Ozone catalysts

Gonalves, A., Figueiredo, J., Orfao, J.,etal. (2010). Influence of the Surface Chemislry of Multi-walled Carbon Nanotubes on their Activity as Ozonation Catalysts, Carbon, 48, pp. 4369-4381. 

Organic sulfides, MA distillation additives, 22 Osmium tetroxide, ozonization catalyst, 69, 70 Osmium tetroxide/ferricyanide, double bond hydroxylation catalyst, 71, 72 Osmometry, CTC detection, 209 Oxalic acid... 

Orge CA, 6rfao JJM, Pereira MFR. Ceria and cerium-based mixed oxides as ozonation catalysts. Chem Eng J. 2012 200-202 499-505. 

In this sequence the Cl also acts as a catalyst and two molecules are destroyed. It is estimated that before the Cl is finally removed from the atmosphere in 1—2 yr by precipitation, each Cl atom will have destroyed approximately 100,000 molecules (60). The estimated O -depletion potential of some common CFCs, hydrofluorocarbons, HFCs, and hydrochlorofluorocarbons, HCFCs, are presented in Table 10. The O -depletion potential is defined as the ratio of the emission rate of a compound required to produce a steady-state depletion of 1% to the amount of CFC-11 required to produce the 1% depletion. The halons, bromochlorofluorocarbons or bromofluorocarbons that are widely used in fire extinguishers, are also ozone-depleting compounds. Although halon emissions, and thus the atmospheric concentrations, are much lower than the most common CFCs, halons are of concern because they are from three to ten times more destmctive to O, than the CFCs. 

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. 

A thkd method utilizes cooxidation of an organic promoter with manganese or cobalt-ion catalysis. A process using methyl ethyl ketone (248,252,265—270) was commercialized by Mobil but discontinued in 1973 (263,264). Other promoters include acetaldehyde (248,271—273), paraldehyde (248,274), various hydrocarbons such as butane (270,275), and others. Other types of reported activators include peracetic acid (276) and ozone (277), and very high concentrations of cobalt catalyst (2,248,278). 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

The calculated half-life of 1 mol % (1.5 wt %) of pure gaseous ozone diluted with oxygen at 25, 100, and 250°C (based on rate constants from Ref. 19) is 19.3 yr, 5.2 h, and 0.1 s, respectively. Although pure ozone—oxygen mixtures are stable at ordinary temperatures ia the absence of catalysts and light, ozone produced on an iadustrial scale by silent discharge is less stable due to the presence of impurities however, ozone produced from oxygen is more stable than that from air. At 20°C, 1 mol % ozone produced from air is - 30% decomposed ia 12 h. 

Above pH 9, decomposition of ozone to the reactive intermediate, HO, determines the kinetics of ammonia oxidation. Catalysts, such as WO, Pt, Pd, Ir, and Rh, promote the oxidation of dilute aqueous solutions of ammonia at 25°C, only two of the three oxygen atoms of ozone can react, whereas at 75°C, all three atoms react (42). The oxidation of ammonia by ozone depends not only on the pH of the system but also on the presence of other oxidizable species (39,43,44). Because the ozonation rate of organic materials in wastewater is much faster than that of ammonia, oxidation of ammonia does not occur in the presence of ozone-reactive organics. 

Unpiotonated hydioxylamine is oxidized rapidly by ozone, / = 2.1 X 10 (39). The reaction of ozone with the lower oxides of nitrogen (NO and NO2) is also rapid and quantitative the end product is nitrogen pentoxide, which is also a catalyst for the decomposition of ozone (45). Nitrous oxide, however, reacts slowly (k < 10 ) (39). Nitrogen-containing anions, eg, nitrite and cyanide, also ate oxidized by ozone (39). Nitrite is oxidized to nitrate (fc = 3.7 X 10 and cyanide is oxidized rapidly to cyanate (fc = 2.6 X 10 (46) and 10 -10 (39)). Cyanate, however, is oxidized slowly. 

Ozonation can be enhanced by the addition of ultraviolet (uv) radiation. This combination can be effective in degrading chlorinated organic compounds and pesticides. In addition, metal ions such as iron, nickel, chromium, and titanium [7440-32-6] can act as catalysts, as can ultrasonic mixing. 

Oxidants commonly used include ozone, permanganate, chlorine, chlorine dioxide, and ferrate, often in combination with catalysts. Standard-type mixed reactors are used with contact times of several minutes to an hour. Special reactors for use with ultraviolet light have been developed. 

Many reagents act as contact catalysts for the destruction of ozone a study of some of them has been made. ... 

The decrease is continuing due to global adherence to the provisions of the Montreal (1989) and London (1990) Protocols, and it is hoped that the most deleterious CFCs will eventually be phased out completely. As a result of their work, Rowland and Molina were awarded the Nobel Prize for Chemistry for 1995 (together with P. Crutzen, who showed how NO and NO2 could similarly act as catalysts for the depletion of stratospheric ozone). Several excellent accounts giving more details of the chemistry and meteorology involved are available. 

Compared with uncatalyzed reactions, catalysts introduce alternative pathways that, in nearly all cases, involve two nr more consecutive reaction steps. Each of these steps has a lower activation energy than does the uncatalyzed reaction. We can nse as an example the gas phase reaction of ozone and oxygen atoms. In the homogeneons uncatalyzed case, the reaction is represented to occur in a single irreversible step that has a high activation energy ... 

Alkenes are reduced by addition of H2 in the presence of a catalyst such as platinum or palladium to yield alkanes, a process called catalytic hydrogenation. Alkenes are also oxidized by reaction with a peroxyacid to give epoxides, which can be converted into lTans-l,2-diols by acid-catalyzed epoxide hydrolysis. The corresponding cis-l,2-diols can be made directly from alkenes by hydroxylation with 0s04. Alkenes can also be cleaved to produce carbonyl compounds by reaction with ozone, followed by reduction with zinc metal. 

PA-4,2 synthesis from, 173 PA-10,2 synthesis from, 172 Oxide catalysts, 64 Oxygen indices (OIs), 424 Ozonation treatment, 543... 

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