Random walk, ionic motion

This notion of occasional ion hops, apparently at random, forms the basis of random walk theory which is widely used to provide a semi-quantitative analysis or description of ionic conductivity (Goodenough, 1983 see Chapter 3 for a more detailed treatment of conduction). There is very little evidence in most solid electrolytes that the ions are instead able to move around without thermal activation in a true liquid-like motion. Nor is there much evidence of a free-ion state in which a particular ion can be activated to a state in which it is completely free to move, i.e. there appears to be no ionic equivalent of free or nearly free electron motion. 

In the random-walk model, the individual ions are assumed to move independently of one another. However, long-range electrostatic interactions between the mobile ions make such an assumption unrealistic unless n is quite small. Although corrections to account for correlated motions of the mobile ions at higher values of n may be expected to alter only the factor y of the pre-exponential factor Aj., there are at least two situations where correlated ionic motions must be considered explicitly. The first occurs in stoichiometric compounds having an = 1. but a low AH for a cluster rotation the second occurs for the situation illustrated in Fig. 3.6(c). 

Attention should be drawn to the fact that there has been a degree of inconsistency in the treatments of ionic clouds (Chapter 3) and the elementary theory of ionic drift (Section 4.4.2). When the ion atmosphere was described, the central ion was considered—from a time-averaged point of view—at rest. To the extent that one seeks to interpret the equilibrium properties of electrolytic solutions, this picture of a static central ion is quite reasonable. This is because in the absence of a spatially directed field acting on the ions, the only ionic motion to be considered is random walk, the characteristic of which is that the mean distance traveled by an ion (not the mean square distance see Section 4.2.5) is zero. The central ion can therefore be considered to remain where it is, i.e., to be at rest. 

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