Solid solution ideal, distribution laws

Distribution Laws For Simple Ideal solid solutions. If a solid solution of Formula (2) is in eguilibrium with an agueous phase (ag), the distribution of A and B ions between the agueous phase and the solid phase (s) can be represented by ... 

Distribution Laws for Complex Ideal Solid Solutions. Let AnX and BnX be two ionic compounds which form a series of solid solutions of the Formula ... 

Solutions and glasses do not follow the third law. If a solid solution continues to persist on cooling a sample to the lowest possible temperature, then at this temperature the molecules of the several components are distributed in some fashion in the same crystal lattice. Under such conditions all of the molecules of the substance could not attain the same quantum state on further cooling to 0 K in the sense of the required extrapolation. Only if the solid solution was separated into the pure components would the value of zero be obtained for the entropy function at 0 K. If the molecules of the components were randomly distributed in the crystal lattice, as in an ideal solution, then the entropy of the substance at absolute zero would be equal to the ideal entropy of mixing, so... 

Thus, in the case of solid solutions of sp Iqrbrid binary compoimds, Vegard s law applies to the average values of the bond lengths d, whereas d and d2 remain independent of the composition of the solid solution. The ideal lattice model with a random distribution of atoms over the sites is strictly applicable to solid solutions only if the values of d and d2 are similar, which implies that it is limited to solid solutions consisting of members of Goldschmidt s iso-electronic series, or members of groups of compounds classified in [9,10]. In all other cases, this approach is only very approximate. 

Figure 10,1 (A) Activity-molar concentration plot. Trace element concentration range is shown as a zone of constant slope where Henry s law is obeyed. Dashed lines and question marks at high dilution in some circumstances Henry s law has a limit also toward inhnite dilution. The intercept of Henry s law slope with ordinate axis defines Henry s law standard state chemical potential. (B) Deviations from Nernst s law behavior in a logarithmic plot of normalized trace/carrier distribution between solid phase s and ideal aqueous solution aq. Reproduced with modifications from liyama (1974), Bullettin de la Societee Francaise de Mineralogie et Cristallographie, 97, 143-151, by permission from Masson S.A., Paris, France. A in part A and log A in part B have the same significance, because both represent the result of deviations from Henry s law behavior in solid.

---