Anion mobility

A concept of anion mobility may be considered a useful paradigm for explaining the net retention and loss of cations from soils, and thus exposure pathways. This paradigm relies on the simple fact that total cations must balance total anions in soil solution (or any other solution), and, therefore, total cation leaching can be thought of as a function of total anion leaching. The net production of anions within the soil (e.g., by oxidation or hydrolysis reactions) must result in the net production of cations (normally H+), whereas the net retention of anions (by either absorption or biological uptake) must result in the net retention of cations. 

Approximate single ion mobilities may be calculated by assuming that the cation and anion mobilities of a selected electrolyte are the same and equal to... 

Another less precise but frequently used method employs a liquid bridge between the analysed solution and the reference electrode solution. This bridge is usually filled with a saturated or 3.5 m KCl solution. If the reference electrode is a saturated calomel electrode, no further liquid bridge is necessary. Use of this bridge is based on the fact that the mobilities of potassium and chloride ions are about the same so that, as follows from the Henderson equation, the liquid-junction potential with a dilute solution on the other side has a very low value. Only when the saturated KCl solution is in contact with a very concentrated electrolyte solution with very different cation and anion mobilities does the liquid junction potential attain larger values [2] for the liquid junction 3.5 M KCl II1 M NaOH, A0z, = 10.5 mV. 

Anion-deficient fluorite oxides are also present, for example, U02- c, Ce02-x The presence of anion vacancies in reduced fluorites has been confirmed by diffraction studies. In reduced ceria for example, some well-ordered phases has been reported (Sharma et al 1999). The defective compounds show very high anion mobilities and are useful as conductors and as catalytic materials as will be described later. However, the structures of many anion-deficient fluorite oxides remain unknown because of the shear complexity of the disordered phases. There are, therefore, many opportunities for EM studies to obtain a better understanding of the defect structures and properties of these complex materials which are used in catalysis. 

The LJP between different solvents consists of three components (i) a component caused by the differences in electrolyte concentrations on the two sides of the junction and the differences between cationic and anionic mobilities (ii) a component due to the differences between ion solvation on the two sides of the junction (iii) a component due to the solvent-solvent interactions at the junction. 

The occurrence of an almost constant, albeit rather low, activity level, which is reached after a number of pulses, signifies that a certain quasiequilibrium concentration of active sites is maintained by transport of bulk oxygen anions to the surface. Such a mobility of oxygen is particularly observed for bismuth molybdates and some related catalysts (see below). Typical examples of catalysts which completely loose their activity at a low degree of reduction are the antimonates this is primarily caused by the absence of anion mobility. 

Christie et al. (45) and Pendleton and Taylor (46) have recently reported the results of propylene oxidation over bismuth molybdate and mixed oxides of tin and antimony and of uranium and antimony in the presence of gas-phase oxygen-18. Their work indicated that for each catalyst, the lattice was the only direct source of the oxygen in acrolein and that lattice and/or gas-phase oxygen is used in carbon dioxide formation. The oxygen anion mobility appeared to be greater in the bismuth molybdate catalyst than in the other two. 

An entirely different selectivity principle known as phase equilibrium comes into play in high-temperature ionic conductors. Many important gases dissolve in ionic solids at elevated temperatures. However, the solubility is rather sharply defined for the gas and the solid by the lattice parameters and the size of the gas molecule. The best example is the solubility of oxygen in zirconium dioxide. When Z1O2 is doped with yttrium ions, it exhibits a high mobility for the O anion. The solubility and anion mobility then become the basis for several electrochemical gas sensors, using yttria-stabilized zirconia (YSZ). 

Liquid junction potentials are the result of different cation and anion mobilities under the influence of an electric field. The potential manifests itself in the interface between two different solutions separated by a porous separator or by a membrane. These junctions can be classified into three distinct types ... 

The basic elements of a SOFC are (1) a cathode, typically a rare earth transition metal perovskite oxide, where oxygen from air is reduced to oxide ions, which then migrate through a solid electrolyte (2) into the anode, (3) where they combine electrochemically with to produce water if hydrogen is the fuel or water and carbon dioxide if methane is used. Carbon monoxide may also be used as a fuel. The solid electrolyte is typically a yttrium or calcium stabilized zirconia fast oxide ion conductor. However, in order to achieve acceptable anion mobility, the cell must be operated at about 1000 °C. This requirement is the main drawback to SOFCs. The standard anode is a Nickel-Zirconia cermet. 

Generally, to increase anion conductivity we must increase anion mobility by creating vacancies in anion sties. This can be achieved via cation substitution doping the compound with a cation of similar size but lower charge will create anion vacancies. 

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