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1.
Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J O1D, J NO2, and J NO3, respectively. Absolute calibration of the J O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J NO2 and J O1D are presented.  相似文献   

2.
Intact soils cores were taken with a stainless steel corer from a sandy podzol and a loamy luvisol, and used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (m a) in the atmosphere of the headspace. These measurements were repeated after stepwise excavation of the soil column from the top, e.g. by removing the upper 2 cm soil layer. The gaseous diffusion coefficients of NO in the soil cores were either computed from soil porosity or were determined from experiments using SF6. The NO fluxes (J) that were actually measured at the soil surface were compared to the fluxes which were calculated either from the vertical NO profiles (J c ) or from the NO production and uptake rates (J m ) determined in the excavated soil samples. In the podzol, the actually measured (J) and the calculated (J m , Jm) NO fluxes agreed within a factor of 2. In the luvisol, the measured NO fluxes (J) and those calculated from the vertical NO profiles (J c ) also agreed well, but in the upper 6 cm soil layer the NO fluxes (J m ) calculated from NO production and uptake rates were up to 7 times higher than the measured NO fluxes. This poor agreement was probably due to the inhomogeneous distribution of NO production and consumption processes and the change of diffusivities within the top layers of the luvisol. Indeed, the luvisol showed a pronounced maximum of the NO mixing ratios at about 6 cm depth, whereas the podzol column exhibited a steady and exponential decrease of the NO mixing ratios with depth. The inhomogeneities in the luvisol were confirmed by incubation of the soil cores under anoxic conditions. This treatment resulted in production of NO at several depths indicating a zonation of increased potential activities within the luvisol profile which may have biased the modelling of the NO surface flux from turnover measurements in soil samples. Inhomogeneities could be achieved even in homogenized soil by fertilization with nitrate solution.  相似文献   

3.
The latitudinal variation of the photolysis frequency of ozone to O(1D) atoms, J(O1D), was measured using a filter radiometer during the cruise ANT VII/1 of the research vessel Polarstern in September/October 1988. The J(O1D) noon values exhibited a maximum of 3.6×10-5 s-1 (2 sr) at the equator and decreased strongly towards higher latitudes. J(O1D) reached highest values for clean marine background air with low aerosol load and almost cloudless sky. The J(O1D) data, measured under these conditions and a temperature of 295 K, can be expressed by: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOsaiaacI% cacaqGpbWaaWbaaSqabeaaiiaacqWF8baFaaGccaqGebGaaeykaiaa% bccacqWF9aqpcaqGGaGaaeyzaiaabIhacaqGWbGaaeiiaiaabUhacq% GHsislcaaI4aGaaiOlaiaaicdacaaIYaGaeyOeI0IaaGioaiaac6ca% caaI4aGaaiiEaiaaigdacaaIWaWaaWbaaSqabeaacqGHsislcaaIZa% aaaOGaaeiiaiaabIhacaqGGaGaam4uaiabgUcaRiaaiodacaGGUaGa% aGinaiaacIhacaaIXaGaaGimamaaCaaaleqabaGaeyOeI0IaaGOnaa% aakiaadofadaahaaWcbeqaaiaaikdaaaGccaGG9bGaaeikaiaaboha% daahaaWcbeqaaiabgkHiTiaaigdaaaGccaGGPaaaaa!5EE9!\[J({\text{O}}^| {\text{D) }} = {\text{ exp \{ }} - 8.02 - 8.8x10^{ - 3} {\text{ x }}S + 3.4x10^{ - 6} S^2 \} {\text{(s}}^{ - 1} )\] where S represents the product of the overhead ozone column (DU) and the secant of the solar zenith angle. The meridional profile of the primary OH radical production rate P(OH) was calculated from the J(O1D) measurements and simultaneously recorded O3 and H2O mixing ratios. While the latitudinal distribution of J(O1D) and water vapour was nearly symmetric to the equator, high tropospheric ozone levels up to 40 ppb were observed in the Southern Hemisphere, SH, resulting in higher P(OH) in the SH.  相似文献   

4.
In view of the uncertainty of the origin of the secular increase of N2O, we studied heterogeneous processes that contribute to formation of N2O in an environment that comes as close as possible to exhaust conditions containing NO and SO2, among other constituents. The N2O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO2, NO, NO2 and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N 2 O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO2, O2 in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N2O. The stoichiometry of the overall reaction is: 2 NO+SO2+H2O N2O+H2SO4. The maximum rate of N2O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N2O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN2O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N2O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.  相似文献   

5.
Using a filter radiometer, the meridional profile of the NO2 photolysis frequency, J(NO2), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b sp=(1–2)×10-5 m-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO2) reached 7.3×10-3 s-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO2) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10-3 s-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO2) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10-5 s-1/mW cm-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).  相似文献   

6.
The atmospheric reaction between HS and NO2 was theoretically investigated at 298 K and 1 atm of pressure. Our results show that the first reaction step will lead to the formation of HSNO2 or HSONO, spontaneously and exothermically. HSONO easily decomposes into HSO + NO. On the other hand, HSNO2 can hardly dissociate in the reactants, and its isomerization to other adducts is much hindered. Production of HNO + SO and SNO + OH was found to be unfavorable. Thus, the main products would be HSO + NO and HSNO2, and new investigations focusing on the atmospheric fate of HSNO2 are suggested. A general discussion of the fate of HS under atmospheric conditions is presented. Recent investigations indicate that NO2, O2 and N2O should be the most important oxidants of HS, while the O3 influence will not be significant.  相似文献   

7.
Zusammenfassung A. undE. Vassy haben in der Frage der Temperatur-abhängigkeit des Ozongehalts der Atmosphäre aus der Gleichung loge n –logJ n logK(T n ) geschlossen, daß auch die Gleichung loge n logJ n +logK(T n ) gültig sei. Es wird hier nun gezeigt, daß die bei der ersten Gleichung erlaubten Vernachlässigungen bei der zweiten zu großen Fehlern führen können und daß daher von A. undE. Vassy kein Beweis für die Richtigkeit der Beziehunge=J.K(T) erbracht ist.
Summary In the question of temperature dependence of ozone content of the atmosphere A. andE. Vassy have concluded from the equation loge n –logJ n logK(T n ) that also the formula loge n logJ n +logK(T n ) must be valid. In this paper it is proved that the neglections which may be admitted for the first equation, can conduct to great errors. Therefore A. andE. Vassy have not produced a proof for the correctness of the equatione=J.K(T).
Résumé A. etE. Vassy en étuidant le problème de la teneur de l'ozone atmosphérique en relation avec la température ont admis que l'équation loge n –logJ n logK(T n ) entraînait aussi la relation loge n logJ n +logK(T n ). On montre ici que les simplifications admises pour la première équation conduisent pour l'application de la seconde à de fortes erreurs, et que par conséquent ces auteurs n'ont pas fourni de preuve de la justesse de la relatione=J.K(T).
  相似文献   

8.
The aqueous phase acid-catalyzed reaction of methanol (CH3OH) with nitric acid (HNO3) to yield methyl nitrate (CH3ONO2) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH3OH] = 0.00005–0.005 M and [HNO3] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH3OH and HNO3 concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k obs [CH3OH][HNO3], where k obs  = 2.337 × 10−13(exp(0.3198*wt.% H2SO4)) when the solubility of CH3ONO2 in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H2SO4, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at  相似文献   

9.
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   

10.
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   

11.
A stainless steel soil corer which was filled with homogenized soil was used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (mm a ) in the atmosphere of the headspace. The NO emission flux decreased linearly with increasing NO mixing ratio and turned into a deposition flux after passage of the compensation point (m c) at about 400 ppbv NO. Almost the same compensation point was obtained when the turnover of NO was measured in flask-incubated soil samples as function of the NO mixing ratio. The flux (J) of NO at the soil-atmosphere interface was calculated from the production rate (P) of NO and the NO uptake rate constant (k) that were measured in these flask-incubated soil samples using the diffusion model of Galbally and Johansson (1989). The calculated fluxes agreed within <15% with those actually measured. The vertical profiles of NO were fitted to an exponential function and analyzed by Fick's first law of diffusion. The shape of the profiles indicated a net production of NO in the upper 10 cm soil layer when the atmospheric NO mixing ratio was below the compensation point and in a net consumption of NO when the atmospheric NO mixing ratio was above the compensation point. In soil layers below 10 cm depth, the turnover of NO resulted in compensation of production and consumption rates. Measurement of the actual diffusion coefficient using SF6 showed that gas transport in the soil core was not only due to molecular diffusion but in addition due to a bidirectional gas flow. The experimentally determined diffusion coefficient was smaller than that computed from soil porosities, but resulted together with the additional transport term in NO fluxes that were close (< ±15%) to those measured. This is the first comprehensive study of NO concentration profiles and turnover rates in soil providing a theoretical basis for modelling NO fluxes at the soil-atmosphere interface.  相似文献   

12.
Accurate values for the rate and temperature dependence of the reaction NO + O3 NO2 + O2 are important in the chemical modelling of photochemical processes in the atmosphere. Previous measurements have been made at low total pressures and/or with very large mixing ratios relative to those observed in the atmosphere. In this study the reaction rate has been measured using a novel approach under tropospheric conditions of temperature and pressure, and at tens of ppb (mixing ratios of 1 in 108) between 263 and 328 K. The resultant Arrhenius expression (k=Ae-Ea/RT) gives a larger activation energy (Ea/R=1670 ± 100) than the recommended literature value (Ea/R=1400 ± 200), and a larger pre-exponential factor (A=5.1 ± 1.6 × 10-12 cf. recommended A=2.0 × 10-12), but the second-order rate constant at 298 K (1.90 × 10-14 molecules cm-3 s-1 ± 10%) is similar to the recommended value. The results confirm a lack of pressure dependence of the reaction, but were made over too small a range in temperature to address the issue of curvature of the simple Arrhenius expression.  相似文献   

13.
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   

14.
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   

15.
A possibility is studied of extending the range of action of the simple three-parameter formula (ITS-90 scale) proposed in the previous work of the author [2] for the dependence of saturation vapor pressure E on temperature T within the range of 250 to 490 K. The results demonstrated that the dependence ln[E(T)/E(T bas)] = (T - T bas)[A - B(T - T bas) + C(T - T bas)2]/T with four sets of coefficients A, B, and C obtained using one base temperature Tbas equal to the temperature of triple point of water T t = 273.16 K and two additional base values T bas2 = 473.16 K and T bas3 = 623.16 K makes it possible to approximate rather accurately the initial experimental and computed data in the temperature range from the point of homogeneous freezing of 235 K to the critical temperature of 647 K for liquid water and from 193 K to T t for ice. A procedure used for obtaining the inverse function T(E) by solving the third-degree algebraic equation is validated. A hypothesis is proposed for the physical substantiation of additional base points in the form of “a noticeable appearance of dimers at the point T bas2 and their 100% concentration at the temperature T bas3.”  相似文献   

16.
Alkyl nitrate yields from the NO x photooxidations of neopentane, 2-methylbutane and 3-methylpentane have been determined over the temperature and pressure ranges 281–323 K and 54–740 torr, respectively. The formation of the alkyl nitrates is attributed to the reaction pathway (1b) $${\text{RO}}_{\text{2}} + {\text{NO}}^{{\text{ }}\underrightarrow {\text{M}}} {\text{ RONO}}_{\text{2}}$$ and rate constant ratios k 1b/(k 1a+k 1b) are estimated, where (1a) is the reaction pathway (1a) $${\text{RO}}_{\text{2}} + {\text{NO}} \to {\text{RONO}}_{\text{2}} .$$ A method for estimating this rate constant ratio for primary, secondary and tertiary alkyl peroxy radicals is presented.  相似文献   

17.
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   

18.
Recent works with energy balance climate models and oceanic general circulation models have assessed the potential role of the world ocean for climatic changes on a decadal to secular time scale. This scientific challenge is illustrated by estimating the response of the global temperature to changes in trace gas concentration from the pre-industrial epoch to the middle of the next century. A simple energetic formulation is given to estimate the effect on global equilibrium temperature of a fixed instantaneous radiative forcing and of a time-dependent radiative forcing. An atmospheric energy balance model couple to a box-advection-diffusion ocean model is then used to estimate the past and future global climalic transient response to trace-gas concentration changes. The time-dependent radiative perturbation is estimated from a revised approximate radiative parameterization, and the recent reference set of trace gas scenarios proposed by Wuebbles et al. (1984) are adopted as standard scenarios. Similar computations for the past and future have recently been undertaken by Wigley (1985), but using a purely diffusive ocean and slightly different trace gas scenarios. The skill of the socalled standard experiment is finally assessed by examining the model sensitivity of different parameters such as the equilibrium surface air temperature change for a doubled CO2 concentration [T ae (2×CO2)], the heat exchange with the deeper ocean and the trace gas scenarios. For T ae (2×CO2) between 1 K and 5 K, the following main results are obtained: (i) for a pre-industrial CO2, concentration of 270 ppmv, the surface air warming between 1850 and 1980 ranges between 0.4 and 1.4 K (if a pre-industrial CO2 concentration of 290 ppmv is chosen, the range is between 0.3 and 1 K); (ii) by comparison with the instantaneous equilibrium computations, the deeper ocean inertia induces a delay which amounts to between 6 years [for lower T ae (2×CO2)] and 23 years [for higher Tae(2×CO2)] in 1980; (iii) for the standard future CO2 and other trace gas scenarios of Wuebbles et al., the surface air warming between 1980 and 2050 is calculated to range between 0.9 and 3.4 K, with a delay amounting to between 7 years and 32 years in 2050 when compared to equilibrium computations.  相似文献   

19.
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   

20.
A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO2 was adsorbed as N2O4 approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO2, NO, O2 and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO2, NO and O2 were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO2 was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N2O4. NO was supposed to be a predissociation product from the electronically excited NO2 prepared through the photodissociation of N2O4.  相似文献   

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