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4 Solid State Chemistry 4

The document discusses the packing of constituent particles in crystals, focusing on close packing in one and three dimensions. It describes different arrangements such as simple cubic, hexagonal close packed, and cubic close packed structures, along with the formation of tetrahedral and octahedral voids. Additionally, it introduces the radius ratio rule, which relates the size of ions to their packing in crystal structures.

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Dilshan Narankotuwa
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16 views13 pages

4 Solid State Chemistry 4

The document discusses the packing of constituent particles in crystals, focusing on close packing in one and three dimensions. It describes different arrangements such as simple cubic, hexagonal close packed, and cubic close packed structures, along with the formation of tetrahedral and octahedral voids. Additionally, it introduces the radius ratio rule, which relates the size of ions to their packing in crystal structures.

Uploaded by

Dilshan Narankotuwa
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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12/11/24

Packing of Constituent Particles in Crystals

• It is assumed that the atoms are hard spheres of identical size.


• Packing is done in such a way that they occupy maximum available space and
leave minimum space empty.
• This type of packing is called close packing.
• Close packing of spheres in one dimension.
• It is shown in the figure this forms an edge of the crystal.

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Close Packing in Three Dimensions


All real structures are three dimensional structures. They can be obtained by stacking
two dimensional layers one above the other.

(i) Three dimensional close packing from two dimensional


square close-packed layers:
While placing the second square close-packed layer above
the first we follow the same rule that was followed when one
row was placed adjacent to the other. The second layer is
placed over the first layer such that the spheres of the upper
layer are exactly above those of the first layer. In this
arrangement spheres of both the layers are perfectly aligned
horizontally as well as vertically as shown in Fig. Similarly, we
may place more layers one above the other. If the
arrangement of spheres in the first layer is called ‘A’ type, all
the layers have the same arrangement. Thus this lattice has
Simple cubic lattice formed
AAA.... type pattern. The lattice thus generated is the simple
by A A A .... arrangement
cubic lattice, and its unit cell is the primitive cubic unit cell
(See Fig. 1.9).

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(i) Three dimensional close packing from two dimensional hexagonal close packed layers:
Three dimensional close packed structure can be generated by placing layers one over the other.

(a) Placing second layer over the first layer

• Take a two dimensional hexagonal close packed layer


‘A’ and place a similar layer above it such that the
spheres of the second layer are placed in the
depressions of the first layer.
• Since the spheres of the two layers are aligned
differently, let us call the second layer as B.
• It can be observed from Fig. that not all the triangular
voids of the first layer are covered by the spheres of
the second layer. This gives rise to different A stack of two layers of close packed spheres and voids
arrangements. generated in them. T = Tetrahedral void; O = Octahedral void
• Wherever a sphere of the second layer is above the
void of the first layer (or vice versa) a tetrahedral void
is formed.
• These voids are called tetrahedral voids (T)
because a tetrahedron is formed when the centres of
these four spheres are joined.

(a) top view (b) exploded side view (c) geometrical shape of the void.

(i) Three dimensional close packing from two dimensional hexagonal close packed layers:
Three dimensional close packed structure can be generated by placing layers one over the other.

(a) Placing second layer over the first layer

At other places, the triangular voids in the second layer


are above the triangular voids in the first layer, and the
triangular shapes of these do not overlap. One of them
has the apex of the triangle pointing upwards and the
other downwards.
These voids have been marked as ‘O’ in Fig.
Such voids are surrounded by six spheres and are
called octahedral voids.

(a) top view (b) exploded side view (c) geometrical shape of the void.

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Let the number of close packed spheres be N, then:


• The number of octahedral voids generated = N
• The number of tetrahedral voids generated = 2N

(b) Placing third layer over the second layer


When third layer is placed over the second, there
are two possibilities.

(i) Covering Tetrahedral voids:


(ii) Covering Octahedral voids:

Covering Tetrahedral Voids:

• Tetrahedral voids of the second layer may be


covered by the spheres of the third layer.
• In this case, the spheres of the third layer are
exactly aligned with those of the first layer.
• Thus, the pattern of spheres is repeated in
alternate layers. This pattern is often written as
ABAB ....... pattern.
• This structure is called hexagonal close packed
(hcp) structure (Fig).
• This sort of arrangement of atoms is found in
many metals like magnesium and zinc.

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(b) Placing third layer over the second layer

(ii) Covering Octahedral Voids:


• Third layer may be placed above the second layer in a
manner such that its spheres cover the octahedral voids.
• When placed in this manner, the spheres of the third layer
are not aligned with those of either the first or the second
layer.
• This arrangement is called ‘C’ type. Only when fourth layer
is placed, its spheres are aligned with those of the first
layer as shown in Figs.
• This pattern of layers is often written as ABCABC ...........
• This structure is called cubic close packed (ccp) or face-
centred cubic (fcc) structure.
• Metals such as copper and silver crystallise in this
structure.

(b) Placing third layer over the second layer

(ii) Covering Octahedral Voids:

• This pattern of layers is often written as ABCABC


• This structure is called cubic close packed (ccp) or face-centred cubic (fcc) structure.
• Metals such as copper and silver crystallise in this structure.

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• Not all octahedral or tetrahedral voids are occupied.


• In a given compound, the fraction of octahedral or tetrahedral voids
that are occupied, depends upon the chemical formula of the
compound.

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What is Radius Ratio Rule?


Radius ratio rule states:
• The difference in the crystal structure depends on the size of the ions
• As the size (ionic radius r) of a cation increases, more anions of a particular size
can be packed around it.

• Knowing the size of the ions à predict which type of crystal packing
• The geometrical requirement for a given structure in terms of the size of the two
ions is expressed by radius ratio

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BCC

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