Packing of spheres 12/11/21

Key words: Coordination

number (number of
nearest neighbours

CCP

HCP

Examples: Al, Cu, Ni Examples: Mg, Co, Zn

Presentation Title 1
Brunel University London
http://www.youtube.com/watch?v=tgKC-awk6p4
Cubic structures 12/11/21

See VESTA, Al ccp, Mg hcp

Of course atoms are in contact,

sometimes we need to play with
the figures to show what we want
and manipulate the truth.

Brunel University London Presentation Title 2

 12/11/21
Packing efficiency
 Packing efficiency = volume of the atoms in a unit cell / total volume of unit cell x 100

This tells you how much of the space is used.

Prove that the packing efficiency for a fcc structure is:

= 74%

(Consider how the balls touch in the fcc lattice)

http://www.youtube.com/watch?v=8T-cmI7QYNg
Calculate the packing efficiency in a bcc and pc structure.

Brunel University London Presentation Title 3

Answers 12/11/21

Brunel University London Presentation Title 4

Interstitial Sites (the gaps between the atoms) 12/11/21

These are very important as they make up

26% of a close packed material.

1 Octahedral and 2 tetrahedral sites are

seen in close packed structures.

Brunel University London Presentation Title 5

 12/11/21

Brunel University London Presentation Title 6

Interstitial sites 12/11/21

When you look at ionic materials you

will see that many material’s
structures are based on close
packed structures but with ions in
the interstitial sites.

Brunel University London Presentation Title 7

 Structures of compounds 12/11/21

What is its packing?

Binary solids have 2 elements. Normally describe the structure based on the larger ion. Chloride ions
with sodium ions at the interstitial sites.

Each ion has coordination number of 6 with octahedral geometries. Na ions occupy the octahedral
interstitial sites of the CCP Chloride lattice.

Group 1 metal halides, many oxides, MgO, FeS2 has the NaCl structure with [S2]2- ions replacing Cl- and
the Fe2+ replacing the Na+.
Brunel University London Presentation Title 8
 Antiflourite has anions as the close packed ions,
Fluorite (CaF2) e.g. Na2O
Another common structure type is the
fluorite structure. Ca2+ is close packed, F-
is at the tetrahedral sites. So there is a
2:1 ratio. Ca2+ has coordination number
of 8 and is in a cubic environment, the F-
have CN 4 and are tetrahedral. Unit cell
has 4 Ca2+ and 8 F- ions.

Others taking this structure are ZrO2 and BaCl2.

Brunel University London Presentation Title 9
 Trigonal Prismatic As ions
Nickel arsenide 12/11/21

Nickeline, HCP packing of As ions, Ni ions are octahedral. CN = 6

Others taking this phase, group 14-16 anions, cobalt(II) selenide, nickel(II) telluride
NiAs (HCP) is analogous to NaCl (CCP), the metal ions occupy all of the octahedral sites.
No hcp equivalent analogue of the fluorite (or antifluorite) structure where all the tetrahedral
sites are occupied, since these sites are too close together and repulsion destabilises lattice.

Brunel University London Presentation Title 10

Sphalerite and Wurtzite (ZnS) 12/11/21

Both are close packed structures based on S2-

anions, Zn2+ ions in half of the tetrahedral sites
where these are alternatingly occupied. CN = 4.

Others, CuCl, AgI = Sphalerite

ZnO, SiC, BN = Wurtzite. SiC and BN both have
covalent bonding.

Brunel University London Presentation Title 11

CdCl2 and CdI2 12/11/21

Anions are close packed, cations in half of

the octahedral sites.

Brunel University London Interactive resources… See Chemistry3 online. 12

Close packed structures 12/11/21

Brunel University London Presentation Title 13

Non close packed structures, e.g. Caesium chloride 12/11/21

Primitive lattice, interstitial site lies at the cube centre and is also
cubic. CN = 8.

Rutile structure (TiO2)

Common polymorph of titania, one cell length is different (longer) to
the other two. (tetrahedral cell) Ti CN 6, distorted octahedral
symmetry with 2 Ti-O distances longer. O2- anions are 3 coordinate
and trigonal planer. Used in self cleaning windows.

Compare to KCl xrd.

Brunel University London Vesta file 14

Spinel, MgAl2O4 (General formula- A B2 O4 - AB2X4)
2+ 3+ 12/11/21

Spinel,

M2+ in tetrahedral coordination of

4O2- ions

M3+ in octahedral coordination of O2-

anions.

Uses, catalysis, anti-corrosion

coating on metals.

Brunel University London Presentation Title 15

Perovskite structure (CaTiO3) 12/11/21

This has recently become highly researched for its use in solar cell technology.

Know for many materials, primitive cubic structure, Ti4+ at the corners, Ca2+ at
the centre and O2- on the vertices. Another representation could show O2- at
the face centres of a cubic Ca2+ representation.

Brunel University London Presentation Title 16