Slow stabilization

There are two main types of must and wine treatment technologies for preventing bitartrate instability based on the phenomenon of low-temperature crystallization. The first uses traditional slow stabilization technology (Section... 

There are quite tangible differences in the performance of slow stabilization when wines have no protective colloids (cf. wine filtered on a membrane retaining any molecule with a molecular weight above 1000 Da). These effects ought to be even more spectacular in the case of rapid stabilization technologies. Indeed, the results presented in Figure 1.16 show the impact of prior preparation on the effectiveness of the contact process. 

Slow stabilization often causes loss of color (OD at 520 nm) in both red and white wines. It is therefore recommended that the length of treatment is reduced by adding small particles of cream of tartar, which are easier to maintain in a homogeneous suspension. Another advantage of seeding is that the wine may be maintained at a less cold temperature (—2°C instead of -4°C). 

Barium, calcium, and strontium salt-based stabilizers belong to the so-called slow stabilizer group. This is illustrated for barium salts as compared to other PVC stabilizers, as shown in Fig. 9.3. Slow stabilizers are never used alone but always in combination with cadmium or zinc salt-based stabilizers. 

The energetics and kinetics of film formation appear to be especially important when two or more solutes are present, since now the matter of monolayer penetration or complex formation enters the picture (see Section IV-7). Schul-man and co-workers [77, 78], in particular, noted that especially stable emulsions result when the adsorbed film of surfactant material forms strong penetration complexes with a species present in the oil phase. The stabilizing effect of such mixed films may lie in their slow desorption or elevated viscosity. The dynamic effects of surfactant transport have been investigated by Shah and coworkers [22] who show the correlation between micellar lifetime and droplet size. More stable micelles are unable to rapidly transport surfactant from the bulk to the surface, and hence they support emulsions containing larger droplets. 

In slow coagulation, particles have to diffuse over an energy barrier (see the previous section) in order to aggregate. As a result, not all Brownian particle encounters result in aggregation. This is expressed using the stability ratio IV, defined as... 

The ketone is added to a large excess of a strong base at low temperature, usually LDA in THF at -78 °C. The more acidic and less sterically hindered proton is removed in a kineti-cally controlled reaction. The equilibrium with a thermodynamically more stable enolate (generally the one which is more stabilized by substituents) is only reached very slowly (H.O. House, 1977), and the kinetic enolates may be trapped and isolated as silyl enol ethers (J.K. Rasmussen, 1977 H.O. House, 1969). If, on the other hand, a weak acid is added to the solution, e.g. an excess of the non-ionized ketone or a non-nucleophilic alcohol such as cert-butanol, then the tautomeric enolate is preferentially formed (stabilized mostly by hyperconjugation effects). The rate of approach to equilibrium is particularly slow with lithium as the counterion and much faster with potassium or sodium. 

Inhibitors slow or stop polymerization by reacting with the initiator or the growing polymer chain. The free radical formed from an inhibitor must be sufficiently unreactive that it does not function as a chain-transfer agent and begin another growing chain. Benzoquinone is a typical free-radical chain inhibitor. The resonance-stabilized free radical usually dimerizes or disproportionates to produce inert products and end the chain process. 

Until now we have been discussing the kinetics of catalyzed reactions. Losses due to volatility and side reactions also raise questions as to the validity of assuming a constant concentration of catalyst. Of course, one way of avoiding this issue is to omit an outside catalyst reactions involving carboxylic acids can be catalyzed by these compounds themselves. Experiments conducted under these conditions are informative in their own right and not merely as means of eliminating errors in the catalyzed case. As noted in connection with the discussion of reaction (5.G), the intermediate is stabilized by coordination with a proton from the catalyst. In the case of autoprotolysis by the carboxylic acid reactant, the rate-determining step is probably the slow reaction of intermediate [1] ... 

Diketene is a flammable Hquid with a flash point of 33°C and an autoignition temperature of 275°C. It decomposes rapidly above 98°C with slow decomposition occurring even at RT. The vapors are denser than air (relative density 2.9, air air = 1). The explosive limits in air are 2—11.7 vol % (135). In case of fire, water mist, light and stabilized foam, as well as powder of the potassium or ammonium sulfate-type should be used. Do not use basic extinguisher powders and do not add water to a closed container. 

Defoamers. Foam is a common problem in papermaking systems (27). It is caused by surface-active agents which are present in the pulp slurry or in the chemical additives. In addition, partially hydrophobic soHd materials can function as foam stabilizers. Foam can exist as surface foam or as a combination of surface foam and entrained air bubbles. Surface foam usually can be removed by water or steam showers and causes few problems. Entrained air bubbles, however, can slow drainage of the stock and hence reduce machine speed. Another serious effect is the formation of translucent circular spots in the finished sheet caused by permanently entrained air. 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

Hydrolysis and Polycondensation. As shown in Figure 1, at gel time (step C), events related to the growth of polymeric chains and interaction between coUoids slow down considerably and the stmcture of the material is frozen. Post-gelation treatments, ie, steps D—G (aging, drying, stabilization, and densification), alter the stmcture of the original gel but the resultant stmctures aU depend on the initial stmcture. Relative rates, of hydrolysis, (eq. 2), and condensation, (eq. 3), determine the stmcture of the gel. Many factors influence the kinetics of hydrolysis and... 

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