ALLOTROPIC

Many substances exist in two or more solid allotropic fomis. At 0 K, the themiodynamically stable fomi is of course the one of lowest energy, but in many cases it is possible to make themiodynamic measurements on another (metastable) fomi down to very low temperatures. Using the measured entropy of transition at equilibrium, the measured heat capacities of both fomis and equation (A2.1.73) to extrapolate to 0 K, one can obtain the entropy of transition at 0 K. Within experimental... 

The scope of tire following article is to survey the physical and chemical properties of tire tliird modification of carbon, namely [60]fullerene and its higher analogues. The entluisiasm tliat was triggered by tliese spherical carbon allotropes resulted in an epidemic-like number of publications in tire early to mid-1990s. In more recent years tire field of fullerene chemistry is, however, dominated by tire organic functionalization of tire highly reactive fullerene... 

EttI R, Chao I, Diederich F and Whetten R L 1991 Isolation of C-g, a chiral (Dg) allotrope of carbon Nature 353... 

Arsenic and antimony resemble phosphorus in having several allotropic modifications. Both have an unstable yellow allotrope. These allotropes can be obtained by rapid condensation of the vapours which presumably, like phosphorus vapour, contain AS4 and Sb4 molecules respectively. No such yellow allotrope is known for bismuth. The ordinary form of arsenic, stable at room temperature, is a grey metallic-looking brittle solid which has some power to conduct. Under ordinary conditions antimony and bismuth are silvery white and reddish white metallic elements respectively. 

White phosphorus is very reactive. It has an appreciable vapour pressure at room temperature and inflames in dry air at about 320 K or at even lower temperatures if finely divided. In air at room temperature it emits a faint green light called phosphorescence the reaction occurring is a complex oxidation process, but this happens only at certain partial pressures of oxygen. It is necessary, therefore, to store white phosphorus under water, unlike the less reactive red and black allotropes which do not react with air at room temperature. Both red and black phosphorus burn to form oxides when heated in air, the red form igniting at temperatures exceeding 600 K,... 

None of the common allotropic forms of these metals is affected by air unless they are heated, when aU burn to the (III) oxide. 

White and red phosphorus combine directly with chlorine, bromine and iodine, the red allotrope reacting in each case at a slightly higher temperature. The reactions are very vigorous and white phosphorus is spontaneously inflammable in chlorine at room temperature. Both chlorine and bromine first form a trihalide ... 

Oxygen, sulphur and selenium are known to exist in more than one allotropic form. 

This exists in two allotropic forms, oxygen, O2 and ozone, O3. 

Like sulphur, selenium exists in a number of allotropic forms. These include both crystalline, rhombic and monoclinic modifications... 

The metal looks like iron it exists in four allotropic modifications, stable over various temperature ranges. Although not easily attacked by air. it is slowly attacked by water and dissolves readily in dilute acids to give manganese(II) salts. The stable form of the metal at ordinary temperatures is hard and brittle—hence man ganese is only of value in alloys, for example in steels (ferroalloys) and with aluminium, copper and nickel. 

Carbon is found free in nature in three allotropic forms amorphous, graphite, and diamond. A fourth form, known as "white" carbon, is now thought to exist. Ceraphite is one of the softest known materials while diamond is one of the hardest. 

In 1824 Berzelius, generally credited with the discovery, prepared amorphous silicon by the same general method and purified the product by removing the fluosilicates by repeated washings. Deville in 1854 first prepared crystalline silicon, the second allotropic form of the element. 

Phosphorus exists in four or more allotropic forms white (or yellow), red, and black (or violet). Ordinary phosphorus is a waxy white solid when pure it is colorless and transparent. White phosphorus has two modifications alpha and beta with a transition temperature at -3.8oC. 

Sulfur is pale yellow, odorless, brittle solid, which is insoluble in water but soluble in carbon disulfide. In every state, whether gas, liquid or solid, elemental sulfur occurs in more than one allotropic form or modification these present a confusing multitude of forms whose relations are not yet fully understood. 

Gobalt is a brittle, hard metal, resembling iron and nickel in appearance. It has a metallic permeability of about two thirds that of iron. Gobalt tends to exist as a mixture of two allotropes over a wide temperature range. The transformation is sluggish and accounts in part for the wide variation in reported data on physical properties of cobalt. 

Selenium exists in several allotropic forms. Three are generally recognized, but as many as that have been claimed. Selenium can be prepared with either an amorphous or crystalline structure. The color of amorphous selenium is either red, in powder form, or black, in vitreous form. Crystalline monoclinic selenium is a deep red crystalline hexagonal selenium, the most stable variety, is a metallic gray. 

Strontium is found chiefly as celestite and strontianite. The metal can be prepared by electrolysis of the fused chloride mixed with potassium chloride, or is made by reducing strontium oxide with aluminum in a vacuum at a temperature at which strontium distills off. Three allotropic forms of the metal exist, with transition points at 235 and 540oC. 

Metallic polonium has been prepared from polonium hydroxide and some other polonium compounds in the presence of concentrated aqueous or anhydrous liquid ammonia. Two allotropic modifications are known to exist. 

The metal has a bright silvery metallic luster. Neodymium is one of the more reactive rare-earth metals and quickly tarnishes in air, forming an oxide that spalls off and exposes metal to oxidation. The metal, therefore, should be kept under light mineral oil or sealed in a plastic material. Neodymium exists in two allotropic forms, with a transformation from a double hexagonal to a body-centered cubic structure taking place at 863oC. 

Ytterbium has a bright silvery luster, is soft, malleable, and quite ductile. While the element is fairly stable, it should be kept in closed containers to protect it from air and moisture. Ytterbium is readily attacked and dissolved by dilute and concentrated mineral acids and reacts slowly with water. Ytterbium has three allotropic forms with transformation points at -13oC and 795oC. The beta form is a room-temperature, face-centered, cubic modification, while the... 

The metal has a silvery appearance and takes on a yellow tarnish when slightly oxidized. It is chemically reactive. A relatively large piece of plutonium is warm to the touch because of the energy given off in alpha decay. Larger pieces will produce enough heat to boil water. The metal readily dissolves in concentrated hydrochloric acid, hydroiodic acid, or perchloric acid. The metal exhibits six allotropic modifications having various crystalline structures. The densities of these vary from 16.00 to 19.86 g/cms. 

AUotropes. Systematic names for gaseous and liquid modifications of elements are sometimes needed. Allotropic modifications of an element bear the name of the atom together with the descriptor to specify the modification. The following are a few common examples ... 

Even at the lowest temperatures, a substantial pressure is required to soHdify helium, and then the soHd formed is one of the softest, most compressible known. The fluid—soHd phase diagrams for both helium-3 and helium-4 are shown in Eigure 1 (53). Both isotopes have three allotropic soHd forms an fee stmeture at high pressures, an hep stmeture at medium and low pressures, and a bcc stmeture over a narrow, low pressure range for helium-4 and over a somewhat larger range for helium-3. The melting pressure of helium-4 has been measured up to 24°C, where it is 11.5 GPa (115 kbar) (54). 

Thin films (qv) of lithium metal are opaque to visible light but are transparent to uv radiation. Lithium is the hardest of all the alkaH metals and has a Mohs scale hardness of 0.6. Its ductiHty is about the same as that of lead. Lithium has a bcc crystalline stmcture which is stable from about —195 to — 180°C. Two allotropic transformations exist at low temperatures bcc to fee at — 133°C and bcc to hexagonal close-packed at — 199°C (36). Physical properties of lithium are Hsted ia Table 3. 

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