Kinetics and Mechanisms of the Gas-Phase Reaction of Water Vapor and Nitrogen Dioxide

England, C.; Corcoran, W. H.

doi:10.1021/i160052a014

Cited by 109 publications

(79 citation statements)

References 15 publications

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“…The observation of increasing yields of NO with decreasing HONO yields at intermediate to high relative humidities in such studies of reaction (1) 10,14,15,17,23,24,73 is consistent with the formation of HONO followed by its conversion to NO on the '' unconditioned '' walls of the reactor as illustrated, for example, by the data in Fig. 2e.…”

supporting

confidence: 77%

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

Syomin

Finlayson-Pitts

2003

Phys. Chem. Chem. Phys.

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Nitrous acid (HONO) is the major source of OH in polluted urban atmospheres, so an understanding of its formation and loss processes both in urban atmospheres and in laboratory systems is important. Earlier studies over a limited range of conditions showed that HONO is taken up and undergoes reaction on surfaces. We report here a comprehensive set of studies of the decay of HONO and the formation of gas phase products over a range of initial HONO concentrations (0.1-11 ppm) at 1 atm pressure in N 2 at 296 K and 0, 20 and 50% relative humidity (RH), respectively. The loss of HONO and increase in gas phase products were measured over time using long path FTIR spectroscopy. Studies were carried out in an unconditioned borosilicate glass cell and in the same cell after pretreatment with dry gaseous nitric acid. In the HNO 3 -conditioned cell, the loss of HONO was first order at all values of relative humidity (RH), and NO 2 was the only significant gas phase product. For the unconditioned cell, the reaction order increased from first order at 0% RH to second order at 50% RH. The gas phase products at 0% RH were equal amounts of NO and NO 2 . The yield of NO increased to > 90% at 50% RH while the yield of NO 2 decreased to 10%. For both the unconditioned and the HNO 3 -treated cell, the rate of loss of HONO decreased with increasing RH. These results suggest that there is a competition between water, HONO and HNO 3 for surface sites. Displacement of HONO from the cell walls by water was observed in separate experiments. Possible mechanisms, and the implications for HONO formation in environmental chambers and in air, are discussed.

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supporting

confidence: 77%

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

Syomin

Finlayson-Pitts

2003

Phys. Chem. Chem. Phys.

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“…The product N 2 O 4 is known to rapidly decompose thermally (DeMore et al, 1997) and to react slowly with water to HONO and HNO 3 (England and Corcoran, 1974). The equilibrium constant for NO 2 + NO 2 ←→ N 2 O 4 , however, gives an N 2 O 4 mixing ratio of the order of 6 pmol mol −1 for an NO 2 mixing ratio of 1 µmol mol −1 , so that formation of N 2 O 4 is expected not to play a role, which was confirmed by inclusion of these reactions into the model.…”

Section: Chemistry In the Plumementioning

confidence: 99%

Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

Glasow

Lawrence²,

Sander³

et al. 2003

Atmos. Chem. Phys.

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Abstract. The chemical evolution of the exhaust plumes of ocean-going ships in the cloud-free marine boundary layer is examined with a box model. Dilution of the ship plume via entrainment of background air was treated as in studies of aircraft emissions and was found to be a very important process that significantly alters model results. We estimated the chemical lifetime (defined as the time when differences between plume and background air are reduced to 5% or less) of the exhaust plume of a single ship to be 2 days. Increased concentrations of NO x (= NO + NO 2 ) in the plume air lead to higher catalytical photochemical production rates of O 3 and also of OH. Due to increased OH concentrations in the plume, the lifetime of many species (especially NO x ) is significantly reduced in plume air. The chemistry on background aerosols has a significant effect on gas phase chemistry in the ship plume, while partly soluble shipproduced aerosols are computed to only have a very small effect. Soot particles emitted by ships showed no effect on gas phase chemistry. Halogen species that are released from sea salt aerosols are slightly increased in plume air. In the early plume stages, however, the mixing ratio of BrO is decreased because it reacts rapidly with NO. To study the global effects of ship emissions we used a simple upscaling approach which suggested that the parameterization of ship emissions in global chemistry models as a constant source at the sea surface leads to an overestimation of the effects of ship emissions on O 3 of about 50% and on OH of roughly a factor of 2. The differences are mainly caused by a strongly reduced lifetime (compared to background air) of NO x in the early stages of a ship plume.

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“…The water content of the aerosol is insensitive to the sticking coefficient. The amount of conversion to nitric acid is very sensitive to this parameter, but a comparatively large number (10" 3 or higher) seems likely in view of earlier studies (England and Corcoran, 1974). The other relationships are more complex.…”

Section: Adiabatic Parcel Evolutionmentioning

confidence: 88%

Use of Surface Chemkin to Model Multiphase Atmospheric Chemistry: Application to Nitrogen Tetroxide Spills

Brady¹,

Martin²

2000

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LABORATORY OPERATIONSThe Aerospace Corporation functions as an "architect-engineer" for national security programs, specializing in advanced military space systems. The Corporation's Laboratory Operations supports the effective and timely development and operation of national security systems through scientific research and the application of advanced technology. Vital to the success of the Corporation is the technical staff's wideranging expertise and its ability to stay abreast of new technological developments and program support issues associated with rapidly evolving space systems. Contributing capabilities are provided by these individual organizations:Electronics and Photonics Laboratory: Microelectronics, VLSI reliability, failure analysis, solid-state device physics, compound semiconductors, radiation effects, infrared and CCD detector devices, data storage and display technologies; lasers and electro-optics, solid state laser design, micro-optics, optical communications, and fiber optic sensors; atomic frequency standards, applied laser spectroscopy, laser chemistry, atmospheric propagation and beam control, LIDAR/LADAR remote sensing; solar cell and array testing and evaluation, battery electrochemistry, battery testing and evaluation.Space Materials Laboratory: Evaluation and characterizations of new materials and processing techniques: metals, alloys, ceramics, polymers, thin films, and composites; development of advanced deposition processes; nondestructive evaluation, component failure analysis and reliability; structural mechanics, fracture mechanics, and stress corrosion; analysis and evaluation of materials at cryogenic and elevated temperatures; launch vehicle fluid mechanics, heat transfer and flight dynamics; aerothermodynamics; chemical and electric propulsion; environmental chemistry; combustion processes; space environment effects on materials, hardening and vulnerability assessment; contamination, thermal and structural control; lubrication and surface phenomena.Space Science Application Laboratory: Magnetospheric, auroral and cosmic ray physics, wave-particle interactions, magnetospheric plasma waves; atmospheric and ionospheric physics, density and composition of the upper atmosphere, remote sensing using atmospheric radiation; solar physics, infrared astronomy, infrared signature analysis; infrared surveillance, imaging, remote sensing, and hyperspectral imaging; effects of solar activity, magnetic storms and nuclear explosions on the Earth's atmosphere, ionosphere and magnetosphere; effects of electromagnetic and paniculate radiations on space systems; space instrumentation, design fabrication and test; environmental chemistry, trace detection; atmospheric chemical reactions, atmospheric optics, light scattering, state-specific chemical reactions and radiative signatures of missile plumes.Center for Microtechnology: Microelectromechanical systems (MEMS) for space applications; assessment of microtechnology space applications; laser micromachining; laser-surface physical and chemical ...

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Kinetics and Mechanisms of the Gas-Phase Reaction of Water Vapor and Nitrogen Dioxide

Cited by 109 publications

References 15 publications

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

Use of Surface Chemkin to Model Multiphase Atmospheric Chemistry: Application to Nitrogen Tetroxide Spills

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