Supersaturation solution

Once nuclei form in a supersaturated solution, they begin to grow by accretion and, as a result, the concentration of the remaining material drops. There is thus a competition for material between the processes of nucleation and of crystal growth. The more rapid the nucleation, the larger the number of nuclei formed before relief of the supersaturation occurs and the smaller the final crystal size. This, qualitatively, is the basis of what is known as von Weimam s law [86] ... 

It is a well-known fact that substances like water and acetic acid can be cooled below the freezing point in this condition they are said to be supercooled (compare supersaturated solution). Such supercooled substances have vapour pressures which change in a normal manner with temperature the vapour pressure curve is represented by the dotted line ML —a continuation of ML. The curve ML lies above the vapour pressure curve of the solid and it is apparent that the vapour pressure of the supersaturated liquid is greater than that of the solid. The supercooled liquid is in a condition of metastabUity. As soon as crystallisation sets in, the temperature rises to the true freezing or melting point. It will be observed that no dotted continuation of the vapour pressure curve of the solid is shown this would mean a suspended transformation in the change from the solid to the liquid state. Such a change has not been observed nor is it theoretically possible. 

Occasionally substances form supersaturated solutions from which the first crystals separate with difficulty this is sometimes caused by the presence of a little tar or viscous substance acting as a protective colloid. The following methods should be tried in order to induce crystallisation —... 

There are, however, practical limitations to minimizing RSS. Precipitates that are extremely insoluble, such as Fe(OH)3 and PbS, have such small solubilities that a large RSS cannot be avoided. Such solutes inevitably form small particles. In addition, conditions that yield a small RSS may lead to a relatively stable supersaturated solution that requires a long time to fully precipitate. For example, almost a month is required to form a visible precipitate of BaS04 under conditions in which the initial RSS is 5. ... 

Precipitation Heat Treatment. The supersaturated solution produced by the quench from the solution temperature is unstable, and the alloys tend to approach equiUbrium by precipitation of solute. Because the activation energies required to form equiUbrium precipitate phases are higher than those to form metastable phases, the soHd solution decomposes to form G-P zones at room temperature (natural aging). Metastable precursors to the equihbrium phases are formed at the temperatures employed for commercial precipitation heat treatments (artificial aging). 

Crystallization. Acidified aluminum sulfate solutions can be supercooled 10 °C or more below the saturation point. However, once nucleation begins, the crystallization rate is rapid and the supersaturated solution sets up. The onset of nucleation in a gentiy stirred supersaturated solution is marked by the appearance of silky, curling streamers of microscopic nuclei resulting from orientation effects of hydraulic currents on the thin, platelike crystals. Without agitation, nucleation in an acidified solution, in glass tubes, can yield extended crystalline membranes of such thinness to exhibit colors resulting from optical interference. 

In the absence of a suitable soHd phase for deposition and in supersaturated solutions of pH values from 7 to 10, monosilicic acid polymerizes to form discrete particles. Electrostatic repulsion of the particles prevents aggregation if the concentration of electrolyte is below ca 0.2 N. The particle size that can be attained is dependent on the temperature. Particle size increases significantly with increasing temperature. For example, particles of 4—8 nm in diameter are obtained at 50—100°C, whereas particles of up to 150 nm in diameter are formed at 350°C in an autoclave. However, the size of the particles obtained in an autoclave is limited by the conversion of amorphous siUca to quartz at high temperatures. Particle size influences the stabiUty of the sol because particles <7 nm in diameter tend to grow spontaneously in storage, which may affect the sol properties. However, sols can be stabilized by the addition of sufficient alkaU (1,33). 

Sodium borate solutions near the Na20 B202 ratio of maximum solubihty can be spray-dried to form an amorphous product with the approximate composition Na20 4B202 4H20 commonly referred to as sodium octaborate (64). This material dissolves rapidly in water without any decrease in temperature to form supersaturated solutions. Such solutions have found apphcation in treating ceUulosic materials to impart fire-retardant and decay-resistant properties (see Cellulose). 

Ammonium tetraborate tetrahydrate is prepared by crystallization from an aqueous solution of boric acid and ammonia having a B202 (NH4)20 ratio of 1.8 2.1. Ammonium pentaborate is similarly produced from an aqueous solution of boric acid and ammonia having a B202 (NH4)20 ratio of 5. Supersaturated solutions are easily formed and the rate of crystallization is proportional to the extent of supersaturation (130). A process for the production... 

StiU another possible role of supersaturation is that it affects the solution stmcture and causes the formation of clusters of solute molecules. These clusters may participate in nucleation, although the mechanism by which this would occur is not clear. Evidence of the existence of cluster formation in supersaturated solutions has been presented for citric acid (21) while others have examined the phenomenon in greater detail (22,23). 

Another type of crystallizer is the Oslo-type unit shown in Figure 24. In units of this type, the object is to form a supersaturated solution in the upper chamber and then reHeve the supersaturation through growth in the lower chamber. The use of the downflow pipe in the crystallizer provides good mixing in the growth chamber. 

Another method of fractional crystallization, in which advantage is taken of different ciystallization rates, is sometimes used. Thus, a solution saturated with borax and potassium chloride will, in the absence of borax seed ciystals, precipitate only potassium chloride on rapid coohng. The borax remains behind as a supersaturated solution, and the potassium chloride crystals can be removed before the slower borax crystalhzation starts. 

Crystal growth is a layer-by-layer process, and the retention time required in most commercial equipment to produce crystals of the size normally desired is on the order of 2 to 6 h. On the other hand, nucleation in a supersaturated solution can be generated in a fraction... 

In accordance with these data, ionic associates (lA) can be precipitated at phosphate concentrations more than 10 M. Below this concentration stabile supersaturated solutions of lA are formed. Colour of lA appeal s immediately after mixing of the solutions and remains constant during several hours. There is a new band in spectmm at 570-590 nm. Appearance of color is caused by formation of stable solid phase in the solution. 

The entire amount of the ammonium chloride-mandelic acid mixture may be boiled with the benzene but this gives a supersaturated solution of the acid in the benzene and much difficulty is met in the filtration. The solubility of mandelic acid in hot benzene is approximately i g. in 50 cc. 

The process of homogeneous nucleation is determined by the formation of stable nuclei in a supersaturated solution. 

Partiele formation ean also oeeur via breakage proeesses that start with existing partieles and form new, smaller, ones of varying sizes. Comminution is the generie name for partiele size reduetion and generation whilst secondary nuclea-tion oeeurs due to the presenee of existing erystals in supersaturated solutions. Thus, the same proeess ean oeeur within erystallizers giving rise to the more eomplex proeess of seeondary nueleation. 

Secondary nucleation is an important particle formation process in industrial crystallizers. Secondary nucleation occurs because of the presence of existing crystals. In industrial crystallizers, existing crystals in suspension induce the formation of attrition-like smaller particles and effectively enhance the nucleation rate. This process has some similarity with attrition but differs in one important respect it occurs in the presence of a supersaturated solution. 

In order to validate the predietions of the theoretieal analysis based on the SFM, Zauner and Jones (2000b) studied the effeet of reaetor seale (eapaeity) on the preeipitation of ealeium oxalate obtained from reaeting supersaturated solutions of ealeium ehloride CaCl2 and sodium oxalate Na2C204. The geometries of the 4.3 1 and 12 1 preeipitation reaetors are shown in Figure 8.2 with the experimental set-up shown in Figure 8.3. 

D. S. Noh, Y. Koh, I. S. Kang. Numerical solutions for shape evolution of a particle growing in axisymmetric flows of supersaturated solution. J Cryst Growth 183 427, 1998. 

Richards, et. al. s idea is to use a genetic algorithm to search through a space of a certain class of cellular automata rules for a local rule that best reproduces the observed behavior of the data. Their learning algorithm (which was applied specifically to sequential patterns of dendrites formed by NH4 Br as it solidifies from a supersaturated solution) starts with no a-priori knowledge about the physical system. R, instead, builds increasingly sophisticated models that reproduce the observed behavior. 

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