Crystals octahedral

A FIGURE 23.8 Octahedral Holes in Closest-Packed Crystals Octahedral holes are found in a closest-packed stmcture. The octahedral hole is surrounded by six of the atoms in the closest-packed structure. 

Mulliken symbols The designators, arising from group theory, of the electronic states of an ion in a crystal field. A and B are singly degenerate, E doubly degenerate, T triply degenerate states. Thus a D state of a free ion shows E and Tj states in an octahedral field. 

Addition of halide ions to aqueous copper(II) solutions can give a variety of halo-complexes for example [CuCl4] (yellow square-planar, but in crystals with large cations becomes a flattened tetrahedron) [CuClj] (red, units linked together in crystals to give tetrahedral or distorted octahedral coordination around each copper). 

Crystal structure of solids. The a-crystal form of TiCla is an excellent catalyst and has been investigated extensively. In this particular crystal form of TiCla, the titanium ions are located in an octahedral environment of chloride ions. It is believed that the stereoactive titanium ions in this crystal are located at the edges of the crystal, where chloride ion vacancies in the coordination sphere allow coordination with the monomer molecules. 

The and 72 states are broadened as a result of slight variations in the crystal field. The 72 and E states are sharper but the E state is split into two components, 29 cm apart, because of the slight distortion of the octahedral field. Population inversion and... 

Analytical Methods. Fluorite is readily identified by its crystal shape, usually simple cubes or interpenetrating twins, by its prominent octahedral cleavage, its relative softness, and the production of hydrogen fluoride when treated with sulfuric acid, evidenced by etching of glass. The presence of fluorite in ore specimens, or when associated with other fluorine-containing minerals, may be deterrnined by x-ray diffraction. 

Tris(2,4-pentanedionato)iron(III) [14024-18-1], Fe(C H202)3 or Fe(acac)3, forms mby red rhombic crystals that melt at 184°C. This high spin complex is obtained by reaction of iron(III) hydroxide and excess ligand. It is only slightly soluble in water, but is soluble in alcohol, acetone, chloroform, or benzene. The stmcture has a near-octahedral arrangement of the six oxygen atoms. Related complexes can be formed with other P-diketones by either direct synthesis or exchange of the diketone into Fe(acac)3. The complex is used as a catalyst in oxidation and polymerization reactions. 

Under most circumstances the equiUbtium shape of silicon crystals is octahedral, ie, the slowest-growing faces are (111). However, external conditions can radically alter that shape. For example, when growth is from the vapor, concentration gradients in the gas stream may affect the shape, and when growth is from the melt, the shape is primarily determined by thermal gradients in the melt. 

Silver bromide crystals, formed from stoichiometric amounts of silver nitrate and potassium bromide, are characterized by a cubic stmcture having interionic distances of 0.29 nm. If, however, an excess of either ion is present, octahedral crystals tend to form. The yellow color of silver bromide has been attributed to ionic deformation, an indication of its partially covalent character. Silver bromide melts at 434°C and dissociates when heated above 500°C. 

The crystal stmcture of photographic silver bromide is often octahedral. 

Crystal Morphology. Size, shape, color, and impurities are dependent on the conditions of synthesis (14—17). Lower temperatures favor dark colored, less pure crystals higher temperatures promote paler, purer crystals. Low pressures (5 GPa) and temperatures favor the development of cube faces, whereas higher pressures and temperatures produce octahedral faces. Nucleation and growth rates increase rapidly as the process pressure is raised above the diamond—graphite equiUbrium pressure. 

In ordinary diamond (2inc-blende stmcture) the wrinkled sheets He in the (111) or octahedral face planes of the crystal and are stacked in an ABCABC sequence. In real crystals, this ABCABC sequence continues indefinitely, but deviations do occur. For example, two crystals may grow face-to-face as mirror images the mirror is called a twinning plane and the sequence of sheets crossing the mirror mns ABCABCCBACBA. Many unusual sequences may exist in real crystals, but they are not easy to study. 

In a typical use of this method, a mixture of hydrogen and methane is fed into a reaction chamber at a pressure of about 1.33 kPa (10 torr). The substrate upon which diamond forms is at about 950°C and Hes about 1 cm away from a tungsten wine at 2200°C. Small diamond crystals, 1 mm or so in si2e, nucleate and grow profusely on the substrate at a rate around 0.01 mm /h to form a dark, rough polycrystalline layer with exposed octahedral or cubic faces, depending on the substrate temperature. 

Siace these masses of polycrystaUine diamond possess extensive diamond-to-diamond bonding, they have, ia contrast to siagle-crystal diamond, excellent crack resistance, siace any crack that begias ia oae crystal oa an easy cracking plane (parallel to an octahedral face) is halted by neighboring crystals that are unfavorably oriented for their propagation. 

This conceptual link extends to surfaces that are not so obviously similar in stmcture to molecular species. For example, the early Ziegler catalysts for polymerization of propylene were a-TiCl. Today, supported Ti complexes are used instead (26,57). These catalysts are selective for stereospecific polymerization, giving high yields of isotactic polypropylene from propylene. The catalytic sites are beheved to be located at the edges of TiCl crystals. The surface stmctures have been inferred to incorporate anion vacancies that is, sites where CL ions are not present and where TL" ions are exposed (66). These cations exist in octahedral surroundings, The polymerization has been explained by a mechanism whereby the growing polymer chain and an adsorbed propylene bonded cis to it on the surface undergo an insertion reaction (67). In this respect, there is no essential difference between the explanation of the surface catalyzed polymerization and that catalyzed in solution. 

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