Ionic crystal decompositions

Figure 1.6. Schematic representation of electron promotion processes in ionic crystals. At the shortest wavelengths, electrons are promoted to the conduction band and photoconductivity is observed. Exciton formation occurs on promotion to levels below the conduction band, this energetic combination of electron and positive hole does not conduct electricity but may participate in decomposition processes. Electrons or positive holes may also be generated from impurities.

Some of the reports are as follows. Mizukoshi et al. [31] reported ultrasound assisted reduction processes of Pt(IV) ions in the presence of anionic, cationic and non-ionic surfactant. They found that radicals formed from the reaction of the surfactants with primary radicals sonolysis of water and direct thermal decomposition of surfactants during collapsing of cavities contribute to reduction of metal ions. Fujimoto et al. [32] reported metal and alloy nanoparticles of Au, Pd and ft, and Mn02 prepared by reduction method in presence of surfactant and sonication environment. They found that surfactant shows stabilization of metal particles and has impact on narrow particle size distribution during sonication process. Abbas et al. [33] carried out the effects of different operational parameters in sodium chloride sonocrystallisation, namely temperature, ultrasonic power and concentration sodium. They found that the sonocrystallization is effective method for preparation of small NaCl crystals for pharmaceutical aerosol preparation. The crystal growth then occurs in supersaturated solution. Mersmann et al. (2001) [21] and Guo et al. [34] reported that the relative supersaturation in reactive crystallization is decisive for the crystal size and depends on the following factors. 

The mechanisms of CD processes can be divided into two different processes formation of the required compound by ionic reactions involving free anions, and decomposition of metal complexes. These two categories can be further divided in two formation of isolated single molecules that cluster and eventually form a crystal or particle, and mediation of a solid phase, usually the metal hydroxide. We consider first the pathways involving free anions and defer to later those where a metal complex decomposes. 

The physical and chemical properties of the tetrahydroborates show more contrasts than the salts of nearly any other anion. The alkali metal salts are the most stable. In dry air, NaBH4 is stable at 300°C and in vacuo to 400°C with only partial decomposition. In contrast, several tetrahydroborates, including the titanium, thallium, gallium, copper, and silver salts, are unstable at or slightly above ambient temperatures. The chemical and physical properties of the tetrahydroborates are closely related to molecular structure. Sodium tetrahydroborate, which is typical of the alkali metal tetrahydroborates except for the lithium salt, has a face-centered cubic (fee) crystal lattice which is essentially ionic and contains the tetrahedral [BHJ- anion. The tetrahydroborates of the polyvalent metals are in many cases the most volatile derivatives of these metals known. Aluminum tris(tetrahydroborate)... 

There is still another type of internal solid state reaction which we will discuss and it is electrochemical in nature. It occurs when an electrical current flows through a mixed conductor in which the point defect disorder changes in such a way that the transference of electronic charge carriers predominates in one part of the crystal, while the transference of ionic charge carriers predominates in another part of it. Obviously, in the transition zone (junction) a (electrochemical) solid state reaction must occur. It leads to an internal decomposition of the matrix crystal if the driving force (electric field) is sufficiently high. The immobile ionic component is internally precipitated, whereas the mobile ionic component is carried away in the form of electrically charged point defects from the internal reaction zone to one of the electrodes. 

The discussion up to this point has been concerned essentially with metal alloys in which the atoms are necessarily electrically neutral. In ionic systems, an electric diffusion potential builds up during the spinodal decomposition process. The local gradient of this potential provides an additional driving force, which acts upon the diffusing species and this has to be taken into account in the derivation of the equivalents of Eqns. (12.28) and (12.30). The formal treatment of this situation has not yet been carried out satisfactorily [A.V. Virkar, M. R. Plichta (1983)]. We can expect that the spinodal process is governed by the slower cation, for example, in a ternary AX-BX crystal. The electrical part of the driving force is generally nonlinear so that linearized kinetic equations cannot immediately be applied. 

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