Precipitation and nucleation

By carefully controlling the precipitation reaction we can significantly increase a precipitate s average particle size. Precipitation consists of two distinct events nu-cleation, or the initial formation of smaller stable particles of precipitate, and the subsequent growth of these particles. Larger particles form when the rate of particle growth exceeds the rate of nucleation. 

Wet preparation of red iron oxides can involve either a hydrothermal process (see Hydrothermal processing) or a direct precipitation and growth of iron oxide particles on specially prepared nucleating seeds of Fe202- In the hydrothermal process, iron(II) salt is chemically oxidized to iron(III) salt, which is further treated by alkahes to precipitate a hydrated iron(III) oxide gel. The gel can be dehydrated to anhydrous hematite under pressure at a temperature around 150°C. 

Precipitation and Generation Methods For a thorough understanding of the phenomena involved, bubble nucleation ould be considered. A discussion of nucleation phenomena is beyond the scope of this Handbook however, excellent coverages are presented by Blander and Katz. 

Thus under ideal circumstances the modes of aggregation can be discriminated by such plots. Deviations below the expected slopes are usually attributed to collision inefficiency leading to imperfect aggregation. In a crystallization or precipitation process, of course, deviations may also occur due to growth and nucleation unless properly accounted for. 

In Nature, however, we always have a contiiinous distribution of particles. This means that we have all sizes, even those of fractional parentage, i.e.-18.56n, 18.57p, 18.58 p, etc. (supposing that we can measure 0.01 p differences). The reason for this is that the mecheuiisms for particle formation, i.e.- precipitation, embryo and nucleation growth, Ostwald ripening, and sintering, are random processes. Thus, while we may speak of the "statistical variation of diameters", and while we use whole numbers for the particle diameters, the actuality is that the diameters are fractional in nature. Very few particle-size" specialists seem to recognize this fact. Since the processes are random in nature, we can use statistics to describe the... 

In both cases, the Au nanoparticles behave as molecular crystals in respect that they can be dissolved, precipitated, and redispersed in solvents without change in properties. The first method is based on a reduction process carried out in an inverse micelle system. The second synthetic route involves vaporization of a metal under vacuum and co-deposition of the atoms with the vapors of a solvent on the walls of a reactor cooled to liquid nitrogen temperature (77 K). Nucleation and growth of the nanoparticles take place during the warm-up stage. This procedure is known as the solvated metal atom dispersion (SMAD) method. 

Alkali ions (salts) influence the formation of the precursor gel for most of the synthetic zeolites (3,34,39,40). Na+ ions were shown to enhance in various ways the nucleation process (structure-directing role) (40-42), the subsequent precipitation and crystallization of the zeolite (salting-out effect) (JO and the final size and morphology of the crystallites (34,43). Informations on the various roles played by the inorganic (alkali) cations in synthesis of ZSM-5, such as reported in some recent publications (7,8,10,14,17,29,30,44,45) remain fragmentary, sometines contradictory and essentially qualitative. 

The rate of nucleation is dependent on the degree of supersaturation as described in section 2.4.1, and because this will always be larger for Form 1 it may be incorrectly assumed that Form I will always precipitate first. The true situation is somewhat more complicated because the critical size, activation energy and nucleation rate also depend on the solid state that is being formed [6]. It is quite feasible and a regular occurrence, that a less stable polymorph will have a higher rate of nucleation than a more stable form, as illustrated in figure 6. 

Adsorption influences the reactivity of surfaces. It has been shown that the rates of processes such as precipitation (heterogeneous nucleation and surface precipitation), dissolution of minerals (of importance in the weathering of rocks, in the formation of soils and sediments, and in the corrosion of structures and metals), and in the catalysis and photocatalysis of redox processes, are critically dependent on the properties of the surfaces (surface species and their strucutral identity). 

A better insight into the mechanisms of the individual steps in the formation of crystals would be of great help in explaining the creation and transformation of sedimentary deposits and biological precipitates. Valuable reviews are available on the principles of nucleation of crystals and the kinetics of precipitation and crystal growth (Zhang and Nancollas, 1990 Steefel and Van Cappellen, 1990 Van Cappellen, 1991). Only a few important considerations are summarized here to illustrate the wide scope of questions to be answered in order to predict rates and mechanisms of precipitation in natural systems. 

As the precursor, e.g., an amorphous phase, precipitates and brings down the supersaturation of the solution, the more stable phase to be precipitated is using the precursor phase as a substrate for its own precipitation (Steefel and Van Cappellen, 1990). A classical example that documents this principle is the precipitation of calcium phosphates, where a metastable calcium phosphate precursor phase is nucleated initially and is then replaced, in some instances via an intermediate phase, by apatite. (Nancollas, 1990 Steefel and Van Cappellen, 1990). 

It is interesting to note that many crystal poisons not only interfer with nucleation and the growth of crystals but may also retard their dissolution. As we have seen (Chapter 6), precipitation and dissolution of solids proceed by the attachment or detachment of ions most favorably at kink sites of the crystalline surface. Solutes such as organic substances, or phosphates may upon adsorption immobilize kinks and thus retard dissolution. 

Stumm, W., F. Furrer, and B. Kunz (1983), "The Role of Surface Coordination in Precipitation (Heterogeneous Nucleation) and Dissolution of Mineral Phases", Croat. Chem. Acta 56, 593-611. 

The geochemical fate of most reactive substances (trace metals, pollutants) is controlled by the reaction of solutes with solid surfaces. Simple chemical models for the residence time of reactive elements in oceans, lakes, sediment, and soil systems are based on the partitioning of chemical species between the aqueous solution and the particle surface. The rates of processes involved in precipitation (heterogeneous nucleation, crystal growth) and dissolution of mineral phases, of importance in the weathering of rocks, in the formation of soils, and sediment diagenesis, are critically dependent on surface species and their structural identity. 

Geometric effects coupled with diffusion and nucleation usually control the rates of all solids deposition phenomena. Such effects can be put to good use in the production of special products such as cellulose yarn (rayon), by the precipitation of cellulose in filament form as it emerges as sodium cellulose xanthate liquid from the spinnerets into a bath containing sulphuric acid, which extracts the sodium as sodium sulphate, and the carbon disulphide. In a similar manner, the fabrication of aromatic polyimide fibres is performed by dissolving the polymer in concentrated sulphuric acid and forcing the solution through spinnerets into water. 

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