Crystalline solids crystal lattice

Crystalline Solids Crystal Lattices and Unit Cells... 

A crystalline solid is never perfect in that all of tire lattice sites are occupied in a regular manner, except, possibly, at the absolute zero of temperature in a perfect crystal. Point defects occur at temperatures above zero, of which the principal two forms are a vacant lattice site, and an interstitial atom which... 

The ionic conductivities of most solid crystalline salts and oxides are extremely low (an exception are the solid electrolytes, which are discussed in Section 8.4). The ions are rigidly held in the crystal lattices of these compounds and cannot move under the effect of applied electric fields. When melting, the ionic crystals break down, forming free ions the conductivities rise drastically and discontinuously, in some cases up to values of over 100 S/m (i.e., values higher than those of the most highly conducting electrolyte solutions). 

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. 

Diffusion and migration in solid crystalline electrolytes depend on the presence of defects in the crystal lattice (Fig. 2.16). Frenkel defects originate from some ions leaving the regular lattice positions and coming to interstitial positions. In this way empty sites (holes or vacancies) are formed, somewhat analogous to the holes appearing in the band theory of electronic conductors (see Section 2.4.1). 

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... 

A polymorph is a solid crystalline phase of a compound resulting from the possibility of at least two different crystal lattice arrangements of that compound in the solid state [42], Polymorphs of a compound are, however, identical in the liquid and vapor states. They usually melt at different temperatures but give melts of identical composition. Two polymorphs of a compound may be as different in structure and properties as crystals of two different compounds [43,44], Apparent solubility, melting point, density, hardness, crystal shape, optical and electrical properties, vapor pressure, etc. may all vary with the polymorphic form. The polymorphs that are produced depend upon factors such as storage temperature, recrystallization solvent, and rate of cooling. Table 2 suggests the importance of polymorphism in the field of pharmaceutics [45],... 

When in solid solution in the solid state, an impurity will alter the crystallinity by introducing impurity defects into the crystal lattice, thereby changing the thermodynamic and other physical properties of the solid, including the solubility and dissolution rate [2,37]. Prolonged equilibration of the solid state with the saturated solution, however, usually leads to recrystallization of the solute and to a consequent return of the crystallinity and the measured solubility of the solid state to that of the pure, highly crystalline solid. 

In ultra pure crystalline silicon, there are no extra electrons in the lattice that can conduct an electric current. If however, the silicon becomes contaminated with arsenic atoms, then there will be one additional electron added to the silicon crystal lattice for each arsenic atom that is introduced. Upon heating, some of those "extra electrons will be promoted into the conduction band of the solid. The electrons that end up in the conduction band are able to move freely through the structure. In other words, the arsenic atoms increase the conductivity of the solid by providing additional electrons that can carry a current when they are promoted into the conduction band by thermal excitation. Thus, by virtue of having extra electrons in the lattice, silicon contaminated with arsenic will exhibit greater electrical conductance than pure silicon at elevated temperatures. 

Gas hydrates are crystalline compounds in which smaller gas molecules (<0.9 nm) are encaged inside the lattices of hydrogen-bonded ice crystals. The gas molecules in the crystalline solids are effectively compressed, volumetrically, by a factor of 164. A comprehensive review of the physical and chemical properties of gas hydrates can be found in Sloan (1998, 2003). 

Crystalline solids display a very regular ordering of the particles in a three-dimensional structure called the crystal lattice. In this crystal lattice there are repeating units called unit cells. See your textbook for diagrams of unit cells. 

The crystal lattice of a crystalline solid is the regular ordering of the unit cells. 

Crystal lattice The regular, repeating framework created by atoms, ions, or molecules constituting a crystalline solid. 

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