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Spinel and Inverse Spinnel

The document discusses the structures of ionic crystals, focusing on MX and MX2 types, including examples like NaCl and CdI2. It also covers perovskite and spinel structures, detailing their chemical formulas, arrangements, and characteristics. Key concepts such as radius ratio rules and the significance of cleavage planes in crystal structures are highlighted.

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satheeshkumar K
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26 views28 pages

Spinel and Inverse Spinnel

The document discusses the structures of ionic crystals, focusing on MX and MX2 types, including examples like NaCl and CdI2. It also covers perovskite and spinel structures, detailing their chemical formulas, arrangements, and characteristics. Key concepts such as radius ratio rules and the significance of cleavage planes in crystal structures are highlighted.

Uploaded by

satheeshkumar K
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 PDF, TXT or read online on Scribd
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CONCEPTS AND MODELS OF

INORGANIC CHEMISTRY
Unit -I
Structures of ionic crystals
 Introduction

 Radius ratio rules

 Structures of some ionic crystals

 MX (NaCl, CsCl, ZnS)

 MX2 (fluorite, rutile, β-crystobalite and cadmium iodide) types


The CdI2 Lattices: Layer Structures
MX2 crystallize in so-called layer structures

CdI2 which has hexagonal symmetry.

I- ions arranged in an hcp array with Cd2+ ions occupying the


octahedral holes in every other layer

the lattice infinitely gives a structure which can be described in terms


of ‘stacked sandwiches’, each ‘sandwich’ consisting of a layer of I- ions,
a parallel layer of Cd2+ ions, and another parallel layer of I- ions; each
‘sandwich’ is electrically neutral. Only weak van der Waals forces
operate between the ‘sandwiches’

this leads to CdI2 crystals exhibiting pronounced cleavage planes


parallel to the layers. If a crystal breaks along a plane related to the
lattice structure, the plane is called a cleavage plane.
Cristobalite is a mineral polymorph of silica that
is formed at very high temperatures.

same chemical formula as quartz, SiO2, but a


distinct crystal structure

Both quartz and cristobalite are polymorphs with


all the members of the quartz group

These frameworks are composed


of SiO4 tetrahedra in which every oxygen atom is
shared with a neighbouring tetrahedron, so that
the chemical formula of silica is SiO2

The unit cell of b-cristobalite, SiO2;


colour code: Si, purple; O, red.
Perovskites and Spinel Structures
Perovskites

 Ternary oxides of general formula ABO3

 More generally, the perovskite formula is ABX3

 Where the anion X can be O, N, or halogen

 The A ions are typically large ions such as Sr2+, Ba2+, Rb+, or a lanthanide 3+ ion

 The B ions are smaller transition metal ions such as Ti4+, Nb5+, Ru4+, etc.

 The mineral after which the structure is named has the formula CaTiO3
 The perovskite structure has simple cubic symmetry, but is related to the fcc lattice in the sense
that the A site cations and the three O atoms comprise a fcc lattice

 The B-site cations fill 1/4 of the octahedral holes and are surrounded by six oxide anions

ABX3 perovskite structure. A, B, and X are white, blue, and red, respectively
Spinel Structures
Types of Spinel

(a) Normal

(b) Inverse
The spinels have the general chemical formula AB2X4

Where:

AII = a divalent cation like Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn

BIII = a trivalent cation like Al, Ga, In, Ti, V, Cr, Mn, Fe, Fe, Co, Ni

X = O, S, Se etc.
A spinel unit cell is made up of 8 FCC cells. The anions (usually oxide ions: O2-)
occupy the FCC lattice points.

The divalent AII cations occupy 1/8th of the tetrahedral voids, whereas the
trivalent BIII cations occupy one half (1/2) of octahedral voids.
Examples of Normal Spinels:

MgAl2O4,

Mn3O4,

ZnFe2O4,

FeCr2O4 (chromite) etc.


Structures of Inverse spinels (B(AB)O4):

The AII ions occupy the 1/4th of octahedral voids,

whereas one half of BIII ions occupy the 1/8th of tetrahedral voids
and the other half occupy 1/4th of octahedral sites.
It can be represented as: (BIII)tet(AIIBIII)octO4.
Thus an inverse spinel can be represented as: (BIII)tet(AII)oct(BIII)octO4

Examples of Inverse spinels: Fe3O4 (ferrite), CoFe2O4, NiFe2O4 etc.

The above inverse spinels can also be written as:

Fe3O4 = FeIII(FeIIFeIII)O4

CoFe2O4 = FeIII(CoIIFeIII)O4

NiFe2O4 = FeIII(NiIIFeIII)O4

The number of octahedral sites occupied may be ordered or random

The random occupation leads to defected spinels

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