Exothermic, generally decomposition

In general, an explosion is an exothermic chemical reaction between two components. A well-known example is the reaction between the oxygen content of the atmospheric air and a combustible substance like petrol. As an exception, there are very few substances - such as acetylene - which are thermodynamically unstable and tend to exothermic self-decomposition. An explosion can start only with an ignition source and a volume or mass ratio of the two components in such a manner that the reaction zone is sustained by itself. Typical values of the peak explosion pressure - when starting with components at atmospheric pressure in a constant volume - are 1 MPa (10 bar) and a propagation velocity of the reaction zone up to 102m/ s (as an order of magnitude). 

Based on bond enthalpy consideration, acconnt for the fact that combination reactions are generally exothermic and decomposition reactions are generally endothermic. 

If the decomposition reaction follows the general rate law, the activation energy, heat of decomposition, rate constant and half-life for any given temperature can be obtained on a few milligrams using the ASTM method. Hazard indicators include heats of decomposition in excess of 0.3 kcal/g, short half-lives, low activation energies and low exotherm onset temperatures, especially if heat of decomposition is considerable. 

Chemical Reactivity - Reactivity with Water No reaction unless in the presence of acids and caustics Reactivity with Common Materials Slow decomposition occurs, but generally the reactions are not hazardous Stability During Transport Stable if cool Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Violent, exothermic polymerization occurs at about 225 of. Acid fumes will also cause polymerization at ordinary temperatures Inhibitor of Polymerization None reported. 

Although the literature contains a very large number of research articles concerned with the kinetics and mechanisms of reactions involving solids, there are comparatively few authoritative, critical and comprehensive reviews of the formidable quantity of information which is available. Probably the most important general account of the field is the book Chemistry of the Solid State, edited by Gamer [63]. Chapters 7—9 are particularly relevant in the present context as they provide a systematic exposition of the kinetic equations applicable to the decomposition of single solids (Jacobs and Tompkins [28]) and their application to endothermic [64] and exothermic [65] reactions. 

In summary thermal decomposition of chlorinated phenols does not generally lead to dioxins. There are, however, several conditions which by themselves or combined would favor dioxin formation. First, of all chlorinated phenols either in bulk or in solution, only pentachlorophenol produced measurable amounts of dioxin. Secondly (Table II), only sodium salts in salid state reactions produced dioxins in reasonable yields. In contrast, the silver salt of pentachlorophenol (Figure 8) undergoes an exothermic decomposition at considerably lower temperatures and produced only higher condensed materials. No dioxin was detected. 

Many, but not all, endothermic compounds have been involved in violent decompositions, reactions or explosions, and in general, compounds with significantly positive values of standard heat of formation may be considered suspect on stability grounds. Notable exceptions are benzene and toluene (AH°f +82.2, 50.0 kJ/mol 1.04, 0.54 kJ/g, respectively), where there is the resonance stabilising effect of aromaticity. Values of thermodynamic constants for elements and compounds are tabulated conveniently [1], but it should be noted that endothermicity may change to exothermicity with increase in temperature [2], There is a more extended account of the implications of endothermic compounds and energy release in the context of fire and explosion hazards [3], Many examples of endothermic compounds will be found in the groups ... 

It was proposed that the increase in activity during the equilibration period was due to the generation of new active sites,consisting of the Mo species located in the cationic position in the secondary framework of the POM. A similar hypothesis was formulated by other authors for the methacrolein oxidation to methacrylic acid." " More generally, it is currently believed that for exothermic reactions, and specifically for oxidations, the true working state of the POM, does not correspond to its crystalline form." The presence of steam and the large amount of heat released provoke an incipient surface decomposition, which leads to the expulsion of the Mo species from the anion as a metastable defective... 

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