Solid stability crystallinity

Some organic cation salts can be isolated as crystalline solids. Stability of carbenium ions is enhanced if the electron-deficient carbon is con jugated with olefin or aromatic groups or with atoms with unshared electron pairs (O, N, S). The positive charge is diflused over a larger region as a consequence. Examples of such initiators are hexachloroantimonate (SbCl ) salts of triphenyl methyl ((Cf,H5)3C ) and cyclohepirienyl (C7H ) carbenium ions. 

Sodium iodide [7681-82-5] Nal, occurs as colorless crystals or as a white crystalline solid. It has a salty and slightly bitter taste. In moist air, it gradually absorbs as much as 5% water, which causes caking or even Hquefaction (dehquescence). The soHd slowly becomes brown when exposed to air because some iodide is oxidized to iodine. Water solutions are neutral or slightly alkaline and gradually become brown for the same reason. Aqueous solutions are stabilized with respect to oxidation by raisiag the pH to 8—9.5 (see Iodine and iodine compounds). 

Salts are obtained by direct neutralization of the acid with appropriate oxides, hydroxides, or carbonates. Sulfamic acid is a diy, non-volatile, non-hygroscopic, colourless, white, crystalline solid of considerable stability. It melts at 205°, begins to decompose at 210°, and at 260° rapidly gives a mixture of SO2, SO3, N2, H2O, etc. It is a strong acid (dissociation constant 1.01 x 10 at 25° solubility 25gper 100g H2O) and, because of its physical form and stability, is a convenient standard for acidimetry. Over 50000 tonnes are manufactured annually and its principal applications are in formulations for metal cleaners, scale removers, detergents and stabilizers for chlorine in aqueous solution. 

This last reaction is typical of many in which F3CIO can act as a Lewis base by fluoride ion donation to acceptors such as MF5 (M = P, As, Sb, Bi, V, Nb, Ta, Pt, U), M0F4O, Sip4, BF3, etc. These products are all white, stable, crystalline solids (except the canary yellow PtFe ) and contain the [F2CIO] cation (see Fig. 17.26h) which is isostructural with the isoelectronic F2SO. Chlorine trifluoride oxide can also act as a Lewis acid (fluoride ion acceptor) and is therefore to be considered as amphoteric (p. 225). For example KF, RbF and CsF yield M [F4C10] as white solids whose stabilities increase with increasing size of M+. Vibration spectroscopy establishes the C4 structure of the anion (Fig. 17.29g). 

Solids and liquids are called condensed phases. The attractive forces in a condensed phase, either a solid or a liquid, tend to hold the molecules close together. In liquids, molecules are irregularly spaced and randomly oriented. In a crystalline solid, the molecules occupy regular positions, resulting in additional stability (relative to the liquid). 

The bisphosphonate - upon reduction with lithiumaluminum hydride in ether at 0°C - produced the amide functionalized primary bisphosphine (1) in good yields [45]. This reaction proceeded to reduce the amide group in 1 to produce the amine functionaUzed primary bisphosphine (2) in <5% yields. The amido bisprimary phosphine 1 is an air stable crystalline solid whereas the amine compound 2 is an oxidatively stable liquid. Separation of 1 and 2 in pure forms was achieved using coliunn chromatography. The amidic bisprimary phosphine 1 was crystallized from chloroform and exhibits remarkable stability not only in the solid state but also in solution as well. The crystal structure of the air stable primary his-phosphine 1 as shown in Fig. 1 is unprecedented to date. 

Storage stability Stable enough for use as a bomb filling even under tropical conditions. However, the agent darkens and deposits a crystalline solid in storage. 

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. 

H.F. Franzen, Physical Chemistry of Solids. Basic Principles of Symmetry and Stability of Crystalline Solids. World Scientific, 1994. 

When determining the solubility and dissolution rate of amorphous or partially crystalline solids, the metastability of these phases with respect to the highly crystalline solid must be considered. While the low diffusivity of the molecules in the solid state can kinetically stabilize these metastable forms, contact with the solution, for example during measurements of solubility and dissolution rate, or with the vapor, if the solid has an appreciable vapor pressure, may provide a mechanism for mass transfer and crystallization. Less crystalline material dissolves or sublimes whereas more crystalline material crystallizes out. The equilibrium solubility measured will therefore approach that of the highly crystalline solid. The initial dissolution rate of the metastable form tends to reflect its higher... 

The utilization of IR spectroscopy is very important in the characterization of pseudopolymorphic systems, especially hydrates. It has been used to study the pseudopolymorphic systems SQ-33600 [36], mefloquine hydrochloride [37], ranitidine HC1 [38], carbovir [39], and paroxetine hydrochloride [40]. In the case of SQ-33600 [36], humidity-dependent changes in the crystal properties of the disodium salt of this new HMG-CoA reductase inhibitor were characterized by a combination of physical analytical techniques. Three crystalline solid hydrates were identified, each having a definite stability over a range of humidity. Diffuse reflectance IR spectra were acquired on SQ-33600 material exposed to different relative humidity (RH) conditions. A sharp absorption band at 3640 cm-1 was indicative of the OH stretching mode associated with either strongly bound or crystalline water (Fig. 5A). The sharpness of the band is evidence of a bound species even at the lowest levels of moisture content. The bound nature of this water contained in low-moisture samples was confirmed by variable-temperature (VT) diffuse reflectance studies. As shown in Fig. 5B, the 3640 cm-1 peak progressively decreased in intensity upon thermal... 

On heating from a crystalline phase, DOBAMBC melts to form a SmC phase, which exists as the thermodynamic minimum structure between 76 and 95°C. At 95°C a thermotropic transition to the SmA phase occurs. Finally, the system clears to the isotropic liquid phase at 117°C. On cooling, the SmC phase supercools into the temperature range where the crystalline solid is more stable (a common occurrence). In fact, at 63°C a new smectic phase (the SmF) appears. This phase is metastable with respect to the crystalline solid such phases are termed monotropic, while thermodynamically stable phases are termed enantiotropic. The kinetic stability of monotropic LC phases is dependent upon purity of the sample and other conditions such as the cooling rate. However, the appearance of monotropic phases is typically reproducible and is often reported in the phase sequence on cooling. It is assumed that phases appearing on heating a sample are enantiotropic. 

Equation (5.2) also implies that a crystalline solid becomes mechanically unstable when an elastic constant vanishes. Explicitly, for a three-dimensional cubic solid the stability conditions can be expressed in terms of the elastic stiffness coefficients of the substance [9] as... 

Cyclotetramethylenetetranitramine or HMX (C4H8N808) is a white crystalline solid with a melting point of 285°C. HMX is superior to RDX in that its ignition temperature is higher and its chemical stability is greater. However, its explosive power is... 

TATB or 1,3,5-triamino-2,4,6-trinitrobenzene (C6H6N6Oe) is a yellow-brown crystalline solid that has excellent thermal stability and is known as a heat-resistant explosive. TATB has a decomposition point of 325°C. Its molecular arrangement provides lubricating and elastic properties. 

A general presentation and discussion of the origin of structure of crystalline solids and of the structural stability of compounds and solid solutions was given by Villars (1995) and Pettifor (1995). For an introduction to the electronic structure of extended systems, see Hoffmann (1987, 1988). In this chapter a brief sampling of some useful semi-empirical correlations and, respectively, of methods of classifying (predicting) phase and structure formation will be summarized. 

Imidazolin-2-ylidenes of type 5 are normally obtained as colorless, diamagnetic, crystalline solids with surprisingly high melting points. In the absence of air and moisture, they exhibit a remarkable stability and even some air-stable derivatives... 

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