Carbon crystal structure: diamond, graphite

Crystal Structure. Diamonds prepared by the direct conversion of well-crystallized graphite, at pressures of about 13 GPa (130 kbar), show certain unusual reflections in the x-ray diffraction patterns (25). They could be explained by assuming a hexagonal diamond stmcture (related to wurtzite) with a = 0.252 and c = 0.412 nm, space group P63 /mmc — Dgj with four atoms per unit cell. The calculated density would be 3.51 g/cm, the same as for ordinary cubic diamond, and the distances between nearest neighbor carbon atoms would be the same in both hexagonal and cubic diamond, 0.154 nm. 

Figure 7 shows the crystal structures of graphite, ordinary (cubic) diamond, and hexagonal diamond. The layers of carbon atoms lie in flat sheets in graphite, but in diamond the sheets are more wrinkled and lie closer together. Taken separately, the sheets are similar, but they may be stacked in various lateral positions and still have bonding between them. 

In chapter 3 we saw that carbon is found in nature as diamond and graphite with the same chemical composition C, but with completely different crystal structures. Diamond and graphite are two different solid phases or modifications which can convert into each other under the influence of certain temperatures and and which can exist simultaneously. 

In a similar way Kekule s theory of the benzene structure has been very completely established by the whole development of aromatic chemistry. The direct physical verification of the presumably planar arrangement was in this case more delayed. The crystal structure of graphite was examined almost as soon as that of diamond, but the early results were inconclusive. The structure is not determined by the symmetry alone, and the later detailed investigation by Bernal (1924) showed that the carbon atoms in the hexagonal net must be coplanar to within at least 0-38 A. Later work by Ott (1928) narrowed this limit still further. Although it is generally assumed that the atoms are coplanar, the exactness with which this can be established depends on... 

In addition to diamond and amorphous films, nanostructural forms of carbon may also be formed from the vapour phase. Here, stabilisation is achieved by the formation of closed shell structures that obviate the need for surface heteroatoms to stabilise danghng bonds, as is the case for bulk crystals of diamond and graphite. The now-classical example of closed-shell stabilisation of carbon nanostructures is the formation of C o molecules and other Fullerenes by electric arc evaporation of graphite [38] (Section 2.4). 

Graphite is another solid form of carbon. In contrast to the three-dimensional lattice structure of diamond, graphite has a layered structure. Each layer is strongly bound together but only weak forces exist between adjacent layers. These weak forces make the graphite crystal easy to cleave, and explain its softness and lubricating qualities. 

A number of chemical elements, mainly oxygen and carbon but also others, such as tin, phosphorus, and sulfur, occur naturally in more than one form. The various forms differ from one another in their physical properties and also, less frequently, in some of their chemical properties. The characteristic of some elements to exist in two or more modifications is known as allotropy, and the different modifications of each element are known as its allotropes. The phenomenon of allotropy is generally attributed to dissimilarities in the way the component atoms bond to each other in each allotrope either variation in the number of atoms bonded to form a molecule, as in the allotropes oxygen and ozone, or to differences in the crystal structure of solids such as graphite and diamond, the allotropes of carbon. 

The allotropy of carbon is due to variations in the crystal structure of the element. There are three allotropes of carbon graphite, diamond, and... 

White powder, hexagonal graphite-like form or cubic crystal cubic form similar to diamond in its crystal structure, and reverts to graphite form when heated above 1,700°C density 2.18 g/cm melts at 2,975°C (under nitrogen pressure) sublimes at 2,500°C at atmospheric pressure insoluble in water and acid attacked by hot alkalies and fused alkali carbonates not wetted by most molten metals or glasses. 

A table of crystal structures for the elements can be found in Table 1.11 (excluding the Lanthanide and Actinide series). Some elements can have multiple crystal structures, depending on temperature and pressure. This phenomenon is called allotropy and is very common in elemental metals (see Table 1.12). It is not unusual for close-packed crystals to transform from one stacking sequence to the other, simply through a shift in one of the layers of atoms. Other common allotropes include carbon (graphite at ambient conditions, diamond at high pressures and temperature), pure iron (BCC at room temperature, FCC at 912°C and back to BCC at 1394°C), and titanium (HCP to BCC at 882°C). 

Fig. 4. Computer-generated crystal structure models nop row. left to right) Cuprite, zinc-blende, rutile, perovskite. iridymite (second row) Cristobalite. potassium dihydrogen phosphate, diamond, pyrites, arsenic (third rowt Cesium chloride, sodium chloride, wurtzite. copper, niccolite (fourth row) Spinel, graphite, beryllium, carbon dioxide, alpha i uanz. [AT T Bel Laboratories ...

PI5.9 Boron nitride (BN) is isoelectronic with carbon and the B, C, and N atoms are about the same size. The result is that BN forms crystal structures similar to those of carbon, in that it crystallizes in a hexagonal (graphite-like hBN) and a cubic (diamond like cBN) structure. The data summarized at the end of the problem are available for the two forms of BN.17... 

The element carbon occurs in nature in two so-called allotropic forms, different crystal structures with the same chemical formula. In Fig. 3.13 the crystal structure of diamond and graphite have been represented. In diamond the C atoms are closely packed and each C atom is linked with four other C atoms. Thus a tight network of atoms is formed which, together with the binding strength, is responsible for the extreme hardness of diamond. Graphite has a layered structure and the space between the layers is relatively large. 

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