Oxidation products of hydrocarbons

Acetyl peroxynitrate (18) and perfluoroacetyl peroxynitrate (19), two important atmospheric oxidation products of hydrocarbons (formation of 18) or chlorofluorocarbon replacements, such as CF3CH3 (formation of 19), preferentially adopt a gauche conformation (C—O—O—N = 84.7° for 18 and 85.8° for 19 electron diffraction). The two peroxides are characterized by comparatively short 0—0 bonds on one side and long 0°—N connectivities (Table 5) on the other. The observed O —N distances may be explained on the basis of an no ct od-n orbital overlap. This type of interaction lowers the 0°—N bond order and could explain the low bond dissociation energies of this connectivity in peroxides 18 and 19 (118 4 klmol for both compounds). It should be noted that this interpretation does not reflect a possible r-type interaction between a lone pair at 0° and virtual orbitals of the nitro group and therefore requires future investigation. 

Several compounds were also found to have a seasonal distribution. Kubatova et al. (2002) found that concentrations of lignin and cellulose pyrolysis products from wood burning were higher in aerosol samples collected during low-temperature conditions. On the other hand, concentrations of dicarboxylic acids and related products that are believed to be the oxidation products of hydrocarbons and fatty acids were highest in summer aerosols. PAHs, which are susceptible to atmospheric oxidation, were also more prevalent in winter than in summer. These results suggest that atmospheric oxidation of VOCs into secondary OAs and related oxidative degradation products are key factors in any OA mass closure, source identification, and source apportionment study. However, additional work is much desirable to assess the extent and seasonal variation of these processes. 

Thus, carbon monoxide, oxalic acid and formic acid are intermediate products in the reduction of carbon di-oxide to elemental carbon. If the reduction is continued beyond the stage of free carbon we shall obtain the hydrocarbons which stand at the other extreme to carbon di-oxide, in respect to the element carbon. The hydrocarbons are thus the reduction product and carbon dioxide the oxidation product of carbon. In other words the final reduction products of carbon dioxide are hydrocarbons and vice-versa the final oxidation product of hydrocarbon is carbon dioxide. 

Table 6-1 Typical groups of oxidation products of hydrocarbons [W. C. Hopkins and J. J. Fritsch, Chem. Eng. 51(8) 361 (1955), by courtesy...

Formaldehyde is emitted from sources and also is an oxidation product of hydrocarbons. It is an essential component of tropospheric chemistry. Thus the chemistry of formaldehyde is common to virtually all mechanisms of tropospheric chemistry. This section therefore serves both as a continuation of our discussion of ozone chemistry as well as an introduction to the chemistry of organic compounds. 

In the complicated reaction networks involved in fuel decomposition and oxidation, intermediate species indicate the presence of different pathways that may be important under specific combustion conditions. While the final products of hydrocarbon/air or oxygenate/air combustion, commonly water and carbon dioxide, are of increasing importance with respect to combustion efficiency—with the perception of carbon dioxide as a... 

In this chapter a two a selectivity model is proposed that is based on the premise that the total product distribution from an Fe-low-temperature Fischer-Tropsch (LIFT) process is a combination of two separate product spectrums that are produced on two different surfaces of the catalyst. A carbide surface is proposed for the production of hydrocarbons (including n- and iso-paraffins and internal olefins), and an oxide surface is proposed for the production of light hydrocarbons (including n-paraffins, 1-olefins, and oxygenates) and the water-gas shift (WGS) reaction. This model was tested against a number of Fe-catalyzed FT runs with full selectivity data available and with catalyst age up to 1,000 h. In all cases the experimental observations could be justified in terms of the model proposed. 

The peroxide theory of Bach [20] and Engler [23] fixed the phenomenon of peroxide formation as the primary product of hydrocarbon oxidation by dioxygen. However, the problem of the mechanism of peroxide formation remained unsolved. The new stage of successful study of organic compound oxidation began after the discovery of free radicals as active intermediates of many chemical processes. 

HYDROPEROXIDES AS PRIMARY MOLECULAR PRODUCTS OF HYDROCARBON OXIDATION... 

A very serious problem was to clear up the formation of hydroperoxides as the primary product of the oxidation of a linear aliphatic hydrocarbon. Paraffins can be oxidized by dioxygen at an elevated temperature (more than 400 K). In addition, the formed secondary hydroperoxides are easily decomposed. As a result, the products of hydroperoxide decomposition are formed at low conversion of hydrocarbon. The question of the role of hydroperoxide among the products of hydrocarbon oxidation has been specially studied on the basis of decane oxidation [82]. The kinetics of the formation of hydroperoxide and other products of oxidation in oxidized decane at 413 K was studied. In addition, the kinetics of hydroperoxide decomposition in the oxidized decane was also studied. The comparison of the rates of hydroperoxide decomposition and formation other products (alcohol, ketones, and acids) proved that practically all these products were formed due to hydroperoxide decomposition. Small amounts of alcohols and ketones were found to be formed in parallel with ROOH. Their formation was explained on the basis of the disproportionation of peroxide radicals in parallel with the reaction R02 + RH. 

The formation of dihydroperoxides as the primary products of hydrocarbon oxidation is the result of peroxyl radical isomerization (see Chapter 2). 

Detailed information about molecular products of hydrocarbon oxidation is given in monographs [45,46,80,82]. The kinetic schemes of the oxidation of alcohols, ketones, aldehydes, and acids are discussed in Chapters 7,8. The thermochemical scale of hydrocarbon oxidation is given in Table 1.7. 

The traditional chain oxidation with chain propagation via the reaction RO/ + RH occurs at a sufficiently elevated temperature when chain propagation is more rapid than chain termination (see earlier discussion). The main molecular product of this reaction is hydroperoxide. When tertiary peroxyl radicals react more rapidly in the reaction R02 + R02 with formation of alkoxyl radicals than in the reaction R02 + RH, the mechanism of oxidation changes. Alkoxyl radicals are very reactive. They react with parent hydrocarbon and alcohols formed as primary products of hydrocarbon chain oxidation. As we see, alkoxyl radicals decompose with production of carbonyl compounds. The activation energy of their decomposition is higher than the reaction with hydrocarbons (see earlier discussion). As a result, heating of the system leads to conditions when the alkoxyl radical decomposition occurs more rapidly than the abstraction of the hydrogen atom from the hydrocarbon. The new chain mechanism of the hydrocarbon oxidation occurs under such conditions, with chain... 

Peroxyl radicals were identified as products of hydrocarbon and polymer oxidation by an 03 02 mixture and were proved by EPR spectroscopy [118,119]. 

Hydroperoxide is the first product of hydrocarbon oxidation and plays a key role in the chain mechanism of autoxidation. Hydroperoxide possesses a weak O—O bond and decomposes... 

The study of the interaction of hydroperoxide with other products of hydrocarbon oxidation showed the intensive initiation by reactions of hydroperoxide with formed alcohols, ketones, and acids [6,134]. Consequently, with the developing of the oxidation process the variety of reactions of initiation increases. In addition to reactions of hydroperoxide with the hydrocarbon and the bimolecular reaction of ROOH, reactions of hydroperoxide with alcohol and ketone formed from hydroperoxide appear. The values of rate constants (in L mol 1 s 1) of these reactions for three oxidized hydrocarbons are given below. 

In the oxidized hydrocarbon, hydroperoxides break down via three routes. First, they undergo homolytic reactions with the hydrocarbon and the products of its oxidation to form free radicals. When the oxidation of RH is chain-like, these reactions do not decrease [ROOH]. Second, the hydroperoxides interact with the radicals R , RO , and R02. In this case, ROOH is consumed by a chain mechanism. Third, hydroperoxides can heterolytically react with the products of hydrocarbon oxidation. Let us consider two of the most typical kinetic schemes of the hydroperoxide behavior in the oxidized hydrocarbon. The description of 17 different schemes of chain oxidation with different mechanisms of chain termination and intermediate product decomposition can be found in a monograph by Emanuel et al. [3]. 

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

Liptinites were made up of hydrogen-rich hydrocarbons derived from spores, pollens, cuticles, and resins in the original plant material. Vitrinites were made up of wood, bark, and roots and contained less hydrogen than the liptinites. Inertinites are mainly oxidation products of the other macerals and are consequently richer in carbon. The inertinite group includes fusinite, most of which is fossil charcoal, derived from ancient peat fires. 

The classic platinum(O) approach to C-H activation, yielding platinum(II) alkyl hydrides as the oxidative addition products, contributed significantly to our understanding of C-H activation. However, the platinum(II)/(IV) approach has proven capable of achieving oxidative functionalization of hydrocarbons, and so this review focuses on the higher oxidation state. 

PCDD/F and other chlorinated hydrocarbons observed as micropollutants in incineration plants are products of incomplete combustion like other products such as carbon monoxide, polycyclic aromatic hydrocarbons (PAH), and soot. The thermodynamically stable oxidation products of any organic material formed by more than 99% are carbon dioxide, water, and HCl. Traces of PCDD/F are formed in the combustion of any organic material in the presence of small amounts of inorganic and organic chlorine present in the fuel municipal waste contains about 0.8% of chlorine. PCDD/F formation has been called the inherent property of fire. Many investigations have shown that PCDD/Fs are not formed in the hot zones of flames of incinerators at about 1000°C, but in the postcombustion zone in a temperature range between 300 and 400°C. Fly ash particles play an important role in that they act as catalysts for the heterogeneous formation of PCDD/Fs on the surface of this matrix. Two different theories have been deduced from laboratory experiments for the formation pathways of PCCD/F ... 

The principle of fluidised bed combustion with simultaneous desulphurisation is based on the thermal decomposition of limestone carbonates to yield oxides which then react with the sulphur oxide products of combustion of both inorganic and organic sulphur compounds in the hydrocarbon fuel. 

Much recent research (7-5) has been devoted to converting methane to products that are more easily transported and more valuable. Such more valuable products include higher hydrocarbons and the partial oxidation products of methane which are formed by either direct routes such as oxidative coupling reactions or indirect methods via synthesis gas as an intermediate. The topic of syngas formation by oxidation of CH4 has been considered primarily from an engineering perspective (7-5). Most fundamental studies of the direct oxidation of CH4 have dealt with the CH4 + O2 reaction system in excess O2 and at lower temperatures (6-10). 

Adolph Wurtz, 1817—1884. Professor of chemistry at the ficole de Medecine in Pans. Discoverer of methyl and ethyl amines and the synthesis of hydrocarbons from alkyl iodides and sodium. He studied the oxidation products of the glycols and the homologs of lactic acid The proof of the elementary nature of gallium was demonstrated in his laboratory by Lecoq de Boisbaudran. 

In 1954, Kotin and co-workers reported the carcinogenicity of atmospheric extracts of Los Angeles air. Subsequently, in 1956, they reported the carcinogenic activity of oxidation products of aliphatic hydrocarbons and, in 1958, of ozonized gasoline. Concurrently, Falk and co-workers (1956) published results... 

Kotin, P., H. L. Falk, and M. Thomas, "Production of Skin Tumors in Mice with Oxidation Products of Aliphatic Hydrocarbons, Cancer, 9, 905-909 (1956). 

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