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What is the significance of radius ratio in deciding the structural arrangement in an ionic solid? - Chemistry (Theory)

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Question

What is the significance of radius ratio in deciding the structural arrangement in an ionic solid?

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Solution

Significance of radius ratio in ionic solids: The ratio of the radius of the cation (r+) to the radius of the anion (r) is called radius ratio. Thus,

Radius ratio = `("Radius of cation"  (r_+))/("Radius of anion"  (r_-))`

Importance in Structural Arrangement:

  1. Predicts Coordination Number: The radius ratio helps determine the coordination number, the number of oppositely charged ions surrounding a given ion.
  2. Determines Geometry: It influences the type of void the cation will occupy (tetrahedral, octahedral, or cubic), thereby deciding the geometrical arrangement of ions in the crystal.
  3. Stability of the Structure: Only certain radius ratio ranges result in stable structures; if the cation is too small, it can’t effectively hold anions in place, causing instability.
Radius ratio Possible coordination number Structural arrangement Structure type Examples
0.155 - 0.225 3 Trigonal planar  B2O3 B2O3
0.225 - 0.414 4 Tetrahedral ZnS, sphalerite ZnS, CuCl, CuBr, CuI, BaS, HgS
0.414 - 0.732 6 Octahedral NaCl NaCl, MgO, MnO, NaBr, CaS, CaO, KBr
0.732 - 1.000 8 Cubic CsCl CsI, CsBr, TlBr, NH4Br
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