EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics

NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

 COVALENT BONDING
Requires shared electrons

Example: CH4
C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.
 EXAMPLES: COVALENT BONDING
H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)
14 different point lattices, called Bravais lattices, make up the crystal system.
The lengths of the sides, a, b, and c, and the angles between them can vary for
a particular unit cell.
Summary: Bravais Lattices (Nets)
in Two Dimensions
Summary: Fourteen Bravais
Lattices in Three Dimensions
Fourteen Bravais Lattices
Three simple lattices that describe metals are Face Centered Cubic (FCC)
Body Centered Cubic (BCC) and Hexagonal Close Packed (HCP)
 SIMPLE CUBIC STRUCTURE (SC)
Rare due to poor packing (only Po has this structure)
Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)

4
 FACE CENTERED CUBIC STRUCTURE (FCC)
Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

Coordination # = 12

6
 BODY CENTERED CUBIC STRUCTURE (BCC)
Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

Coordination # = 8

8
HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
ABAB... Stacking Sequence
3D Projection 2D Projection

A sites

B sites

A sites
Adapted from Fig. 3.3,
Callister 6e.

Coordination # = 12
APF = 0.74

10
HCP Crystal
 CERAMIC BONDING
Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
Large vs small ionic bond character:

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University. 14
 IONIC BONDING & STRUCTURE
Charge Neutrality:
--Net charge in the
structure should
be zero.

--General form:

Stable structures:
--maximize the # of nearest oppositely charged neighbors.

15
 COORDINATION # AND IONIC
RADII
Coordination # increases with
Issue: How many anions can you
arrange around a cation?

16
 AmXp STRUCTURES
r cation 0.100
Consider CaF2 : 0.8
r anion 0.133
Based on this ratio, coord # = 8 and structure = CsCl.
Result: CsCl structure w/only half the cation sites
occupied.
Only half the cation sites
are occupied since
#Ca2+ ions = 1/2 # F- ions.

18
 STRUCTURE OF COMPOUNDS: NaCl
Compounds: Often have similar close-packed structures.
Structure of NaCl Close-packed directions
--along cube edges.

21
Diamond, BeO and GaAs are examples of FCC structures with two atoms per
lattice point
 Higher Order Structure

BCC FCC

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 Attachment
Allotropy is the property of some chemical
elements to be able to take two or more
different forms, where the atoms are
arranged differently by chemical bonds.
The forms are known as allotropes of that
element.[1] The phenomenon of allotropy is
sometimes also called allotropism.
For example, carbon has two common
allotropes: diamond, where the carbon atoms
are bonded together in a tetrahedral lattice
arrangement,
and graphite, where the carbon atoms are
bonded together in sheets of a hexagonal
Three-dimensional structure
of bonding in the covalent
solid, carbon (diamond).
Each carbon atom (C) has
four covalent bonds to four
other carbon atoms. Note,
the bond-line schematic of
covalent bonding is given a
perspective view to
emphasize the spatial
arrangement of bonded
carbon atoms.
 MILLER INDICES

BIDANG KRISTAL
ARAH KRISTAL

Vector r passing from the origin to a lattice point:

r = r1 a + r2 b + r3 c
a, b, c fundamental translation vectors
Miller Indices for directions

(4,3)

(0,0)

5a + 3b

b

a
Miller indices [53]
ARAH KRISTAL
 [001]
[011]

[101]

[010]

[111]
[110]
[110]
[100]

Coordinates of the final point coordinates of the initial point

Reduce to smallest integer values
BIDANG KRISTAL
Family of directions

Index Number in the family for cubic lattice

<100> 3x2=6

<110> 6 x 2 = 12

<111> 4x2=8

Alternate
Symbol
symbol
[] Particular direction
<> [[ ]] Family of directions
Miller Indices for planes

(0,0,1)

(0,3,0)

(2,0,0)

Find intercepts along axes 2 3 1

Take reciprocal 1/2 1/3 1
Convert to smallest integers in the same ratio 3 2 6
Enclose in parenthesis (326)
 Intercepts 1 Intercepts 1 1
Plane (100) Plane (110)
Family {100} 3 Family {110} 6

Intercepts 1 1 1
Plane (111)
Family {111} 8
(Octahedral plane)
(111)

Family of {111} planes within the cubic unit cell

d111 a / 3 a 3 / 3
The (111) plane trisects the body diagonal

(111) Plane cutting the cube into two polyhedra

with equal volumes
The (111) planes:
 Tetrahedron inscribed inside a cube
with bounding planes belonging to the
{111} family

8 planes of {111} family forming a

regular octahedron
 Unknown direction [uvw]
Unknown plane (hkl)
Double digit indices should be separated by commas (12,22,3)
In cubic crystals [hkl] (hkl)

a
d hkl
h2 k 2 l 2
Hexagonal crystals Miller-Bravais Indices

a3 Intercepts 1 1 -
Plane (1 12 0) (h k i l)
i = (h + k)

a2

a1
The use of the 4 index notation is to bring out the equivalence
between crystallographically equivalent planes and directions
Examples to show the utility of the 4 index notation
a3

a2

a1

Intercepts 1 -1 Intercepts 1 -1
Miller (1 1 0 ) Miller (0 1 0)
Miller-Bravais (1 1 0 0 ) Miller-Bravais (0 11 0)
Examples to show the utility of the 4 index notation

a3

a2

a1 Intercepts 1 1 -
Intercepts 1 -2 -2
Plane (2 11 0 ) Plane (1 12 0)