Metastable substance

Glasses typically are metastable substances. Like crystalline solids they exhibit macroscopic form stability, but because of their structures and some of their physical properties they must be considered as liquids with a very high viscosity. Their transition to a thermodynamically more stable structure can only be achieved by extensive atomic movements, but atom mobility is severely hindered by cross-linking. 

The modern industrial iron catalyst is a nanostructured metastable substance, which is formed during the surprisingly complex synthesis of the oxide precursor. 

The modern industrial iron catalyst is a nanostructmed metastable substance, which is formed during the sm-prisingly complex synthesis of the oxide precursor.This differs significantly from pure iron especially in the mesoscopic area despite the similarities in the local structme. Its metastability is the reason for its sensitivity towards thermal overstress dm-ing activation and oxidation of the activated material and confirms the complex structme of this seemingly very simple ammonia iron. 

Many substances exist in two or more solid allotropic fomis. At 0 K, the themiodynamically stable fomi is of course the one of lowest energy, but in many cases it is possible to make themiodynamic measurements on another (metastable) fomi down to very low temperatures. Using the measured entropy of transition at equilibrium, the measured heat capacities of both fomis and equation (A2.1.73) to extrapolate to 0 K, one can obtain the entropy of transition at 0 K. Within experimental... 

Figure A2.5.1. Schematic phase diagram (pressure p versus temperature 7) for a typical one-component substance. The full lines mark the transitions from one phase to another (g, gas liquid s, solid). The liquid-gas line (the vapour pressure curve) ends at a critical point (c). The dotted line is a constant pressure line. The dashed lines represent metastable extensions of the stable phases.

A scintillator, sometimes known as the Daly detector, is an ion collector that is especially useful for studies on metastable ions. The principle of operation is illustrated in Figure 28.4. As with the first dynode of an electron multiplier, the arrival of a fast ion causes electrons to be emitted, and they are accelerated toward a second dynode. In this case, the dynode consists of a substance (a scintillator) that emits photons (light). The emitted light is detected by a commercial photon... 

The importance of linked scanning of metastable ions or of ions formed by induced decomposition is discussed in this chapter and in Chapter 34. Briefly, linked scanning provides information on which ions give which others in a normal mass spectrum. With this sort of information, it becomes possible to examine a complex mixture of substances without prior separation of its components. It is possible to look highly specifically for trace components in mixtures under circumstances in which other techniques could not succeed. Finally, it is possible to gain information on the molecular structures of unknown compounds, as in peptide and protein sequencing (see Chapter 40). 

The study of metastable ions concerns substances that have been ionized by electrons and have undergone fragmentation. The stable molecular ions that are formed by soft ionization methods (chemical ionization. Cl field ionization, FI) need a boost of extra energy to make them fragment, but in such cases other methods of investigation than linked scanning are generally used. 

By measuring a mass spectrum of normal ions and then finding the links between ions from the metastable ions, it becomes easier to deduce the molecular structure of the substance that was ionized originally. 

Metastable ions are useful for determining the paths by which molecular ions of an unknown substance have decomposed to give fragment ions. By retracing these fragmentation routes, it is often possible to deduce some or all of the molecular structure of the unknown. 

Along with the normal, routine mass spectrum, the resulting metastable ion connections often supply enough information to allow a structure of an unknown substance to be deduced or to confirm the identity of one substance with another by comparison with their metastable ion behavior. 

Automated linked scanning of metastable ions is valuable for deducing a whole or partial molecular structure of an unknown substance. 

Acetamide [60-35-5] C2H NO, mol wt 59.07, is a white, odorless, hygroscopic soHd derived from acetic acid and ammonia. The stable crystalline habit is trigonal the metastable is orthorhombic. The melt is a solvent for organic substances it is used ia electrochemistry and organic synthesis. Pure acetamide has a bitter taste. Unknown impurities, possibly derived from acetonitrile, cause its mousy odor (1). It is found ia coal mine waste dumps (2). 

The shape of the equilibrium line, or solubility curve, is important in determining the mode of crystallization to be employed in order to crystallize a particular substance. If the curve is steep, i.e. the substance exhibits a strong temperature dependence of solubility (e.g. many salts and organic substances), then a cooling crystallization might be suitable. But if the metastable zone is wide (e.g. sucrose solutions), addition of seed crystal might be necessary. This can be desirable, particularly if a uniformly sized product is required. If on the other hand, the equilibrium line is relatively flat (e.g. for aqueous common salt... 

During precipitate ageing, a gradual transformation of an initially precipitated metastable phase into a final crystalline form often occurs. The metastable phase may be an amorphous precipitate, a polymorph of the final material, a hydrated species or some system-contaminated substance (Mullin, 2001). In 1896, Ostwald promulgated his rule of stages which states that an unstable... 

Let us consider a clathrate crystal consisting of a cage-forming substance Q and a number of encaged compounds ( solutes ) A, B,. . ., M. The substance Q has two forms a stable modification, which under given conditions may be either crystalline (a) or liquid (L), and a metastable modification (ft) enclosing cavities of different types 1,. . ., n which acts as host lattice ( solvent ) in the clathrate. The number of cavities of type i per molecule of Q is denoted by vt. For hydroquinone v — for gas hydrates of Structure I 1/23 and v2 = 3/23, for those of Structure II vx = 2/17 and v2 = 1/17. 

The glassy state does not represent a true equilibrium phase. Below the transition into a glass phase, the material is regarded as being in a metastable state. If one holds the substances at temperatures somewhat below the glass transition temperature, heat evolution can often be observed over time as the molecules slowly orient themselves into the lower energy, stable crystalline phase. 

Hulbert [77] discusses the consequences of the relatively large concentrations of lattice imperfections, including, perhaps, metastable phases and structural deformations, which may be present at the commencement of reaction but later diminish in concentration and importance. If it is assumed [475] that the rate of defect removal is inversely proportional to time (the Tammann treatment) and this effect is incorporated in the Valensi [470]—Carter [474] approach it is found that eqn. (12) is modified by replacement of t by In t. This equation is obeyed [77] by many spinel formation reactions. Zuravlev et al. [476] introduced the postulate that the rate of interface advance under diffusion control was also proportional to the amount of unreacted substance present and, assuming a contracting sphere (radius r) model... 

Rodebush has also implied that the accuracy with which very low temperatures can be measured is restricted by the uncertainty principle and by the nature of the substance under investigation. However, the accuracy of a temperature measurement is not limited in a serious way by the uncertainty principle for energy, inasmuch as the relation between the uncertainty in temperature and the length of time involved in the measurement depends on the size of the thermometer, and the uncertainty in temperature can be made arbitrarily small by sufficiently increasing the size of the thermometer we assume as the temperature of the substance the temperature of the surrounding thermostat with which it is in either stable or metastable equilibrium, provided that thermal equilibrium effective for the time of the investigation is reached. 

It is a well-known fact that substances like water and acetic acid can be cooled below the breezing 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 pressme curve is represented by the dotted line MU—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 soUd. The supercooled liquid is in a condition of metastability. As soon as crystallisation sets in, the temperatiure 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. 

The structures and properties of numerous substances that are thermodynamically unstable under normal conditions are only known because they are metastable and therefore can be studied under normal conditions. 

Fig. 5 Dissolution profiles obtained from the solubility determination of two polymorphic forms of the same drug substance. A is the stable form with solubility 31 mg/mL. B is the profile of the metastable form with solubility 46 mg/mL. This solubility (circles) is not achieved in many instances, and precipitation of the stable form occurs at a point beyond the solubility of A, and the trace becomes B. C is the hypothetical profile of the metastable form. 

E. L. Shock (1990) provides a different interpretation of these results he criticizes that the redox state of the reaction mixture was not checked in the Miller/Bada experiments. Shock also states that simple thermodynamic calculations show that the Miller/Bada theory does not stand up. To use terms like instability and decomposition is not correct when chemical compounds (here amino acids) are present in aqueous solution under extreme conditions and are aiming at a metastable equilibrium. Shock considers that oxidized and metastable carbon and nitrogen compounds are of greater importance in hydrothermal systems than are reduced compounds. In the interior of the Earth, CO2 and N2 are in stable redox equilibrium with substances such as amino acids and carboxylic acids, while reduced compounds such as CH4 and NH3 are not. The explanation lies in the oxidation state of the lithosphere. Shock considers the two mineral systems FMQ and PPM discussed above as particularly important for the system seawater/basalt rock. The FMQ system acts as a buffer in the oceanic crust. At depths of around 1.3 km, the PPM system probably becomes active, i.e., N2 and CO2 are the dominant species in stable equilibrium conditions at temperatures above 548 K. When the temperature of hydrothermal solutions falls (below about 548 K), they probably pass through a stability field in which CH4 and NII3 predominate. If kinetic factors block the achievement of equilibrium, metastable compounds such as alkanes, carboxylic acids, alkyl benzenes and amino acids are formed between 423 and 293 K. 

The hydration equilibria and phase transformations associated with a cytotoxic drug, BBR3576, have been studied [72]. The initially hydrated form could be made to undergo a phase transition where it lost approximately half of its water content, but the hemidesolvated product could be easily rehydrated to regenerate the starting material. If however, the original sample was completely dehydrated, the substance first formed a metastable anhydrate phase that underwent an irreversible exothermic transition to a new anhydrate crystal form. The hydration of this latter anhydrate form yielded a new hydrate phase whose structure was different from that of the initial material. 

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