Solid ionic conductivities

There is also P(to) = toa(to) where a(co) is the frequency dependent conductivity (see Chapter 25). In the case of a low conductivity ionic solid, P(co) is typically of an oscillating behaviour (a peak at = coq, more or less damped, see Fig. 11.2) and there are only very rare diffusive events which contribute to P(co = 0). In a liquid, the spectrum is centred at (u = 0, since all the particles diffuse. When a liquid becomes (more) viscous a pseudo-oscillating behaviour may be observed (c), while the oscillator damping in a superionic conductor may decrease the difference between the time of flight between two sites and the time of oscillation on a site (Fig. 30.2), leading to a quasi-liquid state ". In order to simplify the model, either the diffusive or the oscillatory behaviour is assumed to be predominant. The choice may depend on the supposition of relaxation time... 

The oxidation by bromine is a step toward making an electrically conducting ionic solid, first a rapid reaction, then a slow one ... 

Ionic conductors arise whenever there are mobile ions present. In electrolyte solutions, such ions are nonually fonued by the dissolution of an ionic solid. Provided the dissolution leads to the complete separation of the ionic components to fonu essentially independent anions and cations, the electrolyte is tenued strong. By contrast, weak electrolytes, such as organic carboxylic acids, are present mainly in the undissociated fonu in solution, with the total ionic concentration orders of magnitude lower than the fonual concentration of the solute. Ionic conductivity will be treated in some detail below, but we initially concentrate on the equilibrium stmcture of liquids and ionic solutions. 

When an ionic solid such as NaCl dissolves in water the solution formed contains Na+ and Cl- ions. Since ions are charged particles, the solution conducts an electric current (Figure 2.12) and we say that NaCl is a strong electrolyte. In contrast, a water solution of sugar, which is a molecular solid, does not conduct electricity. Sugar and other molecular solutes are nonelectrolytes. 

Ionic solids do not conduct electricity because the charged ions are fixed in position. They become good conductors, however, when melted or dissolved in water. In both cases, in the melt or solution, the ions (such as Na+ and Cl-) are free to move through the liquid and thus can conduct an electric current. 

These three solids, sodium chloride, calcium chloride, and silver nitrate are similar, hence they are classified together. They all dissolve in water to form aqueous ions and give conducting solutions. These solids are called Ionic solids. 

When we study a solid that does not have the characteristic lustrous appearance of a metal, we find that the conductivity is extremely low. This includes the solids we have called ionic solids sodium chloride, sodium nitrate, silver nitrate, and silver chloride. It includes, as well, the molecular crystals, such as ice. This solid, shown in Figure 5-3, is made up of molecules (such as exist in the gas phase) regularly packed in an orderly array. These poor conductors differ widely from the metals in almost every property. Thus electrical conductivity furnishes the key to one of the most fundamental classification schemes for substances. 

When an ionic solid like sodium chloride is melted, the molten salt conducts electric current. The conductivity is like that of an aqueous salt solution Na+ and Cl- ions are present. The extremely high melting temperature (808°C) shows that a large amount of energy is needed to tfear apart the regular NaCl crystalline arrangement to free the ions so they can move. 

Each of the following ionic solids dissolves in water to form conducting solutions. Write equations for each reaction. 

In Chapter 6 we saw that the chemistry of sodium can be understood in terms of the special stability of the inert gas electron population of neon. An electron can be pulled away from a sodium atom relatively easily to form a sodium ion, Na+. Chlorine, on the other hand, readily accepts an electron to form chloride ion, Cl-, achieving the inert gas population of argon. When sodium and chlorine react, the product, sodium chloride, is an ionic solid, made up of Na+ ions and Cl- ions packed in a regular lattice. Sodium chloride dissolves in water to give Na+(aq) and C (aq) ions. Sodium chloride is an electrolyte it forms a conducting solution in water. 

Ionic bond, 287, 288 dipole of, 288 in alkali metal halides, 95 vs. covalent, 287 Ionic character, 287 Ionic crystal, 81, 311 Ionic radius, 355 Ionic solids, 79, 81, 311 electrical conductivity, 80 properties of, 312 solubility in water, 79 stability of, 311... 

This relationship makes it possible to calculate the maximum ionic conductivity of solid electrolytes. Assuming that the mobile ions are moving with thermal velocity v without resting and oscillating at any lattice site, this results in a jump frequency... 

Another way of looking at high ionic conductivities of solid electrolytes is to consider the activation enthalpy as illustrated in Fig. 8. Generally, the activation enthalpy is strongly correlated with the room-temperature ionic conductivity the higher the room-temperature ionic conductivity, the lower the activation enthalpy. The straight lines in the Arrhenius... 

Measurements of photoconductivity and of the Hall potential [367] are accurate and unambiguous methods of detecting electronic conduction in ionic solids. Kabanov [351] emphasizes, however, that the absence of such effects is not conclusive proof to the contrary. From measurements of thermal potential [368], it is possible to detect solid-solution formation, to distinguish between electronic and positive hole conductivity in semi-conductors and between interstitial and vacancy conductivity in ionic conductors. 

Detailed information about the conductivity of solid electrolytes can be found elsewhere.2,3,6 8,10,11 As shown in Fig. 3.1, the temperature dependence of the ionic conductivity o can, in general, be described by the semiempirical equation ... 

The presence of ions in solution is what gives a sodium chloride solution the ability to conduct electricity. If positively and negatively charged wires are dipped into the solution, the ions in the solution respond to the charges on the wires. Chloride anions move toward the positive wire, and sodium cations move toward the negative wire. This directed movement of ions in solution is a flow of electrical current. Pure water, which has virtually no dissolved ions, does not conduct electricity. Any solution formed by dissolving an ionic solid in water conducts electricity. Ordinary tap water, for example, contains Ionic Impurities that make It an electrical conductor. 

The conductivity of solid salts and oxides was first investigated by M. Faraday in 1833. It was not yet known at that time that the nature of conduction in solid salts is different from that in metals. A number of fundamental studies were performed between 1914 and 1927 by Carl Tubandt in Germany and from 1923 onward by Abram Ioffe and co-workers in Russia. These studies demonstrated that a mechanism of ionic migration in the lattice over macroscopic distances is involved. It was shown that during current flow in such a solid electrolyte, electrochemical changes obeying Faraday s laws occur at the metal-electrolyte interface. 

In an ideal ionic crystal, all ions are held rigidly in the lattice sites, where they perform only thermal vibratory motion. Transfer of an ion between sites under the effect of electrostatic fields (migration) or concentration gradients (diffusion) is not possible in such a crystal. Initially, therefore, the phenomenon of ionic conduction in solid ionic crystals was not understood. 

The point defects are decisive for conduction in solid ionic crystals. Ionic migration occurs in the form of relay-type jumps of the ions into the nearest vacancies (along the held). The relation between conductivity o and the vacancy concentration is unambiguous, so that this concentration can also be determined from conductivity data. 

These forces affect the boiling point, melting point, hardness, and electrical and heat conductivity of a substance. In this chapter, we will study metals, ionic solids, network solids, dipole-dipole attractions, van der Waals forces and hydrogen bonds. 

In ionic solids, electrons are held in place around the ions so they don t conduct electricity. However, in aqueous solution and molten state, they do conduct electricity. Electrical conductance of ionic compounds is not due to movement of electrons but to the movement of ions. 

KC1, NaNOs and LiF are ionic solids. Ionic solids don t conduct electricity in the solid state, however, aqueous solutions and molten forms of ionic compounds contain mobile ions so they can conduct electricity Thus, aqueous KC1 and LiF conduct electricity but solid NaN03 doesn t. 

K.D. Kreuer, M. Hampele, K. Dolde, and A. Rabenau, Proton Transport in Some Heteropolyacidhydrates. A Single Crystal PRG-NMR and Conductivity Study, Solid State Ionics, 28-30,589-93 (1988). 

In metals, valence electrons are conduction electrons, so they are free to move along the solid. On the contrary, valence electrons in insulators are located around fixed sites for instance, in an ionic solid they are bound to specific ions. Semiconductors can be regarded as an intermediate case between metals and insulators valence electrons can be of both types, free or bound. 

Code, P, Hult, A., Jannasch, P, Johansson, M., Karlsson, L. E., Lindbergh, G., Malmstrom, E. and Sandquist, D. 2006. A novel sulfonated dendritic polymer as the acidic component in proton conducting membranes. Solid State Ionics 177 787-794. 

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