Water metastable

Aluminum trifluoride trihydrate [15098-87-0], AIF. -3H20, appears to exist in a soluble metastable a-form as well as a less soluble P-form (3). The a-form can be obtained only when the heat of the reaction between alumina and hydrofluoric acid is controlled and the temperature of the reaction is kept below 25°C. Upon warming the a-form changes into a irreversible P-form which is insoluble in water and is much more stable. The P-form is commercially available. 

Halides. Gold(III) chloride [13453-07-1] can be prepared directiy from the elements at 200°C (167). It exists as the chlotine-bridged dimer, Au2Clg ia both the soHd and gas phases under an atmospheric pressure of chlorine at temperatures below 254°C. Above this temperature ia a chlorine atmosphere or at lower temperatures ia an iaert atmosphere, it decomposes first to AuCl [10294-29-8] and then to gold. The monochloride is only metastable at room temperature and slowly disproportionates to gold(0) and gold(III) chloride. The disproportionation is much more rapid ia water both for AuCl and the complex chloride, [AuCy, formed by iateraction with metal chlorides ia solution. 

Rapidly quenching to room temperature retains a maximum amount of alloying element (Cu) in soHd solution. The cooling rate required varies considerably with different alloys. For some alloys, air cooling is sufficiently rapid, whereas other alloys require water-quenching. After cooling, the alloy is in a relatively soft metastable condition referred to as the solution-treated condition. 

Calcium Pyrophosphates. As is typical of the pyrophosphate salts of multiple-charged or heavy-metal ions, the calcium pyrophosphates are extremely insoluble ia water. Calcium pyrophosphate exists ia three polymorphic modifications, each of which is metastable at room temperature. These are formed progressively upon thermal dehydration of calcium hydrogen phosphate dihydrate as shown below. Conversion temperatures indicated are those obtained from thermal analyses (22,23). The presence of impurities and actual processing conditions can change these values considerably, as is tme of commercial manufacture. 

Under equiUbrium vapor pressure of water, the crystalline tfihydroxides, Al(OH)2 convert to oxide—hydroxides at above 100°C (9,10). Below 280°—300°C, boehmite is the prevailing phase, unless diaspore seed is present. Although spontaneous nucleation of diaspore requires temperatures in excess of 300 °C and 20 MPa (200 bar) pressure, growth on seed crystals occurs at temperatures as low as 180 °C. For this reason it has been suggested that boehmite is the metastable phase although its formation is kinetically favored at lower temperatures and pressures. The ultimate conversion of the hydroxides to comndum [1302-74-5] AI2O2, the final oxide form, occurs above 360°C and 20 MPa. 

C), the yield of more than 90% purity L-glutamic acid crystals is very high. The glutamic acid crystals appear as both the metastable a- and stable P-forms. The a-form consists of prismatic crystals which are easy to filter, whereas the P-form needle crystals are difficult to filter. Control of crystallisation conditions of a-crystals are requited (13). The cmde L-glutamic acid crystals are suspended ia water and neutralized with caustic soda or sodium hydroxide. The solution is decolorized with activated carbon to produce a transparent solution and MSG is crystallized under reduced pressure. 

Tridymite. Tridymite is reported to be the siUca form stable from 870—1470°C at atmospheric pressure (44). Owing to the sluggishness of the reconstmctive tridymite—quart2 conversion, which requites minerali2ers such as sodium tungstate, alkah metal oxide, or the action of water under pressure, tridymite may persist as a metastable phase below 870°C. It occurs in volcanic rocks and stony meteorites. 

Fig. 11. Effects of pH in the colloidal siUca-water system (1), where A represents the point of zero charge regions B, C, and D correspond to metastable gels, rapid aggregation, and particle growth, respectively. Positive and negative correspond to the charges on the surface of the siUca particle.

Chemical stabilization involves removing the concentration of surface hydroxyls and surface defects, such as metastable three-membered rings, below a critical level so that the surface is not stressed by rehydroxylation in use. Thermal stabilization involves reducing the surface area sufficiently to enable the material to be used at a given temperature without reversible stmctural changes. The mechanisms of thermal and chemical stabilization are interrelated because of the extreme effects that surface hydroxyls and chemisorbed water have on stmctural changes. Full densification of gels, such as the... 

Solubihty data ia water are given ia Figure 5 and ia Table 9, solution pH ia Table 10, and the solubiUty ia organic solvents is given ia Table 7. Heats of solution ia water have been determined (68,73). The pentahydrate, ia contact with its aqueous solution, is metastable with respect to the tetrahydrate (kernite) at temperatures above 58.2°C and metastable to borax decahydrate below 60.6—60.8°C. Kernite can be slowly crystallised from a near saturate... 

Fig. 1.43 Schematic potential/pH diagram for a metal M in equilibrium with water in the absence of complexing species. Line a represents equations 1.117 and 1.122. Line b represents equations 1.118 and 1.123. Line c represents equations 1.119 and 1.124. The stable phases are marked in bold. The metastable phase is in parentheses. The broken line is an extrapolation of equation 1.123 and indicates possible metastable passivity...

On the other hand, a metastable-ion peak at m/e 88.1 (calculated, 88.0) is present in the mass spectrum of 11 (Figure 8) for the formation of m/e 129 from m/e 189, by loss of acetic acid. In the mass spectrum of the D20-exchanged analog, m/e 129 partially shifts to m/e 130 and partially stays at m/e 129. Metastable-ion peaks are also present at m/e 154.8 (calculated, 154.7) and m/e 97.3 (calculated, 97.3) for the loss of water from m/e 189 followed by the loss of ketene, to give an ion at m/e 129. Since m/e 171 from the loss of water remains at m/e 171, the loss of water must involve the hydroxyl hydrogens. Scheme 3 is an attempt to summarize this in terms of structures which are entirely... 

However, measurements of substituent effects supported the hypothesis that the aryl cation is a key intermediate in dediazoniations, provided that they were interpreted in an appropriate way (Zollinger, 1973a Ehrenson et al., 1973 Swain et al., 1975 a). We will first consider the activation energy and then discuss the influence of substituents, as well as additional data concerning the aryl cation as a metastable intermediate (kinetic isotope effects, influence of water acitivity in hydroxy-de-di-azoniations). Finally, the cases of dediazoniation in which the rate of reaction is first-order with regard to the concentration of the nucleophile will be critically evaluated. 

On the other hand, the large activation energy for the formation of sulfate from 8g and water makes it possible to prepare polysulfides as well as other reduced sulfur compounds as metastable products in aqueous solution at ambient conditions. 

The topographic contrast of the islands disappears above 80% RFl [72], and no islands can be observed after tip contact at this and higher humidity. These observations can be explained by assuming that the metastable islands formed by capillary condensation correspond to a second or higher layer of water above the first one (phase-I). As we shah see... 

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