Solid-state Formation Reactions

Formation of FeCp2 is also noted in neutron-irradiated [CpFe(CO)2]2, as will be described later. An important difference here is that the radioferrocene seems to be formed in the dimeric carbonyl only by very fast solid-state reactions. 

The defects of the matrix play an important role on luminescent performances in these materials. Taking into consideration the preparation process of these compounds with the solid-state reaction of mixtures of BaC03, H3BO3, and NH4H2PO4 at different molar ratio, non-equal evaporation during the sintering process of these powders is inevitable and thus results in the formation of intrinsic defects, such as cation and oxygen vacancies. Positional disorder of B and Vacant B (Vb)" have been reported in SrBPOs crystals on the basis of... 

We have Investigated the structure of solids In the second chapter and the nature of point defects of the solid in the third chapter. We are now ready to describe how solids react. This will Include the mechanisms Involved when solids form by reaction from constituent compounds. We will also describe some methods of measurement and how one determines extent and rate of the soUd state reaction actually taking place. We will also show how the presence and/or formation of point defects affect reactivity In solid state reactions. They do so, but not In the memner that you might suspect. We will also show how solid state reactions progress, particularly those involving silicates where several different phases appear as a function of both time and relative ratios of reacting components. 

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. 

We have already dealt with two of these. Section 2 dealt with formation of a phase boundary while we have just completed Section 4 concerning nuclei growth as related to a phase boundary. We will consider diffusion mechanisms in nuclei and diffusion-controlled solid state reactions at a later part of this chapter. 

Let us now turn to diffusion in the general case, without worrying about the exact mechanism or the rates of diffusion of the various species. As an example to illustrate how we would analyze a diffusion-limited solid state reaction, we use the general equation describing formation of a compound with spinel (cubic) structure and stoichiometry ... 

Note carefully the sequence of intermediate reactions that have occurred, as depicted in this diagram. We see that the first solid state reaction involves formation of the orthosilicate. But this is very quickly transformed into meta- and pyro-sllicates. However, it is the metasilicate which predominates as the solid state reaction reaches its maturity. Finally, it predominates over all other forms of silicate present. 

Although we have covered mechanisms relating to solid state reactions, the formation and growth of nuclei and the rate of their growth in both heterogeneous and homogeneous solids, and the diffusion processes thereby associated, there exist still other processes zifter the particles have formed. These include sequences in particle growth, once the particles have formed. Such sequences include ... 

Cr-ZSM-5 catalysts prepared by solid-state reaction from different chromium precursors (acetate, chloride, nitrate, sulphate and ammonium dichromate) were studied in the selective ammoxidation of ethylene to acetonitrile. Cr-ZSM-5 catalysts were characterized by chemical analysis, X-ray powder diffraction, FTIR (1500-400 cm 1), N2 physisorption (BET), 27A1 MAS NMR, UV-Visible spectroscopy, NH3-TPD and H2-TPR. For all samples, UV-Visible spectroscopy and H2-TPR results confirmed that both Cr(VI) ions and Cr(III) oxide coexist. TPD of ammonia showed that from the chromium incorporation, it results strong Lewis acid sites formation at the detriment of the initial Bronsted acid sites. The catalyst issued from chromium chloride showed higher activity and selectivity toward acetonitrile. This activity can be assigned to the nature of chromium species formed using this precursor. In general, C r6+ species seem to play a key role in the ammoxidation reaction but Cr203 oxide enhances the deep oxidation. 

A crystalline sample of this supramolecular assembly was irradiated with UV light and the formation of the corresponding cyclobutane 91 with syn-anti-syn stereochemistry was observed. In contrast, the photodimerisation of trans-stilbenoid-bis(dialkylammonium) salts does not take place in the absence of the macro cycle, indicating the importance of pre-organizing the stilbenoid units (which requires the presence of the anion) for this solid-state reaction to occur. 

These investigations were concerned with the formation of alkaline earth chromates Me2+Cr6+04 during solid state reactions with Cr203. Thermogravimetric methods are especially useful for such studies and allow one to follow the oxidation... 

Fig. 45. Formation of CaCr04 and of CdCr04 by solid state reaction between different mixtures. A) Sample weight 96 mg, heating rate 2 °C/min, atmosphere air B) Sample weight 38 mg, heating rate 2 °C/min, atmosphere air C) Sample weight 43 mg, heating rate 0.5 °C/min, atmosphere oxygen...

Figure 2.19. Examples of systems in which intermediate phases corresponding to small composition ranges are formed. These are SnTe (congruent melting), HfRu (congruent melting), ZrV2 (peritectic formation) and TaV2 (formed through a solid-state reaction).

Alloy crystal and thermal data symbols. A number of tables show, for selected alloys, the highest melting points observed in the systems considered, as well as the mechanism of formation (p = peritectic melting, syn = synthetic reaction, s.s.r. = solid-state reaction, est. = estimated melting point, etc.), the value of the Raynor Index (<1, =1 or>l). The question mark means that no reliable data are available. 

Many solid-state reactions may be pictured as proceeding in two steps. First a homogeneous process leads to product molecules dissolved in residual parent matrix. Curtin and Paul, in a review on thermal solid-state reactions (6), divide this step into a number of stages First, there is a loosening of the molecules at the reaction site to be, then molecular change (the true reaction), and finally solid-solution formation. When the concentration of the accumulated product exceeds the solubility limit the second step, the decomposition of this solid solution into separate reactant and product phases, occurs. However, in some cases the solubility limit is very low, so that the overall process appears to become simpler ... 

To elucidate the process of the solid-state reaction during ball-milling one has wanted to find out how Y2O3 penetrates into the m-Zr02 lattice and how this results in the formation of a tetragonal Zr02 solid solution (t-Zr02 SS). 

R.B. Schwarz, W.L. Johnson, Formation of amorphous alloy by solid-state reaction of the pure polycrystaUine metals, Phys. Rev. Lett. 51(5) (1983) 415 18. 

Aspartame is relatively unstable in solution, undergoing cyclisation by intramolecular self-aminolysis at pH values in excess of 2.0 [91]. This follows nucleophilic attack of the free base N-terminal amino group on the phenylalanine carboxyl group resulting in the formation of 3-methylenecarboxyl-6-benzyl-2, 5-diketopiperazine (DKP). The DKP further hydrolyses to L-aspartyl-L-phenyl-alanine and to L-phenylalanine-L-aspartate [92]. Grant and co-workers [93] have extensively investigated the solid-state stability of aspartame. At elevated temperatures, dehydration followed by loss of methanol and the resultant cyclisation to DKP were observed. The solid-state reaction mechanism was described as Prout-Tompkins kinetics (via nucleation control mechanism). 

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