Crystalline solids atomic structure

Figure 4.5. Atomic Structure of Glass vs. Crystalline-Solid Atomic Structure.

All these works of art include an orderly arrangement of a particular object, similar to the arrangement of structural units in a crystalline solid atoms, ions, or molecules. 

The ordered mesoporous materials (or crystalline mesoporous materials) such as MCM-41 (MCM stands for Mobil composite of matter), MCM-48 and SBA-15 (SBA stands for University of California, Santa Barbara) are a new generation of materials that are different from nonordered (amorphous) mesoporous materials. They are amorphous and not ordered at the atomic level from a classical crystallographic view point, but their regular channels or pores are ordered at the nanometer level. Because of this, these materials have certain characteristics of crystalline solids. Their structural information can be obtained by diffraction methods and other structural analysis techniques. The discovery of periodic mesoporous structures is a major advance in composite organic-inorganic materials synthesis. 

The group 18 elements are the noble gases (see Chapter 17), and Table 5.1 lists selected physical data for these elements. Each element (with the exception of helium, see footnote in Table 5.1) solidifies only at low temperatures. The enthalpy changes accompanying the fusion processes are very small, consistent with the fact that only weak van der Waals forces operate between the atoms in the solid state. In the crystalline solid, ccp structures are adopted by each of solid Ne, Ar, Kr and Xe. 

A FIGURE 3.5 Types of solid matter (a) In a crystalline solid, atoms or molecules occupy specific positions to create a well-ordered, three-dimensional structure, (b) In an amorphous solid, atoms do not have any long-range order. 

The three-dimensional synnnetry that is present in the bulk of a crystalline solid is abruptly lost at the surface. In order to minimize the surface energy, the themiodynamically stable surface atomic structures of many materials differ considerably from the structure of the bulk. These materials are still crystalline at the surface, in that one can define a two-dimensional surface unit cell parallel to the surface, but the atomic positions in the unit cell differ from those of the bulk structure. Such a change in the local structure at the surface is called a reconstruction. 

EXAFS is a nondestructive, element-specific spectroscopic technique with application to all elements from lithium to uranium. It is employed as a direct probe of the atomic environment of an X-ray absorbing element and provides chemical bonding information. Although EXAFS is primarily used to determine the local structure of bulk solids (e.g., crystalline and amorphous materials), solid surfaces, and interfaces, its use is not limited to the solid state. As a structural tool, EXAFS complements the familiar X-ray diffraction technique, which is applicable only to crystalline solids. EXAFS provides an atomic-scale perspective about the X-ray absorbing element in terms of the numbers, types, and interatomic distances of neighboring atoms. 

For a substance to dissolve in a liquid, it must be capable of disrupting the solvent structure and permit the bonding of solvent molecules to the solute or its component ions. The forces binding the ions, atoms or molecules in the lattice oppose the tendency of a crystalline solid to enter solution. The solubility of a solid is thus determined by the resultant of these opposing effects. The solubility of a solute in a given solvent is defined as the concentration of that solute in its saturated solution. A saturated solution is one that is in equilibrium with excess solute present. The solution is still referred to as saturated, even... 

FIGURE 5-16 Crystalline solids have well-defined faces and an orderly internal structure. Each face of the crystal is formed by the top plane of an orderly stack of atoms, molecules, or ions. 

A crystalline solid is a solid in which the atoms, ions, or molecules lie in an orderly array (Fig. 5.16). A crystalline solid has long-range order. An amorphous solid is one in which the atoms, ions, or molecules lie in a random jumble, as in butter, rubber, and glass (Fig. 5.17). An amorphous solid has a structure like that of a frozen instant in the life of a liquid, with only short-range order. Crystalline solids typically have flat, well-defined planar surfaces called crystal faces, which lie at definite angles to one another. These faces are formed by orderly layers of atoms (Box 5.1). Amorphous solids do not have well-defined faces unless they have been molded or cut. 

Six members of this series could be isolated in modest yields as highly air-sensitive, dark blue or dark purple crystalline solids for which analytical, spectroscopic, and single-crystal X-ray analyses were fully consistent with the side-on-biidged N2 structures shown in Scheme 102. These complexes show unusual structural features as well as a unique reactivity. An extreme degree of N = N bond elongation was manifested in rf(N-N) values of up to 1.64 A, and low barriers for N-atom functionalization allowed functionalization such as hydrogenation, hydrosilylation, and, for the first time, alkylation with alkyl bromides at ambient temperature. ... 

Crystalline solids are built up of regular arrangements of atoms in three dimensions these arrangements can be represented by a repeat unit or motif called a unit cell. A unit cell is defined as the smallest repeating unit that shows the fuU symmetry of the crystal structure. A perfect crystal may be defined as one in which all the atoms are at rest on their correct lattice positions in the crystal structure. Such a perfect crystal can be obtained, hypothetically, only at absolute zero. At all real temperatures, crystalline solids generally depart from perfect order and contain several types of defects, which are responsible for many important solid-state phenomena, such as diffusion, electrical conduction, electrochemical reactions, and so on. Various schemes have been proposed for the classification of defects. Here the size and shape of the defect are used as a basis for classification. 

Table 8.53 shows the main features of XAS. The advantages of EXAFS over diffraction methods are that the technique does not depend on long-range order, hence it can always be used to study local environments in amorphous (and crystalline) solids and liquids it is atom specific and can be sensitive to low concentrations of the target atom (about 100 ppm). XAS provides information on interatomic distances, coordination numbers, atom types and structural disorder and oxidation state by inference. Accuracy is 1-2% for interatomic distances, and 10-25 % for coordination numbers. 

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. 

Molecules having the same composition but different structures are called isomers. The corresponding phenomenon for crystalline solids is called polymorphism. The different structures are the modifications or polymorphic forms. Modifications differ not only in the spatial arrangement of their atoms, but also in their physical and chemical properties. The structural differences may comprise anything from minor variations in the orientation of molecules up to a completely different atomic arrangement. 

An enormous variety of solvates associated with many different kinds of compounds is reported in the literature. In most cases this aspect of the structure deserved little attention as it had no effect on other properties of the compound under investigation. Suitable examples include a dihydrate of a diphosphabieyclo[3.3.1]nonane derivative 29), benzene and chloroform solvates of crown ether complexes with alkyl-ammonium ions 30 54>, and acetonitrile (Fig. 4) and toluene (Fig. 5) solvates of organo-metallic derivatives of cyclotetraphosphazene 31. In most of these structures the solvent entities are rather loosely held in the lattice (as is reflected in relatively high thermal parameters of the corresponding atoms), and are classified as solvent of crystallization or a space filler 31a). However, if the geometric definition set at the outset is used to describe clathrates as crystalline solids in which guest molecules... 

Secondly, for some crystalline systems, the structure obtained by diffraction techniques may be incomplete. For example, in some cases the diffraction data may not reveal dynamic aspects of the solid-state structure (as in the case of fluxional organo-metallics) and in others it may not be possible to distinguish clearly between different atoms (as for example 27A1 and 29Si in zeolites) and a combination of the NMR and x-ray data will yield a more complete and meaningful description of the structure. 

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