular reactor and the profile of deposition is subsequently determined. The Cooney-Kim-Davies theoretical treatment of deposition in cylindrical systems is adapted to describe uptake on the walls of the annular reactor as a function of accommodation coefficient and diffusion coefficient. The accommodation coefficient () of ammonia on oxalic acid is determined in both cylindrical and annular systems and good agreement is found. Uptake of nitrogen dioxide on wet alkaline surfaces yields a value for of 2.5×10–4, and on solely wet surfaces a value of 8.7×10–5. Nitric and nitrous acids deposit to aqueous sodium carbonate/glycerol surfaces with values of of 1.5 × 10–2 and 4.3×10–3, respectively.  相似文献   

5.
The exchange of NO3 radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO3 was determined on 0.1 M NaCl solutions and was found to be (NO3) 2 × 10-3 in good agreement with recent studies. The Henry coefficient of NO3 was estimated to be KH(NO3) = 1.8 M · atm-1, with a (2) uncertainty of ±3 M · atm-1. From the upper limit for the Henry coefficient (KH = 5 M · atm-1) and available thermodynamic data, the redox potential of dissolved NO3/NO 3 – is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient KH and the rate coefficient k 10 of the potential reaction NO3 + H2O HNO3 + OH. For KH = 0.6 M · atm-1, we find k 10 < 0.05 s-1 · atm-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO3 is only important under conditions where the dissolved NO3 is removed quickly from equilibrium, for example by reactions with Cl– or HSO 3 – ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N2O5.  相似文献   

6.
We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO4) on the concentrations and budgets of NOx, SOx, O3 and H2O2. Laboratory studies have shown that the aqueous reaction of HNO4aq withHSO– 3aq, and the uni-molecular decomposition of the NO4 – anion to form NO2 – (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO– 3aq with HNO4aq to the overall in-cloud conversion of SO2 to SO4 2–, a simultaneous decrease of other oxidants (most notably H2O2) more than compensated the increase in SO4 2– production. The strongest influence of heterogeneous HNO4 chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H2O2 between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO2 was increased by 10% to 20% and SO4 2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO4 reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO4 in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.  相似文献   

7.
The photodissociation coefficient of NO2, J NO 2, has been measured from a balloon platform in the stratosphere. Results from two balloon flights are reported. High Sun values of J NO 2 measured were 10.5±0.3 and 10.3±0.3×10-3 s-1 at 24 and 32 km respectively. The decrease in J NO 2 at sunset was monitored in both flights. The measurements are found to be in good agreement with calculations of J NO 2 using a simplified isotropic multiple scattering computer routine.  相似文献   

8.
The uptake of water vapor on MgCl2×6H2O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H2O to salt uptake data were obtained from the kinetics of H2O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H2O on MgCl2×6H2O films: γ 0 (MgCl2) = (6.5 ± 1.0) × 10−6 exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H2O adsorption on NaCl was found to be much lower than on MgCl2×6H2O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10−6 at T = 300 K. The results show that the rate of H2O adsorption to salt surfaces is drastically dependent on the salt sample composition.  相似文献   

9.
The present study focuses on the heterogeneous reaction between gaseous atomic chlorine and solid palmitic acid films, used as a proxy of the fatty acids detected in atmospheric airborne particles. This reaction is investigated in a coated wall flow tube reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor. The initial Cl˙ and Cl2 uptake coefficient measured for these heterogeneous reactions is found to be fast: γo Cl?=?0.07. The rapid formation of hydrogen chloride corresponding with the disappearance of atomic chlorine is highlighted. Furthermore, the formation of new chlorinated species on the solid substrate has been detected by TOF SIMS analysis leading to an ageing process of the surface. A heterogeneous recombination of Cl atoms to Cl2 molecules was observed for aged surfaces.  相似文献   

10.
The reaction coefficients of nitrogen dioxide and nitrous acid with monodisperse sodium chloride and ammonium sulphate aerosols have been measured in a flow reactor at atmospheric pressure. These experiments were performed at relative humidities above and below the deliquescence points of both aerosols (r.h. 50 and 85%) at 279 K. The results for NO2 afford a reaction coefficient in the range (2.8–10) × 10-4 and for HONO, (2.8–4.6) × 10-3. For both species, there appears to be an enhancement of the reaction coefficient on sodium chloride aerosol at 50% r.h. The results are compared with reaction coefficients determined by other experimental methods. A good agreement is found for both gases between this method and the coated denuder method previously developed in our research laboratories (Msibi et al., 1993) and with the majority of other published data for NO2. In the case of HONO, our estimate of reaction coefficient is smaller than, or at the lower limits of the ranges reported by other published studies.  相似文献   

11.
The heterogeneous chemistry of nitryl chloride and nitryl bromide by salt containing solutions was studied as a function of temperature in the range from 275 to 293 K with the wetted-wall flowtube combined with FTIR and mass spectrometry detection. Uptake coefficients and values of the product Hk1/2 on these saline solutions have been determined. For nitryl halides interacting with NaI and NaBr solutions, the values of the product Hk1/2 are respectively 4384.7±326.7 and 103.1±18.7 M atm-1 s-1/2 for nitryl chloride at 275 K and 544.2±94.7 and 47.7±15.2 M atm-1 s-1/2 for nitryl bromide at 278 K. When reacting with NaI or NaBr solutions, these heterogeneous reactions release, as major products, the molecular forms of the halogen i.e., respectively I2 and Br2. A simplified reaction scheme explaining the formation of these products is presented and is inserted into a model simulating the chemistry in the marine boundary layer. The modelling effort showed Cl and BrO atoms concentrations up to 5×104 and 1.8×106 molecules cm-3 respectively, which are comparable to values actually measured in field campaigns.  相似文献   

12.
A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO3(g) + NaX(s) (NO3-NaX)(s); (NO3-NaX)(s) NaNO3 + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO3 for raw coating. The initial (t0) is higher than the observable steady-state obs. At room temperature obs is independent of [NO3] at low [NO3] = 3 × 109 - 1011 cm-3, but it is inversely proportional to [NO3] at concentrations higher than 1012 cm-3. At temperatures above 100 °C, obs becomes independent of [NO3] in a wider range of [NO3]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO3 concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.  相似文献   

13.
The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τsurf) of NO2 on NH4Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τsurf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO2 on NH4Cl followed a rate law first order in [NO2] and the uptake coefficient γ is equal to 7 × 10−5 at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10−4) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO2 with NH4Cl is a reverse disproportionation reaction where two moles of NO2 result in ammonium nitrite, NH4NO2, as an intermediate, and nitryl chloride, NO2Cl. NH4NO2 decomposes in two pathways, one to nitrous acid, HONO and NH3, the other to nitrogen and water. The branching ratio for the production of HONO + NH3 to that of N2 + H2O is approximately 20 at 298 K and increases with increasing temperature.  相似文献   

14.
Precipitation samples were collected by filtrating bulk sampler in Kitakyushu City, Japan, from January 1988 to December 1990. Volume weighted annual mean of pH was 4.93, but the pH distribution indicated that most probable value lay in the range pH 6.0–6.4. Volume weighted annual mean concentrations of major ionic components were as follows; SO 4 2– : 84.2, NO 3 – : 28.1, Cl–: 86.3, NH 4 + : 45.5, Ca2+: 63.3, Mg2+: 27.0, K+: 3.4, Na+: 69.0 µ eq l–1. The highest concentrations of these ionic components were observed in winter and the lowest occurred in the rainy season. The ratio of ex-SO 4 2– /NO 3 – exhibited the lowest ratio in summer, and the highest ratio in winter. Good correlations were obtained between Cl– and Na+, ex-SO 4 2+ and ex-Ca2+, NO 3 – and ex-Ca2+, and NH 4 + and ex-SO 4 2– , respectively. However, no correlation between Cl– and Na+ with Ca2+ was observed. The relationship of H+ with (ex-SO 4 2– + NO 3 – ) - (ex-Ca2+ + NH 4 + ) indicated positive correlation.  相似文献   

15.
Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 109 M–1 s–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 108 M–1 s–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO– 4 adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10–5 m3 m–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO2 in the atmosphere.  相似文献   

16.
The kinetics of the aqueous phase reactions of NO3 radicals with HCOOH/HCOO– and CH3COOH/CH3COO– have been investigated using a laser photolysis/long-path laser absorption technique. NO3 was produced via excimer laser photolysis of peroxodisulfate anions (S2O 8 2– ) at 351 nm followed by the reactions of sulfate radicals (SO 4 – ) with excess nitrate. The time-resolved detection of NO3 was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO3 with formic acid (1) and formate (2) rate coefficients ofk 1=(3.3±1.0)×105 l mol–1 s–1 andk 2=(5.0±0.4)×107 l mol–1 s–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k 1(T)=(3.4±0.3)×1010 exp[–(3400±600)/T] l mol–1 s–1 andk 2(T)=(8.2±0.8)×1010 exp[–(2200±700)/T] l mol–1 s–1. The rate coefficients for the reactions of NO3 with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k 3=(1.3±0.3)×104 l mol–1 s–1 andk 4=(2.3±0.4)×106 l mol–1 s–1. The temperature dependences for these reactions are described by:k 3(T)=(4.9±0.5)×109 exp[–(3800±700)/T] l mol–1 s–1 andk 4(T)=(1.0±0.2)×1012 exp[–(3800±1200)/T] l mol–1 s–1. The differences in reactivity of the anions HCOO– and CH3COO– compared to their corresponding acids HCOOH and CH3COOH are explained by the higher reactivity of NO3 in charge transfer processes compared to H atom abstraction. From a comparison of NO3 reactions with various droplets constituents it is concluded that the reaction of NO3 with HCOO– may present a dominant loss reaction of NO3 in atmospheric droplets.  相似文献   

17.
The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO2 (0–860 ppb), H2O2 (0–150 ppb) and sometimes NH3 (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH4)2SO4 and Na2SO4 droplets. For (NH4)2SO4 droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH3 was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO2 by H2O2, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH3 evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.  相似文献   

18.
A programme of ground-based stratospheric and total NO2 column measurements was instituted at the Laboratory of Atmospheric Physics (40.5° N, 22.9° E) in August 1985. We present here the results of the first two years of measurements with a modified Canterbury filter photometer, details of which are given in the text. The stratospheric NO2 column, obtained at twilight during low local NO2 levels, shows the seasonal variation with monthly mean values of about 6×10-15 molec. cm-2 in the summertime to about 2.2×10-15 molec. cm-2 in the wintertime. These measurements compare well with measurements obtained with different instruments by other groups at similar latitudes (about 40° N) but in different places. Also, the asymmetry of the evening-to-morning stratospheric NO2 over Thessaloniki was found to be on the average equal to 1.58. Total NO2 column over Thessaloniki has a pronounced seasonal variation with amplitude of 0.68 matm. cm which can be explained partly from measured local NO2 sources which discharge in the mixing layer and partly from photolysis of the NO2 reservoir species.  相似文献   

19.
南京北郊2011年春季气溶胶粒子的散射特征   总被引：3，自引：2，他引：1       下载免费PDF全文
利用南京北郊2011年春季积分浊度仪的观测资料,结合PM2.5质量浓度、能见度和常规气象资料,分析了南京北郊春季气溶胶散射系数的变化特征、散射系数与PM2.5质量浓度和能见度的关系。结果表明,观测期间气溶胶散射系数平均值为311.5±173.3 Mm-1,小时平均值出现频率最高的区间为100~200 Mm-1;散射系数的日变化特征明显,总体为早晚大,中午及午后小。散射系数与PM2.5质量浓度的变化趋势基本一致,但与能见度呈负相关关系。霾天气期间散射系数日平均值为700.5±341.4 Mm-1,最高值达到近1 900 Mm-1;结合地面观测资料、NCEP/NCAR再分析资料和后向轨迹模式分析显示,霾期间气块主要来自南京南部和东南方向。  相似文献   

20.
Generally, it is assumed that UV-light, high temperature or reactive molecules like O3 and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O2-dissociation rates on natural quartz sand at 40˚C and compared these with O2-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O2-molecules the measured rates are in the 10−12–10−4 range. We have also measured dissociation rates of H2 and N2, water-formation from H2 and O2 mixtures, exchange of N between N2, NO x and a breakdown of HNO3, NO2 and CH4 on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H2, NO2 and CH4. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO x or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N2, O2 and H2O.  相似文献   

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