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Lecture 28 Outline

Chapter 12
4 types of crystalline solids

Recitation: Quiz on Chapter 15 and 12.1-12.4

Proteins, DNA
Crystalline Solids

 
 
 Crystalline Solids
When cooled slowly, atomic and molecular building blocks can
assemble into well-ordered minimum-energy structures: |


Examples

CuSO4‡ 5H2O Quartz SiO2 Cholesterol

Ag Cu MnB(OH)3
Pharmaceutical Example: ³ROY´
5-Methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile

@ @
N C

H
N

S
CH3

* polymorphic forms

more generally«
 Comparison: Amorphous solids
Tar, molten glass, molten plastics,
and molten butter, consist of large
molecules or a mixture of
molecules that cannot move
readily. As the temperature is
lowered, their molecules move
more and more slowly and finally
stop in random positions. The
resulting materials are called
i !"# or glasses.
Such solids lack an ordered
internal structure. Common
examples include candle wax,
butter, glass, and plastics.
 Crystalline Solids
Metallic crystals
Ag, Cu: metallic bonds, soft to hard, low to high melting
points, good conductors of heat and electricity

Crystals of packed molecules

CH4, cholesterol: dispersion, dipole-dipole, H-bonds«,
soft, low melting, poor conductors

Ionic crystals
NaCl, CuSO4: electrostatic attraction, hard, brittle, poor
conductors of heat and electricity

Network covalent crystals

Diamond, -SiO2-: hard, high melting, poor electrical
conductors, poor to excellent heat conduction
 Definitions

Unit Cell: The smallest repeating unit in a three dimensional

structure (lattice)

Different geometric arrangements

depending on the crystal type

Characterized by a coordination number

(number of nearest neighbors)

Bonding

and a lattice parameter, a (edge length)

Atomic radius -- Bulk density
 The crystal lattice and the unit cell

The unit cell is the

minimum repeating
unit necessary to
describe the crystal.
 Definitions

Crystal Systems: Arrangements for stacking spheres, each one

characterized by a packing efficiency (percentage of
total volume occupied by spheres)

Cubic Systems

a=b=c, 4
=90°

CN PE
Simple Cubic (SC) * 54%

 ody-centered Cubic ( CC) 8 *8%

Face-centered Cubic (FCC) 12 74%

 |i"

There are 7 types of crystal systems, 14 units cells, but we will look at
u!$u and the
%i &i" systems.

' "
u!$u!&u
""
8 atoms define corners ± atoms touch along edges, but not along
diagonal
Coordination # = *. 4 in layer, 1 above, 1 below
1 atom/unit cell (1/8 † 8 atoms)

'(#)u
&

#u!$u!&u
""
8 atoms define corners plus one in center ± atoms touch central atom,
not each other
Coordination # = 8. 4 above and 4 below.
2 atoms/unit cell (1/8 † 8 atoms + 1 atom in center)

å'iu
)u
&

#u!$u!&u
""
8 atoms define corners plus * in center of each face ± Corner atoms
touch face atom, not each other
Coordination # = 12. 4 in layer, 1 above, 1 below, * faces
4 atoms/unit cell (1/8 † 8 crnr atoms + ½ † * face atoms)
 Simple Cubic (SC)

‡ SC lattice and crystal structure

Coordination number = 6
a
SC
a = 2R

Where:
R = atomic radius
a = lattice parameter

Packing fraction = 54%

  ody Centered Cubic ( CC)

P cking fr ction 68%

Coordin tion number 8

BCC

Where:
tomic r dius
l ttice p r meter

'

#
 u
*+

 Cubic Packing -  CC

i
¥3a

a
¥2 a ¥2 a

a
´3a=4R
a=4R/´3
Face Centered Cubic (FCC)
A close-picked structure
with i picking friction of 7 %

Coordinition number 1

||

i
Where:
itomic ridius
i littice pirimeter
 Packing Arrangements
How do these packing arrangements arise?

Start always with a layer of atoms, separated center to center

by the lattice parameter, a.

Then, place a layer on top, over atoms or over spaces.

 Thus, for a simple cubic lattice (SC):

The first layer is spaced with a = 2R

Then the second layer is placed with every atom directly atop
the one below
Not a close-packed structure.
Coordination number = 6
(octahedral)
Packing fraction = 54%
 For a body-centered cubic lattice ( CC):

The first layer is spaced with 

Still not a close-packed structure.
Coordination number = 8
(bi-prism)

Packing fraction = 68%

Then, the second layer is placed over the spaces between atoms.

Finally, a third layer lines up directly over the atoms in the first.
 The close-packed crystal systems
Cubic closest packing or face-centered cubic, FCC

Shift every other row in the first layer

to compress packing

Place second layer over triangular spaces

Third layer over gaps that remain

Tilt to find unit cell

A close-packed structure with a packing

fraction of 74%

abcabc«
 The close-packed crystal systems
Hexagonal closest packing, HCP

Shift every other row in the first layer

to compress packing

Place second layer over triangular spaces

Third layer directly over the atoms of the first

Rhombic unit cell

A close-packed structure with a packing

fraction of 74%

Coordination # = 12
(3 above, * in the plane, 3 below)
abab«
Packing efficiency
Describes the total volume occupied by atoms in the unit cell.

For a given atom radius, the higher the coordination, the higher the
packing efficiency:
|
 |

 
  
 

   


    
   $ %

!"
  #
&'
 $ %

You can calculate these from simple geometry, like you did in lab, by
relating the unit cell and atomic radius information.

Most metallic elements pack in hexagonal closest packing lattice.

Many ionic compounds are fcc. (NaCl ± two interspersed fcc lattices.)
 Packing of spheres.

simple cubic
(52% packing efficiency)

body-centered cubic
(*8% packing efficiency)
 layer a

Y
 layer b

  

layer a layer c
   

closest packing of first

and second layers

abab« abcabc«
 The structures of simple ionic
compounds
In simple ionic structures
‡space is filled as compactly as possible
‡ions of one charge are surrounded by as many ions as
possible of the opposite charge
‡positive and negative ions touch
Ionic structures are determined by two principal factors
‡the relative sizes of the ions
‡the ratio of the numbers of positive and negative ions in
the compound
 The structures of simple ionic
compounds
In simple ionic structures we usually find the anions, which
are normally larger than the cations, arranged in a simple
cubic or a closest packed array.
‡Relatively small cations occupy tetrahedral holes
‡Larger cations occupy octahedral holes
‡Even larger cations occupy larger cubic holes in a
simple cubic array of anions
 Holes


i
#i" ,ui
#i" "
|!$u "

"

 The CsCl structure

|"Ë &
|- &
 The CsCl unit cell

CsCl: Cs+ ions occupy all

the cubic holes in a
simple cubic array of Clù
ions.

A unit cell contains 1 Cs+

ion and 1 Clù ion. Ions
touch along the body
diagonal.
 The CaF2 structure

Fù ion

Ca2+ ion
 The CaF2 unit cell

CaF2: Fù ions occupy all

the cubic holes in a
simple cubic array of
Ca2+ ions.
 
*"!
.|i'!u!
/

A unit cell contains 4 Ca2+ ions and 8 Fù

ions. Ions touch along the body diagonal.

F- ions are tetrahedral coordinated, Ca2+ are octahedrally coordinated.

 The NaCl structure

|"Ë &
i- &
The NaCl unit cell
The NaCl unit cell
The sodium chloride structure.

expanded view space-filling

A unit cell contains 4 Na+ ions and 4 Clù ions.

Ions touch along the cell edge
 The ZnS, zinc blende, structure

S2ù ion

Zn2+ ion
 The zinc blende unit cell

A unit cell contains 4 Zn2+ ions and 4 S2ù ions. Ions

touch along the body diagonal.
Õ&- &*&
i
#i" "