INORGANIC CHEMISTRY

Chapter I: Relation between bonding types, states and

physical properties of compounds
Chapter II. Acid – base reaction
Chapter III. Oxidation reaction
Chapter IV. Coordination complex (Coordination
compounds)
Chapter V. Transition metals
Chapter VI. Non-transition elements (main group)
 Chapter I. Relationbetween bonding types, states
and physical properties of compounds
I. States of matter

II. Crystal systems

III. Basic structures

IV. Bonding types, crystal lattice types and physical properties of

compounds

V. Real crystal and structural imperfection

VI. Polymorphism, allotropes, isomorphism and solid solution

 I. States of matter

• General comments
• 4 major states of matter:
– Plasma
– Gas
– Liquid
– Solid crystalline structure
• Three metastable states: (self reading)
– Amorphous
– Supercooling liquid
– Superheating liquid
– Liquid crystal (self reading)
1. Plasma:
– Plasma has neither a definite volume nor a definite shape.
Plasma often is seen in ionized gases, but it is distinct from a
gas because it possesses unique properties. Free electrical
charges (not bound to atoms or ions) cause the plasma to be
electrically conductive. The plasma may be formed by heating
and ionizing a gas. Examples of plasma include stars,
lightning, fluorescent lights, and neon signs.
2. Gas
– In a gas, the particles have a great deal of space between them
and have high kinetic energy. A gas has no definite shape or
volume. If unconfined, the particles of a gas will spread out
indefinitely; if confined, the gas will expand to fill its
container. When a gas is put under pressure by reducing the
volume of the container, the space between particles is
reduced and the gas is compressed.
• At low pressure, high temperature, the
distance between gas molecules are far. Thus,
the size and intermolecular forces are
negligible. The gas is considered as ideal and
followed ideal gas law:
PV = nRT
• In which:
– P is the gas pressure (affecting the container wall).
– V is the volume of the container.
– n is number of moles of gas.
– R is the universal gas constant
– T is the absolute temperature
• At high pressure, low temperature, the distance
between gas molecules becomes closer so that the
size and intermolecular force are important. The
gas is real gas and followed:

a
(P + 2 )(V − b) = RT
V

a
• In which 2
reflects the intermolecular forces
V
– b is the specific volume of the gas molecules
 • Liquefaction of gas
• At normal pressure, gas becomes liquid at a
certain temperature. The temperature is called
condensation point of the gas. At that
temperature, the liquid also becomes vapor.
Therefore, the temperature is also called
boiling point of the liquid.
• The gas becomes liquid because the energy is
removed by increasing the pressure or
reducing the temperature. Therefore, the
condensation point can be lowered by
decreasing the pressure.
• However, increasing pressure to liquefy the
gas has a limit. At high temperature, the
liquid can not exist under any pressure.
• The highest temperature at which the liquid
can exist is critical temperature (Tc) and the
required pressure to liquefy the gas at that
temperature is called critical pressure (Pc).
Volume of 1 mole of gas at Tc and Pc is
critical volume. At critical point, the volume
of gas and solid are equal, thus the densities
of them are identical.
 3. Liquid:
• is an intermediate phase existing between
solid and gaseous phases. At room
temperature, structure of liquid near the
structure of solid crystalline.
• Different from solid crystalline, there are
empty spaces in liquid, the particles in liquid
can move easily. Liquids conform to the shape
of the container and isotropic in magnetic, light
and mechanical properties. Liquid is almost
incompressible.
Comparison between structure of solids (a)
and liquid (b)
 4. Crystalline and amorphous solid state

• Crystalline
• Atoms are arranged in strictly regular 3
dimension
• Therefore:
– Defined structure and shape.
– Long range order.
– Anisotropic.
– Sharp melting point.
Examples

SiO2 crystal

(Cristobalite)
 • Amorphous:
• Structure is similar to liquid, has an irregular
arrangement of solid particles
• Therefore:
– Undefined structure and shape.
– Short range order
– Isotrophic
– No particular melting point.

• Conclusion: crystalline is more stable than

amorphous.
 SiO2
amorphous
 II. Crystal system

1. Symmetry of crystal systems

2. Structure of crystals

3. Crystal system and unit cell

 1. Elements of symmetry

• Center of Symmetry
- If an imaginary straight
line can be passed
through a crystal from
any point on the surface
of crystal such that the
point of entry is similar
to the point of exit, then
the crystal has a center
of symmetry.
• Plane of Symmetry
– When an imaginary
plane is passed through
a crystal such that the
portion of the crystal on
one side of the plane is
a reflection, or mirror
image, of the portion
on the other side of the
plane, the plane is
a plane of
symmetry (often called
a mirror plane).
• Axis of Symmetry
– When an imaginary line
can be passed through a
crystal such that the
crystal can be rotated
360o about the line to
fill the same space n
(two, three, four, or six)
times, it has an axis of
symmetry.
– n is the order of the axis
(L4 in this example)
 2. Internal structure of crystals

• Lattice is composed of lattice plane. The

intersections of lattice plane are lattice
points/sites/nodes.

Lattice plane (a) and lattice with unit cell (b)

• Unit cell is the smallest
part (portion) of a
crystal lattice. It is the
simplest repeating unit
in a crystal structure.
The entire lattice is
generated by the
repetition of the unit
cell in different
directions.
• There are six
parameters of a unit
cell. These are the 3
edges which are a, b, c
and the angles between
the edges which are α,
β, γ. The edges of a unit
cell may be or may not
be perpendicular to
each other.
• In a crystal lattice, each atom, molecule or
ions (constituent particle) is represented by a
single point.

CsCl Ar CO2
 3. Crystal systems and unit cells
• A crystal can be classified according to its
elements of symmetry. For example, it may
belong to one of 230 space groups, 32 point
groups, 14 Bravais lattices, and 7 crystal systems:

• 7 crystal systems are:

 3. Crystal systems and unit cells
• 1. Triclinic: has center of
symmetry. There is no axis
and plane of symmetry.
– Unit cell parameters:
– a0 ≠ b0 ≠ c0 ; α ≠ β ≠ γ ≠ 90o
K2Cr2O7; CuSO4.5H2O ...
• Monoclinic: axis of
symmetry of order 2 (2-
fold rotation symmetry)
and one plane of
symmetry.
• Unit cell parameters:
– a0 ≠ b0 ≠ c0; α = γ = 90o;
β ≠ 90o &1200
– Monoclinic sulfur (Sβ),
gypsum (CaSO4.2H2O)
• Orthorhombic: several
axis of symmetry of order
2 and several planes of
symmetry.
• Unit cell parameters:
– a0 ≠ b0 ≠ c0 ; α = β = γ = 90o
– Orthorhomic sulfur (Sα),
BaSO4 …
• Trigonal: has at least one axis of symmetry of
order 3 (3-fold rotation symmetry).
• Unit cell parameters:
– a0 = b0 = c0 ; α = β = γ ≠ 90o
– Calcite (CaCO3), NaIO4.3H2O …
• Tetragonal: has
one axis of
symmetry of order
4 (4-fold rotation
symmetry).
• Unit cell
parameters:
– a0 = b0 ≠ c0 ; α = β
= γ = 90o
– SnO2, CaWO4 ...
• hexagonal has one axis
of symmetry of order 6
(6-fold rotation
symmetry).
• Unit cell parameters:
– a0 = b0 ≠ c0 ; α = β = 90o
, γ = 120o
– Quartz (SiO2),
Nepheline (NaAlSiO4)…
• Cubic has 3 axis of
symmetry of order 4
(4-fold rotation
symmetry).
• Unit cell parameters:
– a0 = b0 = c0 ; α = β = γ
= 90o
– NaCl, CaF2 ...
14 Bravais lattices
III. Basic lattice structure of inorganic
compound

1. Island-like structure

2. Chain-like structure

3. Layer-like structure

4. Coordination structure
 1. Island-like structure
• Each species form an isolated island located at the
lattice nodes.
• Interaction between lattice nodes/species: Van de
Waals force, Hydrogen bond, electrostatic force
(complex ions) → Ulattice is small → Tfusion Tboiling is
low → gas or liquid at room temperature
• Covalent bond: only within the nodes.
• Lattice nodes: finite molecules, complex ions, noble
gas atoms.
• Molecular lattice and ionic lattice with complex ions
are island-like structure
Example: H2, O2, N2, Ar, CO2, X2, HCHC, H2O, K2[TiCl6]
 2. Chain-like structure

• Chain-like structure: covalent bond in one

direction in space. The chains interact with
each others by Van Der Waals, ionic,
hydrogen bond.
• Chain usually has structure of octahedral
(AB6), tetrahedral or square planar (AB2)
with stoichiometric formula of AB5, AB4,
AB3, AB2 linked by B bridge.
• Chain has unit structure of tetrahedral
AB4 with stoichiometric formula of AB2
(example BeCl2)

BeCl2

AB2
• Chain has unit structure of square AB4
with stoichiometric formula of AB2
(example PdCl2)

PdCl2

AB2
• Chain has unit structure of octahedral AB6 with
stoichiometric formula of AB4 (example MgCl2.2H2O)

MgCl2.2H2O

AB4
• Chain has unit structure of octahedral AB6 with
stoichiometric formula of AB5 (example CrF5- in
CaCrF6 compound)

CaCrF6

AB5
 3. Layer-like structure

• Layer-like structure: the covalent bond in

2D in space. The layers interact with each
others by Van Der Waals force, ionic
(complex), hydrogen bond.
• Layer like structure has unit structure of
octahedral (AB6) with a stoichiometric
formula of AB5, AB4, AB3, AB2 connecting by
bridge B.
• Layer like structure has unit structure of
octahedral (AB6) with a stoichiometric
formula of AB3example: Al(OH)3

Al(OH)3 AB3
• Layer like structure has unit structure of
octahedral (AB6) with a stoichiometric
formula of AB3example: CdI2

AB2
 4. Coordination structure
• In a coordination structure, each species
(lattice node) is surrounded by a definite
number of species (atoms, simple ion),
locating at an equal distance and connected by
the same strong bond (ionic, covalent or
metallic bond)
• Coordination structure includes atomic lattice,
ionic lattice (simple ion) and metallic lattice.
– Ionic bond and metallic bond are unsaturated and
non-directional → crystals of coordination structure
of ionic and metallic lattice have high value of
coordination number. They have been arranged in
most tightly packed.
– Crystals of coordination of covalent lattice
determined by the hybridization of atoms (directional
properties) → low value of coordination number (= 4)
• Coordination structures of stoichiometric
formula of A and different unit cells

Diamond AA4

W AA8
• Coordination structure of stoichiometric
formula of AB and different unit cells :

NaCl (AB6) CsCl (AB8) ZnS (AB4)

• Coordination structure of stoichiometric
formula of AB2 and different unit cells :

TiO2 (AB6)

SiO2 (AB4)
• Coordination
structure of
stoichiometric
formula AB3
and
octahedral
unit cell

ReO3 (AB6)
 IV. Relation between bonding types, crystal
lattice structure and physico-chemical properties
of compounds
1. Metallic bond and metallic lattice
2. Ionic bond and ionic lattice
3. Covalent bond and atomic lattice,
molecular lattice
4. General comments on physical properties
of compounds
1. Compounds with metallic bond and
metallic lattice
a. Crystalline structure

b. Lattice energy

c. Physical properties
 a. Crystalline structure
• In metallic crystal, nodes/points are metallic cation
Mn+ connected with each other by metallic bond and
arranged in most tightly packed structure. Valence e
move freely in entire crystal to form delocalized
bonding. Metallic lattice is a giant molecule. Whole
metallic system is a giant molecule.

• Metals and alloys have this lattice type.

Coordination number equals the number of surrounded
metallic atoms.

W Cu Mg
(SPT = 8) (SPT = 12) (SPT = 12)
 b. Lattice energy

• Determined by the valence electron density

• Lattice energy increases when the atomic

radius decreases and number of valence
electron increases.
 c. Physical properties
• Metals have some characteristic properties. They
are lustrous, malleable, ductile, good conductors
of heat and electricity.

 Ulattice of metals is not low (except Hg) → most

metals are solid at room temperature. Because
the electron density in metals are different→
metals have different melting point and boiling
point
 Compounds K Ca Sc Ti

Melting point, 0C 63 850 1539 1668

Boiling point, 0C 766 1490 2700 3330

Atomic radii, Ǻ 2,36 1,97 1,64 1,46

Valence electron 4s1 4s2 3d14s2 3d24s2

Compounds Li Na K Rb

Melting point, 0C 180 98 63 39

Boiling point, 0C 1330 900 766 700

Atomic radii, Ǻ 1,55 1,89 2,36 2,48

Valence electron ns1

 2. Compounds with ionic bonds and
ionic lattices
a. Crystalline structure

b. Lattice energy

c. Physical properties
 a. Crystalline structure

• Ionic crystals are formed from alternatively

opposite charged ions located at nodes and
connected together by electrostatic forces.

• Single ion can not be separated from the

crystal, thus, ionic crystal is considered as a
giant molecule.
• Coordination number is the number of ions
which surround the central ion.

NaCl: Na and Cl have coordination number of 6

CsCl: Cs and Cl have coordination number of 8
– K have the coordination number of 4 (coordinate species
is hexaclorotitanate(IV) ion).
– Ion [TiCl6]2-has the coordination number of 8
 Lattice energy of Ionic lattice

• Definition: lattice energy is the energy release

when 1 mole of crystal is formed from its
constituent ions.in gas phase at 0K.

• In practice, lattice energy is the energy required to

separate the lattice to its constituent ions or simply,
destroy the lattice.

• Practically, lattice energy can not be directly

calculated, thus, the indirect methods are usually
used.
Lattice energy of some compounds
 Calculation of lattice
energy

Theoretical consideration
Experiment Born-Mayer Equation
Born-Haber Cycle Born-Lande Equation
Kapustinskii Equation

Based on 1st Law of Based on

thermodynamic and electrostatic force
Hess Law between ions
 Trend in lattice energy

• Effect of ionic sizes

• Increasing the ionic size will reduce the lattice
energy (with ions which have the same ionic
charge), because the attraction force
decrease.

• Effect of ionic charges

• Increasing the ionic charge will increase the
lattice energy (with ions which have the same
size)
 BORN – HABER CYCLE
• Lattice energy of NaCl(s) can be estimated
from the reaction:
Na(s) + ½ Cl2(g)  NaCl(s)

 Born – Haber cycle

apply the Hess Law
(thermodynamic) to
calculate the lattice
energy
 Na+(g) + Cl-(g)
INa ECl
Lattice
energy (U)
Na(g) Cl(g)

∆hsub,Na ½ Ediss

∆Hf
Na(s) + ½ Cl2(g) NaCl(s)
In which
∆Hsub,NaCl: heat of sublimation of Na = 108 kJ/mol
INa: ionization energy = 496 kJ/mol
Ediss: heat of dissociation of Cl2(k) = 224 kJ/mol
∆Hf: heat of formation of NaCl (r) = – 411 kJ/mol
ECl: electron affinity of Cl = – 349 kJ/mol

Apply Hess law:

∆Hf = ∆Hsub,Na + INa + ½ Ediss + ECl + U
U = ∆Hf – ∆Hsub,Na – INa – ½ Ediss – ECl
= – 411 – 108 – 496 – 224/2 + 349
= –788 kJ/mol
 COULOMB FORCE –BORN EQUATION
• Coulomb gave equation for
the electrostatic interaction
between two opposite
charged ions:
e 2 z+ z−
F= −
4πε 0 r 2
• The Coulomb energy of
interaction between two ions
is
In which:
e: charge of 1 electron
= 1.6022x10-19 C
r: distance between two ions (m).
z+, z-: magnitude of ionic charges.
ε0: vacuum electric permittivity.
4πε0=1.11265x10-10 C2/(J.m)
K: Coulomb constant
= 9x109 N⋅m2⋅C−2

e 2 z+ z−
E = −K
r
 COULOMB FORCE –BORN EQUATION

NA: Avogadro constant

• Based on this interaction,
= 6.0221415 × 1023
Born proposed an equation
M: Madelung constant
to estimate the energy
lattice for 1 mole of ionic
compound:

MN A e 2 z + z −
E ml = −
4πε0 r
 Madelung constant
• The principle of calculating the Madelung constant can be explained, using
sodium chloride as an example.
• Let us consider one of the sodium ions in the NaCl lattice. The nearest
neighbours of each sodium ion are 6 chloride ions at a distance r. The
Coulomb energy of interaction with these ions will be (other constants are
skipped)
6
U1 = −
r
• Next, 12 sodium ions are arranged around the chosen sodium ion
at a distance of r√2. Since these ions have the same sign as the ion
under consideration, the interaction energy is written
12
U2 = −
r 2
• The following neighbours of this particular ion are 8 chloride ions
at a distance of r√3, which gives the contribution to their interaction energy
8
U3 = −
r 3
M – Madelung constant, depends on the structure of
lattice
Formula Coordination Structural type Radius ratio Madelung
number x = r+/R- Constant M
8 CsCl x > 0.723 1.763

MX 6 NaCl (rock salt) 0.414 < x < 0.732 1.748

4 ZnS (Sphalerite) 0.225 < x < 0.414 1.638

4 ZnS (Wurtzite) x < 0.732 1.641

MX2 8:4 CaF2 (Fluorite) x > 0.732 2.519

MX2 6:3 TiO2 (Rutile) 0.414<x<0.732 2.408

SiO2 (Beta-quartz) 0.225<x<0.414 2.201

CdI2 2.191

CdCl2 2.244

http://www.chem.latech.edu/~upali/chem281/281test/crystal.html
https://daniloroccatano.blog/2017/10/27/calculation-of-the-madelung-constant/
COMPARISON OF RESULTS FROM BORN-HABER CYCLE
AND BORN EQUATION
 BORN – MAYER EQUATION
N A Z + Z − e2  d 
U lattice =
− 1 −  M
4πε o d o  d o 
In which
do = r+ + r-
d : constant (is 34.5 pm if r measured by pm, 10-12m)
Substituted other constants, we have:

1390 Z + Z −  d 
E ml =− 
 1 − M (kJ / mol)
do  do 
 BORN – LANDE EQUATION

MN A Z + Z − e 2 1
U lattice =
− (1 − )
4πε 0 r0 n

• r0 is the distance between two ions (r0 = r+ + r-)

• Z+, Z- are the numeric charge number of ions
• n is the Born exponent.
• r0 is measured by meter, E is in J/mol.
 Determine n
Base on the ion configuration:
Ion
He Ne Ar, Cu+ Kr, Ag+ Xe, Au+
configuration
N 5 7 9 10 12

If the cation and anion have different

configuration, n can be approximately
estimated by the average of their n-value
Some values of n for other compounds/ions:
LiF LiCl LiBr NaCl NaBr Cu+ Ag+ Au+
5.9 8.0 8.7 9.1 9.5 9 10 12
 Example:
Estimate the lattice energy of NaCl.

MN A Z + Z − e 2 1
E ml• = (1 − )
4πε0 r0 n
23 −19 2
1.75x 6.023x10 (+1)(−1)(1.602 x10 ) 1
= −12 −12
(1 − )
4 x 3.142 x8.854 x10 x 282 x10 9.1
= −766376 J / mol = −766.376 kJ / mol
 KAPUSTINSKII EQUATION
(1071.5) n | z + || z − |
E ml = − kJ / mol
r+ + r−
r measured in Å (10-10m).
n: number of ions in the empirical formular
Example: with NaCl
E = -(1071.5x2x1x1)/(2.83) = -757.24 kJ.mol
• The equation is simple, high accuracy and widely used.
• The equation is also used to estimate the thermos
chemical radii of ions as follows.
 c. Stability and physical properties of ionic
crystals
• Polarization in ionic bond will increase the covalent
character of bonding, reduce the effective ionic
charge and therefore, lower the decomposed
temperature, melting point… in ionic crystals.
• Example: CaF2 is very stable, does not decompose
at 1000oC, while CuI2 does not exist at room
temperature.
– Explain: r[Cu2+] = 0.72 Å < r[Ca2+] = 0.99Å.
– And r[I-] >> r[F-], therefore Cu2+ will pull the electron
toward it, reduce the ionic degree. Therefore, Cu2+ easily
changes to Cu+, and I- changes to I2.
– CaF2 almost no , ionic degree is very high
 Polarization in ionic bonding:
• The electron cloud distortion of the ions.
• In the perfect ionic model, the ions would be perfectly
spherical and the positive and negative ions would attract
each other but not distort each other. Reality is a bit
different because the positive ion will pull some of the
electron cloud of the negative ion towards itself.
• If the electron cloud is distorted there will be electron
density between the two ions giving the bond some covalent
character.
 Farjan rule
• If a cation is highly charged it will exert a
strong electrostatic attraction on the anion
and distort the electron cloud.
• If the anion has a large electron cloud it will
be easily distorted.
• Example:
• Consider two series.

• Compound: LiF LiCl LiBr LiI

• tmelting (0C) : 848 607 550 469

• Compound: MgCO3 CaCO3 SrCO3 BaCO3

decompose(0C): 600 897 1100 1400
 SOLUBILITY
• The dissolvability of ionic compounds depends on
two factors: lattice energy Elattice and hydration
energy Eh.
– If Elattice >>Eh then the salt is difficult to dissolve, and
reversely. When Elattice increases and Eh decreases, the
solubility decreases, and reversely.
– Ehydration depends on the power of polarizing water, Eh
increases when the cation has high power (smaller size,
larger charged).
Salt CaSO4 SrSO4 BaSO4
Solubility (mol/l) 8x10-3 5x10-4 1x10-5
Eml (kJ/mol) 2347 2339 2262
Eh (kJ/mol) 1703 1598 1444
3. Compounds with covalent bond and
molecular/atomic lattice
a. Covalent bonds
b. Shape and stability of covalent
molecules
c. The formation of chain, ring, layer
structure of covalent compounds
d. Atomic lattice
e. Molecular lattice
a. Covalent bond: formation and properties.

– Formation: sharing the electron, the electron

density in the internuclear axis increases.

– Properties: saturated, directional, polarization.

 b. Shape and stability of covalent molecules

• Hybridization of AO.

• VSEPR theory

• Stability of covalent molecules.

Which cases sharing the vertices, which case sharing the
edges?
How to calculate the coordination number of a element
when the coordination number of other element is known
in a lattice.
 Predict the hybridization of A in ABn

x y = 2 → sp → hybridization angle is 1800

y = +n y = 3 → sp2 → hybridization angle is 1200
2 y = 4 → sp3 → hybridization angle is 109028’

 Bond order calculation in VB

∑ σ + ∑π
Bond order =
∑σ
Number of π = oxidation No.A– number of σ
= Oxidation No.A – n
 Stability of covalent molecules
• Covalent molecules are not yet stable if the
molecules have:
An empty valence AO.
⇅ free (lone pair).
π2p – 3p bonding (not strong)
Empty AO nd

• If the molecules are not stable, when the temperature

decreases, the central atom will shift to higher
hybridization state by bonding (sharing) their ligands
 Example 1: AlCl3
In gas state, Al hybridize sp2, Coord. No. = 3. π bonds = 3 - 3
=0 3s1 3p2 3d0

sp2
Liquid state Al: sp2 → sp3, Coord. No.=4 sharing 1 edge

Solid state:sp3 → sp3d2: Coord. No.= 6: form layers

including octahedral with 3 sharing edges.
 Example 2: SO3
• Gas: S hybridize sp2, Coord. No= 3, 3 π bonds (1 π3p – 2p bond and 2
π3d – 2p bonds)

O
O
σ
O

 Liquid and solid: sp2 → sp3 form chain structure including tetrahedral
with 2 sharing vertices
Which case sharing the vertices, which case
sharing the edge?
• Coordination species are small size atoms: C, N,
O, F sharing the vertices (single bridge)

• Coordination species are large size atoms: sharing

the edge (double bridge)
 Example 1: SiO2
• Gas: Si hybridize sp. No. of π bonds= 4 – 2 =
2
O
O
 liquid and solid: hybridization sp → sp3
 Example 2: SeO2
•Gas: Se hybridize sp2. No. of π bonds= 4 – 2 = 2

O
O

• Solid: Se hybridization sp2 → sp3 tetrahedral with 2

sharing vertice to form chain structure
 In a lattice.

Coord .A y
AxBy =
Coord .B x

Example: CdI2: Coord.Cd =

6 → Coord. I = 3
 Example CdI2
 Solid: Coord.Cd = 6
→ Cd hybridize
sp3d2 , forming
layer structure
including
octahedrals with 6
sharing edges.
 c. The formation of chain, ring or layer
of covalent compounds.
• Reason: system change to state which is more
stable.

• Consider the stability of molecules at gas phase:

 ABn

Not yet stable

Stable
Coord. NoA > n
Coord. NoA = n
→Increase Coord. No: share B

B = large size B = C, N, O, F
→ Share edge → Share point
→ Double connection → Single connection

Share 2 2 < shared Shared all

2 edges >2 edges
points < all points (4) vertices

Molecular lattice Atomic lattice

Coordination
Island structure Chain structure Layer structure Structure
 MA

M – metal M – metal M – phi kim

A – metal A – non-metal A – phi kim

χA - χM > 1,7 χA - χM < 1,7

Metallic bond Ionic bond Covalent bond

Metallic lattice Ionic lattice Atomic lattice Molecular lattice

Coordination Layer Chain Island

structure structure structure structure
 d. Atomic lattice (coordination
structure)
• The atoms locate at the nodes, bonding between
nodes is covalent bond. Rule for the distribution
of atoms is determined by the hybridization of
the atoms.
• Compounds with atomic lattice are very stable,
hard, almost insoluble in any solvent, difficult to
evaporate or melt. They are insulators or
semiconductor.
 • coordination number of an atom is the
number of σ bonds with surrounding atoms.
– ZnS : Zn and S both have Coord. No = 4 (sp3)
– SiO2: Si = 4(sp3), O = 2(sp)
– Diamond. C = 4(sp3)

SiO2 Diamond ZnS

 e. Molecular lattice (island structure)
• In this lattice, noble gas atoms, molecules or
complex ions are located at the nodes. The
interaction between nodes is the Van de Waal
force.

• Compounds with molecular lattice usually have

low hardness, low melting temperature. Most of
them are high soluble in non-polar solvent, low
soluble in polar solvent.
 XeF2 XeF4 Argon (Ar)
(Coord. No. = 8) (Coord. No = 12)
In molecular lattice, beside Van de Waals force,
hydrogen bond is also possible (compound
containing F – H, O – H, N – H bond)

Hydrogen
bonding

H3BO3 molecules

H2O H3BO3
 4. General comments on physical
properties of compounds
• Stronger bond  higher melting point and
boiling point
• In compounds with Van de Waal interaction,
higher molecular mass  higher melting point
and boiling point. In the case that have
additional hydrogen bond, melting point and
boiling point will increase significantly
 • Stronger bond  higher melting point and boiling
point.
Compounds B Al NaCl H2S H2O
Melting 2076 660 601 -85,6 0
point, 0C

Boiling 3927 2270 1465 -60,4 100

point, 0C 2519
Bonding Covalent Metallic Ionic Van der Van der
Waals Waals +
hydrogen
Existing rhomboh Cubic Center Gas Liquid
states edral faced
cubic
Halogen F2 Cl2 Br2 I2
Melting point, 0C -219,6 -100,1 -7,2 113,5
Boiling point, 0C -187 -34,15 58,75 184,5
Radii, Ǻ 0.64 0,99 1,14 1,33
Bonding Van der Waals
Hydro halogenide HF HCl HBr HI
Melting point, 0C -83,4 -114,2 -86,9 -50,8
Boiling point, 0C 19,5 -85,1 -66,8 -35,4
Radii, Ǻ 1,33 1,81 1,96 2,2
Bonding Van der Waals +
hydrogen Van der Waals
 Compounds K Ca Sc Ti

Melting point, 0C 63 850 1539 1668

Boiling point, 0C 766 1490 2700 3330

Radii, Ǻ 2,36 1,97 1,64 1,46

Valence electron 4s1 4s2 3d14s2 3d24s2

Compounds Li Na K Rb

Melting point, 0C 180 98 63 39

Boiling point, 0C 1330 900 766 700

Radii, Ǻ 1,55 1,89 2,36 2,48

Valence electron ns1

 IDEAL CRYSTAL - REAL CRYSTAL
AND STRUCTURAL DEFECTS

Ideal crystal

• Ideal crystal is:

– The order of particles are strictly periodic and
perfect.
– There is no defect.
• Single crystal can be considered as perfect
crystal
 Real crystal

• Real crystal is:

– There are some types of violation of long

range order.
– There are structural defects.

• Poly crystalline are real crystal.

 Structural defects
• Point defects include:
– Vacancy defects. lattice sites which would be
occupied but are vacant.
– interstitial defects. an atom takes the interstitial
position of the lattice structure.
– Substitution defects: the original atom in the lattice
site of a crystalline solid is replaced by a different
type of atom
 Structural defects
• Line defects (dislocations): A line defect is a
line along which whole rows of atoms in a
solid are arranged anomalously
• Plane defects: consequence of point defects
and line defects, appear in plane or in the
boundary.
 POLYMORPHISM

• polymorphism describes the existence of a

solid material in more than one form or crystal
structure.

– Eg: Carbon have polymorphism: diamond,

graphite

– Iron(III) oxide-hydroxide have 3 polymorphism:

α - FeOOH, β - FeOOH and γ - FeOOH.
Diamond graphite
• Transition temperature of polymorphic phase:
is the temperature at which there is a
transformation from one phase to another
phase.
• The transformation can be reversible or
irreversible
– Sortho  Smonoclinic ôû to = 95,5oC
– Diamond → graphite
 ISOMORPHISM AND SOLID SOLUTION

• Isomorphism: When two or more crystals

have similar chemical composition exist in the
same crystalline form, this property is called
isomorphism.
• They can form substitutional solid solution

– Eg: Olivine is a substitutional solid solution of

Fe2SiO4 and Mg2SiO4
Crystal structure of FeMgSiO4 solid solution of
Olivine, in which red sphere are Fe2+, light blue
sphere are Mg2+, dark blue sphere are O2-, and Si+4
locate at the center of tetrahedral formed by 4 ion
O2-
• Solid solution: is a homogenous mixture of
two different kinds of atoms in solid state and
have a single crystal structure.
• Substitutional solid solution: The solute
replaces solvent particles in the lattice.
• Conditions to form substitutional solid solution:
– Similar atomic radii (15% or less difference)
– Same crystal structure
– Similar electronegativities
– Similar valency.
– Eg: Zn – Cu, KCl – KBr solid solution…
• Interstitial Solid Solutions: If the size
of the solute atom is much smaller
than that of the solvent atom the
solute atom can occupy an interstitial
position.
–Example: Steel, where carbon atoms
are present in interstitial positions
between iron atoms with maximum
percentage of 2. Atomic radius of
carbon is 0.071 nm which is less than
59% of 0.125 nm radius of iron atom.