Tellurium chains

A more complicated model has been used with success by Cutler and others, in which selenium and tellurium chains are broken with increasing temperature, giving rise to dangling bonds in equilibrium with valence alternation pairs this is described in Section 6. 

The subhalides of tellurium are an especially important class of solid state compounds, and they have been the subject of intensive studies, so that a rather complete picture of their chemistry and their properties has been obtained in recent years. Because of their high tellurium content they contain fragments of the homonuclear tellurium chains their modified tellurium structures are of great current interest with respect to possibly significant physical properties. Consequently, the results of various investigations on the synthesis of the compounds, on phase analysis by thermal methods, on crystal growth, on the structures, on spectroscopic, thermodynamic, optical, photoelectric, electrochemical properties have been reported in the last two decades. In a comprehensive review (237) all significant results are reported and discussed in detail so that the present chapter will be restricted to some selected and chemically important features. 

The largest number of selenium atoms in covalent selenium chain compounds isolated so far appears to be three, and even so, the representative compounds known are relatively few in number. In the case of tellurium, the maximum number is two. Rbeinboldt (191) has recently reviewed preparative methods for di- and triselenides, ditellurides, and compounds containing mixed sulfur-selenium and sulfur-tellurium chains. 

Tellurium is diamagnetic below its melting point. Its intrinsic electrical resistivity at room temperature is about 0.25 ohmcm, when the current is parallel to the i -axis, and decreases with increasing temperature and pressure. The element forms a continuous range of isomorphous solutions with selenium, consisting, in the soHd state, of chains of randomly alternating Se and Te atoms. 

Figure 16.1 Structures of various allotropes of selenium and the structure of crystalline tellurium (a) the Seg unit in a- fi- and y-red selenium (b) the helical Se chain along the c-axis in hexagonal grey selenium (c) the similar helical chain in crystalline tellurium shown in perspective and (d) projection of the tellurium structure on a plane perpendicular to the c-axis.

Tellurium has only one crystalline form and this is composed of a network of spiral chains similar to those in hexagonal Se (Fig. 16.1c and d). Although the intra-chain Te-Te distance of 284 pm and the c dimension of the crystal (593 pm) are both substantially greater than for Scjt (as expected), nevertheless the closest interatomic distance between chains is almost identical for the 2 elements (Te Te 350 pm). Accordingly the elements form a continuous range of solid solutions in which there is a random... 

Sulfide ores usually contain small amounts of mercury, arsenic, selenium, and tellurium, and these impurities volatilize during the ore treatment. All the volatilized impurities, with the exception of mercury, are collected in the dust recovery systems. On account of its being present in low concentrations, mercury is not removed by such a system and passes out with the exit gases. The problem of mercury contamination is particularly pertinent to zinc plants since the sulfidic ores of zinc contain traces of mercury (20-300 ppm). The mercury traces in zinc sulfide concentrates volatilize during roasting and contaminate the sulfuric acid that is made from the sulfur dioxide produced. If the acid is then used to produce phosphatic fertilizers, this may lead to mercury entering the food chain as a contaminant. Several processes have been developed for the removal of mercury, but these are not yet widely adopted. 

Tellurium crystallizes isotypic to a-selenium. As expected, the Te-Te bonds in the chain (283 pm) are longer than in selenium, but the contact distances to the atoms of the adjacent chains are nearly the same (Te- Te 349 pm). The shortening, as compared to the van der Waals distance, is more marked and the deviation from a regular octahedral coordination of the atoms is reduced (cf. Table 11.1, p. 111). By exerting pressure all six distances can be made to be equal (cf. Section 11.4). 

Under normal conditions an atom in elemental tellurium has coordination number 2 + 4. It has been known for a long time that pressure causes the interatomic distances to approximate each other until finally every tellurium atom has six equidistant neighboring atoms at 297 pm the structure (now called Te-IV) corresponds to /3-polonium. However, before this is attained, two other modifications (Te-II and Te-III) that are out of the ordinary appear at 4 GPa and 7 GPa. Te-II contains parallel, linear chains that are mutually shifted in such a way that each Te atom has, in addition to its two neighboring atoms within the chain... 

Selenium, tellurium, and polonium have not been as well studied as oxygen and sulfur, but they are known to form several long chains of atoms. Different lengths and arrangements of the chains cause differences in the way the elements look and react. 

Numerous Zind anions are formed by selenium and tellurium, with some of the more prominent species being Se 2 (where n 2, 4, 5, 6, 7, 9, or 11). The species with n = 11 contains two rings that have five and six members that are joined by a selenium atom. Those with smaller numbers of selenium atoms generally consist of zigzag chains. Tellurium forms an extensive series of polyanions that are present in such species as NaTe (n = 1 to 4). One tellurium anion contains the Hg4Te124 ion, but other species such as [( lg2Tes) 2 are also known, such as the Te122 anion that is present in some cases where the cation is a +1 metal. 

A new structure type is found for Ag2Hg(Se03)2. Both Ag+ and Hg2+ ions are in octahedral coordination in this compound.137 The polyhedra are linked by the pyramidal shaped selenite anions.138 In the crystal structure of the red tellurate Ag2Hg2(Te04)3, the tellurium atoms are in octahedral coordination of oxygen atoms, and the octahedra are linked to infinite chains running along the u-axis. 

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