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Electrical Conductivity

Electrical conductivity is the ability of different types of matter to conduct an electric current. The electrical conductivity of a material is defined as the ratio of the current per unit cross- sectional area to the electric field producing the current. Electrical conductivity is an intrinsic property of a substance, dependent on the temperature and chemical composition, but not on the amount or shape. The unit of electrical conductivity in the SI system is the Siemens per meter, where the Siemens is the reciprocal of the ohm, the unit of electrical resistance, represented by the Greek capital letter omega. An older name for the Siemens is the mho, which, of course, is ohm spelled backwards (which was written as an inverted Greek omega). Electrical conductivity is due to the presence of electrons or ions able to move through the material of interest. Electrical conductivity is the inverse quantity to electrical resistivity. For any object conducting electricity, one can define the resistance in ohms as the ratio of the electrical potential difference applied to the object to current passing through it in amperes. For a cylindrical sample of known length and cross sectional area, the resistivity is obtained by dividing the measured resistance by the length and then multiplying by the area. The conductivity is then found by taking the reciprocal of the resistivity. Metals generally have very high electrical conductivity. The electrical conductivity of copper at room temperature, for instance, is over 70 million Siemens per meter. On an atomic level this high conductivity reflects the unique character of the metallic bond in which pairs of electrons are shared not between pairs of atoms, but among all the atoms in the metal, and are thus free to move over large distances. Many metals undergo a transition at low temperatures to a superconducting state, in which the resistance disappears entirely and the conductivity becomes infinite. The superconduction process involves a coupling of electron motion with the vibration of the atomic nuclei and inner-shell electrons, to allow net current flow without energy loss. Electrical conductivity in the liquid state is generally due to the presence of ions. Substances that give rise to ionic conduction when dissolved are called electrolytes. The conductivity of a one molar electrolyte is of the order of 0.01 Siemens per meter, far less than that of a metal, but still very much larger than that of typical insulators. Sodium chloride (common table salt), composed of sodium ions and chloride ions, is a very poor conductor in the solid state. If it is dissolved in water, however, it becomes a good ionic conductor. Likewise, if it is melted, it becomes a good conductor. Substances such as hydrogen chloride or acetic acid are non-conductors in the pure state but give rise to ions and thus electrical conductivity when dissolved in water. In modern electrochemistry, substances of the sodium chloride type, which are actually composed of ions, are termed true electrolytes, while those which require a solvent for ion formation, like hydrogen chloride, are termed potential electrolytes.

As might be expected, the conductivity of a dissolved electrolyte depends on its concentration and so physical chemists find it useful to define molar conductivity of an electrolyte as the electrical conductivity of the solution divided by the concentration of the electrolyte in moles per litre. Because different electrolytes can give rise to ions of different charge, for example, Mg2+ ions instead of Na+ ions, an even more useful measure of conductivity is given by the equivalent conductivity, obtained by dividing the molar conductivity by the number of moles of positive charge released by one mole of the electrolyte. Because the ions+ of an electrolyte solution interact with each other, the equivalent conductivity is found to decrease gradually as the concentration increases. For dilute solutions, the equivalent conductivity can be expressed as a constant, the equivalent conductivity at infinite dilution minus a term proportional to the square root of the concentration. This important relation was discovered by the German physicist Friedrich Wilhelm Georg Kohlrausch (1840-1910). It is the limiting conductivities at infinite dilution that are additive for the ions involved. Thus, there are tabulations in handbooks of these conductivities for different ions (Na+, K+, Mg+, Cl- , Br-, etc.) from which the corresponding conductivities of different electrolytes (NaCl, KCl, KBr, etc) can be calculated. The equivalent conductivities of the individual ions are proportional to their electrical mobilities (ratio of particle velocity to electrical field strength). Ionic crystals do exhibit a limited electrical conductivity even in the crystalline state. This arises from point defects present at any temperature above absolute zero. For compounds like sodium chloride, composed of ions of roughly equal size, there will be a certain number of cation and anion vacancies, which allows a jumping motion of the corresponding cations and anions. For compounds like silver chloride, in which one of the ions, the cation, is much larger than the other ion, the anion, vacancies and interstitials (out of place ions) of the smaller ion will allow an ionic conductivity. In addition, compounds like silver chloride tolerate a range of stoichiometry that is a deviation of the Ag to Cl ratio of one to one. An excess of silver is accommodated by a delocalization of the extra electrons to allow an electronic conductivity in addition to the conductivity of silver ions. A deficit of silver introduces mobile electron vacancies, or holes, in to the electronic structure of the material adding a component to the conductivity which behaves as if positively charged. Semiconductors are covalently bonded materials for which heat energy is sufficient to promote electrons from bonding energy levels to delocalized energy levels. The conductivity of semiconductors is a sensitive function of impurity content (the substitution of semiconductor atoms by atoms with one fewer or more valence electrons) introducing positive (hole) or negative charge carriers into the material.
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