TIPE-TIPE STRUKTUR PADATAN IONIK

SEDERHANA
Ionic Solids
• form when electrostatic attraction sticks
together anions and cations to form a
crystal lattice.
• In an ionic crystal, each ion is surrounded
by ions having an opposite charge.
• Ionic crystals are extremely stable since
considerable energy is required to break
ionic bonds.
Contoh Garam dapur (NaCl)
Most Common MX Structures
NaCl structure
Na+ in fcc lattice
Cl- in Oh “holes”

CsCl structure
Cl- in simple cubic lattice
Cs+ in cubic “hole”

Zinc blende (ZnS) structure

S-2 in fcc lattice
Zn+2 in alternating Td “holes”
COORDINATION # AND IONIC RADII
• Coordination # increases with
Issue: How many anions can you
arrange around a cation?

Adapted from Fig. 12.4,

Callister 6e.

Adapted from Fig. 12.2,

Callister 6e.

Adapted from Fig. 12.3,

Adapted from Table Callister 6e.
12.2, Callister 6e.
16
Most Common MX2 Structures

Fluorite (CaF2) structure

Ca+2 in fcc lattice
F- in all Td “holes”

Rutile (TiO2) structure

Ti+2 in body centered cubic lattice
Oxygens in lower symmetry array.
Sejumlah aturan
• Prinsip Laves
• Model ion Goldschmidt
• Aturan Pauling I-V
• Aturan Fajan
• Triangel Ketelaar
• Plot Mooser-Pearson
• Plot Phillips – van Vechten
 Laves' Principle:
The most stable structure for a solid is one in
which the most efficient use is made of space.
When a compound forms a crystalline solid,
itsatoms, ions, or molecules pack as closely as
possible.
1. Space Principle: Space is used most efficiently
2. Symmetry Principle: Highest possible symmetry is
adopted
3. Connection Principle: There will be the most possible
"connections“ between components (i.e. coordination
numbers are maximized)

Followed by metals and inert gases - close-packed structures

Deviations include:- bcc metals
 GOLDSCHMIDT’S RULES
1. The ions of one element can extensively replace
those of another in ionic crystals if their radii differ
by less than approximately 15%.
2. Ions whose charges differ by one unit substitute
readily for one another provided electrical neutrality
of the crystal is maintained. If the charges differ by
more than one unit, substitution is generally slight.
3. When two different ions can occupy a particular
position in a crystal lattice, the ion with the higher
ionic potential forms a stronger bond with the
anions surrounding the site.
 RINGWOOD’S MODIFICATION OF
GOLDSCHMIDT’S RULES
4. Substitutions may be limited, even when the size
and charge criteria are satisfied, when the
competing ions have different electronegativities
and form bonds of different ionic character.
This rule was proposed in 1955 to explain
discrepancies with respect to the first three
Goldschmidt rules.
For example, Na+ and Cu+ have the same radius
and charge, but do not substitute for one
another.
 Coupled Substitution
• When the ion of a major element in a mineral is
replaced with something having a different
charge, the charge imbalance created must be
neutralized by addition of a counter ion
• Example  addition of Al3+ in a silicate structure
(replacing Si4+) requires addition of a Na+ or K+
(Key to understanding feldspar chemistry…).
When 2 Al3+ are added for Si4+, this then can be
balanced by adding a Ca2+ ion
 Combining phase and composition
diagrams for mineral groups
Mica ternary
Muscovite
KAl2(AlSi3O10)(OH)2

No micas
Miscibility Gap

Biotite series
Annite Phlogopite
KFe3(AlSi3O10)(OH)2 KMg3(AlSi3O10)(OH)2
 Pauling’s Rules of Mineral
Structure
Rule 1: A coordination polyhedron
of anions is formed around each
cation, wherein:
- the cation-anion distance is
determined by the sum of the
ionic radii, and
- the coordination number of the Linus Pauling

polyhedron is determined by the

cation/anion radius ratio (Ra:Rx)
 Pauling’s Rules of Mineral
Structure

Rule 2: The electrostatic valency principle

The strength of an ionic (electrostatic)
bond (e.v.) between a cation and an anion
is equal to the charge of the anion (z)
divided by its coordination number (n):
e.v. = z/n
In a stable (neutral) structure, a charge
balance results between the cation and its
polyhedral anions with which it is bonded.
Charge Balance
of Ionic Bonds
 Formation of Anionic Groups
Results from high valence cations with electrostatic
valencies greater than half the valency of the
polyhedral anions; other bonds with those anions will
be relatively weaker.
Carbonate Sulfate
 Pauling’s Rules of Mineral
Structure
• Rule 3: Anion polyhedra that share edges or
faces decrease their stability due to bringing
cations closer together; especially significant for
high valency cations

• Rule 4: In structures with different types of

cations, those cations with high valency and
small CN tend not to share polyhedra with each
other; when they do, polyhedra are deformed to
accommodate cation repulsion
 Pauling’s Rules of Mineral
Structure
• Rule 5: The principle of parsimony

Because the number and types of different structural

sites tends to be limited, even in complex minerals,
different ionic elements are forced to occupy the same
structural positions – leads to solid solution.

See amphibole structure for example (See Mineralogy CD:

Crystal and Mineral Chemistry – Pauling’s Rules - #5)
 Visualizing Crystal Structure
Beryl - Be3Al2(Si6O18)

Ball and Stick Model Polyhedra Model

Aturan Fajan
• Small highly charged cations are more
polarizing
• Large highly charged anions are more
polarizable
• Polarization is favored for cations that do
not have a noble gas electron
configuration
– Ag+, Cu+, Zn2+, Cd2+, Hg2+, Tl+ etc.
Triangel Ketelaar