Supersaturated solutions, definition

Heat the test tube with its contents to obtain a transparent solution again, carefully cool it, and rub the inner wall of the test tube containing the solution with a glass rod. Explain the precipitation of crystals. Give definitions of saturated, unsaturated, and supersaturated solutions. 

The microscopic image shows a juxtaposition of differently orientated areas whose sizes, varying between a few microns and several tens of microns, are associated particularly with the elementary composition of the initial carbonaceous material (4, 18, 19). The formation of a texture of this type, often called a mosaic structure, can be compared (20) to the crystallization of a supersaturated solution areas, each characterized by a definite orientation, develop from nuclei up to the total consumption of the isotropic material surrounding them. 

Although most additives that have been studied retard growth on all faces of the crystal, there are some which definitely promote growth on certain faces. For example, repeated recrystallization of lactose removes growth-promoting trace substances, so that crystal growth is much slower in supersaturated solutions of this lactose than in less purified solutions. The tendency toward spontaneous nucleation is also lowered upon repeated recrystallization. 

Note that this definition requires a saturated solution to be at equilibrium with undissolved solid. Substances that are more soluble at high temperature than at low temperature can sometimes form what are called supersaturated solutions, which contain a greater-than-equilibrium amount of solute. For example, when a saturated solution of sodium acetate is prepared at high temperature and then cooled slowly, a supersaturated solution results, as shown in Figure 11.5. Such a solution is unstable, however, and precipitation occurs when a tiny seed crystal of sodium acetate is added to initiate crystallization. 

Supersaturated homogeneous solutions are thus metastable, and the metastability decreases with increasing supersaturation. In other words, nucleation starts after the solute concentration has exceeded a definite value, and then solute molecules form aggregates or clusters. If, however, the crystals are placed in a supersaturated solution, the solution eventually attains equilibrium after the growth of the crystals upon crystallization. 

The process of crystallization or precipitation involves the nucleation and growth of crystals (particles) from a supersaturated solution and is often followed by the agglomeration of crystals. Supersaturation is the driving force for precipitation, which is defined by the difference between the real solute concentration c and equilibrium solute concentration c P,T) at given pressure and temperature. The strict definition of supersaturation is linked to the difference of chemical potential Ap ... 

In some circumstances, solutions can be prepared that contain more solute than needed for a saturated solution at a particular temperature. These solutions are said to be supersaturated. However, we must qualify this definition by noting that a supersaturated solution is unstable. Disturbances, such as jarring, stirring, scratching the walls of the container, or dropping in a seed crystal, cause the supersaturation to return to saturation, releasing heat. When a supersaturated solution is disturbed, the excess solute crystallizes out rapidly, returning the solution to a saturated state. 

Definitions. Define briefly (a) mole fraction, (b) molality, (c) molarity, (d) solubility, (e) saturated solution, (f) supersaturated solution, (g) ideal solution, (h) activity, (i) colligative property, (j) freezing-point depression, (k) osmotic pressure. 

When a process is continuous, nucleation frequently occurs in the presence of a seeded solution by the combined effec ts of mechanical stimulus and nucleation caused by supersaturation (heterogeneous nucleation). If such a system is completely and uniformly mixed (i.e., the product stream represents the typical magma circulated within the system) and if the system is operating at steady state, the particle-size distribution has definite hmits which can be predic ted mathematically with a high degree of accuracy, as will be shown later in this section. 

This observation is in accordance with the phenomena of the crystallization in the resolution operation mentioned above in the following points. There are no clear, definite critical supersaturations above which nucleation of D-threonine occurs. Ohtsuki (2), however, reported supersolubility curve for this system, who gave the value of the supersaturation width At=7 C at 50 C. Their definition of the metastablllty was that no nucleation of the enantiomer other than seeded one was observed for two hours of resolution experiments. According to this definition, the supersolubility can be determined to lie somewhere between At=8 and 5 C from the present experimental data, this being in agreement with his result. If the crystallization proceeds further, however, D-threonine crystals may start to crystallize from the solution even if the initial supersaturation is 5 C. In this sense it is no longer the metastablllty limit. 

Precipitation of ferric hydroxide gel was also observed in the preparation of spindlelike hematite (a-Fe203) particles in a dilute ferric chloride solution in the presence of phosphate (9). In this case, however, the positive role of the gel was not definite since similar uniform hematite paricles were obtained as well in homogeneous systems in the presence of the same anions (9). Also, Hamada and Matijevic (10) prepared uniform particles of pseudocubic hematite by hydrolysis of ferric chloride in aqueous solutions of alcohol (10-50%) at I00°C for several days. In this reaction, it was observed that acicular crystals of (3-FeOOH precipitated first, and then they dissolved with formation of the pseudocubic particles of hematite. The intermediate P-FeOOH appears to work as a reservoir of the solute to maintain an ideal supersaturation for the nucleation and growth of the hematite. Since the (3-FeOOH as an intermediate and the pseudocubic shape tire not peculiar to the alcohol/water medium... 

The definition of the saturation ratio originates from the description of the driving force for precipitation from stoichiometric solutions in which S = ajaK. cjcv where a and c,. are the mean ion activities in a supersaturated and equilibrium solution, respectively, and c and ct are the corresponding concentrations, e.g. the saturation ratio of a silver chloride solution is... 

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