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However, as detailed studies of ionic conductivity and diffusion data for alkali halides have shown (cf. 2), the fitting of slightly curved Arrhenius plots with sums of exponentials does not give well-defined values for the parameters, and the results must therefore be viewed with caution. The measurement of the relative diffusion rates of isotopes, particularly two tracer isotopes into a specimen composed primarily of a stable third isotope, has been useful in some cases in sorting out the mechanism of diffusion.
However, in this case, the contribution of the divacancy mechanism to the overall diffusion rate is probably small, since the value observed for EafJ(l) was independent of temperature. In a mixed diffusion process, unless by chance the different mechanisms have the same temperature dependence, the relative contributions of the several mechanisms should change with temperature, and Statistical Thermodynamics of Point Defects 33 therefore so also should the effective value of (D,,/Dp) - 1 in Eq. 26).
Multiplication of Eqs. 29) a result which is independent of the pressure of X 2 in the gas phase, and expresses the Frenkel equilibrium condition for the X sublattice. KF is the Frenkel equilibrium constant in the absence of the interaction between pairs of defects. The weakest point in Anderson's treatment is the assumption that, in spite of the interaction between defects, their distribution is random and pairs are formed on the basis of chance alone. Several refinements of the theory intended to strengthen it on this point have been offered.