Chemistry Lesson 12 Solids

Chemistry Politecnico di Torino A.A.
2018-2019
The solid state

Federico Carosio
Department of Applied Science and Technology
Tel.: +39 0131 229303

E-mail: federico.carosio@polito.it
Chemistry Politecnico di Torino A.A.2018-2019
The solid state

• When the temperature is so low that the molecules of a substance do
not have enough energy to escape even partially from their neighbors,
the substance solidifies.
• The nature of the solid depends on the types of forces that hold the
atoms, ions, or molecules together.
An understanding of solids in terms of the properties

of their atoms will help us to understand why, for
instance, metals can be pounded
into different shapes but salt crystals shatter, and why
diamonds are so hard.
Crystalline and
amorphous solids
Particles placed in a ordered, Particles placed in a disordered
symmetric and standard habit along and random habit along the 3
the 3 space dimensions (long range space dimensions (short range
order): CRYSTALS order) : AMORPHOUS SOLIDS
Macroscopic characteristics of
crystals
• Crystalline solids typically have flat, well-defined planar surfaces
called crystal faces, which lie at definite angles to one another.
Types of Solids
Covalent Solids Na
+ -
Cl
Molecular
Ionic solids
Solids
Metallic 203.199.213.48/834/1/Structuresofsolids.ppt
solids
Types of crystalline solids
Type of Constituting Type of bonding Properties Examples

solids particles forces
Ionic Positive (+) and Electrostatic  Hard NaCl, CaCO3

negative (-) ions attractions  High melting piint
 Electric conduction
in molten and salute
states
 Brittleness.
Covalent Molecules Intermolecular  Soft CO2, H2O, I2
(molecular) forces (van der  Low melting point
Waals)  Isolating
Covalent Atoms (equal or Covalent bond  Very hard C (diamond),
(lattice) different)  High melting point SiO2
 Isolating
Metallic Positive ions + Electrons cloud –  Electric conductors All metals
electrons ions lattice  Glossy
interactions  Ductile
Types of Solids
 An ionic solid is a solid that consists of cations and anions
held together by electrical attraction of opposite charges
(ionic bond).
– Examples include cesium chloride, sodium chloride, and
zinc sulfide (but ZnS has considerable covalent character).
CaF2
NaCl
ZnS
Types of Solids
 A molecular solid is a solid that consists of atoms or molecules held
together by intermolecular forces.
– Many solids are of this type.

– Examples include solid neon,
solid water (ice), and solid
carbon dioxide (dry ice).
• Their physical properties depend on

the strengths of those forces.
Paraffin wax: the forces are so

weak that they can be pushed
past one another very easily
Types of Solids
 A covalent network solid is a solid that consists of atoms held
together in large networks or chains by covalent bonds.
– Examples include carbon, in its forms
as diamond or graphite, asbestos,
and silicon carbide.
Network solids are typically hard and rigid; they have

high melting and boiling points. Ceramic materials are
commonly network solids.
Types of Solids
 A metallic solid is a solid that consists of positive cores of
atoms held together by a surrounding “sea” of electrons
(metallic bonding).
– In this kind of bonding, positively charged atomic
cores are surrounded by delocalized electrons.
– Examples include iron, copper, and silver.
A metallic crystal We can explain the

consists of an array of structures and properties
cations that are bound of many metals if we
together by their suppose that the spheres
interaction with the sea representing the cations
formed by the electrons adopt a close-packed
that they have lost structure
Hexagonal close-packed structure Cubic close-packed structure

Comparison between hexagonal
& face centered cubic cells
layer a
hexagonal layer b
closest cubic closest
layer a packing layer c
packing
closest packing of first

and second layers
abab… (74%)
abcabc… (74%)
hexagonal expanded face-centered

unit cell side views unit cell
Crystals and crystal lattices
Maurits C. Escher
• By repeating a foundamental
unit of the picture we can build
the entire pattern
Crystals and crystal lattices

We do not have to draw the complete crystal lattice every time we want to
convey the structure of a solid. The regular repeating lattice structure allows
us to focus our attention on a representative small region of the crystal.
• Unit cell, the smallest unit that, when stacked

together repeatedly without any gaps and
without rotations, can reproduce the
entire crystal
All crystal structures can be

expressed in terms of only 14
basic patterns of unit
cells called Bravais lattices
Bravais lattices
a, b & c are
IDENTITY
PERIODS
α, β e g
define the
orientation
of CRYSTAL
AXES
The “primitive” cubic cell
Polonium: covalent
forces, which favor
certain directions,
are so strong in this
metalloid that they
overcome the
tendency toward
close packing
1/8 atom at
8 corners
Coordination number = 6 Atoms/unit cell = 1/8 x 8 = 1
• The number of atoms in a unit cell is counted by noting how they are shared
between neighboring cells.
The body centred cubic cell
Examples: Fe a,
Li, Na, Cr, Mo,…
1/8 atom at
8 corners
1 atom at
center
Coordination number = 8 Atoms/unit cell = (1/8 x 8) + 1 = 2

Packing identical spheres
simple cubic
(52% packing efficiency)
body-centered cubic
(68% packing efficiency)
The face centred cubic cell
Examples:
Ni, Pt, Pd, Cu,
Ag, Au, Al, Pb
1/8 atom at
8 corners
1/2 atom at
6 faces
Coordination number = 12 Atoms/unit cell = (1/8 x 8) + (1/2 x 6) = 4

The Fe a and Fe g
Fe a (a0=2,861 Å)
Stable below 912 °C.
Iron is highly compact since it has lots
of electrons in the valence bands.
Fe g (a0=3,601 Å).
Stable in the range 912-1394 °C.
The FCC cell is very common (>50%
of metals have this crystal habit) since
it ensures the maximum degree of
compaction of atoms. Hence it is also
called “compact cubic”.
The hexagonal cell
This lattice (typicalof Ti, Mg, Be,

Ca, Zn, Cd,…) is characterised by
6 atoms per cell.
The crystals are harder and brittler
than those based on the “twin”
face centered cubic cell.
https://www.youtube.com/watch?v=KNgRBqj9FS8
Ionic crystals
The ionic bonds are not directional and thus we can think of ions lattices
Interactions among ions with opposed charge are
maximised. Conversely those among ions with equal charge
are minimised
Electro-neutral crystals
The valence of the ions determines the final chemical formula

A- X+, B2- X2+, ... C23-Y32+,
The dimensions of ions influences the

cell habit and the relative dimensions
As a general rule anions (larger) and

placed at the edges of a cell and
cations (smaller) in the interstices.
Types of interstices
• In an ionic solid, the “coordination number” means the number of ions of

opposite charge immediately surrounding a specific ion.
tetrahedric
octahedric
cubic
• (6,6)-coordination., the first number is the cation coordination number and

the second is that of the anion
Cesium chloride
When the radii of the cations and anions are similar and their ratio
> 0.7, more anions can fit around each cation. The ions may adopt
the cesium chloride structure, CsCl
• The anions form an expanded

primitive cubic array, with a Cl ion at
the eight corners of each cubic unit
cell.
• There is a large “cubic” hole at the
center of the cell, and the Cs ion fits
into it.
This occurs also with ammonium

salts (NH4+)
(8,8)-coordination
Sodium chloride
Ratio from 0.4-0.7
Cl (large) occupies the
sites of a FCC lattice.
Na is at the octahedric
interstices
MgO has the same
structure
(6,6)-coordination
Calcium fluoride (Fluorite)
Ca2+
Ratio > 0.7
Ca, rather large, occupies
F-
the knots of a FCC lattice
F- stands at the
tetrahedric interstices
Li2O has the same
structure
(8,4)-coordination
Zinc sulphide (Blend)
•
When the radius ratio of an ionic
compound is less than about 0.4, cations
are significantly smaller than the anion,
the small tetrahedral holes may be
occupied.
(4,4)-coordination
• This structure is based on an
expanded cubic close-packed
lattice of the big S2- anions, with
the small Zn2+ cations occupying
half the tetrahedral holes.
Allotropy and
Allotropy polymorphism
When an element may exist in different forms
• Elemental sulphur S8: crystals can be either rhombic or

monoclinic
• Elemental Carbon can exist either as diamond, graphite or
fullerene
• Elemental phosphorus can be either white (very reactive)

or red (more inert)
Polymorphism
When a substance (non elemental) has different crystal forms

Carbon allotropes
diamond
Covalent network-Diamond
As for ZnS, only half of the tetrahedric interstices are

occupied. Each atom is at the centre of a tetrahedron.
sp3
Other allotropes and
polymorphs
Red and white phosphorus
Monoclinic and
rhombic Sulphur
Covalent network-Silicates
There are a variety of

silicates, which can be
viewed as various
arrangements
of tetrahedral oxoanions
of silicon in which each
Si-O bond has
considerable
covalent character.
Covalent network-Phyllosilicates
In some minerals, the SiO4 tetrahedra

link together to form sheets.
They are characterised by a layered

structure that enables easy
delamination.
Crystal defects
Crystal punctual
Effects on
defects linear properties
superficial
CaF2
NaCl
Himalayan salt is conceptually

similar to table salt plus mineral NaCl
impurities.
https://www.youtube.com/watch?v=ie-KfQionjY

Chemistry Lesson 12 Solids

Încărcat de

Informații document

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Chemistry Lesson 12 Solids

Încărcat de

Drepturi de autor:

Formate disponibile

Chemistry Politecnico di Torino A.A.

The solid state

Department of Applied Science and Technology

Tel.: +39 0131 229303

The solid state

An understanding of solids in terms of the properties

Type of Constituting Type of bonding Properties Examples

Ionic Positive (+) and Electrostatic  Hard NaCl, CaCO3

– Many solids are of this type.

• Their physical properties depend on

Paraffin wax: the forces are so

Network solids are typically hard and rigid; they have

A metallic crystal We can explain the

Hexagonal close-packed structure Cubic close-packed structure

closest packing of first

hexagonal expanded face-centered

Crystals and crystal lattices

Crystals and crystal lattices

• Unit cell, the smallest unit that, when stacked

All crystal structures can be

Coordination number = 6 Atoms/unit cell = 1/8 x 8 = 1

Coordination number = 8 Atoms/unit cell = (1/8 x 8) + 1 = 2

Coordination number = 12 Atoms/unit cell = (1/8 x 8) + (1/2 x 6) = 4

This lattice (typicalof Ti, Mg, Be,

The valence of the ions determines the final chemical formula

The dimensions of ions influences the

As a general rule anions (larger) and

• In an ionic solid, the “coordination number” means the number of ions of

• (6,6)-coordination., the first number is the cation coordination number and

• The anions form an expanded

This occurs also with ammonium

• Elemental sulphur S8: crystals can be either rhombic or

• Elemental phosphorus can be either white (very reactive)

When a substance (non elemental) has different crystal forms

As for ZnS, only half of the tetrahedric interstices are

Red and white phosphorus

There are a variety of

In some minerals, the SiO4 tetrahedra

They are characterised by a layered

Himalayan salt is conceptually

S-ar putea să vă placă și