INTRODUCTION TO INORGANIC

CHEMISTRY (SKT1013)

CHAPTER 4
SOLID STATE CHEMISTRY 3
X-RAY DIFFRACTOMETER
 X-RAY DIFFRACTOMETER
 A beam of X-rays is directed at a mounted crystal : single crystal
 Atoms in the crystal absorb some of the incoming radiation and reemit it :
the process is called scattering of X-rays
 The shield prevents the strong undiffracted X-rays from damaging the
photographic plate
 X-RAY DIFFRACTION

X-ray diffraction the scattering of X-rays (electromagnetic radiation)

by the units of a crystalline solid

• lattice should be able to diffract X-ray because the wavelength of X-rays (1Å =
10-10 m) is comparable in magnitude to the distances between lattice points in a
crystal

• X-ray diffraction technique offers the most accurate method for determining
bond lengths and bond angles in molecules in the solid state. Why?

X-rays are scattered by electrons

 X-RAY DIFFRACTION

•X-ray energy can be related with wavelength distance with Planck formula:

E = h c = speed of light (3 x 108 ms-1)

= hc  = light frequency
  = wavelength distance (1Å = 10-10 m)
h = Planck constant (6.62 x 10-34 J)

Energy from X-ray : E = 6.62 x 10-34 J x 3 x 108 ms-1

10-10 m
= 19.86 x 10-16 Js-1
1eV = 1.6 x 10-19 J
\ E = 19.86 x 10-16
1.6 x 10-19
= 12.4 x 103 eV
= 1.24 X 104 eV
incident rays reflected rays

Bragg’s Law
 
A
2d sin = n
B   D d
C
d sin d sin
  2d because sin  1

• Consider the scattering of X-rays by atoms in two parallel planes

• Two incident rays are in phase with each other (their maxima and minima occur at
the same positions)
• The upper wave is scattered or reflected by an atom in the first layer while the lower
wave is scattered by an atom in the second layer
• In order for these two scattered waves to be in phase again, the extra distance
traveled by the lower wave must be an integral multiple of the wavelength () of the
X-ray; that is,
BC + CD = 2d sin  = n n = 1,2,3……
q: is the angle between the X-rays and the plane of the crystal
d: distance between adjacent planes
incident rays
reflected rays

 A 

B   d
D

d sin C d sin
The distance between layers in a NaCl crystal is 282 pm. X-rays are
diffracted from these layers at an angle of 23.0°. Assuming that n=1,
calculate the wavelength of the X-rays in nm

2d sin = n
First order, n = 1
 = 2d sin
n
= 2 x 282 pm x 1nm x sin 23.0°
1000pm
 = 0.22 nm
When X-rays of wavelength 0.090nm are diffracted by a metallic crystal,
the angle of first-order diffraction (n=1) is measured to be 15.2°. What is
the distance (in pm) between the layers of atoms responsible for the

2d sin = n
First order, n = 1
d = n = 
2 sin 2 sin
= 0.090 nm x 1000 pm
1 nm
2 sin 15.2°
= 171.66 pm
X-rays of wavelength 0.154 nm strike an aluminium crystal; the rays are
reflected at an angle 19.3°. Assuming that n=1, calculate the spacing
between the planes of aluminium atoms (in pm) that is responsible for this
angle of reflection. The conversion factor is obtained from 1 nm = 1000pm

2d sin = n
First order, n = 1
d = n = 
2 sin 2 sin
= 0.154 nm x 1000 pm
1 nm
2 sin 19.3°
= 233 pm
 MILLER INDICES (hkl)

 Miller Indices (hkl) : A set of numbers which quantify the

intercepts and thus may be used to uniquely identify the
plane or surface

 Cubic crystal system (unit cell with dimensions a x a x a)

y
a
x a
 RULES FOR FINDING PLANES

Identify the intercepts on the x-, y- and z- axes

Specify the intercepts in fractional coordinates. Take the
reciprocals of the fractional intercepts
Express as integers
Divide the integers with the highest common factor
Enclosed in brackets (…) :
( ) for an individual plane
{ } for all planes of that crystallographic type
Replace negative integer with bar over the number –h to h
If the plane parallel to an axis, say it cuts at 
 Miller Indices : (1 0 0) x y Z

Intercept length a  
z

Reciprocal 1/a 1/ 1/

As integer 1 0 0
(cleared
y fractional)

Common factor 1 0 0
x

Miller indice (100)

 Other examples:
x y Z
1. The (1 1 0) surface
z
Intercept a a 
length

reciprocal 1/a 1/a 1/

As integer 1 1 0
(cleared
(0,a,0) fractional)
y Common 1 1 0
factor
x (a,0,0)
Miller indice (110)
 x y Z
2. The (1 1 1) surface

z Intercept a a a
length

Reciprocal 1/a 1/a 1/a

(0,0,a)

As integer 1 1 1
(cleared
fractional)
(0,a,0)
y Common 1 1 1
factor
x (a,0,0)
Miller indice (111)
3. The (2 1 0) surface x y Z

z Intercept 1/2a a 
length

reciprocal 1 1 1
1/2a a 

As integer 2 1 0
(cleared
fractional)
(0,a,0)
y
Common 2 1 0
factor
x (1/2a,0,0)
Miller indice (210)
 x y Z
z
Intercept 3/4a 1/2a 1/4a
length

Reciprocal

As integer
(cleared
fractional)
y
Common
factor
x
Miller indice
 x y Z
z
Intercept 3/4a 1/2a 1/4a
length

Reciprocal 1 1 1
3/4a 1/2a 1/4a
As integer
(cleared 4 6 12
fractional)
y
Common
factor 2 3 6
x
Miller indice (2 3 6)
 Exercise 1: Draw the following planes in the given cubic lattice.
z
z
(1 0 1) (0 1 1)

y
y
x
x
z z
(0 0 1) (0 1 0)

y y
x x
 Exercise 1: Draw the following planes in the given cubic lattice.
z
z
(1 0 1) (0 1 1)

y
y
x
x
z z
(0 0 1) (0 1 0)

y y
x x
Exercise 2: Determine the Miller Indices of the following planes:
Exercise 3: Determine the Miller Indices of the following planes:
 Types of crystal structure:
 Rock-salt – Sodium chloride (NaCl)- halite Cl-

Cl- Na+
Na+
Coordination Number (CN) : (6,6)

Cl- Na+ Number of ions in a unit cell

8Cl- (corners) x 1/8 = 1 Cl- ion

6Cl- (faces) x 1/2 = 3 Cl- ions
Total = 4 Cl- ions

12Na+ (edges) x 1/4 = 3 Na+ ions

1Na+ (body) x 1 = 1 Na+ ion
Total = 4 Na+ ions

Ratio of cation and anion – 4:4  1:1

Chemical formula = NaCl

 Cesium chloride (CsCl)
Cl-

Cl- Cs+
Cs+
Coordination Number (CN) : (8,8)

Cl- Cs+

Number of ions in a unit cell

8Cl- (corners) x 1/8 = 1 Cl- ion

1Cs+ (body) x 1 = 1 Cs+ ion

Ratio of cation and anion – 1:1

Chemical formula = CsCl

 Sphalerite – Zinc blende (ZnS)

S2- Zn2+
Coordination Number (CN) : (4,4)

S2- Zn2+
Number of ions in a unit cell

8S2- (corners) x 1/8 = 1 S2- ion

6S2- (faces) x 1/2 = 3 S2- ions
Total = 4 S2- ions

4Zn2+ (body) x 1 = 4 Zn2+ ions

Ratio of cation and anion – 4:4  1:1

Chemical formula = ZnS

 Wurtzite – ZnS
Number of ions in a unit cell
 Fluorite – CaF2

F- Ca2+
Coordination Number (CN) : (8,4)

F- Ca2+ Number of ions in a unit cell

8F- (body) x 8 = 8 F- ions

8Ca2+ (corners) x 1/8 = 1 Ca2+ ions

6Ca2+ (faces) x 1/2 = 3 Ca2+ ions
Total = 4 Ca2+ ions

Ratio of cation and anion – 4:8  1:2

Chemical formula = CaF2

 Rutile – TiO2

O2- Tiiv
Coordination Number (CN) : (6,3)

O2- Tiiv Number of ions in a unit cell

4O2- (faces) x 1/2 = 2 O2- ions

2O2- (body) x 1 = 2 O2- ion
Total = 4 O2- ions

8Ti4+ (corners) x 1/8 = 1 Ti4+ ions

1Ti4+ (body) x 1 = 1 Ti4+ ion
Total = 2 Ti4+ ions

Ratio of cation and anion – 2:4  1:2

Chemical formula = TiO2

 Perovskite

 Perovskite is a calcium titanium oxide mineral species

composed of calcium titanate, with the chemical
formula CaTiO3.

The simplest way to picture

perovskite is a cubic unit cell with
titanium atoms at the corners
(blue), oxygen atoms at the
midpoints of the edges (red), and
a calcium atom (green) in the
center. 
Examples of Gemstone

Blue sapphire Ruby Emerald

CORUNDUM
Corundum is the naturally occurring crystalline form
of aluminium oxide. Impure crystalline forms of
Al2O3 are valuable. Their characteristic colors due to
trace impurities in the corundum structure.

red ruby - Cr3+,

Blue sapphire - Fe2+, Fe3+, Ti4+
green oriental emerald - Cr3+, Ti3+
violet oriental amethyst - Cr3+, Ti4+
yellow oriental topaz - Fe3+