Solid State Chemistry: Basic Concepts

Na Cl

Dr. Bhaskar Devu Mukri

Assistant Professor
Department of Chemistry
Motilal Nehru National Institute of Technology Allahabad,
Prayagraj, Uttar Pradesh – 211004, India
Definition:
“It is the study of synthesis, structure and properties of solid materials”

 Solid is one of the four fundamental states of matter (solid, liquid, gas and plasma)
Increasing Energy

Solid Liquid Gas Plasma

Ex:

 Solid materials broadly classified into two types:

• Crystalline solid
• Amorphous solid
 Crystalline solid: A solid material whose constituents like atoms or molecules or ions are arranged in a
highly regular order. Ex: NaCl, diamond, etc.

 Amorphous solid: A solid material whose constituents do not arranged in regular order.
Ex: Glass, rubber, etc.
 In crystalline solid, atoms or molecules are geometrically arranged or packed within the unit volume

Crystal lattice:

 Lattice – It is a translationally periodic arrangement of points in 3D space.

 Unit cell - It is defined as the smallest repeating unit having the geometrically arranged constituents.
 Crystal systems

Tetragonal Orthorhombic Hexagonal

Cubic
b b
b a a b
a a
c
c c c
β α β α
β α β α
γ
γ γ γ

a=b=c a=b≠c a≠b≠c a =b ≠ c

and α = β = γ = 90° and α = β = γ = 90° and α = β = γ = 90° and α = β = 90°, γ = 120°
 Crystal systems

Monoclinic Triclinic
Rhombohedral
b b
a a
a b

c c
α c β α
β β α
γ
γ γ

a=b=c a≠b≠c a≠b≠c

and α = β = γ ≠ 90° and α = γ = 90° ≠ β and α ≠ β ≠ γ ≠ 90°
 Bravais lattices
Crystal systems Primitive (P) Body centered (I) Face centered (F) Base centered (C)

Cubic

Tetragonal

Orthorhombic

Hexagonal
 Bravais lattices
Crystal systems Primitive (P) Body centered (I) Face centered (F) Base centered (C)

Rhombohedral

Monoclinic

Triclinic
Cubic crystal system
Lattice point locations

Cubic Unit cells

Simple Cubic Body-Centered Cubic (BCC) Face-Centered Cubic (FCC)

 Atomic packing factor (APF)
 It is defined as the volume of atoms arranged in the unit cell divided by the volume of the unit cell.

 Close packing – hexagonal close packing (HCP) and cubic close packing (CCP)

AB

ABABAB – ABCABCABC –
HCP structure CCP structure

ABA ABC
Simple cubic

 APF = 0.52 and the percentage of packing = 52%

Body-centered cubic (BCC)

Close-packed directions:
length = 4R
= 3a

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell

atoms volume
4 3
unit cell 2 ( 3a/4)
3 atom
APF =
volume
a3
unit cell
 APF = 0.68 and the percentage of packing = 68%
Face-centered cubic

Close-packed directions:
length = 4R
= 2a

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

atoms volume
4 3
unit cell 4 ( 2a/4)
3 atom
APF =
volume
a3
unit cell
 APF = 0.74 and the percentage of packing = 74%
 In simple cubic system,
2R = a

In body-centered cubic system,

In face-centered cubic system,

Number of atoms Volume of an atom

in a unit cell × (sphere)
R % of atomic packing factor (APF) =
Volume of a unit cell
× 100
R R

n ×
= × 100
a3
 Density of a unit cell
The unit cell contains atleast one formula unit.

where N is Avogadro’s number. If the unit cell of volume, V contains Z formula units, then

V = Volume of one formula unit × Z

Therefore,

D=

V is usually expressed as Å3 i.e. 10-24 cm3 and Avogadro’s number is 6.023 × 1023. Then, above formula reduces to

D= in g/cm3

For cubic unit cell, V = a3, where a is the edge length of the unit cell.
 Crystalline solids:
4 types of crystalline solids

• Ionic crystalline solid: It consists of positively and negatively charged ions held together by electrostatic
forces.
High melting and boiling points, hard and brittle, and electrically
insulator, but highly conductive when it melt or dissolve in water.
Ex: NaCl, CdI2, NH4NO3, etc.

Ionic bond:
An ionic bond is formed by the complete transfer of some electrons from one atom to another. The atom losing one or more
electrons becomes a cation—a positively charged ion. The atom gaining one or more electron becomes an anion—a negatively
charged ion.

Na+ Cl−

Na atom Cl atom Na+ ion Cl− ion

(a cation) (an anion)

Sodium Chloride (NaCl)

• Covalent crystalline solid: The atoms are bonded by covalent bonds in a continuous network, resulting in a big
crystal.
High melting point, very hard and little brittle, and variable electrical conductivity, but
low conductivity when it melted.
Ex: Diamond, graphite, quartz, SiC, etc.

Covalent bond:
A covalent bond consists of the mutual sharing of one or more pairs of electrons between two atoms. These electrons are
simultaneously attracted by the two atomic nuclei. A covalent bond forms when the difference between the electronegativities of
two atoms is too small for an electron transfer to occur to form ions.
Single bond Double bond Triple bond

H2O: H−O−H CO2: O═C═O N2: N≡N

Diamond structure Graphite structure

• Molecular crystalline solid: It consists of discrete molecules, which bind together by the cohesive forces.
Low melting and boiling points, soft, ductile or brittle, and electrically insulator.
Ex: Ice, naphthalene, fullerene, As4, etc.

 The cohesive forces that bind the molecules together are van der Waals forces, dipole-dipole interactions,
quadrupole interactions, π−π interactions, hydrogen bonding, halogen bonding, London dispersion forces.

Hydrogen Bonding:
It is a primarily electrostatic force of attraction between an hydrogen atom which is covalently bound to a more
electronegative atom or group and another electronegative atom bearing a lone pair of electrons. This bond is weaker than an
ionic bond or covalent bond but stronger than van der Waals forces.

Salicylic acid
Intramolecular hydrogen bonding

P-hydroxy benzoic acid Hexagonal Ice crystal structure

Intermolecular hydrogen bonding
Naphthalene monoclinic crystal structure Fullerene (C60) cubic crystal structure
 • Metallic crystalline solid: The metal atoms are held together by metallic bonding, which one between an electron
cloud of delocalized electrons and positively charged metal ion.
Variable melting point, ductile and malleable, high electric
and thermal conductivity, and luster.
Ex: Fe, Cu, Zn, etc.

Metallic Bonding:
It is a type of chemical bonding that arises from the electrostatic attractive force between conduction electrons and positively
charged metal ions.

Delocalized electrons Metal ions

 Close packed structures
Hexagonal close packed (hcp)

Cubic close packed (ccp) or face-centered cubic (fcc)

A
 Interstitial sites in close packed structures

Tetrahedral void or site Octahedral void or site Cubic close packed (ccp) or fcc

Hexagonal close packed (hcp)

Metal atom Metal atom

Octahedral void or site Tetrahedral void or site

 In a close packed structure, the number of tetrahedral voids is two times the
number of spheres and number of octahedral voids is same as the number of
spheres.
 Radius ratio rule
The ratio of the radius of a cation (r+) and the radius of an anion (r–) is known as the radius ratio (r+/r–).

 The arrangement ions in an ionic crystal is greatly influenced by the ratio of radii of the ions.

 The number of anions that surround a cation is called the coordination number of the cation and vice versa.

 The crystal structures are determined by the coordination numbers of the ions.

 Using the radius ratio, we can predict the coordination number and structure of ionic crystals.
Coordination number 3 (planar triangle):
The smaller positive ions with radius r+ interacted with 3 larger negative ions with radius r-. Plainly AB = BC = AC = 2r–,
BE = r–, BD = r+ + r–, the angle DBE is 30o.

Cation cos DBE =

Anion

Coordination number 4 (tetrahedral):

Tetrahedral arrangement inscribed in a cube. The angle ABC is the tetrahedral angle of 109o28′ and hence the angle ABD is half
of this, that is 54o44′ (54.73°). In the triangle ABD,

D
Coordination number 6 (octahedral):
The smaller positive ion of radius r+ touches six larger negative ions of radius r-. In the triangle ABD

45°

Coordination number 8 (cube):

B In triangle ABC,
54.73°

A
C Taking reciprocals,
Base diagonal

54.73°
Rearranging,
Base diagonal Hence,
109.46°
54.73°
 Limitation of radius ratio rule

 The radius ratio rules can only be used to estimate the cation’s coordination number, not the anion’s
coordination number.

 It can only be used successfully on crystals of the AB type, which have a cation and an anion in its formula.
The rules cannot be applied to A2B or AB2 crystals.

 In actuality, the extremely high coordination number expected by this rule does not occur in practice.

 The rules are applicable only to crystals made up of ions, that too only when ionic radii are known
accurately.
 Structural classification of binary and tertiary compounds
Binary compounds:
They contain two elements: one is a metal and another one is a nonmetal. It can be denoted as ‘AX’.
Ex:

AX or MX type : NaCl, CsCl, ZnS (zinc blende and wurtzite), NiAs, and MgO

AX2 or MX2 type: Fluorite (CaF2), Antifluorite (Na2O), Rutile (TiO2), Antirutile (Ti2N), Cristobalite (SiO2), and CdI2

AX3 or MX3 type: ReO3

Others: Corundum (Al2O3) and Mn2O3

Ternary compounds:
They contain three elements, atleast one metal and one nonmetal. It can be denoted as ‘ABX’.
Ex:

ABX3 type: Perovskite (CaTiO3 and SrTiO3) and Ilmenite (FeTiO3)

AB2X4 type: Normal Spinel (MgAl2O4) and Inverse Spinel (Mg2TiO4 and NiFe2O4)

Others: Calcite (CaCO3)

MX type: NaCl (Rock salt structure)

The radius of Na+ is 1.02 Å and that of Cl− ion is 1.81 Å.

Hence, the coordination number of Na+ ion is 6.

A cation is surrounded by six anions.

i.e. a Na+ ion is coordinated with six adjacent Cl− ions.
If Na+ ions are occupied as a fcc structure, then Cl− ions can occupy the
octahedral voids or sites.
Since Cl− ions are occupied in the octahedral voids, each Cl− ion is
surrounded by six Na+ ions.
i.e. Both Na+ and Cl− ions have 6 coordination number in the NaCl
crystal. So, NaCl crystal is a 6:6 coordination type.
Na+

Cl-
In a NaCl unit cell, 12 Cl− ions are occupied at edge centers and one Cl−
ion is occupied at body-centered. Therefore, 4 Cl− ions are present in each
Na+
unit cell. And 4 Na+ ions are present because of its fcc structure.
Cl-
Hence, 4 NaCl formula units are occupied in each NaCl unit cell.
 CsCl

The radius of Cs+ is 1.69 Å and that of Cl− ion is 1.81 Å.

Hence, the coordination number of Cs+ ion is 8.

 CsCl is a primitive cube, containing Cs+ ions at the corners and a Cl− ion at the
body center, or vice versa.
 It is not a body centered cubic since there are different ions at the corner and
body center positions.
 The coordination numbers of both Cs+ and Cl− ion are 8. Hence, CsCl crystal
is a 8:8 coordination type.
 CsCl structure is not a close packed structure.
In NaCl, each Cl− ion has 12 other Cl− ions as next nearest neighbours, which
is a characteristic feature of close packed structures. But in CsCl, each Cl−
ion has only 6 Cl− ions as the next nearest neighbours.
 CsCN, NH4Br, TlI, AuZn, etc are some compounds that exhibit the CsCl
structure.
 ZnS
The radius of Zn2+ is 0.60 Å and that of S2− ion is 1.84 Å. It has a tetrahedral ion arrangement with four nearest
neighbours.
0.326 Therefore, each zinc atom is surrounded by four sulfur atoms
and each sulfur atom is surrounded by four neighbour zinc
atoms.
Hence, the coordination number of Zn2+ ion is 4.
Hence, both Zn2+ ion and S2− ion have 4 coordination numbers
in the ZnS crystal structure. i.e. ZnS crystal is a 4:4
coordinated type.
ZnS exists in two main crystalline forms (polymorphism).
Zinc blende or sphalerite: Wurtzite:
 It is a cubic close packed  It is a hexagonal close
(ccp) or face-centered cubic packed (hcp) structure.
structure.  Zn2+ ions are occupied in a
 Zn2+ ions are occupied in a hcp array and S2− ions are
fcc array and S2− ions are occupied one half of the
occupied one half of the tetrahedral voids.
tetrahedral voids.  Each wurtzite unit cell
 Each unit cell contains 4 contains 6 ZnS formula
ZnS formula units. units.
 Interpenetrated sulfur fcc  Interpenetrated sulfur hcp
lattice is obtained when the lattice is obtained by a
origin shifted by ¼ of a body translation of 5/8th of the
diagonal. lattice constant, c.
MX2 type: CaF2 (Fluorite structure)

 Fluorite or fluorspar is the mineral form of calcium fluoride,

Ca2+ CaF2.
F−
 The Ca2+ ions are occupied in cubic close packing or fcc lattices.

 The F− ions are occupying all the tetrahedral sites.

 The number of tetrahedral sites in fcc is 8, which are occupied by 8

F− anions and 4 Ca2+ cations are present in fcc lattices. Therefore,
the stoichiometry of the compound is 1:2 and 4 CaF2 formula units
are present in a fluorite unit cell.

 Each Ca2+ ion is surrounded by the nearest 8 F− ions while each F−

ion is surrounded by 4 Ca2+ ions. Therefore, the Ca2+ ion has cubic
8 coordination, and F− ion has tetrahedral 4 coordination.
The CaF2 crystal structure is a 8:4 coordination type.

 The other common examples of fluorite structure are CuF2, BaF2,

SrF2, CeO2, UO2, etc.

 The mineral form of fluorite is usually deep in colour due to the

presence of F-centers.
 Rutile (TiO2)

 Rutile, anatase, and brookite are the main polymorphs

of TiO2.

 Rutile is the mineral form of titanium dioxide, TiO2.

 Ti4+ ions are occupied in a body centered tetragonal

structure and the oxide anions (O2−) are arranged in
distorted hexagonal close-packing.

Rutile  O2− ions are occupying all the tetrahedral voids.

 Each Ti4+ ion is surrounded by six O2− ions, and each

O2− ion is surrounded by 3 Ti4+ ions.

 The coordination geometry of the Ti4+ ion is octahedral,

and the O2− ion is trigonal in nature.
The rutile TiO2 crystal is a 6:3 coordination type.

 Each unit cell has 2 TiO2 formula units.

 The other common examples of rutile structure are

CrO2, WO2, PbO2, ZnF2, etc.
MX3 type: ReO3

 Rhenium trioxide (ReO3) crystallizes with a primitive cubic unit cell.

Re6+ ions are occupied at corners, and O2− ions are situated at the edge
centers.

 Each Re cation is surrounded by 6 O2− anions, and each O2− ion is

connected by 2 rhenium ions.

 Rhenium ion is octahedral, and oxide ion is linear coordination.

Therefore, ReO3 crystal structure is a 6:2 coordinated type.

 One ReO3 formula unit is present in a unit cell.

 ReO3 can use as a catalyst for organic reactions.

 Ternary compounds
ABX3 type: Perovskite (SrTiO3)
O2− Ti4+  The idealized form of perovskite is a cubic structure.
 The perovskite structure is named after CaTiO3, this mineral forms a
non-idealized form.
Sr2+  SrTiO3 is an example of cubic perovskites.
 SrTiO3 crystallizes in the cubic crystal structure in which Ti4+ ions are
occupied at all corners, O2− ions are placed at the center of edges, and a
large Sr2+ ion is present at the body center of the cubic structure.
 Each Ti4+ ion is surrounded by 6 oxide ions as octahedral geometry while each O2−
ion is connected with two Ti4+ ions as linear coordination. Therefore, the
coordination number ratio between Ti4+ and O2− ions is 6:2.
 The central cation, Sr2+ ion is surrounded by 12 O2− ions.
 Each unit cell has only one SrTiO3 formula unit.
 The octahedron units, TiO6 are shared corners to form the 3D structure.
 Four general categories of cation-pairing are possible: A+B2+X−3, A2+B4+X2−3,
A3+B3+X2−3, and A+B5+X2−3 perovskites.
 The relative ionic size stabilizes the perovskite in the cubic structure. So, a slight
distortion can change to lower symmetry distorted versions, in which the
coordination numbers of A or B or both are reduced. Tilting of the BO6 octahedra
reduces the coordination of an undersized A cation from 12 to as low as 8.
 The orthorhombic and tetragonal phases are the most common non-cubic
variants.
 Methylammonium lead halides
CaTiO3
(CH3NH3PbX3)
 The perovskite structure is
named after calcium titanate  Methylammonium tin halides
(CaTiO3), this mineral forms a (CH3NH3SnX3) and
non-idealized form. methylammonium lead halides
 CaTiO3 is obtained as an (CH3NH3PbX3) are used in dye-
orthorhombic crystal, which is sensitized solar cells.
more specifically perovskite  In the CH3NH3PbX3 cubic crystal
structure. structure, the methylammonium
 In this crystal structure, the cation (CH3NH3+) is surrounded
Ti4+ ions are octahedral by PbX6 octahedra.
coordination, and the Ca2+  The X ions are not fixed and can
ions occupy a cage of 12 oxide migrate through the crystal.
ions.
 The complex perovskite structures [A(BB’)O3] contain two different B-site cations and hence, there are the
possibilities of ordered and disordered variants.
 In a double perovskite (AA’BB’O6 or A2BB’O6), the cation arrangement will differ based on charge, coordination
geometry, and the ratio between A cation and B cation radii.
 Perovskites are used as sensors, catalyst electrodes in fuel cells, catalytic converters for diesel vehicles, dye-
sensitized solar cells, memory devices, etc.
 Yttrium barium copper oxide (YBa2Cu3O7−x) is a family of double perovskites that show high-temperature
superconductivity.
 Yttrium barium copper oxide (YBCO or Y123)

 Many YBCO compounds have the general formula YBa2Cu3O7−x, that

Cu2+, Cu3+
display high-temperature superconductivity at about 93 K.
Ba2+
 YBCO crystallizes in a defect perovskite structure consisting of layers.
Y3+
 As high-temperature superconducting materials, they can use as magnets in
O2−
magnetic resonance imaging, magnetic levitation, and Josephson junctions.
AB2X4 type MgAl2O4 (Normal spinel structure)

 The spinel, AB2X4 crystallizes in the cubic crystal system,

with the X anions (oxygen or sulfur) arranged in a cubic
close-packed lattice, and the cations A and B occupied some
or all of the octahedral and tetrahedral sites in the lattice.
 In MgAl2O4 i.e. normal spinel structure, there is a close-
packed lattice of O2− ions.
 The Mg2+ ions filled 1/8 of the tetrahedral holes and the Al3+
ions filled 1/2 of the octahedral holes.
 Each Mg2+ ion is surrounded by 4 oxide ions as a tetrahedral
coordination, each Al3+ ion is surrounded by 6 O2− ions as an
octahedral geometry, and each oxide ion is coordinated with
3 Al3+ ions and one Mg2+ ion as a tetrahedral geometry.
 Each unit cell contains 8 formula units and has a composition
A8B16O32.
 The other common examples of normal spinel structure are
Mn3O4, FeCr2O4, ZnFe2O4, etc.
 Inverse spinel structure
Mg2TiO4 NiFe2O4

Mg2+t Fe3+t
Mg2+O Fe3+O
Ti4+O Ni2+O
O2− O2−

 Mg2TiO4 is an inverse spinel and crystallizes in the  Nickel ferrite (NiFe2O4) is an inverse spinel and
orthorhombic crystal system. crystallizes in the cubic crystal system.
 There are two inequivalent Mg²⁺ sites. One is occupied at  The divalent ion, Ni2+ occupies the octahedral sites
tetrahedral holes, and another one is at octahedral sites. and the trivalent ions, Fe3+ occupy both the
Ti4+ ions are occupied at octahedral holes. tetrahedral and octahedral sites.
 For transition metal oxide spinels, the choice of the normal vs. inverse spinel structure is driven primarily by
the crystal field stabilization energy (CFSE) of ions in the tetrahedral and octahedral sites.
 For spinels that contain 3d elements such as Cr, Mn, Fe, Co, and Ni, the electron configuration is typically
high spin because O2− is a weak field ligand.
Examples:
 MgAl2O4 is a normal spinel since both Mg2+ and Al3+ are non-transition metal ions and thus CFSE = 0. The
more highly charged Al3+ ion prefers the octahedral site, where it is surrounded by six negatively charged
oxygen atoms.

 Mn3O4 is a normal spinel since the Mn2+ ion is a high spin d5 system with zero CFSE. The two Mn3+ ions are
high spin d4 with higher CFSE on the octahedral sites (3/5 ΔO) than on the tetrahedral site (2/5 Δt ~ 1/5 ΔO).

 Fe3O4 is an inverse spinel since the Fe3+ ion is a high spin d5 system with zero CFSE. Fe2+ is a high spin d6
system with more CFSE on an octahedral site than on a tetrahedral one.

 NiFe2O4 is again an inverse spinel since Ni2+ (d8) ion prefers the octahedral site and the CFSE of the Fe3+ (d5)
ion is zero.

 FeCr2O4 is a normal spinel since Fe2+ is high spin d6 ion with CFSE = [4(2/5)−2(3/5)]Δo= 2/5Δo on an octahedral
site, and Cr3+ is a d3 ion with CFSE = 3(2/5) ΔO = 6/5 ΔO. Hence, it is more energetically favorable for Cr3+ to
occupy both of the octahedral sites.

 Co3O4 is a normal spinel. Co3+ is a low spin d6 ion with very high CFSE (2/5Δo) on the octahedral sites, because
of the high charge and small size of the Co3+ ion. Hence, the Co3+ ions occupy both octahedral sites, and Co2+
occupies the tetrahedral site.
The Crystal Field Stabilization Energy (CFSE) is defined as the energy of the d-electron configuration in the ligand field minus
the energy of the d-electronic configuration in the isotropic field.
CFSE = E = Eligand field − Eisotropic field
 CaCO3 (Calcite structure)

 Calcite is a carbonate mineral and the most stable polymorph of calcium

carbonate (CaCO3).
Other polymorphs of calcium carbonate are the minerals aragonite and
vaterite.

 CaCO3 crystallizes in the trigonal crystal system in which layers of Ca2+ ions
are in alternation with stacks of carbonate layers.

 Carbonate layers are made up of triangular shaped CO32− ions.

 This triangular unit is the key component in the trigonal symmetry of this
type of mineral.

 Each Ca2+ ion is surrounded by 6 oxide ions and each oxide ion is
coordinated by 2 Ca2+ ions and one carbon atom.

 The coordination geometry of the Ca2+ ion is octahedral, and that of O2− is
triangular planar.
 Miller Indices and planes

 Miller indices form a notation system in crystallography for lattice planes in Bravais lattices.
 In particular, a family of lattice planes of a given Bravais lattice is determined by three integers h, k, and ℓ,
which are called the Miller indices.
 There are several related notations:
• (h,k,l) denotes a point
• (hkl) denotes a plane
• {hkl} represents a family of planes
• [hkl] represents a direction
• <hkl> denotes a family of directions
• Negative numbers/directions are denoted with a bar on top of the number
z

y
x
 Determination of the miller indices of a plane

 Determine the intercepts of the plane along the crystal axes.

Ex: Consider 2a, 3b and 1c

 Divide intercepts with lattice points translation distances along the axes to obtain
intercept of the planes in terms of multiples of unit cell translation lengths.
2a/a, 3b/b and 1c/c which gives the values 2, 3 and 1, respectively.

 Take the reciprocals.

1/2, 1/3 and 1 are reciprocals

 Convert the fractions in the lowest integers in the same ration by multiplying with
lowest common multiple.
LCM is 6 and multiply each fraction by 6.
1/2×6, 1/3×6, and 1×6
=> 3, 2 and 6 are obtained

 Represent the plane as (326).

 Crystallographic planes

(001)

(010) (110)
(100)
(100)

(1a,0,0)

(210)
(111)
 Interplanar (dhkl) spacing
 Interplanar spacing or d-spacing in a
crystal refers to the distance between
adjacent parallel planes of atoms within
a crystal lattice.
 In the crystallography, this parameter is
used to analyze the crystal structures
through the techniques like X-ray
diffraction.
 Bragg’s law

From figure,
AB = BC = dsinθ,
where d is interplanar distance or d-spacing and θ
is the angle of incidence or Bragg angle.
θ
Path difference between two incident beams,
 = AB + BC θ
A C
= dsinθ + dsinθ = 2dsinθ
B
For constructive interference between two reflected beams, the
difference must be an integer multiple of wavelength, λ.
i.e. path difference,  = nλ

n = 2dsinθ
 X-ray Diffraction (XRD)
X-ray diffraction is a phenomenon to determine the atomic and molecular structure of a crystal, in which the
crystalline structure causes a beam of incident X-rays to diffract in specific directions.

Powder X-ray Diffractometer

 The most commonly used modern powder X-ray instrument is the

powder diffractometer.
 It has a proportional, scintillation or Geiger counter as the detector,
which connected to a chart recorder or a digital output means
computer.
 The data scale is linear in 2θ and the d-spacings of the peaks may be
calculated from Bragg’s law or obtained from standard tables of d
versus 2θ.
 Intensities are taken as peak heights and the most intense peak is given
intensity of 100 and the rest are scaled accordingly.

 There are two types of powder XRD instruments:

• A θ:θ instrument – the sample is fixed, and both X-ray tube and
Intensity (a. u.)

detector rotate at the rate of θ°/min.

• A θ:2θ instrument − the X-ray tube is fixed, the sample rotates at
θ°/min, and the detector rotates at 2θ°/min.
35 40 45 50 55
2θ (°)
Single crystal Diffractometer:
Rotation

Rotation
Beam trap

Incident X-ray beam

Counter Diffracted Collimator

beam

Rotation

Rotation

 In the single crystal diffractometer, a Geiger counter or

other electronic detector can be used to detect both the
presence and intensity of each diffraction.
 Modern single crystal diffractometers use CCD (charge-
coupled device) technology to transform the X-ray
photons into an electrical signal which are then sent to a
computer for processing.
 The data collection of any normal crystal structure will
take one to three days or more days.