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Exercise · Q14

Q.Explain the Frenkel defect: the condition under which it arises, why it is common in compounds with a large difference between cationic and anionic radii, and why (unlike a Schottky defect) it does not change the density of the crystal. Give one example.

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A Frenkel defect arises when a smaller ion — almost always the cation, since it is usually the smaller of the pair — is dislodged from its regular lattice site and instead squeezes into an otherwise-empty interstitial space between the surrounding lattice points, leaving a vacancy behind at its original site. This defect occurs preferentially when there is a large difference between the cationic and anionic radii, because only a sufficiently small cation can physically fit into the confined interstitial gap; a similarly sized anion generally cannot. AgCl\text{AgCl}, AgBr\text{AgBr} and ZnS\text{ZnS}, where the cation is considerably smaller than the anion, are typical examples. Crucially, no ion actually leaves the crystal in a Frenkel defect — it is merely relocated from a regular lattice site to a nearby interstitial one — so the total number of particles present, and hence the total mass, …

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