Hydrocarbon Reaction Mechanisms

Because kinetic isotope effects depend on the hydrocarbon reaction mechanism, one would expect different isotopic fractionations involving water-organic interaction. Some preliminary results (Xiao 1998) on the carbon isotopic fractionations associated with hydrolysis reaction indicate that they are much smaller than those associated with HC thermal cracking. This suggests that a different isotopic model is needed for oil and gas generation in many environments with high water concentration. 

At temperatures above about 1200 K, hydrocarbon reaction mechanisms are simplified by the fact that alkyl radicals react primarily by means of p-decomposition. Thus the complex sequence (discussed below) of reactions initiated by addition of molecular oxygen to alkyl radicals... 

Flame or Partial Combustion Processes. In the combustion or flame processes, the necessary energy is imparted to the feedstock by the partial combustion of the hydrocarbon feed (one-stage process), or by the combustion of residual gas, or any other suitable fuel, and subsequent injection of the cracking stock into the hot combustion gases (two-stage process). A detailed discussion of the kinetics for the pyrolysis of methane for the production of acetylene by partial oxidation, and some conclusions as to reaction mechanism have been given (12). 

Bateman, Gee, Barnard, and others at the British Rubber Producers Research Association [6,7] developed a free radical chain reaction mechanism to explain the autoxidation of rubber which was later extended to other polymers and hydrocarbon compounds of technological importance [8,9]. Scheme 1 gives the main steps of the free radical chain reaction process involved in polymer oxidation and highlights the important role of hydroperoxides in the autoinitiation reaction, reaction lb and Ic. For most polymers, reaction le is rate determining and hence at normal oxygen pressures, the concentration of peroxyl radical (ROO ) is maximum and termination is favoured by reactions of ROO reactions If and Ig. 

Aromatic hydrocarbons, like paraffin hydrocarbons, react by substitution, but by a different reaction mechanism and under milder conditions. Aromatic compounds react by addition only under severe conditions. For example, electrophilic substitution of benzene using nitric acid produces nitrobenzene under normal conditions, while the addition of hydrogen to benzene occurs in presence of catalyst only under high pressure to... 

Converting methanol to hydrocarbons is not as simple as it looks from the previous equation. Many reaction mechanisms have been proposed. 

We postulated a reaction mechanism with participation of an aromatic radical cation which was formed by one electron transfer from an aromatic hydrocarbon to copper(II) chloride. Activated alumina has electron-acceptor properties, and formation of a radical cation of an aromatic hydrocarbon adsorbed on alumina has been observed by ESR (ref. 13). Therefore, it seemed to us that alumina as a support facilitates the generation of the radical cation of the aromatic hydrocarbon. 

Predictive equations for the rates of decomposition of four families of free radical initiators are established in this research. The four initiator families, each treated separately, are irons-symmetric bisalkyl diazenes (reaction 1), trans-phenyl, alkyl diazenes (reaction 2), tert-butyl peresters (reaction 3) and hydrocarbons (reaction 4). The probable rate determining steps of these reactions are given below. For the decomposition of peresters, R is chosen so that the concerted mechanism of decomposition operates for all the members of the family (see below)... 

Data accunnilated in the last years on the Ft/Cu alloys, in particular on the 1) surface composition, 2) electronic structure, 3) adsorption properties, 4) catalytic behaviour and 5) various side effects, make a detailed discussion possible of the catalytic selectivity and mechanism of hydrocarbon reactions. 

Both heterogeneous and homogeneous catalysts have been found which allow the hydroamination reaction to occur. For heterogeneously catalyzed reactions, it is very difficult to determine which type of activation is involved. In contrast, for homogeneously catalyzed hydroaminations, it is often possible to determine which of the reactants has been activated (the unsaturated hydrocarbon or the amine) and to propose reaction mechanisms (catalytic cycles). 

Another way to work in transient conditions is to stop suddenly (or conversely to instantaneously introduce) one of the reactants, in order to destabilize the system and to enhance the concentration of labile species. With this method, for example, Poignant et al. studied the DeNO. reaction mechanism on a H—Cu-ZSM-5 catalyst, using propane or propene as reducing agents. The introduction of 2000 ppm of hydrocarbon in a flow of NO (2000 ppm) + 5% 02 allowed to evidence the formation of acrylonitrile, which behaved as an intermediate. Its reactivity with NO+ species constituted a fundamental point to describe a detailed SCR mechanism for NO removal on zeolitic compounds [137],... 

When hydrocarbons are present in the gas mixture, NO removal by oxidation to NOz occurs at much lower input energy and the reaction paths change significantly as compared to the case without hydrocarbons. Numerous works analyze the reaction mechanism of NO. conversion in non-thermal plasma with addition of hydrocarbons, especially ethylene [33,37,77,79,81-83], propylene [35,76,81,83-87], and propane [76,81,85,87],... 

On the basis of the analysis presented in Tables II, III, and IV and measurements of the mass of C02 evolved during oxidation, Figure 1 was constructed to display the fraction of original carbon mobilized by heating, the fraction of the remaining (available) carbon mobilized as incompletely oxidized hydrocarbon by oxidation, and the fraction of available carbon deposited as coke by oxidation. The distribution of available carbon between the mobile and non-mobile products of oxidation lends additional support to our proposed "two-reactions" mechanism. 

First there are the physical chemists, chemical engineers, and surface scientists, who study mainly nonpolar hydrocarbon reactions on clean and relatively clean metals and metal oxides. These have been the traditional studies formerly driven by the petroleum industry and now driven by environmental concerns. These workers typically treat the surface as a real entity composed of active sites (usually not identified, but believed in). These investigators typically, although not always, interpret mechanisms in terms of radical reactions on metals and in terms of acid-base reactions on metal oxides. 

Hydrocarbon formation involves the removal of one carbon from an acyl-CoA to produce a one carbon shorter hydrocarbon. The mechanism behind this transformation is controversial. It has been suggested that it is either a decarbonylation or a decarboxylation reaction. The decarbonylation reaction involves reduction to an aldehyde intermediate and then decarbonylation to the hydrocarbon and releasing carbon monoxide without the requirement of oxygen or other cofactors [88,89]. In contrast, other work has shown that acyl-CoA is reduced to an aldehyde intermediate and then decarboxylated to the hydrocarbon, releasing carbon dioxide [90]. This reaction requires oxygen and NADPH and is apparently catalyzed by a cytochrome P450 [91]. Whether or not a decarbonylation reaction or a decarboxylation reaction produces hydrocarbons in insects awaits further research on the specific enzymes involved. 

Considerable interest in the subject of C-H bond activation at transition-metal centers has developed in the past several years (2), stimulated by the observation that even saturated hydrocarbons can react with little or no activation energy under appropriate conditions. Interestingly, gas phase studies of the reactions of saturated hydrocarbons at transition-metal centers were reported as early as 1973 (3). More recently, ion cyclotron resonance and ion beam experiments have provided many examples of the activation of both C-H and C-C bonds of alkanes by transition-metal ions in the gas phase (4). These gas phase studies have provided a plethora of highly speculative reaction mechanisms. Conventional mechanistic probes, such as isotopic labeling, have served mainly to indicate the complexity of "simple" processes such as the dehydrogenation of alkanes (5). More sophisticated techniques, such as multiphoton infrared laser activation (6) and the determination of kinetic energy release distributions (7), have revealed important features of the potential energy surfaces associated with the reactions of small molecules at transition metal centers. 

But even in the case of electron-transfer reactions between radical ions of the same hydrocarbon, the mechanism leading to emission is simple only in the case of direct formation of the respective hydrocarbon... 

Based on in situ 13C NMR data, surface methoxy groups are reported to form hydrocarbons at temperatures of 523 K and above [273]. The authors have suggested that these hydrocarbons may contribute to the hydrocarbon pool that is established to participate in the catalytic reaction mechanism to form higher hydrocarbons from methanol. Other reactions with amines or halides have also been published [276]. 

The readsorption and incorporation of reaction products such as 1-alkenes, alcohols, and aldehydes followed by subsequent chain growth is a remarkable property of Fischer-Tropsch (FT) synthesis. Therefore, a large number of co-feeding experiments are discussed in detail in order to contribute to the elucidation of the reaction mechanism. Great interest was focused on co-feeding CH2N2, which on the catalyst surface dissociates to CH2 and dinitrogen. Furthermore, interest was focused on the selectivity of branched hydrocarbons and on the promoter effect of alkali on product distribution. All these effects are discussed in detail on the basis... 

Wacker (1) A general process for oxidizing aliphatic hydrocarbons to aldehydes or ketones by the use of oxygen, catalyzed by an aqueous solution of mixed palladium and copper chlorides. Ethylene is thus oxidized to acetaldehyde. If the reaction is conducted in acetic acid, the product is vinyl acetate. The process can be operated with the catalyst in solution, or with the catalyst deposited on a support such as activated caibon. There has been a considerable amount of fundamental research on the reaction mechanism, which is believed to proceed by alternate oxidation and reduction of the palladium ... 

---