Atomic Bonding

PRIMARY
Covalent
sharing electrons
strong
directional
Ionic
trading of elecrons
electrostatic attraction or
ions
strong
non-directional
Metallic
metal ions in sea or
electrons
moderately strong
non-directional
SECONDARY
Van der Waals
H-bonding
electrostatic attraction of
electric dipole (local charge
distribution
weak
KEADAAN KRISTAL
Crystalline State

1. Sifat anisotrofik : - Cleavage
(anisotropic ) - Pleochroism
- Scratch
- Thermal conductivity
2. Sifat isotropik : gas,liquid,amorf
(isotropic)
Definition of Crystal
A crystal is an anisotropic, homogeneous
body, consisting of a three-dimensional
periodic ordering of atoms, ions or
molecules
Unit cells & description of crystal
structures.
A crystal can be regarded as consisting of
regularly repeating structural elements.
The crystal lattice is the pattern formed by the
points.
A unit cell is a subdivision of a crystal that,
when stacked together without rotation or
reflection, reproduces the crystal.

The lattice is a three-dimensional, infinite array of points,
the lattice points, each of which is surrounded in an
identical way by neighbouring points, and which defines
the basic repeating structure of the crystal.
Lattice and Unit cells
The line of dots is called the
lattice and each lattice point
(dot) must have identical
surroundings.
A unit cell is an imaginary
parallelepiped from which the
entire crystal can be built by
simple displacement operations
only.
Unit cell fit perfectly without any
empty space.
Unit cell parameters
a, b and c are the unit cell edge
lengths
o, | and are the angles (a
between b and c, etc....)
Unit cells may be chosen in a
variety of ways.
A primitive unit cell has only one
lattice point per unit cell.




(b) Generally preferred to
(a) because its smaller
The relationship between
the lattice parameters in
3D gives rise to the
seven crystal systems.
Bravais Lattice
Crystal System Centering
a
b
c
| o

P: Primitive: (x,y,z)
I: Body-centered: (x,y,z); (x+,y+,z+)
C: Base-centered: (x,y,z); (x+,y+,z)
F: Face-centered: (x,y,z); (x+,y+,z)
(x+,y,z+); (x,y+,z+)
(x,y,z): Fractional coordinates -
proportion of axis length, not
absolute distanct
Centering must apply to all atoms
in unit cell.
Bravais Lattices (14)
Crystal
System
Parameters
Primitive
(Simple)
Body-
Centered
Face-
Centered
Base-
Centered
Cubic
a=b=c
o=|==90
X X X
Tetragonal
a=b=c
o=|==90
X X
Orthorhombic
a=b=c
o=|==90
X X X X
Rhombohedral
a=b=c
o=|==90
X
Hexagonal
a=b=c
o=|=90, =120
X
Monoclinic
a=b=c
o==90, |=120
X X
Triclinic
a=b=c
o=|==90
X


4
Rare due to poor packing (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
SIMPLE CUBIC STRUCTURE (SC)
back
Body-Centered Cubic (BCC)
Face-Centered Cubic (FCC)
Atoms Per Unit Cell
(General Rule)
Corners - shared by eight unit
cells (x 1/8)
(0,0,0)=(1,0,0)=(0,1,0)=(0,0,1)=
(1,1,0)=(1,0,1)=(0,1,1)=(1,1,1)
Edges - shared by four unit cells
(x 1/4)
(0,0,)= (1,0,)= (0,1,)=
(1,1,)
Faces - shared by two unit cells (x
1/2)
(,,0)= (,,1)
Packing Factor
Fraction of space occupied by atoms
For FCC



For BCC
c b a
r
F P
i

=

3
3
4
t
. .
a
a
r
r a r a a
2
4
4 diagonal face
2 2
= = + =
( ) ( )
74 0
2 3
2
4
4 4
3
3
3
4
3
3
3
4
.
r
a
r
. F . P =
t
=
|
.
|

\
|
t
=
t
=
r a r a a a
3
4
4 diagonal body
3 2 2
= = + + =
( ) ( )
68 0
8
3
3
4
2 2
3
3
3
4
3
3
3
4
.
r
a
r
. F . P =
t
=
|
.
|

\
|
t
=
t
=
Calculating the unoccupied space in a
close-packed array
The dimensions involved in the calculation of the packing fraction in a
close-packed arrangement of identical spheres of radius r
Density
volume
mass
NaxV ZxMr
c u
volume
mole
atom
mole
mass
c u
atom
Density = =
|
.
|

\
|

|
.
|

\
|
|
.
|

\
|

|
.
|

\
|
= /
. .
. .
( )
3 3
8 24
915 8
10 5239 3 10 602 0
71 58
4
cm
g
.
cm x .
mole
atom
x .
mole
g
.
. c . u
atom
Density =

|
.
|

\
|
|
.
|

\
|

|
.
|

\
|
=

For nickel:
- Atomic weight = 58.71 g/mole
- Lattice parameter = 3.5239 =3.5239 x 10
-8
cm
- Avogrados No. = 6.02 x 10
23
= 0.602 x 10
24
= atoms/mole
Miller Indices
Planes
Directions
(hkl)
{hkl}
[hkl]
<hkl>
specific
family
specific
family
A family of planes includes all planes which are
equivalent by symmetry - depends on crystal system.
- For cubic: (110),(011) and (101) are all {110}
- For tetragonal: (011) and (101) are {101}
but (110) is not (c=a)
- No commas
- No fractions
- Negative
indicated by bar
overnumber
Miller Index
Defining particular plane of the atom with Miller Index
3 steps to determine the Miller Index
Find the intercepts x = 2, y = 3, and z = 2 from figure
Take the reciprocal of the axis length, 1/2, 1/3, and 1/2
Find the lowest common multiplier and then multiply the reciprocal
Then, the Miler Index is (3, 2, 3) 6*1/2, 6*1/3, 6*1/2.. Note ( )
Example,
z
x
y
b=3
a=2
c=2
Miller Indices - Directions
b
a
c
1
1/4
1/2
-1/3
1/2
-1
x
1
y
1/4
z
1/2 (x 4)
| | 2 1 4
x
1/2
y
-1
z
-1/3 (x 6)
| | 2 6 3
Miller Indices - Planes
4
1
2
1
b
a
c
4
1
2
1
b
a
c
x
1/4
4
y

0
z
-1/2
-2
( ) 2 0 4

intercept
reciprocal
Miller Indices - Planes
3
1
2
1
b
a
c
4
1
3
1
2
1
b
a
c
4
1
x
1/4
4
y
-1/3
-3
z
-1/2
-2
( ) 2 3 4

intercept
reciprocal
Crystal Chemistry
Crystals can be classified into 4 types:
1. Molecular Crystals
Neutral molecules held together by weak van der Waals
bonds
Rare as minerals
Mostly organic
Weak and readliy
decompose, melt, etc

Example: graphite
Crystal Chemistry
2. Covalent Crystals
Atoms of similar high e-neg and toward right side of PT
Also uncommon as minerals (but less so than molecular)
Network of strong covalent
bonds with no weak links
Directional bonds low
symmetry and density

Example: diamond
Crystal Chemistry
The diamond structure
All carbon atoms in IV coordination
ball-and-stick model polyhedral model
blue C only
hard-sphere model
FCC unit cell
Crystal Chemistry
3. Metallic Crystals
Atoms of similar e-neg and toward left side of PT
Metallic bonds are directionless bonds high
symmetry and density
Pure metals have same sized atoms
Closest packing 12 nearest mutually-touching
neighbors
Cubic Closest Packing (CCP) abcabcabc stacking =
FCC cell
Hexagonal Closest Packing (HCP) ababab = hexagonal
cell
Also BCC in metals, but this is not CP (VII coordination)

More on coordination and closest packing a bit later
Crystal Chemistry
4. Ionic Crystals
Most minerals
First approximation:
Closest-packed array of oxygen atoms
Cations fit into interstices between oxygens
Different types of interstitial sites available
Occupy only certain types where can fit
Occupy only enough of them to attain electric
neutrality

3
tend to be densely packed.
have several reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.

- Metallic bonding is not directional.
have the simplest crystal structures.
Metallic Crystals
Common Metal Structures
Simple Cubic (SC)
Face-Centered Cubic (FCC)
Body-Centered Cubic (BCC)
Hexagonal Close-Packed (HCP)

Metallic Crystal Structures
The atoms in most simple metals are
arranged in one of the configurations
below
Simple Cubic (sc) Po-type :Po (sangat jarang)
Body-Centered Cubic (bcc) W-type:Ba, Cs, Cr
Face-Centered Cubic (fcc)/ccp Cu-type, Ag,
Hexagonal Close-Packed (hcp) Mg-type:Zn, Co
Nearest-neighbors atoms touch in all of
these cases.

Body centered cubic- atom centered in the cube
Atomic packing factor (APF) is 0.68 and represents the fraction of the
unit cell occupied by the two atoms.
Ba, Ce, Li, K, molybdenum (less ductile metals)
Face centered cubic- atom centered on each of the faces
Atomic packing factor (APF) is 0.74 and represents the fraction of the
unit cell occupied by the two atoms.
Regular stackings of close-packed planes
Fourth close pack layer lies precisely above the first one
Al, Cu, Au, Pb, Ni, Platinum, Ag (soft metals)
Hexagonal close packed (HCP)
Two atoms are associated with each Bravais lattice point
One atom centered within the unit cell and various fractional atoms at
unit cells (four 1/6
th
atoms and four 1/12
th
atoms)
Close pack is efficient packing shperes as is the fcc structure.
Atomic packing factor (APF) is 0.74 and represents the fraction of the
unit cell occupied by the two atoms.
Regular stackings of close-packed planes
The third close-packed layer lies precisely above the first.
Be, Mg, Ti, Zn, Zr


Hexagonal Close-packed structure (continued)
the distance between atoms in the bases are equal in the
hexagonal structure. The bases are perpendicular to the
sides. The angle between the sides is 120.
Graphite has Close-packed hexagonal structure of Carbon
diamond has a form of face-centered closed -pack cubic
structure, or complex cubic structure (diamond structure)
other materials with closed-packed hexagonal structure
include Be, Cadmium, Co, Mg, Titanium, Zn, Zirconium



Hexagonal Close-Packed (HCP)
10
Coordination # = 12
ABAB... Stacking Sequence
APF = 0.74
3D Projection
2D Projection
A sites
B sites
A sites
Adapted from Fig. 3.3,
Callister 6e.
Hexagonal Close-Packed Structure
(hcp)
Note: this structure is NOT cubic
back
Cubic close-packed structure (c.c.p.) /
Face-centred cubic (f.c.p.)
Also known as
abcabctype
Each atom is
surrounded by / in
contact with 12 other
atoms its
coordination number
is also 12
12
Element
Aluminum
Argon
Barium
Beryllium
Boron
Bromine
Cadmium
Calcium
Carbon
Cesium
Chlorine
Chromium
Cobalt
Copper
Flourine
Gallium
Germanium
Gold
Helium
Hydrogen
Symbol
Al
Ar
Ba
Be
B
Br
Cd
Ca
C
Cs
Cl
Cr
Co
Cu
F
Ga
Ge
Au
He
H
Atomic radius
(nm)
0.143
------
0.217
0.114
------
------
0.149
0.197
0.071
0.265
------
0.125
0.125
0.128
------
0.122
0.122
0.144
------
------
Adapted from
Table, "Charac-
teristics of
Selected
Elements",
inside front
cover,
Callister 6e.
Characteristics of Selected Elements at 20C
IONIC CRYSTAL STRUCTURES
Ions form a crystal such that they are
closest packed.
This is a consequence of Coulombs
law.
Ions arrange themselves such that
interionic distances are minimized.
If we assume ions are hard,
incompressible spheres (like billiard
balls), we can use the concept of radius
ratio as a key to explaining crystal
structures.
Consider coordination of anions about a central
cation
Coordination Polyhedra
Halite
Cl
Cl
Cl
Cl
Na
[6]
NaCl
Packing and Geometry

close packing
ABC.ABC... cubic close-packed CCP
gives face centered cubic or
FCC(74.05% packed)
AB.AB... or AC.AC... (these are equivalent).
This is called hexagonal close-packing
HCP
Close Packed (CN=12)
Highest packing density for same sized spheres
FCC and HCP structures
Cube Center (CN=8)
Same atoms: BCC
Different atoms: CsCl
Octahedral Site (CN=6)
In FCC:
- Center (,,)
- Edges (0,0,),(0,,0),(,0,0)
- 4 per unit cell
- All filled - NaCl structure
8-sided shape
Tetrahedral Site (CN=4)
In FCC:
- Divide cell into 8 boxes - center of small box
- (,,),(,,),(,,),(,,)
(,, )(,, ),(,, )(,, )
-8 per unit cell
-All filled - CaF
2
structure; half-filled - ZnS
4-sided shape
Radius Ratio Rules
Critical Radius for CN 8 = 0.732
Critical Radius for CN 6 = 0.414
Critical Radius for CN 4 = 0.225
CN 8
CN 6
CN 4
CN 3
planar
Critical radius is size of atom which just fits in site
Define minimum for bonding (i.e. atoms must touch to bond)
Close Packed Plane
A B A B A
C
HCP: ABABABABABABABAB
FCC: ABCABCABCABCABC
Same packing density (0.74)
Same coordination (CN=12)