Sulfur with ozone

Type (a) is illustrated by the reaction of sulfur with ozone (Scheme 1), in which the first step is the excitation of the sulfur oxide SO. The latter transfer energy to the uranyl ion inside its coordination sphere. The yield of U02 excitation in this reaction is close to unity. 

Two other compounds containing carbon and sulfur should be mentioned. The first of these is carbon monosulfide, CS. This compound has been reported to be produced by the reaction of CS2 with ozone. The second compound is COS or, more correctly, OCS (m.p. -138.2 °C and b.p. -50.2 °C). It is prepared by the reaction... 

The chemiluminescent reaction of SO with ozone is the basis of the sulfur chemiluminescence detector (SCD) [23] discussed later in this chapter,... 

Electronically excited S02 has been found to be the principal emitter in the multistep reactions of a number of reduced sulfur compounds such as H2S, CH3SH, (CH3)2S, CS2, and thiophene with ozone [25, 27, 33, 34], Unfortunately, the mechanisms of these complex reactions are not understood. 

Kohno, Y., Matsumura, H., Kobayashi, T. (1998). Differential sensitivity of 16 tree species to simulated acid rain or sulfur dioxide in combination with ozone. In Bashkin, V. N., Park,... 

With various tests of ventilatory function, it has been shown that healthy male college students experienced no effect of sulfur dioxide at 0.37 ppm, a 10% decline in function with ozone at 0.37 ppm, and a 20-40% decline in function with a combination of sulfur dioxide at 0.37 ppm and ozone at 0.37 ppm. Other experiments have suggested an adaptation of southern Californians to chronic exposure to ambient ozone. 

It is well known that ozone is quite soluble in water. Therefore, one expects that ozone absorption wi sulfur dioxide would contribute to significant oxidation of sulfur dioxide. Experiments of Penkett have shown that oxidation of sulfur dioxide in air at 7 ppb when absorbed in water droplets with ozone, which is present in surrounding air at 0.05 ppm, can be as large as 13%/h. Thus, foggy or cloudy air mixed with... 

Gifford and Hanna tested their simple box model for particulate matter and sulfur dioxide predictions for annual or seasonal averages against diffusion-model predictions. Their conclusions are summarized in Table 5-3. The correlation coefficient of observed concentrations versus calculated concentrations is generally higher for the simple model than for the detailed model. Hanna calculated reactions over a 6-h period on September 30, 1%9, with his chemically reactive adaptation of the simple dispersion model. He obtained correlation coefficients of observed and calculated concentrations as follows nitric oxide, 0.97 nitrogen dioxide, 0.05 and rhc, 0.55. He found a correlation coefficient of 0.48 of observed ozone concentration with an ozone predictor derived from a simple model, but he pointed out that the local inverse wind speed had a correlation of 0.66 with ozone concentration. He derived a critical wind speed formula to define a speed below which ozone prediction will be a problem with the simple model. Further performance of the simple box model compared with more detailed models is discussed later. 

Other combinations of pollutants with ozone, PAN, or both may be important, but have received little study. Matsushima reported additive foliar effects on pinto bean and tomato from a mixture of sulfur dioxide and PAN and a less than additive effect on tomato from mixtures of ozone and nitrogen dioxide. Fujiwara reported a greater than additive effect on pea from a mixture of ozone and nitrogen dioxide. Kress and Kohut studied the response of hybrid poplar to ozone-PAN mixtures. Kress used sequential exposures and found a greater than additive effect after most exposures after others, he reported mixed responses. Kohut used simultaneous exposure and found all three responses in three replicates of a study. The reasons for these variations are unclear. 

Even that kind of information is not available for forest species. Other than chronic injury to white pine (associated with ozone, sulfur dioxide, and their mixtures), no clearly defined examples of chronic injury from ozone have been reported for eastern forests, and no information is available on PAN. It is of interest that both Virginia and jack pine appear more sensitive than white pine to acute ozone exposures, but chronic symptoms have not been observed in either species. The relationship between oxidant dose and injury in the San Bernardino Mountains area suggests that ponderosa pine is moderately to severely injured in areas that receive oxidant at above 0.08 ppm for 12-13 h each day (Chapter 12). Ponderosa pine seems to be the most sensitive western pine, but in some areas Jeffrey pine is about as sensitive. White fir, incense cedar, and sugar pine all appear more tolerant, even to the high oxidant concentrations in the San Bernardino Mountains. PAN may play some role in the chronic responses noted in the western forest species, particularly by broadleaf deciduous trees and some shrubs. 

Early work with sulfur dioxide showed a linear relationship between visible injury and reduction in yield for many crop species. The assessment was made that no reduction in yield would be found unless visible injury were noted. Definitive research with ozone, other oxidants, or mixtures of these pollutants with other gases has not been done. Thus, we do not know whether such relationships between visible injury and yield hold for the oxidants, but data in Table 11-3 suggest that for acute exposures there may be good correlations between injury and yield reductions. Many researchers have hypothesized that the oxidants may have an effect on plants that will produce a yield reduction with little or no visible injury. Such studies need to be designed in a more defmitive manner before it is concluded that yield reductions without visible symptoms are clearly acceptable. Projections of yield losses have made use of some of the data reported earlier. ... 

Cathey, H. M., and H. E. Heggestad. Effects of growth retardants and fumigations with ozone and sulfur dioxide on growth and flowering of Euphorbia pulcherrima WUld. J. Amer. Soc. Hort. Sci. 98 3-7, 1973. 

CASRN 79-92-2 molecular formula C1OH10 FW 136.23 Chemical/Physical. In the gas phase, camphene (0.25 mg/L) reacted rapidly with ozone (0.2 mg/L) at 40 °C producing camphenilone and 6,6-dimethyl-e-caprolactone-2,5-methylene at a product ratio of 1 1. The product ratios increased to 4 1 and 8 1 when sulfur dioxide was present at concentrations of 0.02 and 0.04 mg/L, respectively (Jay and Stieglitz, 1989). 

Crystallization yields the commercial product, pink heptahydrate. Further oxidation of this salt in dilute H2SO4 with ozone or fluorine produces hydrated cobalt(III) sulfate, 002(804)3 I8H2O. This blue octadecahydrate, 002(804)3 I8H2O also is obtained by electrolytic oxidation of cobalt(II) chloride or any cobalt(II) salt solution in 8M sulfuric acid. 

Oxidation with ozone in aqueous conditions yields sulfur and sulfuric acid 3HaS + O3 — 3S + 3HaO S + O3 + H2O H2SO4... 

Approximately half of the world s population now lives in urban areas, and half of these people suffer an atmosphere containing harmful amounts of substances such as sulfur dioxide, ozone, and particulate matter. Approximately 4000 people died from lung and heart conditions during a London smog episode in December 1952. Globally, around 50% of cases of chronic respiratory illness are now connected with ah pollution. The most... 

Oxidation of sulfur monoxide diethyl acetal with ozone [35]. 

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