Course: Principles of Chemistry 2

Lecturer: PhD Ngo Tuan Cuong

 Faculty of Chemistry and Center for
Computational Science
 Hanoi National University of Education
Course: Principles of Chemistry 2
Contents
 Chapter 1: Solids and advanced materials
 Chapter 2: Solution
 Chapter 3: Chemical kinetics
 Chapter 4: Chemical Equilibrium
 Chapter 5: Gibbs energy and thermodynamics
 Chapter 6: Acids and Bases
 Chapter 7: Electrochemistry
Chapter 1: Solids and advanced materials

Contents
 1.1. X-ray diffraction method. Bragg's equation.
 1.2. Unit cell, primitive cell
 1.3. Types of solid crystals: molecular, ionic, metal
and covalent.
 1.4. Ionic crystals: Structural characteristics,
lattice energy, some properties.
 1.5. Covalent crystals: Structural features, some
properties.
 1.6. Glass, porcelain and cement.
 1.7. Polimer and plastics.
 1.8. Band theory in solid.
I. X-Ray Diffraction (XRD)
 Theory and Analytical Technique
X-Ray Analysis

 X-rays discovered in 1895

 Fundamental to understanding of crystal
structure and symmetry
 Powder diffraction analyses are a simple and
inexpensive method for identifying minerals,
especially fine-grained minerals
 X-ray Crystallography

X-ray wavelengths are on the same order of

magnitude as atomic spacings.
Crystals thus make excellent diffraction
gratings
Can use the geometry of the x-ray spots to
determine geometry of grating (i.e. the
crystal)
nλ = 2d sin θ
 Bragg Diffraction
 Diffraction from a three dimensional periodic
structure such as atoms in a crystal is called
Bragg Diffraction.
 Similar to diffraction though grating.
 Consequence of interference between waves
reflecting from different crystal planes.
 Constructive interference is given by Bragg's
law: nλ = 2d sin θ
 Where λ is the wavelength, d is the distance
between crystal planes, θ is the angle of the
diffracted wave. and n is an integer known as
the order of the diffracted beam.
Following Bragg's law, each dot (or reflection), in this
diffraction pattern forms from the constructive interference of
X-rays passing through a crystal. The data can be used to
determine the crystal's atomic structure.
 X-ray Generation
X-rays – High energy*, highly penetrative
electromagnetic radiation

*E = hc/λ λ(X-rays) = 0.02-100Å (avg. ~1 Å)

λ(visible light) = 4000-7200Å

X-ray Vacuum Tube

Cathode (W)– electron

generator

Anode (Mo, Cu, Fe, Co, Cr) –

electron target,
X-ray generator
Our instrument uses a copper target
 When light hits an electron, the
X-ray Spectra electron jumps to a higher energy
level, then drops back to its original,
shell, emitting light

 Continuous spectra (white

radiation)– range of X-ray
wavelengths generated by the
absorption (stopping) of
electrons by the target
 Characteristic X-rays –
particular wavelengths created
by dislodgement of inner shell
electrons of the target metal; x-
rays generated when outer
shell electrons collapse into
vacant inner shells
 K peaks created by collapse
from L to K shell;
K K peaks created by collapse
K from M to K shell
X
X-ray Crystallography Methods
Single-Crystal: Laue Method

Several directions simultaneously fulfill Bragg equations

Good for symmetry, but poor for analysis because distorted

Fig 7.39 of Klein (2002) Manual of Mineral

Science, John Wiley and Sons
X-ray Diffraction (Bragg’s Law)
nλ = 2d sinθ
Defines the spacing (d) of atomic planes and incident
angle (θ) at which X-rays of a particular wavelength
will reflect in phase (i.e., diffract)

GE+EH = nλ

θ’

≠ nλ
GE + EH is the path difference, waves add if equal to nλ
 X-ray Crystallography Methods:
Single-Crystal: Precession

Use motors to move crystal & sensor to satisfy

Bragg equations for different planes without
distortions

Fig 7.40 of Klein (2002)

Manual of Mineral Science,
John Wiley and Sons
 X-ray Crystallography Methods

Powder

Easiest
Infinite orientations at once, so only need to vary q ,
the angle of the incident beam of x-ray light.
Powder Diffraction Method
 Requires random
orientation of very fine
crystals
 Incident beam of a certain
X-ray wavelength will
diffract from atomic
planes oriented at the
appropriate θ angles for
the characteristic d
spacing
 Random orientation of
crystals will produce more
intense diffraction peaks
for particular angles that
correspond to
characteristic atomic
planes
Powder Diffraction Plots
θ = arcsin (nλ / 2d)

λ(Cu) = 1.54Å
d - Qtz [101] = 3.342
θ = 13.32° ; 2θ = 26.64°

Quartz
 Interpreting X-ray data
 We will use the data obtained to
 identify the mineral
 determine the dimensions of the unit
cell.
II. Unit cell and primitive cell
Solid

Crystalline Solid Amorphous Solid

 II. Unit cell and primitive cell
 Primitive vector: Associate with Bravais lattice are one
or more sets of primitive vectors ai that can translate
any point in the lattice to any other point with a suitable
set of integers ni
r’ = r + n1a1 + n2a2 + n3a3
The choice of primitive vectors is NOT unique:
 II. Unit cell and primitive cell
 Primitive vector: The choice of primitive vectors is
NOT unique:
II. Unit cell and primitive cell

Primitive vector
 II. Unit cell and primitive cell

The unit cell is defined as the smallest repeating unit having the full symmetry of
the crystal structure.
- A repetitive arrangement (pure translation) of them can build up the whole crystal
without overlaps/gaps.
- There is no further partition of the unit cell that could itself be used as a unit cell.

 Ô đơn vị: Là đơn vị thể tích mà bằng cách tịnh tiến nó theo các
hướng ta thu được toàn bộ tinh thể:
 II. Unit cell and primitive cell
The primitive cell
A primitive cell is a unit cell that contains exactly one lattice point. It
is the smallest possible cell.[5] If there is a lattice point at the edge
of a cell and thus shared with another cell, it is only counted half.
Accordingly, a point located on the corner of a cube is shared by 8
cubes and would count with 1/8.

 Ô cơ sở: Là ô đơn vị có thể tích nhỏ nhất.

Cách chọn ô cơ sở:

Có nhiều cách chọn, trong đó phổ biến nhất là lấy luôn hình hộp
không gian do ba vectơ cơ sở ax, ay, az trên ba hướng x, y, z
thích hợp làm ô cơ sở .
 II. Unit cell and primitive cell
 Primitive cell:

A two dimensional lattice with different possible

choices of primitive cell.
II. Unit cell and primitive cell

Primitive cells in cubic lattices.

II. Unit cell and primitive cell

Primitive cell in hexagonal lattice.

 II. Unit cell and primitive cell

 Wigner-Seitz unit cell:

(1) Chose a lattice point (2) Find its nearest
neighbors.
(3) Draw a line from the point to its neighbors.
(4) Bisect this line with a plane.

(5) The smallest volume enclosed is the Wigner-Seitz

primitive unit cell.
 II. Unit cell and primitive cell

 Wigner-Seitz unit cell:

b.c.c Wigner-Seitz cell f.c.c Wigner-Seitz cell

 III. Close packing
 Considering the packing of circles in two
dimensions, how efficiently do the circles pack for
the square array? In aclose packed array?

Square arrays of circles Closed-pack arrays of circles

 III. Close packing

 Layer A  Layer B
 III. Close packing

Place one sphere over every

other hollow in layer A

(c) Layer A: red spheres

Layer B: grey spheres
Layer C: blue spheres
→ cubic closed packed: CCP

 (a) Layer A  (b) Layer A: red spheres

Layer B: grey spheres
(d) Layer A: red spheres
Layer B: grey spheres
(c) cubic closed packed: CCP
Layer A: red spheres
(d) Hexagonal close packed: HCP
→ hexagonal close packed: HCP
 III. Close packing

(a) One layer (layer A) of closed-packed spheres contains

hollows that exhibit a regular pattern. (b) A second layer (layer
B) of close-packed spheres can be formed by occupying
every other hollow in layer A. In layer B, there are two types of
hollow; one lies over a spheres in layer A, and three lie over
hollows in layer A. By stacking spheres over these different
types of hollow, two different third layers of spheres can be
produced. The blue spheres in diagram © form a new layer C;
this gives an ABC sequence of layers. Diagram (d) shows that
the second possible third layer replicates layer A; this gives an
ABA sequence.
III. Close packing
 III. Close packing

In ionic crystals, ions pack themselves so as to maximize the

attractions and minimize repulsions between the ions.

- A more efficient
packing improves
these interactions.
- Placing a sphere
in the crevice or
depression
between two
others gives
improved packing
efficiency.
III. Close packing
III. Close packing
 IV. Classes of crystalline solids
Crystalline substances can be described by the types of
particles in them and the types of chemical bonding that
takes place between the particles.

There are four types of crystals: (1) ionic, (2) metallic,

(3) covalent network, and (4) molecular. Properties
and several examples of each type are listed in the
following table and are described in the table below.
 IV. Classes of crystalline solids
There are four types of crystals: (1) ionic, (2) metallic, (3) covalent network,
and (4) molecular. Properties and several examples of each type are listed
in the following table and are described in the table below.
Table 1: Crystalline Solids - Melting and Boiling Points
Type of Crystalline Examples Normal Boiling
Melting Point (°C)
Solid (formulas) Point (°C)
NaCl 801 1413
Ionic
CaF2 1418 1533
Hg -39 630
Na 371 883
Metallic
Au 1064 2856
W 3410 5660
B 2076 3927
Covalent Network C (diamond) 3500 3930
SiO2 1600 2230
H2 -259 -253
I2 114 184
Molecular
 IV. Classes of crystalline solids
Ionic crystals
- The ionic crystal structure consists of alternating positively-charged
cations and negatively-charged anions (see figure below). The ions
may either be monatomic or polyatomic.
- Generally, ionic crystals form from a combination of Group 1 or 2
metals and Group 16 or 17 nonmetals or nonmetallic polyatomic ions.
- Ionic crystals are hard and brittle and have high melting points. Ionic
compounds do not conduct electricity as solids, but do conduct when
molten or in aqueous solution.

NaCl crystal
 IV. Classes of crystalline solids
Metallic crystal
- Metallic crystals consist of metal cations surrounded by a
"sea" of mobile valence electrons (see figure below). These
electrons, also referred to as delocalized electrons, do not
belong to any one atom, but are capable of moving through
the entire crystal.
- As a result, metals are good conductors of electricity. As seen
in the table above, the melting points of metallic crystals
span a wide range..

Figure 12.7.212.7.2: Metallic crystal lattice with free electrons able o move
among positive metal atoms.
 IV. Classes of crystalline solids
Covalent network crystals
- A covalent network crystal consists of atoms at the lattice
points of the crystal, with each atom being covalently bonded
to its nearest neighbor atoms (see figure below). The
covalently bonded network is three-dimensional and contains
a very large number of atoms.
- Network solids include diamond, quartz, many metalloids,
and oxides of transition metals and metalloids.
- Network solids are hard and brittle, with extremely high
melting and boiling points. Being composed of atoms rather
than ions, they do not conduct electricity in any state.

Figure. Diamond is a network solid and consists of

carbon atoms covalently bonded to one another in a
repeating three-dimensional pattern. Each carbon
atom makes for single covalent bonds in a tetrahedral
geometry.
 IV. Classes of crystalline solids
Molecular crystals
- Molecular crystals typically consist of molecules at the lattice
points of the crystal, held together by relatively weak
intermolecular forces (see figure below). The intermolecular
forces may be dispersion forces in the case of nonpolar
crystals, or dipole-dipole forces in the case of polar crystals.
- Some molecular crystals, such as ice, have molecules held
together by hydrogen bonds. When one of the noble gases is
cooled and solidified, the lattice points are individual atoms
rather than molecules.
- In all cases, the intermolecular forces holding the particles
together are far weaker than either ionic or covalent bonds.
- As a result, the melting and boiling points of molecular
crystals are much lower. Lacking ions or free electrons,
molecular crystals are poor electrical conductors
 IV. Classes of crystalline solids
Molecular crystals

Figure: Ice crystal structure

 IV. Classes of crystalline solids
Table: Properties of the Major Classes of Solids

Ionic Solids Molecular Solids Covalent Solids Metallic Solids

poor conductors poor conductors of poor conductors
good conductors of heat
of heat and heat and of heat and
and electricity
electricity electricity electricity*
melting points depend
relatively high high melting
low melting point strongly on electron
melting point point
configuration
hard but brittle; easily deformed under
very hard and
shatter under soft stress; ductile and
brittle
stress malleable
relatively dense low density low density usually high density
dull surface dull surface dull surface lustrous
*Many exceptions exist. For example, graphite has a relatively high electrical
conductivity within the carbon planes, and diamond has the highest thermal
conductivity of any known substance.
 IV. Classes of crystalline solids
Example
Classify Ge, RbI, C6(CH3)6, and Zn as ionic, molecular, covalent, or metallic solids
and arrange them in order of increasing melting points.
Strategy:
A. Locate the component element(s) in the periodic table. Based on their
positions, predict whether each solid is ionic, molecular, covalent, or metallic.
B. Arrange the solids in order of increasing melting points based on your
classification, beginning with molecular solids.
Solution:
A Germanium lies in the p block just under Si, along the diagonal line of
semimetallic elements, which suggests that elemental Ge is likely to have the
same structure as Si (the diamond structure). Thus Ge is probably a covalent
solid.
RbI contains a metal from group 1 and a nonmetal from group 17, so it is an ionic
solid containing Rb+ and I− ions.
The compound C6(CH3)6 is a hydrocarbon (hexamethylbenzene), which consists
of isolated molecules that stack to form a molecular solid with no covalent bonds
between them.
Zn is a d-block element, so it is a metallic solid.
 IV. Classes of crystalline solids
Solution:

B Arranging these substances in order of increasing melting points is

straightforward, with one exception. We expect C 6(CH3)6 to have the
lowest melting point and Ge to have the highest melting point, with RbI
somewhere in between. The melting points of metals, however, are
difficult to predict based on the models presented thus far. Because Zn
has a filled valence shell, it should not have a particularly high melting
point, so a reasonable guess is
C6(CH3)6 < Zn ~ RbI < Ge.
The actual melting points are C6(CH3)6, 166°C; Zn, 419°C; RbI, 642°C;
and Ge, 938°C. This agrees with our prediction.
 V. Metallic Crystals
Metallic Crystals
- Metals – elements from the left side of the periodic table from
crystals in which each atom has been ionized to form a cation
and a correcponding number of electrons.
- The cations are pictured to form a crystal lattice that is held
together by a “sea of electrons” – sometime called a Fermi sea.
- The electrons of the sea are no longer associated with any
particular cation but are free to wander about the lattice of
cations.
- We can therefore define a metallic crystal as a lattice of cations
held together by a sea of free electrons.

- The sea analogy allows us to picture

electrons flowing from one place in the
lattice to another.
 V. Metallic Crystals
Metallic Crystals
- If we shape the metal (copper is a good example) into a wire. If we put
electrons in one end of the wire, electrons will be pumped along the
lattice of cations until some electrons will be pushed out of the other
end.
- The mobility of the delocalized electrons accounts for electrical
conductivity.
- Metals are characterized by their tensile strength and the ability to
conduct electricity.
- Both properties are the result of the special nature of the metallic
bond. Bonding electrons in metals are highly delocalized over the
entire crystal.
- The great cohesive force resulting from the delocalization is
responsible for the great strength noted in metals.
- The bonding strength in metals varies with the number of electrons
available as well as with the size of the atoms.
- i.e. Na – 1 valence electron m.p. 98oC. Mg – 2 valence electrons m.p.
649oC. W – 6 valence electrons m.p 6000oC.
 V. Metallic Crystals
Primary Metallic Crystalline Structures: Body centered
cubic (BCC), Face centered cubic (FCC), Hexagonal close-
packed (HCP)

- There are 14 different types of crystal unit cell structures or

lattices are found in nature. However most metals and many
other solids have unit cell structures described as body center
cubic (bcc), face centered cubic (fcc) or Hexagonal Close
Packed (hcp). Since these structures are most common, they
will be discussed in more detail.

Two other important characteristics of a crystal structure

are the coordination number and the atomic packing
factor (APF).
 V. Metallic Crystals
Body centered cubic (BCC)

How many atoms in the unit

cell of the Body centered cubic
lattice? 2
Coordination Number? 8

Atomic packing factor (APF)? 0.68

 V. Metallic Crystals
Faced centered cubic (FCC)

How many atoms in the unit

cell of the Face centered
cubic lattice? 4

Coordination Number? 12

Atomic packing factor (APF)?

0.74
 V. Metallic Crystals
Faced centered cubic (FCC)

The fraction of space occupied by spheres is (Atomic

packing factor, or Packing Efficiency):
 V. Metallic Crystals
Faced centered cubic (FCC)
Atomic packing factor (APF): 0.74. It is the most efficient
(tied with hcp) packing scheme

The density expression is:

 V. Metallic Crystals
Hexagonal close-packed (HCP)

How many atoms in the HCP unit cell? 6

Each of the 12 atoms in the corners of the top and bottom layers contribute
1/6 atom to the unit cell, the two atoms in the center of the hexagon of both
the top and bottom layers each contribute ½ atom and each of the three atom
in the middle layer contribute 1 atom.
Coordination Number? 12
Atomic packing factor (APF)? 0.74
 VI. Covalent Network Crystals
Covalent Network Crystals
- A covalent network crystal is composed of atoms or group of atoms
arranged into a crystal laatice that is held together by an interlocking
network of covalent bonds.
- Covalent bonds (the result of the sharing of one or more pairs of
electrons in a region of overlap between two or perhaps more atoms)
are directional interactions as opposed to ionic and metallic bonds,
which are non directional.
- For example diamond – each carbon is best thought of as being sp 3-
hybridized and that to maximize the overlap of these hybrid orbitals, a
C-C-C bond angle of 109.5o is necessary.
- Hence the interactions are directional in nature.
- Other examples of compounds that form covalent network crystals are
silicon dioxide (quartz), graphite, elemental silicon, boron nitride (BN)
and black phosphorous.
 VI. Covalent Network Crystals

Covalent Network Crystals

Structures of diamond, graphite,

and quartz. In quartz, the filled
circles represent silicon and the
open circles represent oxygen.

- The structure of diamond is based on a fcc lattice. There are 8 C atoms at

the centre of the cube, 6 C atoms in the face centre, and 4 more within
the unit cell. Each C is tetrahedrally bonded to four others. This tightly
bound lattice contributes to diamond’s unusual harness. In graphite each
C is bonded to three others and the layers are held together only weakly.
- Covalent crystals are hard solids that possess very high melting points.
They are poor conductors of electricity.
 VII. Molecular Crystals
Molecular Crystals
- Very soft solid that possess low melting points.
- They are poor conductors of electricity.
- Molecular crystals consist of such substances as N 2, CCl4 I2 and
benzene.
- Generally, the molecules are packed together as closely as their size
and shape will allow.
- The attractive forces are mainly van der Waals (dipole-dipole)
interactions.
- Water molecules are held together by directional H-bonds.
- Intermolecular forces in this case can either be nondirectional as is the
case of crystals of argon, or directional, as in the case of ice.
- In the latter case, the H-O…H angle is 109.5o, and angle determined
by the geometry of the individual water molecules.
 VII. Molecular Crystals
Molecular Crystals
- Examples of molecular crystals

Molecules of Argon gas

H-bonding of water molecules to form

the diamond structure of ice.
 VIII. Ionic Crystals
Ionic Crystals
- Hard and brittle solids.
- They possess high melting points.
- They are poor conductors of electricity, but their ability to conduct
increases drastically in melt.
- The packing of spheres in ionic crystals is complicated by two factors:
- Charge species are present.
- Anions and cations are generally quite different in size.
- Some general conclusions can be drawn from ionic radii:
- Within the same period the anions always have larger radii than
the cations.
- The radius of the trivalent cations is smaller than that of the
divalent cation which is smaller than that of the monovalent cation.
- It should be realized that the value of any ionic radius only serves as a
useful but approximate size of the ion. The fact that the ionic radius of
Na+ is 0.98 Å does not mean that the electron cloud of the ion never
extends beyond this value. It is significant because when it is added
together with the radius of an anion, e.g. Cl-, the sum is approximately
equal to the observed interionic distance.
 VIII. Ionic Crystals
Formation of an Ionic Crystal – when two elements, one a
metal with a low ionization energy and the other a nonmetal with
a highly exothermic electron affinity are combined, electrons are
transferred to produce cations and anions.

- These forces are held together by non-directional, electrostatic forces

known as ionic bonds.

- A hypothetical view of the formation of sodium

chloride, the constituent elements are combined,
electrons are transferred and ionic bonds among
the sodium and chloride ions are formed.
 VIII. Ionic Crystals
Examples of compounds that form ionic crystals are CsCl,
CaF2, KNO3, alumina Al2O3, zirconia, ZrO2 (very hard).
- Cubic zirconia is an imitation diamond, when crystallized it can be used
as a jewel or it can be used as an industrial product for abrasion.

Melting Points of a Class of Ionic Compounds

 VIII. Ionic Crystals
Lattice Energy

- The energy change that accompanies the process in which the isolated
gaseous ions of a compound come together to form 1 mol of the ionic
solid.
- For a solid composed of monoatomic, single charge ions, such as NaCl,
the lattice energy is the energy corresponding to the reaction shown
below:
- Na+ (g) + Cl- (g) → NaCl (s)
- Energy is released in such a process; the energy of the products is
lower than the energy of the reactants. (Remember exothermic
thermodynamic quantities carry a negative sign).

Theoretical evaluation of Lattice Energy

- First we consider the electrostatic interaction within an ion pair made up
of one sodium cation and one chloride anion.
- Assuming the energy of the isolated gaseous ions is taken to be zero,
 VIII. Ionic Crystals
Theoretical evaluation of Lattice Energy
- First we consider the electrostatic interaction within an ion pair made up of one
sodium cation and one chloride anion.

- Assuming the energy of the isolated gaseous ions is taken to be zero,

the potential energy of the ion pair is given by Coulomb’s law:
- E = (Z+e)/(Z-e)/r
- where Z+ = integral charge on cation
- Z- = integral charge on anion
- e = fundamental charge on an electron
- r = interionic distance as measured from center of cation to the
center of the anion
- If we want the interionic distance to be in Angstrom units and the energy
to be in kJ the exact relationship for Coulomb’s law for one Na +Cl- ion
pair is:
- E = AZ+Z-/r
- where A = 2.308x10-21; E = energy kJ; r = interionic distance, Å.
 VIII. Ionic Crystals

Theoretical evaluation of Lattice Energy

 VIII. Ionic Crystals

Theoretical evaluation of Lattice Energy

- If sodium cations and chloride anions assumed the CsCl or zinc blende
structure, this equation would be different.
- These unique series for each crystal structure are known as Madelung
constants (M).
Madelung Constants for Some Common Crystal
Structures:
 VIII. Ionic Crystals

Theoretical evaluation of Lattice Energy

- Using the symbol MNaCl for the Madelung constant unique to NaCl
- Ecoul = AZ+Z-MNaCl/r
- We can see that M varies with structure type and that it is higher for
higher coordination numbers.
- Ecoul is the total Coulombic energy for one sodium chloride cation,
assuming that all of the ions are point charges, charge that act as if they
are at the very centre of the hard spheres representing the ions.
- If this is the case then Ecoul would be the lattice energy for NaCl.
- In reality however, this model must be used with caution as ions are not
really hard spheres, but electrons surrounding a nucleus.
- If hard spheres approach too closely to one another, a strong repulsive
force will result and we must also consider the energy of this interaction.
 VIII. Ionic Crystals

Solubilities of Ionic Compounds

For example NaCl

- You need to put in energy to get the ions (salt) into ions in the gas
phase.
- This energy will be recovered when the ions become hydrated.
- “high” lattice energy, “low” hydration energy – salt will be insoluble
- “low” lattice energy, “high” hydration energy – salt will be soluble.
 VIII. Ionic Crystals

Solubility’s as a Function of Lattice Energy and Hydration

Energies

- Example 1

- Reverse of the lattice Energy

- i.e. exothermic; G = H - TS

 VIII. Ionic Crystals

Solubility’s as a Function of Lattice Energy and Hydration

Energies

- Example 2
- CaF2 or fluorite is insoluble in H2O

- Reaction is endothermic
 IX. Ceramic Crystal Structures
Because ceramics are composed of at least two elements, and often
more, their crystal structures are generally more complex than those for
metals. The atomic bonding in these materials ranges from purely ionic to
totally covalent; many ceramics exhibit a combination of these two
bonding types, the degree of ionic charater being dependent on the
electronegativities of the atoms. Table 2 presents the percent ionic
character for several common ceramic materials.
Table 2. For several ceramic materials, percent ionic character of the
interatomic bonds
Material Percent Ionic Character
CaF2 89
MgO 73
NaCl 67
Al2O3 63
SiO2 51
Si3N4 30
ZnS 18
IX. Ceramic Crystal Structures
IX. Ceramic Crystal Structures
IX. Ceramic Crystal Structures
 X. Band Theory in Solids
Origin of energy bands formation in solids
An isolated atom possesses discrete energies of different electrons.
Suppose two isolated atoms are brought to very close proximity, then the
electrons in the orbits of two atoms interact with each other. So, that in the
combined system, the energies of electrons will not be in the same level but
changes and the energies will be slightly lower and larger than the original
value. So, at the place of each energy level, a closely spaced two energy
levels exists. If ‘N’ number of atoms are brought together to form a solid and
if these atoms’ electrons interact and give ‘N’ number of closely spaced
energy levels in the place of discrete energy levels, it is known as bands of
allowed energies. Between the bands of allowed energies, there are empty
energy regions, called forbidden band of energies. Kronig-Penney model
supports the existence of these bands of energies (allowed bands and
forbidden bands). The mathematical solution for Schrödinger’s wave
equation is very tedious but it provides a clue in understanding the origin of
energy bands.
 X. Band Theory in Solids
Origin of energy bands formation in solids

The formation of energy

bands has been explained
taking Sodium (Na) metal
as an example. When
isolated sodium atoms are
brought together to form a
solid, then the energy
levels of the valence
electrons spread into
bands. The 3S and 3P
orbitals electrons energies
are shown in Fig. below.
These bands are seen to
overlap strongly at the
interatomic spacing of Figure. Sprending of energy levels into
sodium. energy bands in sodium metal
 X. Band Theory in Solids
Origin of energy bands formation in solids
Atoms have been seen to have discrete energy levels.

When a huge number of

atoms are combined to
form a solid however,
these discrete energy
levels are replaced by
discrete ranges of
energy, or energy bands,
within which there are so
many individual allowed
energy values that within
the bands the distribution
can be considered to be
continuous. This idea is seen in the above figure:
 X. Band Theory in Solids
Origin of energy bands formation in solids
In between energy bands are ranges of energy which are entirely
impossible known as band gaps
Different substances have different band structures which in many ways
dictate the characteristics of that substance in terms of electrical
conduction, as there exists an energy band called the conduction band, in
which electrons can be propagated as current. The valence band on the
other hand is the energy level of valence electrons which are bound into
the atomic structure of the substance
When a substance is placed in an electric field its electrons gain potential
energy. For a metal (conductor) the conduction and valence bands
overlap, and so the additional energy is enough to free electrons and
cause current as there are allowable energy values directly above the
initial state. For insulators however, there is often a band gap between the
initial energy state and the next possible value, and so a huge amount of
energy is required to cause the electron to be freed and accelerated as
current.
 X. Band Theory in Solids
For semiconductors there is still a band gap however it is a lot smaller.
This is all seen in the following band diagram: