Formation of ozone

O2 + UV radiation (at about 30 km altitude) — 20 atoms, usually written as 20, where the shows the splitting of the covalent bonds equally to give oxygen atoms with unpaired electrons. Then  

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Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Eormaldehyde is classified as an air toxic and its emissions should be minimized. Eormaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especiaHy if the engine mns lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Although the naturally occurring concentration of ozone at the earth s surface is low, the distribution has been altered by the emission of pollutants, primarily by automobiles but also from industrial sources which lead to the formation of ozone. The strategy for controlling ambient ozone concentrations arising from automobile exhaust emissions is based on the control of hydrocarbons, CO, and NO via catalytic converters. As a result, peak ozone levels in Los Angeles, for instance, have decreased from 0.58 ppm in 1970 to 0.33 ppm in 1990, despite a 66% increase in the number of vehicles. 

Because of the expanded scale and need to describe additional physical and chemical processes, the development of acid deposition and regional oxidant models has lagged behind that of urban-scale photochemical models. An additional step up in scale and complexity, the development of analytical models of pollutant dynamics in the stratosphere is also behind that of ground-level oxidant models, in part because of the central role of heterogeneous chemistry in the stratospheric ozone depletion problem. In general, atmospheric Hquid-phase chemistry and especially heterogeneous chemistry are less well understood than gas-phase reactions such as those that dorninate the formation of ozone in urban areas. Development of three-dimensional models that treat both the dynamics and chemistry of the stratosphere in detail is an ongoing research problem. 

Reaction (12-9) shows the photochemical dissodation of NO2. Reaction (12-10) shows the formation of ozone from the combination of O and molecular O2 where M is any third-body molecule (principally N2 and O2 in the atmosphere). Reaction (12-11) shows the oxidation of NO by O3 to form NO2 and molecular oxygen. These three reactions represent a cyclic pathway (Fig. 12-4) driven by photons represented by hv. Throughout the daytime period, the flux of solar radiation changes with the movement of the sun. However, over short time periods (—10 min) the flux may be considered constant, in which case the rate of reaction (12-9) may be expressed as... 

In densely populated areas, traffic is responsible for massive exhausts of nitrous oxides, soot, polyaromatic hydrocarbons, and carbon monoxide. Traffic emissions also markedly contribute to the formation of ozone in the lower parts of the atmosphere. In large cities, fine particle exposure causes excess mortality which varies between one and five percent in the general population. Contamination of the ground water reservoirs with organic solvents has caused concern in many countries due to the persistent nature of the pollution. A total exposure assessment that takes into consideration all exposures via all routes is a relatively new concept, the significance of which is rapidly increasing. 

Precursor A substance involved in the formation of new air pollutants, i.e., a hydrocarbon is the precursor to the formation of ozone. 

One strategy in limiting the formation of ozone and other photochemical oxidants has been the use (in the past) of low reactivity fuels in internal combustion engines. More recently, alternate fuels (methanol, for instance) have been proposed for regions that suffer from elevated levels of photochemical air pollution. The effect of switching to such a low-reactivity fuel may be seen in Equation E2 for methanol, which has a simple atmospheric reaction mechanism. 

The chemistry of the stratospheric ozone will be sketched with a very broad brush in order to illustrate some of the characteristics of catalytic reactions. A model for the formation of ozone in the atmosphere was proposed by Chapman and may be represented by the following "oxygen only" mechanism (other aspects of... 

This is the main reaction for the formation of ozone although, under equilibrium conditions, the concentrations of NO2, NO, and O3 are interdependent and no net synthesis of O3 occurs. When, however, the equilibrium is disturbed and NO is removed by reactions with alkylperoxy radicals (reactions 1+2+3), synthesis of O3 may take place. 

Stohl A, E Williams, G Wotawa, H Kromp-Kolb (1996) A European inventory of soil nitric oxide emissions and the effect of these emissions on the photochemical formation of ozone. Atmos Environ 30 3741-3755. 

Which of these is most necessary for the formation of ozone ... 

At more positive potentials, processes occur that depend on the composition of the electrolyte, such as the formation of H2S2Og and HS05 in sulphuric acid solutions, while the CIO radical is formed in perchloric acid solutions, decomposing to form C102 and 02. The formation of ozone has been observed at high current densities in solutions of rather concentrated acids. 

Chapman was the first to provide a clear picture of the formation of ozone in the stratosphere.9 Figure 1 summarizes the principal production... 

In 1899, the Curies first reported the coloration of glass and porcelain and the formation of ozone from oxygen by radioactive radiation. Giesel (1900) noted that the coloration of alkali halides under these radiations was similar to the effect of cathode rays he also observed the decomposition of water. R Curie and Debierne (1901) observed continuous evolution of hydrogen and oxygen... 

The reality of using thermodynamics is somewhat simpler than the preceding derivations imply. Consider the reaction we have been using in the formation of ozone in the Chapman mechanism ... 

Note that A fG° for G2 is zero because this is the energy of formation of ozone in its standard state and is defined as zero. The ArG° for the reaction is negative and so the reaction is spontaneous. Using Equation 8.12, the equilibrium constant at 298 K can be calculated ... 

The reaction favours the formation of ozone with a significant equilibrium constant. Appendix C also lists the enthalpies of formation and the standard enthalpy of the reaction ArH° can be calculated. The answer for the enthalpy calculation is ArH° = —106.47 kJ mol, showing this to be an exothermic reaction, liberating heat. The entropy change at 298 K can also be calculated because ArG° = ArH° — T ArS°, so ArS° = 25.4 Jmol-1 K-1, indicating an increase in the entropy of the reaction as it proceeds by creating one molecule from two. 

Low concentrations of VOCs in ambient ah of 1 to 1,000 ppmv (parts per million based on volume) are often harmful to human health. VOCs also promote the photochemical formation of ozone and other contaminants, and in high concentrations are a fire hazard. These severe environmental implications have resulted in increasingly stringent legislation in the U.S.A. and elsewhere to limit release of VOCs into the atmosphere. Control technologies for VOCs release include combustion and vapor recovery. Vapor recovery is preferred as combustion may result in the production of other air pollutants, and destroy valuable VOCs. 

An important aspect of the Gao-Marcus model is that it provides a theoretical structure for the understanding of quantum state density isotope effects in general, and is not specifically confined to the formation of ozone itself. This feature is important because as discussed above we are now aware that MIF s occur widely in nature. The theory aids in prediction of where MIF s will be likely found, and once found, in rationalizing how they were chemically produced. 

Nitrous oxide (N2O) is an important greenhonse gas with a radiative forcing effect 310 times that of CO2 and a lifetime in the troposphere of approximately 120 years. Part of the N2O is converted to NO in the stratosphere, and so contributes to depletion of ozone. Nitric oxide (NO) is very reactive in the atmosphere and has a lifetime of only 1-10 days. It contribntes to acidification and to reactions leading to the formation of ozone in the troposphere, and so also to global warming. 

No one pollutant can be blamed as the major cause of ozone formation. Replacing the more reactive hydrocarbons with less reactive ones would delay the formation of ozone, but would not prevent it. Reducing the NO, concentration seems to reduce the maximal oxidant concentrations observed, but the effect is nonlinear. Heavy injections of nitric oxide into the air can temporarily reduce the local ozone concentration, as often happens in urban centers, but additional oxidant formation can be expected later downwind. Although these effects can be understood qualitatively, it is not yet possible to make accurate predictions of oxidant formation, even in lalx)ratoty experiments. 

Expressions of volume per volume units (ppm, pphm, or ppb) simplify measurements, because their value is independent of atmospheric temperature and barometric pressure. The volume units are equivalent to the ratio of the number of molecules of ozone to the number of molecules of air. This facilitates quantification of the atmospheric chemical reactions that lead to the formation of ozone. These units are also preferable when the molecular weight of a substance is uncertain, as in the reporting of total nitrogen oxides or total aldehydes. 

A number of experimental and theoretical studies have focused on the causes of mass-independent fractionation effects, but as summarized by Thiemens (1999), the mechanism for mass-independent fractionations remains uncertain. The best studied reaction is the formation of ozone in the stratosphere. Mauersberger et al. (1999) demonstrated experimentally that it is not the symmetry of a molecule that determines the magnitude of enrichment, but it is the difference in the geometry of the molecule. Gao and Marcus (2001) presented an advanced model, which has led to a better understanding of nonmass-dependent isotope effects. 

Nitrogen oxides (NO ) are formed during the combustion at high temperature of fossil fuels and of biomasses and are blamed for the production of acid rain, the formation of ozone in the troposphere and of secondary particulate matter and for causing a reduction in breathing functionality and damage to the cardio-circulatory system in humans. 

An interesting aspect of fluoride applications in electrochemistry is the beneficial effect that fluoride-containing electrolyte media have on the anodic formation of ozone. Oxidized forms of fluoride are known to result in the formation of persulfate and peroxide, but for the... 

Today in many major urban areas around the world, air pollution is characterized more by the formation of ozone and other oxidants rather than by S02, particles, and sulfuric acid. In these regions, the primary pollutants are NOx (mainly NO) and volatile organic compounds (VOC), which undergo photochemical reactions in sunlight to form a host of secondary pollutants, the most prominent of which is Ov Some of these are... 

Termolecular. The formation of ozone by the reaction of a ground-state oxygen atom, 0(3P), with 02 ... 

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