In clouds

Because of the mixture of VOCs in the atmosphere, the composition of smog reaction products and intermediates is extremely complex. formed via reaction 16, is important because when dissolved in cloud droplets it is an important oxidant, responsible for oxidising SO2 to sulfuric acid [7664-93-9] H2SO4, the primary cause of acid precipitation. The oxidation of many VOCs produces acetyl radicals, CH CO, which can react with O2 to produce peroxyacetyl radicals, CH2(C0)02, which react with NO2... 

Oxidation of sulfur dioxide in aqueous solution, as in clouds, can be catalyzed synergistically by iron and manganese (225). Ammonia can be used to scmb sulfur dioxide from gas streams in the presence of air. The product is largely ammonium sulfate formed by oxidation in the absence of any catalyst (226). The oxidation of SO2 catalyzed by nitrogen oxides was important in the eady processes for manufacture of sulfuric acid (qv). Sulfur dioxide reacts with chlorine or bromine forming sulfuryl chloride or bromide [507-16 ]. 

When bubbles are produced in clouds, as by a porous disperser, their behavior during rising is further comphcated by interadion among themselves. In addition to the tendency for small bubbles to coalesce and large ones to disintegrate, there are two additional... 

FIG. 14-93 Velocity of rising biihhles, singly and in clouds. To convert feet per second to meters per second, multiply hy 0.305. [From Chem. Eng. Sci., 7, 48 (1957).]... 

FIG. 17-14 Biihhling-hed model of Kunii and Levenspiel. dy = effective hiih-ble diameter, = concentration of A in hiihhle, = concentration of A in cloud, = concentration of A in emulsion, y = volumetric gas flow into or out of hiihhle, ky,- = mass-transfer coefficient between bubble and cloud, and k,. = mass-transfer coefficient between cloud and emulsion. (From Kunii and Leoen-spiel, Fluidization Engineering, Wiley, New York, 1.96.9, and Ktieger, Malahar, Fla., 1977.)... 

We saw in Chapter 5 that there is a driving force tending to make dispersions of precipitates in alloys coarsen and we would expect a dispersion of droplets in water vapour to do the same. Water droplets in clouds, however, carry electrostatic charges and this gives a different result for the driving force. 

Fig. 9.1. Rain falls when the water droplets in clouds turn to ice. This con only happen if the clouds are below 0°C to begin with. If the droplets are clean, ice can form only in the unlikely event that the clouds cool down to the homogeneous nucleation temperature of -40°C. When dust particles are present they can catalyse nucleation at temperatures quite close to 0°C. This is why there is often heavy rainfall downwind of factory chimneys.

Fig. 17-4. Radiation heat balance. The 100 units of incoming shortwave radiahon are distributed reflected from earth s surface to space, 5 reflected from cloud surfaces to space, 20 direct reaching earth, 24 absorbed in clouds, 4 diffuse reaching earth through clouds, 17 absorbed in atmosphere, 15 scattered to space, 9 scattered to earth, 6. The longwave radiation comes from (1) the earth radiating 119 units 101 to the atmosphere and 18 directly to space, and (2) the atmosphere radiating 105 units back to earth and 48 to space. Additional transfers from the earth s surface to the atmosphere consist of latent heat, 23 and sensible heat, 10. Source After Lowry (4).

Scavenging of particles or gases may take place in clouds (rainout) by cloud droplets or below clouds(washout) by precipitation. A scavenging ratio or washout ratio W can be defined as... 

Another relatively recent technique, in its own way as strange as Mossbauer spectrometry, is positron annihilation spectrometry. Positrons are positive electrons (antimatter), spectacularly predicted by the theoretical physicist Dirac in the 1920s and discovered in cloud chambers some years later. Some currently available radioisotopes emit positrons, so these particles arc now routine tools. High-energy positrons are injected into a crystal and very quickly become thermalised by... 

Output mass rate and vapor temperature of release, mass rate of air entrained, density of mixtu >1 mass fraction in cloud. Limitations single chemical source terms, limited chemical... 

In-cloud overpressure is dependent on outflow velocity, orifice diameter, and the fuel s laminar burning velocity. 

To allow for spray- and aerosol-formation, the mass of fuel in the cloud is assumed to be twice the theoretical flash of the amount of material released, so long as this quantity does not exceed the total amount of fuel available. Blast effects are modeled by means of TNT blast data according to Marshall (1976), while 1 bar is considered to be upper limit for the in-cloud overpressure (Figure 4.18). Because experience indicates that vapor clouds which are most likely to explode... 

Water is constantly evaporated from rivers, lakes, and oceans, and released from vegetation through evapo-transpiration. Water vapor travels through the atmosphere, eventually forming small droplets or ice crystals in clouds. Some particles grow sufficiently... 

The air-mass thunderstorm is the least severe of all thunderstorms. In its simplest form, an air-mass thunderstorm grows as a single cell when solar radiation heats the surface air in an unstable atmosphere. Its life cycle lasts around 30 minutes. Towering cumulus clouds are formed as in-cloud updrafts push moisture upward. The tower may reach a height about five times the diameter of the cloud base in the growth phase. 

Mixing with the environment lowers vertical wind velocities by reducing the in-cloud temperatures through evaporation and mechanical mixing with the cooler surrounding air. 

When NMHC are significant in concentration, differences in their oxidation mechanisms such as how the NMHC chemistry was parameterized, details of R02-/R02 recombination (95), and heterogenous chemistry also contribute to differences in computed [HO ]. Recently, the sensitivity of [HO ] to non-methane hydrocarbon oxidation was studied in the context of the remote marine boundary-layer (156). It was concluded that differences in radical-radical recombination mechanisms (R02 /R02 ) can cause significant differences in computed [HO ] in regions of low NO and NMHC levels. The effect of cloud chemistry in the troposphere has also recently been studied (151,180). The rapid aqueous-phase breakdown of formaldehyde in the presence of clouds reduces the source of HOj due to RIO. In addition, the dissolution in clouds of a NO reservoir (N2O5) at night reduces the formation of HO and CH2O due to R6-RIO and R13. Predictions for HO and HO2 concentrations with cloud chemistry considered compared to predictions without cloud chemistry are 10-40% lower for HO and 10-45% lower for HO2. 

Figure 4-13 shows an example from a three-dimensional model simulation of the global atmospheric sulfur balance (Feichter et al, 1996). The model had a grid resolution of about 500 km in the horizontal and on average 1 km in the vertical. The chemical scheme of the model included emissions of dimethyl sulfide (DMS) from the oceans and SO2 from industrial processes and volcanoes. Atmospheric DMS is oxidized by the hydroxyl radical to form SO2, which, in turn, is further oxidized to sulfuric acid and sulfates by reaction with either hydroxyl radical in the gas phase or with hydrogen peroxide or ozone in cloud droplets. Both SO2 and aerosol sulfate are removed from the atmosphere by dry and wet deposition processes. The reasonable agreement between the simulated and observed wet deposition of sulfate indicates that the most important processes affecting the atmospheric sulfur balance have been adequately treated in the model. 

Fig. 6-2 Comparison of infrared absorbance of a vertical column of atmospheric CO2 and H2O vapor. The nearly total absorbance by H2O between 5 and 7 /

Condensed phase interactions can be divided roughly into two further categories chemical and physical. The latter involves all purely physical processes such as condensation of species of low volatility onto the surfaces of aerosol particles, adsorption, and absorption into liquid cloud and rainwater. Here, the interactions may be quite complex. For example, cloud droplets require a CCN, which in many instances is a particle of sulfate produced from SO2 and gas-particle conversion. If this particle is strongly acidic (as is often the case) HNO3 will not deposit on the aerosol particle rather, it will be dissolved in liquid water in clouds and rain. Thus, even though HNO3 is not very soluble in... 

SO2 oxidation to H2SO4 on aerosols, in cloud droplets, and by gas phase reactions following attack by OH. 

Anthropogenic Modifications of the Acid-Base Balance of Rainwater Alkalinity in Cloud Water "Acid Rain"... 

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