SOLIDS

can be divided into two catagories.

Crystalline
Amorphous

Crystalline has long range order

Amorphous materials have short range order

Effect of Crystallinity on Physical properties - ex. Polyethylene
1

TYPES OF CRYSTALLINE SOLIDS

Crystal
Type

Particles

Interparticle
Forces

Physical Behaviour

Examples

Atomic

Atoms

Dispersion

Group 8A
Ne to Rn

Molecular

Molecules

Dispersion
Dipole-dipole
H-bonds

Metallic

Atoms

Metallic bond

Ionic

Positive and
negative
ions

Ion-ion
attraction

Soft
Very low mp
Poor thermal and electrical
conductors
Fairly soft
Low to moderate mp
Poor thermal and electrical
conductors
Soft to hard
Low to very high mp
Mellable and ductile
Excellent thermal and electrical
conductors
Hard and brittle
High mp
Good thermal and electrical
conductors in molten condition
Very hard
Very high mp
Poor thermal and electrical
conductors

Network

Atoms

Covalent

O2, P4, H2O,

Sucrose

Na, Cu, Fe

NaCl, CaF2,
MgO

SiO2(Quartz)
C (Diamond)
2

STRUCTURES OF CRYSTALLINE SOLID TYPES

Na+
Cl-

Molecular Solids

Covalent Solids

Ionic solids

Metallic solids
3

DIAMOND

QUARTZ

GRAPHITE

CRYSTAL STRUCTURE
Crystal structure is the periodic arrangement of atoms in the
crystal. Association of each lattice point with a group of
atoms(Basis or Motif).
Lattice: Infinite array of points in space, in which each point has
identical surroundings to all others.
Space Lattice Arrangements of atoms
= Lattice of points onto which the atoms are hung.

Space Lattice + Basis = Crystal Structure

Elemental solids (Argon): Basis = single atom.
Polyatomic Elements: Basis = two or four atoms.
5
Complex organic compounds: Basis = thousands of atoms.

ONE DIMENTIONAL LATTICE

a

ONE DIMENTIONAL UNIT CELL

UNIT CELL : Building

block, repeats in a regular way

TWO DIMENTIONAL LATTICE

TWO DIMENTIONAL UNIT CELL TYPES

b
a b, 90
a
a
a b, = 90

a
b a b, = 90

a = b, =120

a = b, = 90 a
a

a
a

EXAMPLE OF TWO DIMENTIONAL UNIT CELL

TWO DIMENTIONAL UNIT CELL POSSIBILITIES OF NaCl

Na+
Cl-

10

THREE DIMENTIONAL UNIT CELLS / UNIT CELL SHAPES

1

2
3
4
5

6
11

LATTICE TYPES

Primitive ( P )

Face Centered ( F )

Body Centered ( I )

C-Centered (C )
12

BRAVAIS LATTICES

7 UNIT CELL TYPES + 4

LATTICE TYPES = 14
BRAVAIS LATTICES
13

COUNTING ATOMS IN THE THREE DIMENTIONAL

UNIT CELL

Atoms in different positions in a cell are shared by

differing numbers of unit cells
Vertex(corner) atom shared by 8 cells 1/8 atom per cell
Edge atom shared by 4 cells 1/4 atom per cell
Face atom shared by 2 cells 1/2 atom per cell
Body unique to 1 cell 1 atom per cell
14

CLOSE-PACKING OF SPHERES

15

SINGLE LAYER PACKING

SQUARE PACKING

CLOSE PACKING

Close-packing-HEXAGONAL
coordination of each sphere
16

TWO LAYERS PACKING

17

THREE LAYERS PACKING

18

19

Hexagonal close packing

Cubic close packing

20

CUBIC CLOSE PACKED

HEXAGONALCLOSE PACKED

V. 1 atom = 4/3 r3
V. Unit cell = a3 = r3
Efficiency of packing = V. 4 atom : V. unit cell
= V. 4 atom : V. cubic
= 0,7405

74% Space is occupied.

V. 1 atom = 4/3 r3
V. Unit cell = 6.a.c = 6.(r.r3).c
Eff. Of pack.= V. 6 atom : V. hexagonal
= 0,7405

Coordination number = 12 21

NON-CLOSE-PACKED STRUCTURES
a) Body centered cubic
( BCC )

b) Primitive cubic
( P)

V. 1 atom = 4/3 r3
V. 1 atom = 4/3 r3
V. Unit cell = a3 = r3
V. Unit cell = a3 = r3
Eff. Of pack. = V. 2 atom : V. cubic Eff. Of pack. = V. 1 atom : V. cubic
= 0,6802
= 0,5238
68% of space is occupied
Coordination number = 8

52% of space is occupied

Coordination number = 6

22

CRYSTAL DENSITIES
D = mass per sel satuan / Volume sel satuan
= massa molar x Z/ molar volum
= FW x Z / (V x N)
V= volume sel satuan
N= bilangan avogadro
Z= jumlah atom dalam sel satuan
D = ( FW x Z x1,66)/ V (0A)

gram/cm3

23

Nonclose
packing

Close
packing

Structure

Coordination
number

Stacking
pattern

Primitive
Cubic

AAAAA

Bodycentered
Cubic

ABABAB

Hexagonal
close packed

12

ABABAB

Cubic close
packed

12

ABCABC
24

Primitive cubic Body centered cubic Face centered cubic

Coordination
number

12

25

26

ALLOTROPES

Existence of same element in different crystal

structures.
eg. Carbon

Diamond

Graphite

Buckminsterfullerene

27

TYPE OF HOLES IN CLOSE PACKING

TETRAHEDRAL HOLES

OCTAHEDRAL HOLES

28

LOCATION OF OCTAHEDRAL HOLES IN CLOSE PACKING

29

LOCATION OF TETRAHEDRAL HOLES IN CLOSE PACKING

30

IONIC CRYSTAL STRUCTURES

Ionic structures may be derived from the

occupation of holes by oppositely charged
ions (interstitial sites) in the close-packed
arrangements of ions.

31

Hole Occupation - RADIUS RATIO RULE

Radius of the positive ion
Radius ratio

Radius of the negative ion

Radius ratio

Coordinate
number

Holes in which
positive ions pack

0.225 0.414

Tetrahedral holes

0.414 0.732

Octahedral holes

0.732 1

Cubic holes
32

IONIC CRYSTAL TYPES

Ionic crystal
type

Co-ordination
number
A
X

Structure type

AX

6
8

6
8

NaCl
CsCl

AX2

6
8

3
4

Rutile(TiO2)
Fluorite (CaF2)

ReO3

AX3
33

STRUCTURE TYPE - AX
CLOSE PACKED STRUCTURES
a) ROCK SALT STRUCTURE (NaCl)

CCP Cl- with Na+ in all Octahedral

holes
Lattice: FCC
Motif: Cl at (0,0,0); Na at (1/2,0,0)
4 NaCl in one unit cell
Coordination: 6:6 (octahedral)
Cation and anion sites are topologically
identical

34

b) SPHALERITE OR ZINC BLEND (ZnS) STRUCTURE

CCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-}

filled)
Lattice: FCC
4 ZnS in one unit cell
Motif: S at (0,0,0); Zn at (1/4,1/4,1/4)
Coordination: 4:4 (tetrahedral)
Cation and anion sites are topologically identical
35

c) NICKEL ARSENIDE (NiAs)

HCP with Ni in all Octahedral holes

Lattice: Hexagonal - P
Motif: 2Ni at (0,0,0) & (0,0,1/2) 2As at (2/3,1/3,1/4)
& (1/3,2/3,3/4)
2 NiAs in unit cell
Coordination: Ni 6 (octahedral) : As 6 (trigonal
prismatic)
36

d) WURTZITE ( ZnS )

HCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-}

filled )
Lattice: Hexagonal - P
Motif: 2 S at (0,0,0) & (2/3,1/3,1/2); 2 Zn at (2/3,1/3,1/8) &
(0,0,5/8)
2 ZnS in unit cell
Coordination: 4:4 (tetrahedral)

37

COMPARISON OF WURTZITE AND ZINC BLENDE

38

STRUCTURE TYPE - AX

NON CLOSE PACKED STRUCTURES

CUBIC-P (PRIMITIVE) ( eg. Cesium Chloride ( CsCl ) )

Motif: Cl at (0,0,0); Cs at (1/2,1/2,1/2)

1 CsCl in one unit cell
Coordination: 8:8 (cubic)
Adoption by chlorides, bromides and iodides of larger cations,
e.g. Cs+, Tl+, NH4+
39

STRUCTURE TYPE - AX2

CLOSE PACKED STRUCTURE eg. FLUORITE (CaF2)

CCP Ca2+ with F- in all Tetrahedral holes

Lattice: fcc
Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4)
4 CaF2 in one unit cell
Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral)
In the related Anti-Fluorite structure Cation and
Anion positions are reversed

40

STRUCTURE TYPE - AX2

CLOSE PACKED STRUCTURE eg. FLUORITE (CaF2)

CCP Ca2+ with F- in all Tetrahedral holes

Lattice: fcc
Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4)
4 CaF2 in one unit cell
Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral)
In the related Anti-Fluorite structure Cation and
Anion positions are reversed

41

ALTERNATE REPRESENTATION OF FLUORITE

STRUCTURE

AntiFlourite structure (or Na2O structure) positions of

cations and anions are reversed related to Fluorite structure
42

RUTILE STRUCTURE, TiO2

HCP of O2- ( distorted hcp or Tetragonal)

Ti4+ in half of octahedral holes

43

STRUCTURE TYPE - AX2

NON-CLOSE PACKED STRUCTURE
LAYER STRUCTURE ( eg. Cadmium iodide ( CdI2 ))

HCP of Iodide with Cd in Octahedral holes of alternate layers

CCP analogue of CdI2 is CdCl2
44

COMPARISON OF CdI2 AND NiAs

45

HCP ANALOGUE OF FLOURITE (CaF2) ?

No structures of HCP are known with all Tetrahedral sites (T+
and T-) filled. (i.e. there is no HCP analogue of the Fluorite/AntiFluorite Structure).
The T+ and T- interstitial sites above and below a layer of closepacked spheres in HCP are too close to each other to tolerate the
coulombic repulsion generated by filling with like-charged species.

Fluorite

Unknown HCP
analogue of
Fluorite

46

HOLE FILLING IN CCP

47

SUMMARY OF IONIC CRYSTAL STRUCTURE TYPES

Formula
AX

AX2

CCP

Type and fraction of sites

occupied

HCP

All octahedral

Rock salt (NaCl)

Nickel Arsenide (NiAs)

Half tetrahedral (T+ or T-)

Zinc Blend (ZnS)

Wurtzite (ZnS)

All Tetrahedral

Fluorite (CaF2),

Not known

Half octahedral (ordered

framework)
Half octahedral (Alternate
layers full/ empty)

Anti-Fluorite (Na2O)
Anatase (TiO2)

Rutile (TiO2)

Cadmium Chloride
(CdCl2)

Cadmium iodide (CdI2)

A3X

All octahedral & All

Tetrahedral

Li3Bi

Not known

AX3

One third octahedral

YCl3

BiI3

48

Examples of CCP Structure Adoption

Rock salt(NaCl) occupation of all octahedral holes
Very common (in ionics, covalents & intermetallics )
Most alkali halides (CsCl, CsBr, CsI excepted)
Most oxides / chalcogenides of alkaline earths
Many nitrides, carbides, hydrides (e.g. ZrN, TiC, NaH)
Fluorite (CaF2) occupation of all tetrahedral holes
Fluorides of large divalent cations, chlorides of Sr, Ba
Oxides of large quadrivalent cations (Zr, Hf, Ce, Th, U)
Anti-Fluorite (Na2O) occupation of all tetrahedral holes
Oxides /chalcogenides of alkali metals
Zinc Blende/Sphalerite ( ZnS ) occupation of half tetrahedral holes
Formed from Polarizing Cations (Cu+, Ag+, Cd2+, Ga3+...) and
Polarizable Anions (I-, S2-, P3-, ...)
e.g. Cu(F,Cl,Br,I), AgI, Zn(S,Se,Te), Ga(P,As), Hg(S,Se,Te)

49

Examples of HCP Structure Adoption

Nickel Arsenide ( NiAs ) occupation of all octahedral holes
Transition metals with chalcogens, As, Sb, Bi e.g. Ti(S,Se,Te);
Cr(S,Se,Te,Sb); Ni(S,Se,Te,As,Sb,Sn)
Cadmium Iodide ( CdI2 ) occupation half octahedral (alternate) holes
Iodides of moderately polarising cations; bromides and chlorides of
strongly polarising cations. e.g. PbI2, FeBr2, VCl2
Hydroxides of many divalent cations. e.g. (Mg,Ni)(OH)2
Di-chalcogenides of many quadrivalent cations . e.g. TiS2, ZrSe2, CoTe2
Cadmium Chloride CdCl2 (CCP equivalent of CdI2) half octahedral holes
Chlorides of moderately polarising cations e.g. MgCl2, MnCl2
Di-sulfides of quadrivalent cations e.g. TaS2, NbS2 (CdI2 form as well)
Cs2O has the anti-cadmium chloride structure

50

PEROVSKITE STRUCTURE

Formula unit ABO3

CCP of A atoms(bigger) at the corners
O atoms at the face centers
B atoms(smaller) at the body-center

51

PEROVSKITE

Lattice: Primitive Cubic (idealised structure)

1 CaTiO3 per unit cell
A-Cell Motif: Ti at (0, 0, 0); Ca at (1/2, 1/2, 1/2);
3O at (1/2, 0, 0), (0, 1/2, 0), (0, 0, 1/2)
Examples: NaNbO3 , BaTiO3 ,
Ca 12-coordinate by O (cuboctahedral) CaZrO3 , YAlO3 , KMgF3
Ti 6-coordinate by O (octahedral)
O distorted octahedral (4xCa + 2xTi)

Many undergo small distortions:

52
e.g. BaTiO3 is ferroelectric

SPINEL STRUCTURE
Formula unit AB2O4 (combination of Rock Salt
and Zinc Blend Structure)
Oxygen atoms form FCC
A2+ occupy tetrahedral holes
B3+ occupy octahedral holes

INVERSE SPINEL
A2+ ions and half of B3+ ions
occupy octahedral holes
Other half of B3+ ions occupy
tetrahedral holes
Formula unit is B(AB)O4
53