Allotropy - States of Matter

Basic physical properties of sulfur, selenium, and tellurium are indicated in Table 1.3. Downward the sulfur sub-group, the metallic character increases from sulfur to polonium, so that whereas there exist various non-metallic allotropic states of elementary sulfur, only one allotropic form of selenium is (semi)metallic, and the (semi)metallic form of tellurium is the most common for this element. Polonium is a typical metal. Physically, this trend is reflected in the electrical properties of the elements oxygen and sulfur are insulators, selenium and tellurium behave as semiconductors, and polonium is a typical metallic conductor. The temperature coefficient of resistivity for S, Se, and Te is negative, which is usually considered 

Because of the conversion of orthorhombic sulfur to monoclinic form, the above values of melting points are difficult to observe, as the resulting allotropic mixture melts at only 115 C. Amorphous or plastic sulfur can be produced through the rapid cooling of molten sulfur. X-ray crystallographic studies show that the amorphous form may have a helical structure with eight atoms per turn. This form is metastable at room temperature and gradually reverts back to crystalline within hours to days but this conversion can be rapidly catalyzed. 

Trigonal selenium is variously called metallic gray or black selenium and occurs in lustrous hexagonal crystals, which melt at 220.5 °C. Its structure, which has no sulfur analogue, consists of infinite, unbranched helical chains. Its density, 4.82 g cm , is the highest of any form of the element. Trigonal selenium is a semiconductor (intrinsic p-type with a rather indirect transition at about 1.85 eV [5]), and its electronic and photoelectric properties are the basis for many industrial uses of this element. 

The trend toward more metallic character of the elements in Group 16 is complete at polonium, which has two allotropes, both with typically metallic structures a-cubic, which converts at 36 °C to P-rhombohedral (m.p. 254 C). 

Liquid tellurium boils at 990 °C to a golden yellow vapor, with density that corresponds to the molecular formula T 2- Likewise, in polonium vapor only P02 species are present. Clearly, the decreasing complexity of the solid state of the three elements Se, Te, and Po, as compared to sulfur, is reflected in the vapor state. 

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