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usually
determined
by
X-ray
Introducti
on
Solids are substances characterised by
i. definite shape
ii. definite volume
iii. non-compressibility
iv. very slow diffusion
v. rigidity and
vi. mechanical strength.
The atoms, molecules or ions in solids are closely packed and cannot move
randomly.
They are held together by strong forces (Intermolecular, interatomic, ionic forces).
Solids can be either crystalline or amorphous.
A crystal or crystalline solid is a solid material whose constituent atoms,
molecules, or ions are arranged in an ordered pattern extending in all three spatial
dimensions.
Most inorganic solids are not crystals but polycrystals, i.e. many microscopic
crystals fused together into a single solid.
Examples: most metals, rocks, ceramics, and ice.
A third category of solids is amorphous solids, where the atoms have no
periodic structure. They have completely random particle arrangement.
Examples: glass, wax, and many plastics.
Crystal
Particles
Attractive
forces
Melti
ng
point
Other properties
Ionic
Positive
and
negative
ions
Electrostatic
attractions
High
London force
and dipoledipole
attraction
Low
non-conductor or
extremely poor
conductor of electricity in
liquid state
Molecula Polar
r
molecules
Amorphous
Crystalline
Random particle
arrangement
Regular geometry
Sharp M.Pt
Isotropic
Anisotropic
No cleavage planes
Cleavage planes
No symmetry
Crystal symmetry
Intermolecular interactions
Charge-Dipole Interactions
1/r2
Dipole-Dipole Interactions
1/r3
Intermolecular interactions
Crystal Structure
A crystal is a solid substance having a definite geometrical shape with flat faces
and sharp edges.
Crystallography deals with geometry, properties and structures of crystalline
compounds.
Fundamental laws of crystallography
i.Law of constancy of interfacial angles- The shape and size of the crystals
may vary with crystallization conditions, but the interfacial angles ( Angle
between the two intersecting faces) remain constant.
Miller indices of a given crystal face are inversely proportional to the intercepts of that
face on the various axes.
(0,3,0)
(2,0,0)
Intercepts 1
Plane (100)
Family {100} 3
Intercepts 1 1
Plane (110)
Family {110} 6
Intercepts 1 1 1
Plane (111)
Family {111} 8
(Octahedral plane)
Miller indices
It is possible to choose along the three coordinates unit distances from the origin
(a, b and c), which may or may not be of same length, such that the ratio of the
three intercepts of any plane in the crystal is given by (ha:kb:lc), where h, k and l
are integral numbers.
Say for a plane that makes intercepts 2a, 2b & 3c respectively, then the ratio of
the intercepts in terms of the standard is 2:2:3. The coefficients of a,b & c are
known as Weiss indices.
Miller indices are obtained by taking the reciprocal of Weiss indices and
multiplying throughout by the least common multiple to obtain integral values.
Miller indices
Positions within the unit cell are
specified in terms of
translations along the three
lattice vectors, e.g. the atoms
in a bcc unit cell are at (0,0,0)
and (,,).
Lattice planes are indexed by
their intercepts of the
coordinate axes. Lattice planes
are identified by their Miller
indices, (h k l). To obtain the
indices of a lattice plane, the
reciprocals of the intercepts are
taken, and the set of smallest
integers giving the same ratio
between them is determined.
These are the Miller indices for
the lattice plane, usually
represented as (h k l).
Law of symmetry
All crystals of the same subtance possess the same elements of symmetry
Three main types of symmetry
Plane of symmetry
Axis of symmetry
Centre of symmetry
Axes of Symmetry:
Proper axes of rotation (Cn)
Rotation with respect to a line (axis of
symmetry) which molecules rotate.
Cn is a rotation of (360/n), where n is the
order of the axis.
C2 = 180 rotation, C3 = 120 rotation, C4
= 90 rotation, C5 = 72 rotation, C6 = 60
rotation
Each rotation brings you to the
indistinguishable state for original
Ru(CO)6
C2H6
Symmetry
Symmetry is useful when it comes to describing the
shapes of both individual molecules and regular
repeating structures.
Point symmetry - is the symmetry possessed
by a single object that describes the repetition
of identical parts of the object.
Symmetry operations are actions such as
rotating an object or molecule.
Symmetry elements arenthe rotational
axes, mirror planes, etc., possessed by objects
Schoenflies (or Schnflies) notation Sn: one of
two conventions commonly used to describe
point groups used in spectroscopy.
Herman-Mauguin can describe the point
symmetry of individual molecules, and also the
relationship of different atoms to one another
in space (space symmetry). HermannMauguin
notationdescribe the space group of a crystal lattice
and is used in crystallography.
CRYSTAL STRUCTURE
CRYSTAL STRUCTURE
Crystals contain highly ordered molecules or atoms held together by noncovalent interactions
Unit cell is the smallest building unit in space of crystal which when repeated
over and over again in 3 dimensions results in a space lattice of the crystalline
substance.
At lattice points:
lattice
point
Unit Cell
Atoms
Molecules
Ions
The simplest repeating unit in a crystal is called a unit cell. Each unit cell
is defined in terms of lattice points the points in space about which the
particles are free to vibrate in a crystal.
The structures of the unit cell for a variety of salts are shown below.
Cubic
- sodium chloride
4.
Rhombic
- iodine
2.
Tetragonal
- urea
5.
Monoclinic
- sucrose
3.
Hexagonal
- iodoform
6.
Triclinic
- boric acid
7.
Trigonal
Bravais Lattices
1.
End-centred
i.
Monoclinic
ii.
orthorombic
2.
Face-centred
i.
Cubic (NaCl)
ii.
Orthorombic
3.
Body-centred
i.
Cubic tetragonal
ii.
Orthorombic
Triclinic
2.
Monoclinic
3.
Orthorombic
Shared by 8 unit
cells
Shared by 2 unit
cells
When silver crystallizes, it forms face-centered cubic cells. The unit cell edge
length is 408.7 pm. Calculate the density of silver.
d=
V = a3
m = 4 Ag atoms x
d=
m
V
107.9 g
mole Ag
1 mole Ag
6.022 x 1023 atoms
7.17 x 10-22 g
6.83 x 10
-23
cm
= 7.17 x 10-22
= ___________________
Extra distance =
BC + CD =
2d sin
= n
(Bragg Equation)
n = 2d sin
d=
n=1
= 14.170
1 x 154 pm
2sin
2 x sin14.17
= 0.154 nm = 154 pm
= ____________
Types of Solids
Ionic Crystals or Solids
CsCl
ZnS
CaF2
Types of Solids
Molecular Crystals or Solids
Types of Solids
Network or covalent Crystals or Solids
carbon
atoms
diamond
graphite
Types of Solids
Metallic Crystals or Solids
mobile sea
of e-
Types of Crystals
Metallic Crystals
The structure of metals may be
visualized as a lattice of cations held
together by a Fermi sea (of
electrons).
The electrons are no longer
associated with any particular cation.
Valence electrons are delocalized
about the lattice of cations.
This type of electron movement
enables high conductivity typically
associated with metals.
Ionic crystals
Na+
Cl-
Ionic bonding in
NaCl
Crystalline
quartz (SiO2)
Non-crystalline
quartz glass
Formu
la
Cation :
anion
Coordinati
on
Examples:
Cubic close
packing
Examples:
Hexagonal
close packing
MX
6:6
All octahedral
4:4
Half tetrahedral;
every
alternate site
occupied
Sodium chloride:
NaCl,
FeO, MnS, TiC
Zinc blende: ZnS,
CuCl, -AgI
Nickel arsenide:
NiAs, FeS, NiS
Wurtzite: ZnS,
-AgI
MX2
8:4
6:3
All tetrahedral
Half octahedral;
alternate layers have
fully occupied sites
None
Cadmium iodide:
CdI2
MX3
6:2
One-third octahedral;
alternate pairs of
layers
have two-thirds of
the
octahedral sites
occupied.
Bismuth iodide:
BiI3, FeCl3, TiCl3,
VCl3.
M 2 X3
6:4
Two-thirds octahedral
ABO3
Structures
related to close-packed arrangements
of anions
Two-thirds octahedral
Ilmenite: Fe O
2
Lattice Packing
Lattice Packing
hexagonal close
packed (hcp)
ABABAB
Space Group:
P63/mmc
HCP
cubic close
packed (ccp)
ABCABC
Space Group:
Fm3m
Close
Packing
Octahedral Holes
The green atoms are
in a cubic closepacked arrangement.
The small orange
spheres show the
position of octahedral
holes in the unit cell.
Each hole has a
coordination number
of 6.
Octahedral Holes
The size of the octahedral hole =
0.414 r
where r is the radius of the cubic
close-packed atom or ion.
Tetrahedral Holes
The orange spheres
show atoms in a
cubic close-packed
arrangement. The
small white spheres
behind each corner
indicate the
location of the
tetrahedral holes.
Tetrahedral Holes
For a close-packed
crystal of n atoms,
there are 2n
tetrahedral holes.
The size of the
tetrahedral holes =
0.225 r
where r is the radius
of the close-packed
atom or ion.
Atoms/Unit
Cell
For atoms in a cubic unit cell:
Atoms in corners are within the cell
# of Atoms/Unit Cell
For atoms in a
cubic unit cell:
Atoms on faces
are within the
cell
# of Atoms/Unit Cell
A facecentered cubic
unit cell contains
a total of 4
atoms: 1 from
the corners, and
3 from the faces.
# of Atoms/Unit Cell
For atoms in a cubic unit cell:
Atoms in corners are within
the cell
Atoms on faces are within
the cell
Atoms on edges are within
the cell
Polymorphism
Many metals exhibit different crystal
structures with changes in pressure
and temperature. Typically, denser
forms occur at higher pressures.
Higher temperatures often cause
close-packed structures to become
body-center cubic structures due to
atomic vibrations.
#
Relative radius
1.000
0.97
0.96
0.88
Most Common MX
Structures
NaCl structure
Na+ in fcc lattice
Cl- in Oh holes
CsCl structure
Cl- in simple cubic lattice
Cs+ in cubic hole
AX Crystal Structures
Since 0.732 < 0.939 < 1.0, cubic
sites preferred. So each Cs+has 8
neighbor ClAXType Crystal Structures include
NaCl, CsCl, and zinc blende
AX2Crystal Structures
Fluorite structure
ABX3Crystal Structures
Perovskite structure
Ex: complex oxide BaTiO3
SPINELS
Class of minerals of general formula A2+B3+2O2-4
Crystallise in the cubic (isometric) crystal system, with the oxide anions arranged in a
cubic close-packed lattice and the cations A and B occupying some or all of the
octahedral and tetrahedral sites in the lattice.
A and B can be divalent, trivalent, or quadrivalent cations, including magnesium, zinc,
iron, manganese, aluminium, chromium, titanium, and silicon.
Although the anion is normally oxide, the analogous thiospinel structure includes the
rest of the chalcogenides.
A and B can also be the same metal under different charges, as is the case with
magnetite, Fe3O4 (as Fe2+Fe3+2O2-4), which is the most abundant member of the Spinel
group.
Spinels are grouped in series by the B cation.
A common example of a normal spinel is MgAl2O4.
Mg2+
Al3+
O2-
Spinel is the name given to the mineral MgAl2O4. It has a common structural
arrangement shared by many oxides of the transition metals with formula
AB2O4.
In the normal pattern the oxygens form a cubic close packed (ABCABC or face
centred) array and the Mg(II) and Al(III) sit in tetrahedral (1/8 occupied) and
octahedral (1/2 occupied) sites in the lattice, giving a Unit Cell with 8 Mg's, 16
Al's and 32 O's.
An inverse spinel is an alternative arrangement where the divalent ions swap
with half of the trivalent ions so that the M(II) now occupy octahedral sites
i.e. B(AB)O4. NiFe2O4
In this case Ni(II) is octahedral and half of the Fe(III) are tetrahedral.
Complexes that share this structure include a number of 1st row TM oxides and
sulfides.
Normal spinel structures are usually cubic close-packed oxides with one
octahedral and two tetrahedral sites per oxide.
The tetrahedral points are smaller than the octahedral points. B3+ ions occupy the
octahedral holes because of a charge factor, but can only occupy half of the
octahedral holes.
A2+ ions occupy 1/8 of the tetrahedral holes. A common example of a normal
spinel is MgAl2O4.
Inverse spinel structures however are different in the cation distribution, in that all
of the A cations and half of the B cations occupy octahedral sites, while the other
half of the B cations occupy tetrahedral sites. A common example of an inverse
spinel is Fe3O4, if the Fe2+ (A2+) ions are d6 high-spin and the Fe3+ (B3+) ions are d5
high-spin.
Spinels
Spinel
Point defects in non-ionic and ionic solids occur in different ways, as described by following chart:
Frenkel DefectAn ion missing from the lattice occupies any interstitial void.
Electrical neutrality and stoichiometry remains same.
Density is not affected.This defect are found in AgCl, AgBr etc.
This defect are found in AgCl, AgBr etc.