Mechanism of Propene Oxidation

Let us consider what are the intermediates in the formation of carbon dioxide. Isaev, Margolis, and Sazonova (116) attempted to elucidate the mechanism of propene oxidation to acrolein using the kinetic tracer method. 

The mechanism of propene oxidation over silver catalysts was studied between 423 and 673 K at pressures of 3 Pa under transient conditions using Multitrack, a TAP-like system. Both supported and unsupported silver catalysts showed low selectivities to propene oxide. Acrolein was observed as oxidation product and might be an intermediate for total combustion products. Total combustion is favored over supported silver catalysts, compared to unsupported silver. Arrhenius plots for total and partial oxidation products could be constructed. 

Ethene can be very selectively epoxidized over supported silver catalysts. The last decades the mechanism of this epoxidation has been studied in great detail [1,2]. Epoxidation of propene using the same silver catalysts has not been successful. However, a direct gas-phase epoxidation process to produce propene oxide is highly desired. The mechanism of propene oxidation is currently being investigated in order to develop new catalysts. 

More than 140 different alkenes have been identified in the atmosphere [27]. The sources of alkenes are similar to those for the alkanes with combustion of fossil fuel being a major source. The presence of unsaturated bonds makes these compounds much more reactive than the alkanes. The most persistent member of this class of compounds (ethene) has an atmospheric lifetime of the order of a day, while more typically the lifetimes for alkenes are measured in hours. As a result of their short lifetimes the atmospheric concentrations of alkenes are highly variable and decrease dramatically away from their source locations. The mechanisms of atmospheric oxidation of alkenes have recently been reviewed [55]. As with the alkanes the reaction of OH radicals is an important loss mechanism. This reaction proceeds mainly via addition to the unsaturated bond as illustrated for ethene in Fig. 4. In one atmosphere of air at 298 K the dominant atmospheric fate of the alkoxy radical HOCH2CH2O is decomposition via C - C bond scission, while reaction with O2 makes a 20% contribution [56]. The fate of alkoxy radicals resulting from addition of OH to alkenes is generally decomposition via C - C bond scission [8]. Thus, the OH radical initiated oxidation of propene gives acetaldehyde and HCHO, oxida-... 

Variations in the selectivity of propene oxidation as a function of the catalyst composition are shown in Fig. 19a and b. If the suggested electronic mechanism of the action of mixed catalysts is true, the electron work function () of mixtures should be higher than that of pure molybdenum and bismuth oxides. The dependence of A on the composition of a molybdenum-bismuth catalyst is shown in Fig. 19b. The maximum change in the electron work function corresponds to highest selectivity. Such a proportional change in catalytic and electronic properties seems to provide evidence for the electronic mechanism of the effect of these mixed catalysts. 

It is believed that SCR by hydrocarbons is an important way for elimination of nitrogen oxide emissions from diesel and lean-burn engines. Gerlach etal. [115] studied by infrared in batch condition the mechanism of the reaction between nitrogen dioxide and propene over acidic mordenites. The aim of their work was to elucidate the relevance of adsorbed N-containing species for the F>cNOx reaction to propose a mechanism. Infrared experiments showed that nitrosonium ions (NO+) are formed upon reaction between NO, NOz and the Brpnsted acid sites of H—MOR and that this species is highly reactive towards propene, forming propenal oxime at 120°C. At temperatures above 170°C, the propenal oxime is dehydrated to acrylonitrile. A mechanism is proposed to explain the acrylonitrile formation. The nitrile can further be hydrolysed to yield... 

Catalysis is a special type of closed-sequence reaction mechanism (Chapter 7). In this sense, a catalyst is a species which is involved in steps in the reaction mechanism, but which is regenerated after product formation to participate in another catalytic cycle. The nature of the catalytic cycle is illustrated in Figure 8.1 for the catalytic reaction used commercially to make propene oxide (with Mo as the catalyst), cited above. 

Most industrially desirahle oxidation processes target products of partial, not total oxidation. Well-investigated examples are the oxidation of propane or propene to acrolein, hutane to maleic acid anhydride, benzene to phenol, or the ammoxidation of propene to acrylonitrile. The mechanism of many reactions of this type is adequately described in terms of the Mars and van Krevelen modeE A molecule is chemisorbed at the surface of the oxide and reacts with one or more oxygen ions, lowering the electrochemical oxidation state of the metal ions in the process. After desorption of the product, the oxide reacts with O2, re-oxidizing the metal ions to their original oxidation state. The selectivity of the process is determined by the relative chances of... 

A study of the regioselectivity of the 1,3-dipolar cycloaddition of aliphatic nitrile oxides with cinnamic acid esters has been published. AMI MO studies on the gas-phase 1,3-dipolar cycloaddition of 1,2,4-triazepine and formonitrile oxide show that the mechanism leading to the most stable adduct is concerted. An ab initio study of the regiochemistry of 1,3-dipolar cycloadditions of diazomethane and formonitrile oxide with ethene, propene, and methyl vinyl ether has been presented. The 1,3-dipolar cycloaddition of mesitonitrile oxide with 4,7-phenanthroline yields both mono-and bis-adducts. Alkynyl(phenyl)iodonium triflates undergo 2 - - 3-cycloaddition with ethyl diazoacetate, Ai-f-butyl-a-phenyl nitrone and f-butyl nitrile oxide to produce substituted pyrroles, dihydroisoxazoles, and isoxazoles respectively." 2/3-Vinyl-franwoctahydro-l,3-benzoxazine (43) undergoes 1,3-dipolar cycloaddition with nitrile oxides with high diastereoselectivity (90% de) (Scheme IS)." " ... 

Mechanical mixtures of Bi2Mo30i2 and solid solution FexCoi.xMo04 phases of variable relative composition and variable x value have been studied for propene oxidation to acrolein. A huge synergy effect was observed when Bi, Co and Fe were present and a maximum in... 

The allylic oxidation of propene is catalyzed by (compound) metal oxides, which essentially contain metal ions of variable valency. It is commonly accepted that a redox mechanism is operative in such a way that the catalyst acts as the oxidizer and that lattice oxygen is incorporated in the oxidation products. The assumptions have been proved for several catalysts by the analysis of cation valency changes and by experiments with labelled oxygen. 

Mechanism. The mechanism outlined for the propene oxidation over metal oxides is, in general, fully applicable to bismuth molybdate. The occurrence of a symmetrical allyl intermediate and the participation of lattice oxygen is well established (Hucknall [160], Voge and Adams [343]). 

The hypothesis of a bifunctional mechanism involving allyl radical formation and oxygen incorporation on distinct sites is advocated by Haber et al. [147,152], This hypothesis is particularly based on experiments with Mo03, Bi203 and mechanical mixtures of these oxides, which are compared with bismuth molybdate catalysts. The reaction was carried out in cyclic operation (alternating feeds of oxygen and of propene diluted with nitrogen). The results are collected in Table 5. The authors con-... 

The conversion of isobutene to methacrolein is closely related to the selective oxidation of propene to acrolein and demands similar catalysts. It has been verified that the same mechanism applies, involving a symmetrical allylic intermediate, viz. 

With respect to the mechanism, the adsorption measurements of Matsuura and Schuit [207—209] are of interest. The assumption of A-and B-sites is reported in some detail for the propene oxidation in Sect. 2.2.2(d)(i). As for the oxidation of propene, the abstraction of (both) H-atoms is assumed to occur on the molybdenum layers by initially forming HOb groups, followed by H-transfer from Ob to Oa and desorption of water (H2Oa). 

The mechanism of the toluene and xylene oxidation bears a close resemblance to the oxidation of propene. Abstraction of a H-atom from the reactive methyl group and formation of a complex between the resulting radical and the catalyst is the first and probably the rate-determining step for both. However, the effect of the mesomeric stabilization of this radical complex is different. While a symmetrical allyl structure is formed from propene, an asymmetrical situation occurs for toluene and xylene, which is illustrated below for the case of toluene, viz. 

The molecular mechanism of the selective oxidation pathway is believed to be the one shown in Scheme 2 (Section I). Adsorbed butene forms adsorbed 7r-allyl by H abstraction in much the same way as xc-allyl is formed from propene in propene oxidation (28-31). A second H abstraction results in adsorbed butadiene. Indeed, IR spectroscopy has identified adsorbed 71-complexes of butene and 7t-allyl on MgFe204 (32,33). On heating, the 7r-complex band at 1505 cm 1 disappears between 100-200°C, and the 7t-allyl band at 1480 cm-1 disappears between 200-300°C. The formation of butadiene shows a deuterium isotope effect. The ratio of the rate constants for normal and deuterated butenes, kH/kD, is 3.9 at 300°C and 2.6 at 400°C for MgFe204 (75), 2.4 at 435°C for CoFe204, and 1.8 at 435°C for CuFe204 (25). The large isotope effects indicate that the breaking of C—H (C—D) bonds is involved in the slow reaction step. 

The field is defined here around the activation of butane, propane and ethane plus the oxidation of propene. The reason for this boundary is the similarity of the chemistry and the great need to understand the mechanism of selectivity of activated oxygen in these multi-step reactions. The processes cannot be conducted at high temperatures such as with methane activation as the target products are not stable under conditions where alkane activation is fast. The selective oxidation of... 

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