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Solid State Last Lecture Dr. D.K. Srivastava Compounds Based On FCC Packing of Ions

The document discusses the structures of several important solid state compounds. It begins by describing the spinel structure of compounds with the formula AB2O4, which can exist in normal or inverse forms depending on how the cations occupy the interstices. It then discusses the structures of perovskites like ABO3, which have a primitive cubic lattice and tolerance factors that influence their structure. Finally, it briefly mentions the structures of compounds with the formulas MX3 and MX.

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Dharmendra Kumar Srivastava
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71 views

Solid State Last Lecture Dr. D.K. Srivastava Compounds Based On FCC Packing of Ions

The document discusses the structures of several important solid state compounds. It begins by describing the spinel structure of compounds with the formula AB2O4, which can exist in normal or inverse forms depending on how the cations occupy the interstices. It then discusses the structures of perovskites like ABO3, which have a primitive cubic lattice and tolerance factors that influence their structure. Finally, it briefly mentions the structures of compounds with the formulas MX3 and MX.

Uploaded by

Dharmendra Kumar Srivastava
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOCX, PDF, TXT or read online on Scribd
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SOLID STATE LAST LECTURE Dr. D.K.

Srivastava

 Formulae – (A2+)(B3+)2O4 or AB2O4 or AO.B2O3


 FCC Packing of anions
 Partial occupancy of both tetrahedral and octahedral sites i.e.1/8th of tetrahedral and ½ of the octahedral s
 A spinel unit-cell is made up of eight FCC cells made by oxygen ions in the configuration 2×2×2, so it is
 Depending on how cations occupy different interstices, spinel structure can be Normal or Inverse.

 Chemical formula: (A2+)(B3+)O4


 Examples are many aluminates such as MgAl2O4, FeAl2O4, CoAl2O4 and a few ferrites such as ZnFe2O4
 In this structure, all the A2+ ions occupy the tetrahedral sites and all the B3+ ions occupy the octahedral si
 Apply bond strength rule to verify the stoichiometry
 Cations: - A2+ - 2⁄4 ; B3+ - 3⁄6
Oxygen valence = (2⁄4x1)+ (3⁄6x3) = 2

 Chemical formula: (A2+)(B3+)2O4 but can be more conveniently written as B(AB)O4.


 Most ferrite follow this structure such as Fe3O4 (or FeO.Fe2O3), NiFe2O4, CoFe2O4 etc.
 In this structure, ½ of the B3+ ions occupy the tetrahedral sites and remaining ½ B3+ and all A2+ ions occu

Dr. D. K. Srivastava
There are a few structures, which appear as if they are based on cubic closed packing of anions. Howeve
structure.

 ABO3 type compounds


 Examples are many titanates like BaTiO3, SrTiO3, PbTiO3 etc. which happen to be technologically very
 In ABO3 structured compounds, A ion is twelve fold coordinated by oxygen (like a dodecahedra) and B
 Oxygen atoms form an FCC-like (not FCC) cell with atoms missing from the corners which are occupied
 Bond strength check:
Cation: Ba: 2⁄12 = 1⁄6 and Ti: 4⁄6 = 2⁄3
Oxygen valence = 1⁄6 x Coordination number by Ba + 2⁄3 x coordination number by Ti .
 Lattice type: Primitive Cubic (NOT FCC!)
 Motif: A ion - 0 0 0, B ion – ½ ½ ½, O ion - ½ ½ 0, 0 ½ ½, ½ 0 ½
 One Formula unit per unit cell
 Coordination
o B cation is surrounded by oxygen octahedra which share corners.
o A cation is surrounded by oxygen dodecahedra which touch faces of octahedra.
 An important parameters about perovskites is the their “Tolerance Factor (t)” which is defined as

 This is derived from the geometry of a cube in which the atoms are of such sizes that they touch each oth

 However, due to variations in ionic radii of various ions, many perovskites show deviations from t = 1 an
 For example, BaTiO3 has cubic structure only above ~120°C while it is tetragonal at room temperature a
 Perovskites can also have various combinations of ionic valence such as
o e.g. A2+B4+O4 , BaTiO3, PbTiO3, CaTiO3, SrTiO3 etc.
o e.g. A3+B3+O4 , LaAlO3, LaGaO3, BiFeO3 etc.
o Mixed Perovskites:
 A2+(B2+1/3B5+2/3)O3 eg. Pb(Mg1/3Nb2/3)O3
 A2+(B3+1/2B5+1/2)O3 eg. Pb(Sc1/2Ta1/2)O3

Dr. D. K. Srivastava

 Stoichiometry : MX3
 Lattice type: Primitive cubic
 Atomic Positions: M- 0 0 0; X - ½ 0 0, 0 ½ 0, 0 0 ½
 Coordination Numbers
M CN = 6 Octahedral coordination
X CN = 2 Linear coordination
 Can be visualized as perovskite ABO3 structure with empty B-sites
 Representative Oxides
o ReO3, UO3, WO3
 Used for gas sensing and electrochromic applications
 MX type compounds, parent compound being CsCl.
 Examples: Halides such as CSCl, AgI, AgBr etc.
 Radius ratio governs cubic co-ordination of both cations and anions.
 Lattice type: Primitive cubic lattice.
 Motif: Anions (X): 0 0 0, Cations (M): ½ ½ ½
 One formula unit per unit cell.

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