|


|
  

Atoms (and later ions) will be viewed as hard
spheres. In the case of pure metals, the packing
pattern often provides the greatest spatial
efficiency (closest packing).
Ionic crystals can often be viewed as a close-
close-
packed arrangement of the larger ion, with the
smaller ion placed in the ´holesµ of the
structure.
 
|

|rystals consist of repeating asymmetric
units which may be atoms, ions or molecules.
The ?

 is the pattern formed by the
points that represent these repeating structural
units.
 
|

A ÷  of the crystal is an imaginary
parallel--sided region from which the entire
parallel
crystal can be built up.
Usually the smallest unit cell which exhibits
the greatest symmetry is chosen. If repeated
(translated) in 3 dimensions, the entire crystal is
recreated.
 |


àince metal atoms and ions lack directional
bonding, they will often pack with greatest
efficiency. In ? or ??
 
,

, each metal
atom has 12 nearest neighbors.
The number of nearest neighbors is called
the 

  ÷

÷
.. àix atoms surround an
atom in the same plane, and the central atom is
then ´cappedµ by 3 atoms on top, and 3 atoms
below it.
 |


If the bottom ´capµ and the top ´capµ are
directly above each other, in an ABA pattern,
the arrangement has a hexagonal unit cell, or is
said to be !


?
 .

 .
If the bottom and top ´capsµ are staggered,
the unit cell that results is a face-
face-centered cube.
This arrangement is called ÷?
 

..
|


 |


6ither arrangement utilizes 74% of the
available space, producing a dense arrangement
of atoms. àmall holes make up the other 26%
of the unit cell.
Ú

|

|

There are two
types of holes created
by a close-
close-packed
arrangement.
lie

!

!?lie

!

!?
within two staggered
triangular planes of
atoms.
Ú

|

|

The coordination
number of an atom
occupying an
octahedral hole is 6.
For atoms in a
close--packed
close
structure, there are
octahedral holes.
 
 Ú

The green atoms are in
a cubic close-
close-packed
arrangement. The small
orange spheres show the
position of octahedral
holes in the unit cell.
6ach hole has a
coordination number of 6.
  
 Ú

The size of the octahedral hole = .414 r
where r is the radius of the cubic close-
close-packed
atom or ion.
Ú

|

|

ð

!

!? are formed by a planar
triangle of atoms, with a 4th atom covering the
indentation in the center. The resulting hole has
a coordination number of 4.
ð
 
 Ú

The orange spheres
show atoms in a cubic
close--packed
close
arrangement. The small
white spheres behind
each corner indicate the
location of the
tetrahedral holes.
ð
 
 Ú

For a close-
close-packed
crystal of atoms, there
are 2 tetrahedral holes.
The size of the
tetrahedral holes = .225 r
where r is the radius of
the close-
close-packed atom or
ion.
G
|

For atoms in a
cubic unit cell:
£ Atoms in corners are
ȴ within the cell
G
|

For atoms in a
cubic unit cell:

£ Atoms on faces are ½

within the cell
G
|


A face-
face-centered
cubic unit cell
contains a total of 4
atoms: 1 from the
corners, and 3 from
the faces.
 G
|

For atoms in a cubic unit cell:

£ Atoms in corners are ȴ within the cell

£ Atoms on faces are ½ within the cell
£ Atoms on edges are ¼ within the cell



|
  

V  
÷ unit cells have an atom in
V 
the center of the cube as well as one in each
corner. The packing efficiency is 68%, and the
coordination number = 8.



|
  

à ÷ (or primitive cubic) unit cells are
relatively rare. The atoms occupy the corners of
a cube. The coordination number is 6, and the
packing efficiency is only 52.4%.
 
 

ÿany metals exhibit different crystal
structures with changes in pressure and
temperature. Typically, denser forms occur at
higher pressures.
Higher temperatures often cause close-
close-
packed structures to become body-
body-center cubic
structures due to atomic vibrations.
 




ÿetallic radii are defined as half the
internuclear distance as determined by X- X-ray
crystallography. However, this distance varies
with coordination number of the atom;
increasing with increasing coordination number.
 




[?!

 correct all metallic radii for a
coordination number of 12.

|oord # Relative radius

12 1.000
8 0.97
6 0.96
4 0.88
 

 ? are solid solutions of metals. They are
usually prepared by mixing molten components.
They may be homogeneous, with a uniform
distribution, or occur in a fixed ratio, as in a
compound with a specific internal structure.
 

 

à÷?÷

 ? have a structure in which
sites of the solvent metal are occupied by solute
metal atoms. An example is brass, an alloy of
zinc and copper.
 

 

These alloys may form if:
1. The atomic radii of the two metals are within
15% if each other.
2. The unit cells of the pure metals are the same.
3. The electropositive nature of the metals is
similar (to prevent a redox reaction).
 ˜ 




˜ 
?

 ? are solid solutions in which
the solute atoms occupy holes (interstices)
within the solvent metal structure. An
example is steel, an alloy of iron and carbon.
 ˜ 




These alloys often have a non-
non-metallic solute
that will fit in the small holes of the metal
lattice. |arbon and boron are often used as
solutes. They can be dissolved in a simple
whole number ratio (Fe3|) to form a true
compound, or randomly distributed to form
solid solutions.
 ˜ 


| 
àome mixtures of metals form alloys with
definite structures that may be unrelated to the
structures of each of the individual metals. The
metals have similar electronegativities, and
molten mixtures are cooled to form compounds
such as brass (|uZn), ÿgZn2, |u3Au, and
Na5Zn2.
 ˜
| 
àince anions are often larger than cations,
ionic structures are often viewed as a close-
close-
packed array of anions with cations added, and
sometimes distorting the close-
close-packed
arrangement.
| |
ð


1. The Rock àalt (Na|l)
structure--
structure
|an be viewed as a
face--centered cubic array
face
of the anions, with the
cations in all of the
octahedral holes, or
| |
ð


1. The Rock àalt (Na|l)
structure--
structure
A face-
face-centered cubic
array of the cations with
anions in all of the
octahedral holes.
| |
ð


1. The Rock àalt (Na|l)
structure--
structure
The coordination
number is 6 for both ions.
| |
ð


2. The |s|l structure-
structure-
|hloride ions occupy the
corners of a cube, with a
cesium ion in the center
(called a ÷!
÷!)) or vice
versa. Both ions have a
coordination number of 8,
with the two ions fairly
similar in size.
 | |
ð


3. The Zinc-
Zinc-blende or àphalerite structure-
structure-
Anions (à2-) ions are in a face-
face-centered cubic
arrangement, with cations (Zn2+) in half of the
tetrahedral holes.
 | |
ð


4. The Fluorite (|aF2) and Antifluorite structures
face-centered cubic arrangement of |a2+
A face-
ions with F- ions in all of the tetrahedral holes.
 | |
ð


4. The Fluorite (|aF2) and Antifluorite structures
The antifluorite structure reverses the
positions of the cations and anions. An example
is K2O.
 ˜



Ionic radii are difficult to determine, as x-
x-ray
data only shows the position of the nuclei, and
not the electrons.
ÿost systems assign a radius to the oxide ion
(often 1.40Å), and the radius of the cation is
determined relative to this assigned value.
 ˜



mike metallic radii, ionic radii seem to vary
with coordination number. As the coordination
number increases, the apparent ionic radius
increases.
 ˜



1. Ionic radii increase as you go down a group.
2. Radii of ions of similar charge decrease across a
period.
3. If an ion can be found in many environments,
its radius increases with higher coordination
number.
4. For cations, the greater the charge, the smaller
the ion (assuming the same coordination #).
5. For atoms near each other on the periodic
table, cations are generally smaller than anions.
 


|
  

[eneral ´rulesµ have been developed, based
on unit cell geometry, to predict crystal
structures using ionic radii.
Radius ratios, usually expressed as the (radius
of the cation)/(radius of the anion) are used.
 


|
  

[eneral ´rulesµ have been developed, based
on unit cell geometry, to predict crystal
structures using ionic radii.
Radius ratios, usually expressed as the (radius
of the cation)/(radius of the anion) are used.
This assumes that the cation is smaller than the
anion.



|
  

|N r+/r- accuracy
8 •0.70 quite reliable
6 0.4 -0.7 moderately reliable
4 0.2 ²0.4 unreliable
3 0.10 -0.20 unreliable
 6


˜
 
The 
 

is a measure of the strength
of ionic bonds within a specific crystal structure.
It is usually defined as the energy change when a
mole of a crystalline solid is formed from its
gaseous ions.
ÿ+(
) + X-(
) † ÿX(s)
 m

6


ÿ+(
) + X-(
) † ÿX(s) ¨6 = mattice 6nergy

mattice energies cannot be measured directly,

so they are obtained using Hess· maw. They will
vary greatly with ionic charge, and, to a lesser
degree, with ionic size.
 


 | 6lectron
Affinity of |l

˜

 


 

Ú  mattice 6nergy

of K|l

Ú   
|
Ionic charge has a
huge effect on
lattice energy.
 m

6


Attempts to predict lattice energies are
generally based on coulomb·s law:
VAB = (Zae)(Zbe)
4ưƥorAB
Za and Zb = charge on cation and anion
e= charge of an electron (1.602 x 10-19|)
4ưƥo=permittivity of vacuum (1.1127 x 10-10J-1|2m-1)
rAB = distance between nuclei
 m

6


àince ionic crystals involve more than 2 ions,
the attractive and repulsive forces between
neighboring ions, next nearest neighbors, etc.,
must be considered.
 ð

 |  
The ÿadelung constant is derived for each
type of ionic crystal structure. It is the sum of a
series of numbers representing the number of
nearest neighbors and their relative distance
from a given ion.
The constant is specific to the crystal type
(unit cell), but independent of interionic
distances or ionic charges.
 
 |  
|rystal àtructure ÿadelung |onstant
|esium chloride 1.763
Fluorite 2.519
Rock salt (Na|l) 1.748
àphalerite 1.638
Wurtzite 1.641
 6

m

6


6c = Nÿ(Z+)( Z-) e2
4ưƥor
where N is Avogadro·s number, and
ÿ is the ÿadelung constant (sometimes
represented by A)

This estimate is based on coulombic forces,

and assumes 100% ionic bonding.