Solid-state reactions decomposition

Glass transition determinations Decomposition reaction Reaction kinetics Phase diagrams Dehydration reactions Solid-state reactions Heats of absorption Heats of reaction Heats of polymerization Heats of sublimation Heats of transition Catalysis... 

Decomposition Reactions. Berthelot stated that AN can decompose according to any of the seven equations given below. The heats of decompn (indicating the heat evolved at const vol and 300°K) were calcd by C.G. Dunkle of Pic Arsn, based on the latest NDRC values. Unless otherwise stated, these values are for the solid salt. For molten AN, add about 4,000 cal/mol to these values. Values in square brackets are those of Scott and Grant (Ref 90), and were calcd from the... 

Sato M, Tajimi S, Okawa H, Uematsu K, Toda K (2002) Preparation of iron phosphate cathode material of Li3Fe2(P04)3 by hydrothermal reaction and thermal decomposition processes. Solid State Ionics 152-153 247-251... 

Synthetic routes derived from molecular and non-molecular precursors have expedited the development of technologically important 2- and 3- dimensional materials. Such approaches have often proved superior to conventional ceramic techniques in that high purity bulk samples or thin films can be prepared at lower temperatures much more rapidly. Predominant among the precursor methods are those based on decomposition reactions. These either involve gaseous species, such as those used in chemical vapor deposition (CVD), or solids. Examples include the pyrolysis of the gas-phase precursor [(CH3)2A1(NH2)]3 to produce aluminum nitride (i) and the thermal decomposition of solid state carbonate precursors of calcium and manganese (Cai j,Mn C03, 0 < x < 1) to produce several of the known ternary compounds in the Ca-Mn-O system (2). Single-displacement reactions are also common as precursor methods. These approaches usually involve gas-phase reactions and are also used in CVD techniques. Examples here include the formation oi... 

Exothermic Decompositions These decompositions are nearly always irreversible. Sohds with such behavior include oxygen-containing salts and such nitrogen compounds as azides and metal styphnates. When several gaseous products are formed, reversal would require an unlikely complex of reactions. Commercial interest in such materials is more in their storage properties than as a source of desirable products, although ammonium nitrate is an important explosive. A few typical exampes will be cited to indicate the ranges of reaction conditions. They are taken from the review by Brown et al. ( Reactions in the Solid State, in Bamford and Tipper, Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980). 

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. 

The process of calculation becomes more complicated on adding further terms. Coats and Redfem [555] effectively put (U-2)/U equal to a constant value and the relationship is equivalent to that already given for In g i/T2 from the single term expansion. They assumed that f(q) = (1 — q)" and determined n by testing values which have significance in solid state decomposition reactions (i.e. n = 0, 0.5, 0.67 and 1.00). Sharp [75,556] has shown that the approach may be applied to other functions of g(q). If it is assumed that the zero-order equation applied at low a, as q -> 0, then g(q) == a. 

The reactions of some aromatic metal carboxylates are on the borderline of classification as solid-state processes. While there is no evidence of liquefaction, rates of decomposition in the poorly crystallized or vitreous reactant obey kinetic expressions more characteristic of reactions proceeding in a homogeneous phase. 

The catalytic activity of doped nickel oxide on the solid state decomposition of CsN3 decreased [714] in the sequence NiO(l% Li) > NiO > NiO(l% Cr) > uncatalyzed reaction. While these results are in qualitative accordance with the assumption that the additive provided electron traps, further observations, showing that ZnO (an rc-type semi-conductor) inhibited the reaction and that CdO (also an rc-type semi-conductor) catalyzed the reaction, were not consistent with this explanation. It was noted, however, that both NiO and CdO could be reduced by the product caesium metal, whereas ZnO is not, and that the reaction with NiO yielded caesium oxide, which is identified as the active catalyst. Detailed kinetic data for these rate processes are not available but the pattern of behaviour described clearly demonstrates that the interface reactions were more complicated than had been anticipated. 

The BaO is produced in the form of very small particles of nearly atomic proportions which react immediately to form the silicate. Actually, the rate of reaction is proportional to the number of nuclei produced per unit vdlume. A nucleus is a point where atoms or ions have reacted and begun the formation of the product structure. In the case of the BaO reaction, the number of nuclei formed per unit of time is small and formation of the structure is diffusion limited. In the case of BaCOa decomposition, the atomic-proportioned BaO reacts nearly as fast as it is formed so that the number of nuclei per unit volume is enormously increased. It is thus apparent that if we wish to increase solid state reaction rates, one way to do so is to use a decomposition reaction to supply the reacting species, we will further address this type of reaction later on in our discussion. 

One of the major uses of DTA has been to follow solid-state reactions as they occur. All decomposition reactions (loss of hydrates, water of constitution, decomposition of inorganic anions, e.g.- carbonate to carbon dioxide gas, etc.) are endothermic and irreversible. Likewise are the synthesis reactions such as... 

In the solid state reaction depicted, A begins to decompose to B at Ti and the reaction temperature for decomposition is T2, with a weight loss of Wi Likewise, the reaction of B to form C begins at T3 and the reaction temperature (where the rate of reaction is maximum) is T4. Note that the weight loss becomes constant as each reaction product is formed and the individual reactions are completed. If we program the temperature at 6 °C/min., we would obtain the results in 7.3.4. This is called d3mamic thermogravimetry. 

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