Oxidation reactions, thermochemistry

As described in the Introductory Chapter, attention was focused [1] prior to 1961 mainly on the morphology of the cool-flame and ignition regions, rates were followed by pressure change, and essentially chemical techniques were used for product analysis. The acceptance of free radicals, followed by the masterly and elegant Semenov theory [2], which established the principles of branched chain reactions, provided the foundation for modern interpretations of hydrocarbon oxidation. This chapter builds on these early ideas, and pioneering experiments such as those carried out by Knox and Wells [3] and Zeelenberg and Bickel [4], to provide a detailed account of the reactions, thermochemistry and detailed mechanisms involved in the gas-phase chemistry of hydrocarbon oxidation. 

The behaviour of the tyrosyl radicals involved in different processes and environments is not yet well understood Relatively little is known about the structure and selectivity of aryloxylium cations (Ar—0+) that are produced in the phenolic oxidation reactions and implicated in biological processes such as isoflavone synthesis . The thermochemistry which is relevant to the antioxidant properties of phenols as well as the solvent effects on their reactivity ° remain also a largely under-explored topic. Finally, the structure of phenol dimers and oligomers or even of some specific phenols also deserve more attention. We expect that these problems will be subjects for theoretical research in the coming years. 

Table 4.1 Thermochemistry and volumetric changes of a selection of oxidation reactions of sodium alanate by oxygen or water vapor. Free energy and enthalpy changes are given per mol of NaAIH4. Volumetric changes refer to the solid compounds only and are percentages based on NaAIH4...

Our principal concern is to utilize both kinetics and product formation as diagnostic tools for elucidating the detailed mechanisms of oxidation reactions in terms of elementary steps, rate coefficients, thermochemistry and structure—reactivity relationships. Accordingly, our emphasis throughout the chapter will be on these relationships, exemplified by reactions of simple molecules and the way in which they may be used to interpret and predict the rates and products of oxidation reactions involving more complex molecules or extreme conditions. ... 

The initial steps in oxidative reaction of aromatic, poly-aromatic and other cyclic and linear unsaturated hydrocarbons in the atmosphere or in combustion involve radical formation. These radicals react with molecular oxygen. The subsequent reactions of these peroxy radicals, as shown e.g. in Figure 4.1, result in unsaturated linear or cyclic, oxygenated or multi-oxygenated hydrocarbon intermediates. The thermochemistry for these unsaturated - oxygenated species is needed to evaluate their stability and likely reaction paths in the environment, in combustion and in other thermal and oxidative processes. 

Thermochemistry. From an overall heat and mass balance point of view, the main chemical reactions of the blast furnace include oxidation of carbon in the zone in front of the tuyeres (raceway) to give CO plus heat. 

IsoxazoIidine-3,3-dicarboxylic acid, 2-methoxy-dimethyl ester reaction with bases, 6, 47 Isoxazolidine-3,5-diones synthesis, 6, 112, 113 Isoxazoli dines conformation, 6, 10 3,5-disubstituted synthesis, 6, 109 oxidation, 6, 45-46 PE spectra, 6, 5 photolysis, 6, 46 pyrolysis, 6, 46 reactions, 6, 45-47 with acetone, 6, 47 with bases, 6, 47 reduction, 6, 45 ring fission, S, 80 spectroscopy, 6, 6 synthesis, 6, 3, 108-112 thermochemistry, 6, 10 Isoxazolidin-3-ol synthesis, 6, 111 Isoxazolidin-5-oI synthesis, 6, 111... 

The present volume deals with the properties of dienes, described in chapters on theory, structural chemistry, conformations, thermochemistry and acidity and in chapters dealing with UV and Raman spectra, with electronic effects and the chemistry of radical cations and cations derived from them. The synthesis of dienes and polyenes, and various reactions that they undergo with radicals, with oxidants, under electrochemical conditions, and their use in synthetic photochemistry are among the topics discussed. Systems such as radialenes, or the reactions of dienes under pressure, comprise special topics of these functional groups. 

The reaction between OH and phenol lends itself to an analysis of its thermochemistry. On the basis of E7( OH) = 2.3V/NHE and E7(PhO ) = 0.97 V/NHE [42], the formation of PhO and H2O via an electron-transfer mechanism is exothermic byl.33V = 31 kcal mor In spite of this, the reaction proceeds by addition, as outlined in Eq. 24. Again, the propensity of OH to add rather than to oxidize can be understood in terms of the transition state for addition being stabilized by contributions from bond making, in contrast to electron transfer which requires pronounced bond and solvent reorganization which results in a large (entropy-caused) free energy change. 

The CBS-QB3 potential energy surface accounts for the various experimentally observed products, including hydroperoxyl radical, propene, HO, propanal, and oxirane (c-CsHgO). The activation barrier for simultaneous 1,4-H transfer and HO2 expulsion, obtained via calculations, compares well to the experimentally observed barrier (26.0kcal/mol) of DeSain et al. This work provides some ramifications for larger alkylperoxy radicals multiple conformers of long alkylperoxy radicals are likely to play a role in the overall oxidation chemistry and dictate consideration for correct treatment of thermochemistry at lower temperatures T< 500 K), unimolecular reactions dictate peroxy radical chemistry. 

One common application of thermochemistry in everyday life is the use of hot and cold packs. A variety of these are used to treat injuries and provide warmth. One type of pack used to provide heat utilizes the exothermic oxidation of iron to produce heat. The reaction can be represented as... 

The slow combustion reactions of acetone, methyl ethyl ketone, and diethyl ketone possess most of the features of hydrocarbon oxidation, but their mechanisms are simpler since the confusing effects of olefin formation are unimportant. Specifically, the low temperature combustion of acetone is simpler than that of propane, and the intermediate responsible for degenerate chain branching is methyl hydroperoxide. The Arrhenius parameters for its unimolecular decomposition can be derived by the theory previously developed by Knox. Analytical studies of the slow combustion of methyl ethyl ketone and diethyl ketone show many similarities to that of acetone. The reactions of methyl radicals with oxygen are considered in relation to their thermochemistry. Competition between them provides a simple explanation of the negative temperature coefficient and of cool flames. 

It was suggested earlier in this section that oxoacid salts such as CaC03 could be viewed as products of reactions between basic oxides (containing O2- discrete ions) and covalent (molecular/polymeric) oxides in which oxide ions are transferred to form oxo-anions. Analysis of the thermochemistry of such reactions has led to the formulation of a numerical scale of acidity for oxides. In Table 9.1 the acidity parameter a is listed for the most important binary oxides. Highly-negative values indicate a basic oxide, while acidic oxides have positive values. 

Reaction of an oxide with hydrogen halide is a fairly obvious route. This is an acid/base reaction, and its thermochemistry will depend on the... 

Thermochemistry of Gas-Metal Reactions", in "Oxidation of Metals and Alloys" American Society for Metals, Metals Park Ohio, 1971. 

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