CHM 103 Fundamental Chemistry

Solids
Department of Chemistry, Faculty of Science
KingMongkutsUniversityofTechnologyThonburi

Solids
Contents

1. Type of Solids

2. Crystalline and Unit cell

3. The crystals System
4. Structure of Solids

5. Calculations (density, radius,

packing factor)
6. Structure of salts

7. Lattice Defect (Insulator,

Semiconductor )
2

Matter and Change

Important properties of the States of Matter
Property

Solid

Liquid

Shape

Definite

Indefinite

Indefinite

Volume

Definite

Definite

Indefinite

Moderate

Great

Almost
incompressible

Readily
compressible

Expansion on
Very slight
heating
Almost
Compressiincomprebility
ssible

Gas or vapor

1.Type of Solid

1.1 Crystalline
Crystal is a solid formed by a
repeating, three-dimensional
pattern of atoms, ions, or
molecules and having fixed
distances between the
different parts.

1.2 Amorphous
Amorphous solid that do
not grow in these regular
or crystalline patterns are
called Amorphous solids

1. TYPE OF

SOLIDS

1.1 Crystalline solids

-arranged of geometrical structure

- arranged in three dimensional pattern

1.1 Crystalline Solids

When cooled slowly, atomic and molecular building blocks can
assemble into well-ordered minimum-energy structures :Crystals
Examples

CuSO45H2O

Quartz SiO2

Cholesterol

Ag

Cu

MnB(OH)3

Characteristic of Crystallizes

- Geometric

- rigidity
- incompressibility
- sharp melting point

- anisotropy [

]
7

Types of Crystalline Solids and Their

Characteristics
Type of Solid

Intermolecular
Forces

Properties

Examples

Ionic

Ion-ion forces

Brittle, hard
High-melting

NaCl, KCl
MgCl2

Molecular

Dispersion forces,
dipole-dipole forces,

Soft, low-melting,
nonconducting

H2O, Br2
CO2, CH4

Covalent
network

Covalent bonds

Metallic

Metallic bonds

Hard,
high-melting

Variable hardness
and melting point,
conducting

C(dimond,
graphite),
SiO2

Na, Zn,
Cu, Fe
8

Type of Crystalline Solids

1.1.1 Ionic crystal , Ionic solids
Particle of solid
anions-

ions
cations+

( electrostatic attraction )
eg. NaCl ,
Na+

Cl9

Interionic Forces

10

Characteristic
of
ionic
solids

:
:
:
:

Hard and brittle

Soluble in water but not in polar solvent
High melting point
Poor conductivity in solid state
(when melts become good conductors

11

1.1.2 Molecular solids

Particles of solids=molecules
non polar molecule
london forces
I2 , N2 , C6H6 , S8 , P4, Sucrose(C12H22O11)

polar molecule
dipole - dipole , H2O
Hydrogen bond (NH3) Alcohol

Glycine [van der waal, H bond ]

12

Characteristic of Molecular solids

: Soft
: Poor conductivity of heat and electricity
: low melting point < 300oC

13

1.1.3Covalent crystal or Network solid

Particles of solid=atoms
: Intermolecular forces ; dipole-dipole , London dispersion
and H-bonds
: Atoms held together in large networks

Example
Carbon , graphite ,diamond , SiC,SiO2 (Quartz)
14

Characteristic of Covalent crystals

: Very hard
: High melting point { dimond > 3550oC
SiO2 1610oC, SiC 2700oC }
: Poor conductivity
: Insoluble , chemical inert

15

Nanotubes

Fullerene (C60)
(soccer ball)

C60 : is a molecular solid whose

molecules have the shape
of a soccer ball.

16

4.Metalliccrystal
: consist of cations (Mn+) held together by a
sea of electron (e-)

: Metals conduct because the electrons are

delocalizes and are mobile

: Metal eg. Au, Ag, etc

Metal in sea of electron

17

Characteristic of Metallic crystals

: Melting point and hardness are variable

[ Sb = 3300oC, Hg= -39oC]
: Excellent electrical and thermal conductors
: lustrous
: Malleable and ductile

18

1.2 Amorphous solid , isotropic substance,

supercooled liquid

:Random arrangement , no geometrical

structure
: Not sharp melting point
: Isotropic (mechanical strength electrical and
optical properties are all the same direction)
Example
Glasses , rubber and plastics
19

Crystalline and amorphous silicon dioxide

Heating 1,600oC

Quartz glass
Crystalline

Amorphous
20

Probing Structures of Solids:

X-Ray Crystallography
Wemustuselightwithawavelengthofapproximately10-10 m,
( = 10-10m
X ray region of the electromagnetic spectrum)

ToseeatomsinStructuresofsolids
(Diameters of around 2 x 10-10 m)
In 1912 Max von Laue
work with X ray
Crystallography on passing X-ray through a crystal
of Sodium Chloride.
21

Structures of Solids

X-Ray Diffraction

22

X-Ray Diffraction

X-ray diffraction (X-ray crystallography)

:X-rays are passed through the crystal and are detected
on a photographic plate.
:The photographic plate has one bright spot at the center
(incident beam) as well as a diffraction pattern.
:Each close packing arrangement produces a different
diffraction pattern.
:Knowing the diffraction pattern, we can calculate the
positions of the atoms required to produce that pattern.
:We calculate the crystal structure based on a
knowledge of the diffraction pattern.
23

Extra distance = BC + CD = 2d sin

=n

(Bragg Equation)
24
11.5

 X-rays will be diffracted by an array of

atoms in an ordered solid. The
diffraction is due to scattering of X-rays
by the atoms.
Bragg Equation

n = 2dsin
n= whole number
= wavelength of the x rays
d= distance between plans of atoms producing the diffracted beam
= the angle at which the diffracted x-ray beam emerges relation to
the plans of atoms producind the diffracted bean.
25

X rays of wavelength 0.154 nm are

diffracted from a crystal at an angle of
14.170. Assuming that n = 1, what is the
distance (in pm) between layers in the
crystal?
n = 2d sin

d=

n=1

n
2sin

= 14.170

= 0.154 nm = 154 pm

1 x 154 pm
= 77.0 pm
2 x sin14.17

26

11.5

2. Crystal lattice and Unit cell

Crystalline - have a repeating unit = unit cell

Unit cell : The smallest repeating unit in a three

dimensional structure that contains the
characteristics of the crystal as a whole
Lattice points : The points in space about which
the particles are free to vibrate in a crystal
A lattice isaninfinite1,2, or 3-D regular arrangement of
points, each of which has identical surrounding
27

Crystal lattice ,space lattice

Space lattice :The 3-D array of points which
represents and identical environment with in
the crystal

Space lattice in 2-dimension

28

Space lattice in 2-dimension

29

Space lattice in 3-dimension

30

Crystal Structures

31

Arrangement of crystal solids structure

Square arrangement

Closestpacking

32

A.Square arrangement

Packing of spheres

simple cubic
(52% packing
efficiency)

body-centered cubic
(68% packing efficiency)
33

B. Closestpacking
layer a

layer a

hexagonal
closest
packing

layer b
cubic
closest
packing

layer c

closest packing of first

and second layers

abab

abcabc

34

Closestpacking

Type of Closest Packing

1.Hexagonal closest packed (HCP)

Hexagonal closest packed arrangement has two alternating

layers, ABAB....
Each sphere has coordination number = 12
2.Cubic closest packing (CCP )

Cubic closest packed arrangement has two alternating

layers, ABCABC....
Each sphere has coordination number = 12

35

hexagonal closest -packed

structure (hcp)

Stacking Pattern: ABABABAB

Coordination number = 12

cubic closest -packed

structure (ccp)

Stacking Pattern: ABCABC

Coordination number = 1236

Co-ordination Number ( C.N.)

In chemistry, ( Alfred Werner) is the total number of neighbors of a
central atom in a molecule or ion.[
In materials science, (the interior of a crystal lattice) is the number of
atoms touching the given atom

C.N. = 6

C.N. = 3

37

Coordination Number

C.N. = 12
38

Structures of Solids
Close Packing of Spheres

39

3. The Crystals System

: Classify crystals system by the symmetry of the unit cell
: A unit cell is described by specifying the lengths and the

angles

The crystal system

Classify crystal system by the
symmetry of the unit cell.

A unit cell is described by

specifying the lengths and the
angles.

Crystallographic axes

40

The Seven Crystal Systems

41

Bravias Lattice
Seven crystal systems containing
fourteen different lattice type

1. Cubic
2. Tetragonal
3. Orthorhombic
4. Rhombohedral
5. Monoclinic
6. Triclinic
7. Hexagonal

3
2
4
1
2
1
1

Simple , fcc , bcc

Simple , bcc
Simple , fcc, bcc, base C
Simple
Simple , base C
Simple
Simple
42

Bravais Lattices

43

4. Structure of Solids
The
cubic system

1. Simple Lattice (Primitive cubic) (SC)

Atoms at the corners of a simple cube

44

Simple Cubic

1/8 atom
at 8
corners

Co-ordination number = 6

Atoms/unit cell = 1/8 x 8 = 1

45

2. Body centered Lattice (BCC)

Atoms at the corners of a cube plus one
atom in the center of the body of the cube

46

Body-centered Cubic

1 atom at
center
1/8 atom at 8
corners
Co-ordination
number = 8
47

3. End centered orBase centered Lattice

Atoms at the corners of a cube plus one
atom in the center of only one opposite the face.

48

4. Face centered Lattice (FCC)

Atoms at the corner of a cube plus one
atom in the center of each face of the cube

49

Face-centered Cubic
1/8 atom at 8
corners
1/2 atom
at 6 faces

coordination number
= 12

Atoms/unit cell = (1 8 8)+(1 2 6)=4

50

4. Face centered cubic (FCC) , Cubic

closest packing (CCP )

Ag(s) , KCl gived a layer sequence ABCABC....

51

layer a
layer b

layer
c

closest packing of first

and second layers

abcabc(74%)

facecenteredunit
cell

52

5. Hexagonal Lattice (HCP)

53

Hexagonal Closestpacking
hexagonal closest
packing

layer a

layer a
layer b

abab(74%)

closest packing of first and

second layers
hexagonal unit
cell

54

5. Hexagonal Unit Cell (HCP)

Mg (s) give a layer sequence ABAB....

55

Holes in Closest Packing

1.Tetrahedral holes

2.Octahedral holes

56

Holes in Crystals

57

5. Ionic Solid
Assume the anion is larger than the cation.
The anions will pack together in a ccp or hcp structure. The
cations will then be inserted into holes in the closest-packed
structure.

http://www.chm.davidson.edu/vce/crystals/IonicSolids.html

58

 cubic >

Octahedral >

r+/r- > 0.732

cubic

0.732 > r+/r- > 0.414

0.414 > r+/r-

Tetrahedral

> 0.225

octahedral hole
tetrahedral hole

59

Co-ordination number with ratio rcation/ranion

rc / r a

coordination
ofcation

0.00 0.15
2
0.115 0.22
3
0.22 0.41
4
0.41 0.732
6
> 0.732
8

arrangement of

anion
linear
Triangular
Tetrahedral (Zinc blend)
Octahedral (NaCl)
Cubic (CsCl)

60

5.1 Coordination number of ionic solid

In Simple ionic structures are described by two coordination
numbers, one for each type of ion.
Sodium chloride (NaCl) the numbers of
cations and anions are equal, and both
coordination numbers are six so that the
structure is (6, 6).

61

5.1 Coordination number of ionic solid

Calcium fluoride (CaF2) is an (8, 4) structure, meaning that each

cation Ca2+ is surrounded by eight F - anion neighbors, and each
anion F - is surrounded by four Ca2+.
62

5.2 Structure of salts

Common structures for a variety of salts
A.Rock salt structure

ex: NaCl, KCl, LiF, AgCl

Cl- [anion] FCC

Na+[cation] fill inoctahedral
Most of Halides-alkaline, oxides and sulfides-alkaline
earth compound are in Rock-salt structure, e.g. KCl, KBr,
KI, LiI, CaO, Cas, and other compounds such as AgCl,
AgBr, NH4I, MnS, MnO, NiO, and PbS, etc.

63

Coordination No. = 6:6 (Number of ion) Na+ : Cl- = 4 : 4

Cation to anion ratio is 1 : 1
Simple structure :AB
64

B. CsCl Structure

Atomic radiusCs = 169 pm

Atomic radius Cl = 181 pm
- Cs pack simple cubic structure
Cl- are in cubic hole
- each unit cell is in body-centered cubic,
each ion are surrounded with other 8 ions
-Coordination number of Cs : Cl = 8 : 8
- No of ions, Cs : Cl = 1:1

Other compounds packed this structure are CsBr, CsI, RbCl, RbBr,
NH4Cl, NH4Br, etc.
65

The CsCl structure

Cl ion

Cs+ ion

66

Cesium Chloride

67

C. Zinc blende Structure

Simple formula AB

The zinc blende structure

Typical example ZnS.
Other compounds packed this structure
2S ions fcc
are CuF, CuCl, BeS, CuBr, CuI, CdS,
Zn2+ tetrahedral hole (Fractionfill=) AgI, HgS, SiC.
Co-ordination number, Zn2+: S2 - = 4 : 4
Number of ions,

Example: CuCl

Zn2+: S2 - = 4 : 4
68

D.Wurtzite Structure
Simple formulaAB

Typical example ZnS.

S2- ions hcp
Zn2+ tetrahedral hole (Fractionfill=)
Co-ordination number, Zn2+: S2 - = 4 : 4
Number of ions,

Zn2+: S2 - = 4 : 4

hcp

69

E. Fluorite Structure

Simple formulaAB2,

ex: CaF2

Ca2+ FCC , F- fill in Tetrahedral holes

Number of ion, Ca2+: F- = 4 : 8
Co-ordination No. Ca2+ : F- = 8 : 4

Other compounds packed fluorite structure are SrF2, SrCl2, BaF2,

BaCl2, CdF2, PbF2, ZrO2, HfO2, NpO2, ThO2, PuO2, AmO2

70

F. Anti fluorite structure

Simple formula:AB2 , ex : Na2O

O=

Na+
O= FCC , Na+ fill in Tetrahedral holes
Number of ion, O= : Na+ = 4 : 8
Co-ordination No., O= : Na+= 8 : 4

71

Fluorite Structure, ZrO2

Antifluorite Structure, Li2O

Zr4+ pack ccp (fcp)

O2- are in all tetrahedral holes

O2- pack ccp (fcp)

Li+ are in all tetrahedral holes
72

73

6. (Number of atom, density,

radius, packing factor)

74

Number of atoms perunit cell

1. Corner
An atom at the corner of a cube forms a
part of eight different cubes that at the
point

only 1/8 of a corner atom belongs to a particular cell

75

2. Face
An atom at the center of the face of a cube is
shared by another cube that touches that face.

onlyofthatatomcanbeassignedtogivencell

76

3.

Edge

An atom at the edge of a cube is shared by

another cube that touches that edge

Onlyofthatatomcanbeassignedtogivencell
77

4. Body
An atom is not shared by another cube

78

How many atoms are in each of following unit cells ?

Simple Cubic
8 corner x 1/8 = 1 atom
Body-Centered Cubic
(8 corner x 1/8) + 1 body= 2 atoms

Face-Centered Cubic
(8 corner x 1/8) +(6facesx)=4 atoms
79

Determine the net number of particles in

FCC
Corner = 8 atoms= 8

x
Edge

1
8

=1

= 0 atom = 0 x14 = 0

1
Face=6atoms=6x

=3
2

Body=0atom=0x1=0
Total =4atoms
80

Lithium metal has a body centered

cubic unit cell . How many Li atoms
are there in a unit cell ?

Sol n Two ( one at the corners ,

equivalent to 1/8 at each of eight
corners , plus one at the body center )
81

Packing Efficiency (Packing factor)

The percent of the volume occupied by
the spheres themselves

Packing efficiency = V particle in unit cell

V of unit cell

82

Calculate Packing factor of Simple Cubic

Number of particles insimple cubic = 1
Volume ofunitcell= (2r)3

Packingfactor
Packing efficiency of simple cubic = 52 %
and space of cubic =48 %
Packingfactor( BCC )=68%
Packingfactor (FCC , CCP)=74%

83

84

11.4

Cubic Summary

Net atoms

SCC
1

BCC
2

FCC
4

Edge

2r

4r/(3)1/2

(8)1/2r

Stacking

aa

aba

aba

% packing
efficiency

52%

68%

74%

85

Calculate the density of NaCl

Edge length = 5.628 Ao, Atomic weight
Na = 23, Cl = 35.5, Ao=10-8 cm
The sodium chloride structure

86

Number ofCl- in1 unit Number of Na+ in 1

cell
unit cell

Corner
Face
Edge

Body
Total

1
8

8x

=1

1
2

6x = 3

=0

1xo=0
0x

1
4

0 x 18=0
6x

1
2

12 x 14 =3
1 x 1=1
4
87

Number of atoms Na: Cl = 4 : 4 or 1 : 1

Mass of unit cell = 4 [massNa+ 1 ion] + 4[mass Cl- 1 ion]

= 3.89 x 10-22 gm
a3 = [5.628 x 10-8 cm]3
= 1.785 x 10-22 cm3
Density ofNaCl = Mass
Volume
Volume of unit cell ,

3.89x10 22 gm
1.785x1022 cm3

2.177 gm / cm3

88

Calcium crystallizes in a FCC that has an

edge length of 0.556 nm. The density of
Calcium is 1.54 g/cm3.
CalculateAvogadrosNumber.

Volume of Unit cell l3 = [0.556 nm]3

= 0.172 nm3
Mass of unit cell
g
cm
3
-7
3
= 0.172 nm x (10 )
x 1.54
cm
nm
-22
= 2.646 x 10 g
3

89

There are four atoms in FCC.

4atoms

Mass of Calcium2.649 x10-22

40.08

4 x 40 . 08
2 . 649 x10

22

AvogadrosNumber = 6.052 x 1023

90

Krypton crystallizes in a
structure that has four Kr
atoms in each unit cell ,
and the unit cell is a cube .
The edge length of the unit
cell is 0.559 nm . Calculate
the density of crystalline Kr
in kg/m3.

91

Soln
= 5.57x10-25 kg
V = (0.559 x 10-9m)3 = 1.75 x 10-28 m3

= 3190 kg/m3
92

Platinum crystallizes in a face

centered cubic lattice will all
atoms at the lattice points , It
has a density of 21.45 g/cm3 and
an atomic weight of 195.08 amu.

Calculate the length of a unit cell edge . Compare with the

value of 3.924 Ao obtained from
X ray diffraction.
93

Soln Convert molar mass

(Pt) mass per

atom
There are 4 atoms/unit cell mass/unit cell
can be calculated as follows:

94

The volume of the unit cell is

If the edge length of the unit cell is denoted
as l , the volume is v = l3 Hence , the edge
length is

The edge length is 3.924 Ao (392.4 pm)

95

Magnesium crystallizes in a HCP . The density of

Magnesium crystallizes is 1.74 g/cm3 . Calculate the
volume and atomic radius of Magnesium.
(At.W Mg = 24.3)

Volume of Mg 1 mole [Vm]

Vm =

1
1 . 74

cm x 24 . 3 gMg
molMg
gMg
3

cm
14.0
molMg
3

Vm consist of Volume of particles and Volume of free space

Packing efficiency Mg (HCP) = 74 %

96

cm
74
x
Volume of 1 moleMg=14.0molMg 100

Volume of one atoms Magnesium

=10.3 cm
molMg
3

x1

r =

mol
6 . 02 x10 atoms
23

cm
atomMg
V = 43
3

= 1.72 x 10-23

Radius of Magnesium atom

cm
=10.3
molMg

3V
4

=1.60 x 10-8 cm

=0.160nm
=160pm

97

Crystal Structure of Metals

98

7. Crystal Lattice energy

Theamountofenergyrequiredtoseparatetheions
in one mole of crystal from their positions in the
latticetoaninfiniteseparationinthegasesstate
Na+(g) + Cl-NaCl(s) + U

U = Lattice energy
99

Lattice energy depends on

- radius of ions
- ionic charge
-distances between the ions - the kind of crystal
lattice
Lattice energy,
Ex:LiF U = 238 kcal /mol
KF U = 190 kcal/mol
MgO U = 918 kcal/mol
Effect of small radius and ionic charge
radius, F- = 1.36 Ao , Li+ = 0.60 Ao
K+ = 1.33 Ao , Mg++ = 0.65 Ao

O= = 1.40 Ao

100

Higher lattice energy

divalent andtrivalent

Cation, small radius ex: Mg2+ , Al3+

anddivalent anion ex:oxide ion , O2-

101

Calculate of lattice energy

-Born Lande , Born - Mayer equation
-Born Harber cycle
Born Mayer equation
Born Lande equation

U lattice energykJ/mol

102

NA =AvogadrosNo.
A = Madelung Constant, depends on crystal structure
e
= 1.602 x 10-19 coulomb
Z+ , Z- = electric charge
o
= permittivity of free space
= 8.854 x 10-12 Fm-1 (107/4 c2 Fm-1) ,
c = 2.99x108ms-1
re
= internuclear distance
n
= constant (depends on configuration of ions)
(7-12 )
= constant( for alkaline metal =31-35 pico metre )

103

Born Harber cycle

Born HarbercycleisbasedonHessslaw
Lattice energy can be determined from
thermochemicalcycle
(S)

104

Hf

Hsub
IE
Ea
Hf
U

= Lattice Energy
= Heat of formation
= Dissociation Energy
= Heat of Sublimation
= Ionization Energy
= Electron affinity
=D+Ea+U+ Hsub + IE
= Hf - [D+Ea+ Hsub + IE ]
105

Calculate the lattice energy of magnesium

sulfide using the following energies (all in
kcal/mol)

Heat of formation( Hf)MgS

Heat of sublimation HsubMg
Ionization energy Ip1+Ip2
Dissociation energy Hatom
Electron affinity Ea1 + Ea2

=
=
=
=
=

-82.2
36.5
520.6
1065.6
-72.4
106

Mg2+(g) + S2-(g)
EA -72.4
IE 520.6

Mg(g)

S(g)

1
8

Hdiss
133.2

HSub
36.5

MgS(s)
-82.2
1
8

Hf

S8(g)
+
Mg(s)

All quantities are given in kcal .

The lattice is thus
U = (-82.2)-(36.5+133.2-72.4+520.6)
= -700.1 kcal/mol
= -2929 kj/mol.

107

8. Lattice defect
Chemical impurities

FormationoftheLattice

108

Type of Defect
1.Point defect
involve only one or a very few

lattice sites

1.1 Frenkel defect

particles in the wrong position
1.2 Schottky defect
Missing particles from Schottky
May still maintain electrostatic
neutrality
109

110

4. Interstitial impurity atom

1. Substitution impurity atom

Self interstitial

Vacancy
111

2. Line defect

edge dislocation
screw diclocation

edge dislocation
The distortion is produced in the crystal if there is one of
the planes being shorter

112

Screw dislocation

Screw dislocation is produced when one side of a crystal is

displaced relative to the other sides.

113

Effect of Lattice defect

- mechanical
- electric properties
( semi- conductor, insulator, conductor)

114

Example
1. Ruby Al2O3 [ aluminium oxide]Colourless
IfAl3+ is packed byCr3+ red colour
2. Brass : Copper atom is packed by Zinc atom
hardness brass > Copper
3. Steel
mixture of Iron and Carbon increased hardness
Fe + C [0.12 0.25%] hardness > pure iron
Fe + C [0.15 1.5%] increase hardness
Fe + C [2.2 2.5%] hardness and brittle
115

Cu/Zn alloy
Substitutional alloy

Fe/C alloy
Interstitial alloy
116