Carbon monoxide oxidation overall reaction

The practical motivation for understanding the microscopic details of char reaction stem from questions such as How does the variability in reactivity from particle to particle and with extent of reaction affect overall carbon conversion What is the interdependence of mineral matter evolution and char reactivity, which arises from the catalytic effect of mineral matter on carbon gasification and the effects of carbon surface recession, pitting, and fragmentation on ash distribution How are sulfur capture by alkaline earth additives, nitric oxide formation from organically bound nitrogen, vaporization of mineral constituents, and carbon monoxide oxidation influenced by the localized surface and gas chemistry within pores ... 

Examples of catalysts in combustion reaction include the effect of H2O on the carbon monoxide oxidation reaction CO H- 2 C02- Nitric oxide also catalyzes CO oxidation through the mechanism 2 NO 4-O2 2NO2 (overall) and NO2 -f CO NO H- CO2. In both of these examples, an intermediate compound (for example, NO2) is formed and then destroyed. The addition of a small amount of NO2 to an H2 — O2 mixture leads to a branched-chain explosion by introducing the relatively rapid initiation step NO2 H- X NO H- O H- X, with the O atoms so produced generating the usual H2 — O2 chain. The NO2 also participates in the efficient termination step NO2 H- O NO H- O2, which is sufficiently important at large concentrations of NO2 to cause a slow reaction to be... 

Suppose this nonspontaneous decomposition reaction is coupled with the partial oxidation of carbon to carbon monoxide—a spontaneous reaction. The overall reaction (13.27) is spontaneous when reactants and products are in their standard states because Aj.G° has a negative value. 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Finally, the large amounts of carbon monoxide formed are oxidized to carbon dioxide and most of the heat released from the overall reaction is obtained. Recall that the CO is not oxidized to C02 until most of the fuel is consumed owing to the rapidity with which OH reacts with the fuel compared to its reaction to CO (see Table 3.1). 

The appropriate stoichiometric coefficient for oxidation of carbon is not readily apparent, because there are two different oxidation states of carbon, namely carbon monoxide and carbon dioxide, which may be present when a carbon surface is oxidized. These products form according to the overall reaction steps... 

Acrolein is immediately passed through a second oxidation reactor to form acrylic acid. The reaction talces place at 475-575 E, over a tin-antimony oxide catalyst. A few by-products form, namely, formic acid (HCOOH), acetic acid (CH3COOH), low molecular weight polymers, carbon monoxide, and dioxide. But overall yields of propylene to acrylic acid are high—85 to 90%. 

The overall reaction is quite complex but involves a rearrangement similar to that described for the hydroboration-oxidation of alkenes (Section 11-6E). The first step is hydroboration of the alkene to a trialkylborane. When the trialkylborane is exposed to carbon monoxide, it reacts (carbonylates) to form a tetracovalent boron, 9 ... 

Reasons for interest in the catalyzed reactions of NO, CO, and COz are many and varied. Nitric oxide, for example, is an odd electron, hetero-nuclear diatomic which is the parent member of the environmentally hazardous oxides of nitrogen. Its decomposition and reduction reactions, which occur only in the presence of catalysts, provide a stimulus to research in nitrosyl chemistry. From a different perspective, the catalyzed reactions of CO and COz have attracted attention because of the need to develop hydrocarbon sources that are alternatives to petroleum. Carbon dioxide is one of the most abundant sources of carbon available, but its utilization will require a cheap and plentiful source of hydrogen for reduction, and the development of catalysts that will permit reduction to take place under mild conditions. The use of carbon monoxide in the development of alternative hydrocarbon sources is better defined at this time, being directly linked to coal utilization. The conversion of coal to substitute natural gas (SNG), hydrocarbons, and organic chemicals is based on the hydrogen reduction of CO via methanation and the Fischer-Tropsch synthesis. Notable successes using heterogeneous catalysts have been achieved in this area, but most mechanistic proposals remain unproven, and overall efficiencies can still be improved. 

A single step in a reaction mechanism is called an elementary reaction or elementary step. To clarify the crucial distinction between an elementary reaction and an overall reaction, let s consider the gas-phase reaction of nitrogen dioxide and carbon monoxide to give nitric oxide and carbon dioxide ... 

Here we shall briefly summarize the effects of individual poisons on various catalytic reactions taking place on automotive catalysts. There are three main catalytic processes oxidation of carbon monoxide and hydrocarbons and reduction of nitric oxide. Among secondary reactions there are undesirable ones which may produce small amounts of unregulated emissions, such as NH3, S03 (6), HCN (76, 77), or H2S under certain operating conditions. Among other secondary processes which are important for overall performance, in particular of three-way catalysts, there are water-gas shift, hydrocarbon-steam reforming, and oxygen transfer reactions. Specific information on the effect of poisons on these secondary processes is scarce. 

The partial combustion (partial oxidation) of natural gas (Fig. 1) is probably the most widely used method of producing acetylene. The overall reaction of the methane (combustion and splitting) is 90 to 95 percent whereas the oxygen is 100 percent converted. The residence time is 0.001 to 0.01 seconds. The acetylene and gases are cooled rapidly by quench oil or water sprays to 38°C and have the following typical composition (percent by volume acetylene, 8 to 10 hydrogen, 50 to 60 methane, 5 carbon monoxide, 20 to 25 and carbon dioxide, <5. The soot is removed in a carbon filter and the clean gases are compressed to 165 psi (1.14 MPa). 

The carbon monoxide produced from the preceding reaction continues to bum. At the same time, the nitrogen in the coal is converted into nitrogen oxides through complicated mechanisms, but the overall reaction can be expressed as... 

In addition to cationic cyclizations, other conditions for the cyclization of polyenes and of ene-ynes to steroids have been investigated. Oxidative free-radical cyclizations of polyenes produce steroid nuclei with exquisite stereocontrol. For example, treatment of (259) and (260) with Mn(III) and Cu(II) afford the D-homo-5a-androstane-3-ones (261) and (262), respectively, in approximately 30% yield. In this cyclization, seven asymmetric centers are established in one chemical step (226,227). Another intramolecular cyclization reaction of iodo-ene poly-ynes was reported using a carbopaUadation cascade terminated by carbonylation. This carbometalation—carbonylation cascade using CO at 111 kPa (1.1 atm) at 70°C converted an acycHc iodo—tetra-yne (263) to a D-homo-steroid nucleus (264) [162878-44-6] in approximately 80% yield in one chemical step (228). Intramolecular aimulations between two alkynes and a chromium or tungsten carbene complex have been examined for the formation of a variety of different fiised-ring systems. A tandem Diels-Alder—two-alkyne annulation of a triynylcarbene complex demonstrated the feasibiHty of this strategy for the synthesis of steroid nuclei. Complex (265) was prepared in two steps from commercially available materials. Treatment of (265) with Danishefsky s diene in CH CN at room temperature under an atmosphere of carbon monoxide (101.3 kPa = 1 atm), followed by heating the reaction mixture to 110°C, provided (266) in 62% yield (TBS = tert — butyldimethylsilyl). In a second experiment, a sequential Diels-Alder—two-alkyne annulation of triynylcarbene complex (267) afforded a nonaromatic steroid nucleus (269) in approximately 50% overall yield from the acycHc precursors (229). 

For example, G. Ertl (Catalysis Science and Technology, J. R. Anderson and M. Boudart, Eds., vol. 4, Springer-Verlag, Berlin, 1983, p. 245) proposed the thermochemical kinetic profile depicted in Figure 5.1.1 for the platinum-catalyzed oxidation of carbon monoxide according to the overall reaction CO + 2 O2 CO2. The first step in the profile represents the adsorption of carbon monoxide and... 

Species profiles have not been measured directly for dry CO/air or CO/O2 flames in the same way as they have for hydrogen flames. Several investigations, however, have been concerned with the oxidation of carbon monoxide in lean hydrocarbon flames (e.g. refs. 406, 413, 417, 429) or in moist CO flames flames of H2 /CO mixtures in air [167, 406, 414, 418] or O2 [523]. The interest in the oxidation in hydrocarbon flames has arisen since the overall reaction in such flames is a two stage process. In the first rapid stage (the main flame reaction zone) the hydrocarbon is essentially converted to CO and water, with traces of hydrogen also appearing. The second, more extended, stage is devoted to radical recombination and to the slower oxidation of CO, predominantly by reaction (xxiii). 

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