Semi-metals electrical conductivity

Zinc—bromine storage batteries (qv) are under development as load-leveling devices in electric utilities (64). Photovoltaic batteries have been made of selenium or boron doped with bromine. Graphite fibers and certain polymers can be made electrically conductive by being doped with bromine. Bromine is used in quartz—haUde light bulbs. Bromine is used to etch aluminum, copper, and semi-conductors. Bromine and its salts are known to recover gold and other precious metals from their ores. Bromine can be used to desulfurize fine coal (see Coal conversion processes). Table 5 shows estimates of the primary uses of bromine. 

Many liquid alloys, in particular, the alkali-group IV alloys, exhibit (Zintl) anion clustering and show strong effects of compound formation. A typical example of such Zintl systems are sodium-tin alloys. In the solid NaSn crystal the Zintl anions Sn appear [1]. An interesting question is the stability of these anions in the liquid. Furthermore, the electrical conductivity of these alloys shows a strong dependence on composition [2] For the limiting (sodium-rich or tin-rich) cases a metallic (small) conductivity appears, but for the nearly equimolar compositions a semi-metallic behavior - with a considerably smaller conductivity - is observed. 

A comprehensive report which focussed on the La2 xSrxCu O4-x/2+S ser es was published (139) in 1983 by this research group. In this broad review they reported the magnetic and electrical transport properties of these mixed-valent copper oxides in the temperature range 120-650 K. They concluded that the original semiconducting behavior in La2Cu04 transformed to semi-metallic behavior as the Cu3+ content increased with Sr-substitution. No experiments were conducted below 50 K, and therefore superconductivity was not observed. Three series of compounds, with 0.00 < x < 1.20 were... 

Throughout the book, theoretical concepts and experimental evidence are integrated An introductory chapter summarizes the principles on which the Periodic Table is established and describes the periodicity of various atomic properties which are relevant to chemical bonding. Symmetry and group theory are introduced to serve as the basis of all molecular orbital treatments of molecules. This basis is then applied to a variety of covalent molecules with discussions of bond lengths and angles and hence molecular shapes. Extensive comparisons of valence bond theory and VSEPR theory with molecular orbital theory are included Metallic bonding is related to electrical conduction and semi-conduction. 

In a typical spectroelectrochemical measurement, an optically transparent electrode (OTE) is used and the UV/vis absorption spectrum (or absorbance) of the substance participating in the reaction is measured. Various types of OTE exist, for example (i) a plate (glass, quartz or plastic) coated either with an optically transparent vapor-deposited metal (Pt or Au) film or with an optically transparent conductive tin oxide film (Fig. 5.26), and (ii) a fine micromesh (40-800 wires/cm) of electrically conductive material (Pt or Au). The electrochemical cell may be either a thin-layer cell with a solution-layer thickness of less than 0.2 mm (Fig. 9.2(a)) or a cell with a solution layer of conventional thickness ( 1 cm, Fig. 9.2(b)). The advantage of the thin-layer cell is that the electrolysis is complete within a short time ( 30 s). On the other hand, the cell with conventional solution thickness has the advantage that mass transport in the solution near the electrode surface can be treated mathematically by the theory of semi-infinite linear diffusion. 

The electrical conduction characteristics of ceramics can range from those of superconductors through those of metals to those of the most resistive of materials in between the extremes are characteristics of semi-conductors and semi-insulators. It is the purpose of this section to provide a framework for an understanding of this very diverse behaviour of apparently basically similar materials. The monographs by C. Kittel [5] and B.I. Bleaney and B. Bleaney [6] are recommended to supplement the discussion. 

Electrical conductivity of metals is very high and is of the order of 106 108 ohm-1 cm-1 while that of insulators is of the order of 10-12 ohm-1 cm-1. Semi-conductors have intermediate conductivity which lies in the range 102 10-9 ohm-1 cm1. Electrical conductivity of solids may arise through the motion of electrons and positive holes (electronic conductivity) or through the motion of ions (ionic conductivity). The conduction through electrons is called n-type conduction and through positive holes is called p-type conduction. Pure ionic solids where conduction can take place only through motion of ions are insulators. However, the presence of defects in the crystal structure increases their conductivity. 

An electric generator or battery forces electrons into tl e cathode and pumps them away from the anode—electrons move freely in a metal or a semi-metallic conductor such as graphite. But electrons cannot ordinarily get into a substance such as salt the crystalline substance is an insulator, and the electrical conductivity sliowu by the molten salt is not electronic conductivity (metallic conductivity , but is conductivity of a different kind, called ionic conductivity or electrolytic conductivity This sort of conductivity results from the motion of the ions in the liquid the cations, Na+, are attracted by the negatively charged cathode and move toward it, and the anions. Cl , are attracted by the anode and move toward it (Fig. 10-1). 

Finally, the data of electrical conductivity and thermopower of Lai xSrxMn03.5 at elevated temperature has been treated by a hopping mechanism for x < 0.2, and by a band model for the semi-metallic behaviour observed at x > 0.3 by Mizusaki [161]. On the other hand, to explain their results of Laj. Sr MnOs and Lai. rxMn03 5 for compositions with 0.30 < x 0.80, Stevenson et al. [209] included the thermally activated charge disproportionation of Mn " into Mn " and Mn " pairs. 

Another class of thermally stable materials with electroactivity are polyacene quinone radical (PAQR) polymers. The thermal stability of PAQR polymers was. studied up to 1200°C under helium. The electrical conductivity was found to go through a minimum at about 500"C, showing that the original synthetic structure of a PAQR polymer is unique and thermally sensitive and that the negative temperature dependence of e.c. makes it similar to degenerate semi-metals [237]. 

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