Solid State Chemistry CHM4627

Prerequisite Courses : Inorganic Chemistry, CHM3610, and

Physical Chemistry, CHM4410C, or permission of the instructor.

Prerequisite Knowledge:
Geometry and Trigonometry – Cosine, sine, tangent, triangle rules
General Chemistry I - periodic table, ions and ionic compounds, stoichiometry, formula
weights, interconverting masses and moles, thermochemistry, enthalpy, wave behavior of
matter, quantum mechanics and atomic orbitals, representations of orbitals (s,p,d,f), electron
spin and Pauli exclusion principle, electron configurations, effective nuclear charge, sizes of
atoms and ions (trends), electron affinity, electronegativity, group trends, Lewis symbols, ionic
bonding and energetics, covalent bonding, molecular geometry and bonding theories,
VSEPR, covalent bonding and orbital overlap, molecular orbitals for simple diatomic
molecules.
General Chemistry II – Phase changes, phase diagrams, structures of solids, unit cells,
close packing of spheres, bonding in solids (molecular, covalent network, ionic, metallic),
chemical kinetics, Le Chatelier’s Principle, classical thermodynamics, entropy, Gibbs Free
energy, oxidation states, balancing oxidation-reduction reactions, crystal field theory, electron
configuration in complexes.

Solid State Chemistry

The solid state chemistry course is an in-depth examination of the principles
and concepts underlying the synthesis, structure, bonding, reactivity, and
physical properties of solid state materials. Three hours lecture.

Tentative Topics:
•Introduction to Crystal
Structures
•Physical Methods for
Characterizing Solids
•Synthesis Methods
•Bonding and Electronic
Properties
•Defects and Non-Stoichiometry
•Microporous and mesoporous
solids
•Optical Properties of Solids
•Magnetic and Dielectric
Properties
•Superconductivity
•Nanostructures and Low
Dimensional properties

1
 Solid state chemistry - the study of synthesis, structure,
bonding, reactivity, and physical properties of solids.
•interdisciplinary overlap with condensed matter physics, mineralogy,
crystallography, metallurgy, ceramics, and materials science.

Brief history and notable contributions from solid state chemistry

•X-ray crystallography in the early 1900’s by William L Bragg
•Zeolite and platinum-based catalysts for petroleum processing in the 1950’s
•High-purity silicon, a core component of microelectronic devices in the 1960’s
•Microwave dielectrics (wireless communications) in the 1970’s
•‘High temperature’ superconductivity in the 1980’s
•Giant and colossal magnetoresistive (CMR) materials in the 1990’s
•Nano-, energy storage and generation, and functional materials in the 2000’s

It’s a
portable
phone!

Solids
Solid State Chemistry, a subdiscipline of Chemistry,
primarily involves the study of extended solids.
•Except for helium*, all substances form a solid if
sufficiently cooled at 1 atm.
•The vast majority of solids form one or more crystalline
phases – where the atoms, molecules, or ions form a
regular repeating array (unit cell).
•The primary focus will be on the structures of metals,
ionic solids, and extended covalent structures, where
extended bonding arrangements dominate.
•The properties of solids are related to its structure and
bonding.
•In order to understand or modify the properties of a
solid, we need to know the structure of the material.
•Crystal structures are usually determined by the
technique of X-ray crystallography.
•Structures of many inorganic compounds may be initially
described in terms of simple packing of spheres.

2
 Close-Packing

Square array of circles Close-packed array of circles

Considering the packing of spheres in only 2-dimensions, how efficiently do the

spheres pack for the square array compared to the close packed array?

3
Layer A

Layer B

ccp

cubic
close
packed

hcp

hexagonal
close
packed

4
 Layer B
(dark lines)

CCP HCP

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.

hexagonal close
packed (hcp)
ABABAB
Space Group:
P63/mmc

cubic close
packed (ccp)
ABCABC
Space Group:
Fm3m

5
 Face centered cubic (fcc)
has cubic symmetry.

Atom is in contact
with three atoms
above in layer A,
six around it in
layer C, and three
atoms in layer B.

A ccp structure has a fcc unit cell.

6
 Coordination Number

hcp ccp

The coordination number of each atom is 12.

Primitive Cubic

7
 Body Centered Cubic (bcc)

How many atoms in the

unit cell of the
following?
Primitive (P)
Body Centered (I)
Face-Centered (A, B, C)
All Face-Centered (F)

8
 8(1/8) +
6(1/2) = 4
atoms per
unit cell

Spheres are in contact along the face diagonal, thus l = d√2.

The fraction of space occupied by spheres is:
Packing Efficiency:
4 3
ratio of space occupied
V spheres  3  ( d / 2 )   4 by spheres to that of
  0 . 74 the unit cell
V unitcell (d 2 )3 It is the most efficient
(tied with hcp) packing
scheme.
The density expression is:

number of formula units  ( FW / 6.022 10 23 (in g/atom))

Density( g / cm3 ) 
Vunitcell (cm 3 )

Occurrence of packing types assumed by elements

The majority of the elements crystallize in hcp, bcc,

or ccp(fcc). Polonium adopts a simple cubic structure
Other sequences include ABAC (La, Pr, Nd, Am), and
ABACACBCB (Sm). Actinides are more complex.

9
Pressure-temperature phase diagram for iron

10
 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 – are the rotational
axes, mirror planes, etc., possessed by objects

Schoenflies- useful in describing the point

symmetry of individual molecules
(spectroscopists)

Hermann-Mauguin – can describe the point

symmetry of individual molecules, and also the
relationship of different atoms to one another
in space (space symmetry)

Axes of Symmetry: Hermann-Mauguin:

Proper axes of rotation (Cn) 2, 3, 4, 6

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.

However, rotation by 90° about

the same axis does not give back XeF4 is square planar.
the identical molecule.
Therefore H2O does NOT possess It has four different C2 axes.
a C4 symmetry axis.
A C4 axis out of the page is
called the principle axis
because it has the largest n.
By convention, the principle
axis is in the z-direction

11
 Hermann-Mauguin:
Planes and Reflection (σ) m

Molecules contain mirror planes, the symmetry element is

called a mirror plane or plane of symmetry.
•σh(horizontal): plane perpendicular to principal axis
•σd(dihedral), σv(vertical): plane colinear with principal axis
•σv: Vertical, parallel to principal axis
•σd: σ parallel to Cn and bisecting two C2' axes

Hermann-Mauguin:
Inversion, Center of Inversion (i) 1

A center of symmetry: A point at the center of the molecule. (x,y,z) → (-x,-y,-z).

Tetrahedrons, triangles, and pentagons don't have a center of inversion symmetry.

C 2H 6
Ru(CO)6

12
 Rotation-reflection, Improper axis (Sn) Hermann-Mauguin: n

•This is a compound operation combining a rotation (Cn) with a reflection through

a plane perpendicular to the Cn axis σh.(Cn followed by σh) σCn=Sn (Schoenflies)
•It may be viewed as a combination of a rotation (1/n of a rotation) and inversion.
(Hermann-Mauguin)
Equivalent Symmetry elements in
Schoenflies and Hermann-Maguin Systems

Schoenflies Hermann-
Mauguin

S1 ≡ m 2≡m
S2 ≡ i 1≡i
S3 6
S4 4
S6 3

molecular solid state

spectroscopy

Hermann-Mauguin inversion axis n

1
4

13
 Symmetry: Individual Molecules to Crystals

The molecules are related in space by a symmetry element they do not

possess, this is the site symmetry.

Crystals

14
 Lattices and Unit Cells
A crystal is a solid in which the constituent atoms, molecules, or
ions are packed in a regularly ordered, repeating pattern of ‘building
blocks’, extending in all three spatial dimensions.
-the ‘building block’ is known as the unit cell.

Simplest regular array is a line of evenly spaced objects (one-dimensional).

The line of dots is called the lattice, and each lattice point (dot)
must have identical surroundings.

The choice of unit cell is arbitrary.

a

Lattice + basis = crystal structure

+ =

Lattice points are associated to a basis

+ =

lattice basis

CRYSTAL STRUCTURE = lattice + basis (atoms or ions)

15
 Crystal Lattices

Space lattice a pattern of points that describes the arrangement of

ions, atoms, or molecules in a crystal lattice.

Unit Cell the smallest, convenient microscopic fraction of a space lattice

that:
1. When moved a distance equal to its own dimensions (in various
directions) generates the entire space lattice.
2. reflects as closely as possible the geometric shape or symmetry of
the macroscopic crystal.

Although crystals exist as three dimensional forms, first consider 2D.

A crystal contains approximately Avogadro’s number of atoms, ions, or

molecules. The points in a lattice extend pseudo infinitely.

How does one describe the entire space lattice in terms of a single unit
cell? What kinds of shapes should be considered?

Square 2d array

Select a unit cell based on,

1. Symmetry of the unit cell should be identical with
symmetry of the lattice
2. Unit cell and crystal class (triclinic…) are related
3. The smallest possible cell should be chosen

16
Rectangular 2d array

Centered cell (C)

– have a lattice
point at each
corner and one
totally enclosed
in the cell.

Primitive cell (P)

– have a lattice
point at each
corner and
contain one
lattice point.

17
 Five Types of Planar 2-D Lattices

Translational Symmetry Elements – Glide Plane and Screw Axis

Glide plane – combination of translation with reflection.

z
x

a
y

+ ,
Glide plane Glide
direction

+ +

a/2

Comma indicates that some molecules when reflected through a plane

of symmetry are enantiomorphic, meaning the molecule is not
superimposable on its mirror image.

18
 Translational symmetry elements:

Glide plane
1. Reflection at a mirror plane
2. Translation by t/2 (glide component)

Axial glides a, b, c
a/2, b/2, c/2

Diagonal glides n
Vector sum of any two a/2, b/2,
c/2, e.g. a/2 + b/2

Diamond glide d
Vector sum of any two a/4, b/4,
c/4, e.g. a/4 + b/4

Screw axis

–combination of translation with rotation.

–uses the symbol ni, where n is the rotational order of the axis
(twofold, threefold, etc.) and the translation distance is given by
the ratio i/n.

y
z Example of a 21 screw axis
c
x

21 Screw
axis

+ +

c/2

19
Screw axis Rotation axis

Symmetry elements with respect to an axis

Rotation angle q = 360°/ X,
X = # of rotations

q Symbol

1-fold axis: 360° 1

2-fold axis: 180° 2
3-fold axis: 120° 3
4-fold axis: 90° 4
6-fold axis: 60° 6

5-fold, 7-fold, 8-fold, 10-fold (…) axes

are not possible in 3 dimensional space.*

*2011 Nobel Prize in Chemistry, Dan Shechtman "for the discovery of quasicrystals“
notwithstanding

20
 http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2011/press.html

Three-Dimensional Unit Cells

The unit cell of a three-dimensional lattice is a parallelepiped
defined by three distances (a, b, c) and three angles (a, b, g).

7 Lattice systems
14 Bravais lattices
Different ways to combine 3
non-parallel, non-coplanar
axes
Compatible with 32 3-D point
groups (or crystal classes)

Combine 14 Bravais Lattices,

32 translation free 3D point
groups, and glide plane and
screw axes result in 230
space groups.

21
 Seven Lattice systems

Seven Crystal Systems or Classes

Minimum symmetry
requirement
Four threefold axes at 109°28’ to
each other

One fourfold axis or one fourfold

improper axis.

Any combination of three mutually

perpendicular twofold axes or
planes of symmetry

(H) One sixfold axis or one sixfold

improper axis; (R) one threefold axis

One twofold axis or one symmetry

plane

None

22
 Miller Indices
A lattice plane is a plane which passes through any three points
which are not in a straight line. A set of parallel lattice planes is
characterized by its Miller indices (hkl). The set of lattice planes
(hkl) divides a into h parts, b into k parts, and c into l parts, where
a, b, and c are the lengths of the unit-cell sides.
Two-dimensional example The indices of a line hk are
defined so that the line
intercepts a at a/h and b at b/k.

1. Consider the line that is adjacent

to the one that passes through the
origin.

2. Find the intersections and write

these as fractions of the cell edges.

3. Take the reciprocal of the

fractions.

z
y
x The indices of a line hkl are
defined so that the line intercepts
a at a/h, b at b/k, and c at c/l.

1. Consider the plane that is adjacent to the

one that passes through the origin.

2. Find the intersections and write these as

fractions of the cell edges.

3. Take the reciprocal of the fractions,

which give the (hkl) or index of the plane.

23
Intercepts: a, ,  Intercepts: a, a,  Intercepts: a, a, a

Reciprocals: Reciprocals: Reciprocals:

a/a, a/, a/ = 1, 0, 0 a/a, a/a, a/  = 1, 1, 0 a/a, a/a, a/a = 1, 1, 1

Miller index for this Miller index for this Miller index for this
plane: hkl = (1 0 0) plane : hkl = (1 1 0) plane : hkl = (1 1 1)

Interplanar Spacing
The perpendicular spacing (d spacing) between parallel planes
(Miller indices hkl) may be calculated using the following equations.

24
 Fractional Coordinates
The position of an atom or ion in a unit cell is described by its fractional coordinates.

Fractional coordinates (x, y, z) are expressed as fractions of the length of the sides
of the unit cell (a, b, c)

c
b
(0.5, 0.5, 0.5)
(0, 0, 0) (0, 0, 0)
a

(0, 0, 0)

(0, 0.5, 0.5)

(0.5, 0, 0.5) (0, 0, 0) (0.5, 0, 0.5)
(0.5, 0.5, 0)

Crystalline Solids
Ionic
•Consider an interaction between a metal with a low ionization energy
and a nonmetal with a highly exothermic electron affinity.
•Electrons are transferred to produce cations and anions, forming a
strong, non-direction electrostatic attraction between the ions.
•Ions pack together to maximize the coulombic attraction between
oppositely charged ions and minimize the repulsion between ions of the
same charge.
Covalent
•In many structures, the bonding is not completely ionic, but possesses
some degree of covalency, where the electrons are shared between the
two bonding atoms and not merely transferred from one to the other.
Other
•In addition to ionic and covalent bonding, other bonding and
interactions include metallic bonding and intermolecular forces such as
hydrogen bonds, dipole-dipole forces, and London dispersion forces.

25
 Ionic Solids (MX)

CsCl

Other Compounds:
CsBr, CsI, TlCl, TlBr,
TlI, NH4Cl

Rock Salt - NaCl

2x2 supercell

Other Compounds (200+): Most alkali halides, all the alkali hydrides,
AgF, AgCl, AgBr, MO (M = Mg, Ca, Sr, Ba), MS (M = Mg, Ca, Sr, Ba)

26
 Linked Octahedra

[MX6] Octahedron Solid Octahedron (polyhedral)

Corner-sharing Edge-sharing Face-sharing

Two octahedra = M2O11 Two octahedra =M2O10 Two octahedra= M2O9

NaCl showing edge-sharing of octahedra

and an enclosed tetrahedral space.

27
Structure Type - Nickel Arsenide (NiAs)
Equivalence to the sodium chloride structure in hcp. It can
be described as an hcp array of arsenic atoms with nickel
atoms occupying the octahedral holes. As is located in the
center of a trigonal prism of six nickel atoms.

Structure Type – Fluorite (CaF2)

The structure can be described as a
ccp array of calcium ions, with
fluoride ions occupying all the
tetrahedral holes.
•Note that Ca2+ ions are smaller
than F-, so it is not fully described
as a ccp array, but this description
gives an exact description of the
relative positions of the ions.
•The larger octahedral holes are
unoccupied in this structure, which
is important when considering the
movement of ions in defect
structures.
•By drawing cubes of fluoride ions,
the structure is now divided into
octants with alternate octants
occupied by calcium.
•In antifluorite, the positions of
cation and anions are reversed.

28
Structure Type – Zinc Blende / Sphalerite (ZnS)
A ccp array of sulfide ions with zinc ions occupying every other
tetrahedral hole in an ordered manner.

Compounds adopting this If all atoms are the same,

structure include copper halides, the structure would be
Zn, Cd, and Hg sulfides. identical to C (diamond).

Structure Type – Wurtzite (ZnS)

The Wurtzite structure type is

composed of an hcp array of sulfide
ions with alternate tetrahedral holes
occupied by zinc ions.

BeO, ZnO, NH4F also adopt this structure type.

29
 Structure Type – Cadmium Chloride (CdCl2)

Close packing of anions (ccp)

with half of the octahedral
holes occupied by cations.
•The cations occupy all the
octahedral holes in every
other layer, giving an overall
layer structure with 6:3
coordination.

Structure Type – Cadmium Iodide (CdI2)

The CdI2 structure can be viewed as a hexagonal close packing (hcp) of iodine,
with half of the octahedral holes occupied by cadmium.
•There is a weak van der Waals attraction between neighboring iodine layers.
•This structure is unstable if the cation-anion bonds have significant
ionic character, because of significant anion-anion repulsion.
•This structure is seen primarily when the anion is one of the larger halides or chalcogenides.

30
 Structure Type – Rutile (TiO2)

High refractive index and widely used as white pigments in paints and plastics.
-Tetragonal unit cell, but not close packed. Each Ti4+ is coordinated by six O2-.
-Each oxygen is surrounded by three planar titaniums, which lie at the corners of an
almost equiliateral triangle

Structure Type – Corundum (Al2O3)

Mineral form is the basis for ruby (Cr) and sapphire (Ti).

It is composed of an hcp array of

oxygen atoms with two-thirds of the
octahedral holes occupied by Al3+.

31
 Structure Type – Rhenium Trioxide (ReO3)

Also called the aluminum fluoride structure, which is adopted by the

fluoride of Al, Sc, Fe, Co, Rh, and Pd, the high temperature form of
WO3, and ReO3.
-Corner-sharing network of [ReO6] that give a highly symmetrical
structure with cubic symmetry.

Structure Type – Spinel (MgAl2O4)

Spinels have the general formula AB2O4, where generally A is a divalent

ion A2+, B is trivalent ion B3+.
The structure can be described as being based on a cubic close-packed
array of oxide ions, with A2+ ions occupying tetrahedral holes and B3+
ions occupying octahedral holes.
A spinel crystal structure containing n AB2O4 structural units has 8n
tetrahedral holes and 4n octahedral holes.
-1/8th of the tetrahedral holes are occupied by A2+ ions and ½ of the
octahedral holes by the B3+ ions.

32
 Structure Type – Perovskite (CaTiO3)

The structure is named after the mineral CaTiO3.

-It has the same octahedral network as the ReO3 structure, with the A ion
added into the cavity.
-The structure may also be visualized as a ccp array of A and X ions with
the B ions occupying the octahedral holes. (Compare with NaCl)
-Structures of high-temperature superconductors are based on perovskite.

Structure Type – Ilmenite (ABO3)

Typically adopted for ABO3 structures where A and B are

similar in size and their total charge adds up to +6.
-Structure is named after the mineral FeIITiIVO3.
-Similar to corundum structure type, where there is a hcp
array of oxygen ions, but in ilmenite two different cations
are present occupying two-thirds of the octahedral holes.

33
 Structures related to close-packed arrangements of anions
Formula Cation:anion Type and number of Examples: Examples:
Coordination holes occupied Cubic close packing Hexagonal
close packing
MX 6:6 All octahedral Sodium chloride: NaCl, Nickel arsenide:
FeO, MnS, TiC NiAs, FeS, NiS

4:4 Half tetrahedral; every Zinc blende: ZnS, Wurtzite: ZnS,

alternate site occupied CuCl, γ-AgI β-AgI

MX2 8:4 All tetrahedral Fluorite: CaF2, ThO2, ZrO2, None

CeO2
6:3 Half octahedral; alternate
Cadmium chloride: CdCl2 Cadmium iodide:
layers have fully occupied CdI2
sites

MX3 6:2 One-third octahedral; Bismuth iodide:

alterate pairs of layers BiI3, FeCl3, TiCl3,
have two-thirds of the VCl3.
octahedral sites occupied.
M2X3 6:4 Two-thirds octahedral Corundum: α-
Al2O3, α-Fe2O3,
V2O3, Ti2O3, α-
Cr2O3
ABO3 Two-thirds octahedral Ilmenite: Fe2O3

AB2O4 One-eighth tetrahedral Olivine: Mg2SiO4

and one-half octahedral

Ionic Radii

How does one determine when one atom ‘ends’ and another ‘begins’?
-easy for the same atom (e.g. F2), ½ of the distance between the atoms.
-what about Na+-Cl- (for example)?

High Resolution X-ray

diffraction contour map
of electron density.
-the minimum of
electron density along
the interionic distances
enables accurate
determination of the
values of the radius for
the cation and anion.

34
 The effective ionic radii vary depending on coordination number.

Size of ions depends on oxidation state.

35
Ionic Radii

36
 Trends in sizes of ions
1. The radii of ions within a group increase with atomic number Z.
More electrons are present and the outer electrons are further
away from the nucleus.
2. In a series of isoelectronic cations (e.g. Na+, Mg2+, Al3+) the
radius decreases with increasing positive charge.
3. In a series of isoelectronic anions (e.g. F-, O2-) the radius
increases with increasing negative charge.
4. For elements with more than one oxidation state (e.g. Ru4+,
Ru5+), the radii decease as the oxidation state increases.
5. As you move from left to right across a row of the periodic table,
there is an overall decrease in radius for an similar ions with the
same charge. See also the lanthanide contraction.
6. The spin state (high or low spin) affects the ionic radius of
transition metals.
7. The radii increase with an increase in coordination number.

These trends in the sizes of ions may be explained by consideration of the

shielding and effective nuclear charge. Zeff = Z – S

Tetrahedral hole Octahedral hole

37
 Radius Ratios

What are the relative sizes and

coordination numbers of the cubic,
octahedral, and tetrahedral holes?

Size of hole cubic > octahedral > tetrahedral

Coord. no. 8 6 4
If a cation were to occupy one of these holes, it would have the
coordination number indicated.
-the coordination number is proportional to the size of the hole.
How does one calculate the size of a hole? Enables one to
predict which size cation would fit into that hole.

Cross Section

r  r
sin(45 )   0.707
2r 
r
 0.414
r
Radius ratio for an
octahedral hole.

38
 Calculate radius ratio for a trigonal hole

r 3
cos(30 )   

r r 2
30°

r
 0.155
r+ r
r-
Relatively
r- uncommon
coordination
environment.

Use this information to predict which type of

hole will be occupied with given ions.
Electron-electron repulsion also plays a role in determining the hole the
atom occupies.
For example, consider the ionic compound NaCl.
The 6 coordinate ionic radius (Shannon) of Na+ is 1.16Å and Cl- is 1.67Å.
The radius ratio is 1.16/1.67Å = 0.695, therefore
falls in the range 0.41 to 0.73 so the Na+ is
expected to occupy an octahedral hole.
The Cl- is expected to form an A-type lattice – it
has a ccp type. The sodium cations occupy the
octahedral holes in that lattice.

39
 AB Structures
Radius ratios, coordination numbers, and coordination environment for
both the cations and anions for four representative AB-type ionic lattices.

Anions Cations
Structure r+/r- Structure C.N. Structure C.N.

Sodium 1.16 ccp (fcc) 6 All octahedral 6

chloride 1.67 holes
(NaCl)
Zinc 0.88 ccp (fcc) 4 Half tetrahedral 4
blend 1.70 holes
(ZnS)
Wurtzite 0.88 hcp 4 Half tetrahedral 4
(ZnS) 1.70 holes

Cesium 1.81 All cubic 8 Simple cubic 8

chloride 1.67 holes

Compounds with common AB structures

Structure Compounds Correlation %
Rock alkali halides and hydrides, 58
Salt AgF, AgCl, AgBr, MO (M = Mg,
Ca, Sr, Ba, Mn, Fe,Co, Ni,
Cd), MS (M = Mg, Ca, Sr, Ba,
Mn, Pb), TiC, VC, InP, InAs,
SnP, SnAs, NH4I, KOH, KSH,
KCN
Zinc BeX, ZnX, CdX, HgX (X = S, 33
blende Se, Te), diamond, silicon,
germanium, gray tin, SiO2
(cristabolite), BN, BP, SiC,
CuX (X = F, Cl, Br, I), XY (X =
Al, Ga, In; Y = P, As, Sb)
Wurtzite ZnX (X = O, S, Te), CdX (X = 33
S, Se), BeO, MgTe, NH4F, MN
(M = Al, Ga, In), AgI
Cesium CsX (X = Cl, Br, I, SH, CN), 100
Chloride TlX (X = Cl, Br, I, CN), NH4X
(X = Cl, Br,CN)

40
 (C.N. of A)(no. of A in formula)=(C.N. B)(no. of B in formula)

AB2 –type structures Anions Cations

Structure r+/r- structure C.N. structure C.N.
Fluorite 1.14/1.19 1. Simple 4 1. ½ 8
(CaF2) = 0.96 cubic cubic
2. All tetra. holes
2. fcc
Cadmium 1.09/2.06 hcp 3 ½ of 6
Iodide = 0.53 octahedral
(CdI2) holes
Rutile 0.745/1.26 simple tetra. 3 Octahedral 6
(TiO2) = 0.59 holes

Extended Covalent Arrays

Several elements for covalently bonded solids at room
temperature, including B, C, Si, Ge, P, As, Se, Te.

Unit cell of C (diamond).

All C-C bond length are identical (1.54 Å).
Covalent C-C bonds are strong and the
rigid 3d network of atoms give diamond
the hardest substance known and it also
has a high melting point.

Unit cell of C (graphite).

All C-C bond length are identical (1.42 Å).

Two dimensional layers of carbon atoms in
a hexagonal layer.
The distance between layers is 3.40 Å.

41
 Covalent Network Crystals
A covalent network crystal is composed of atoms or groups of atoms
arranged into a crystal lattice, which is held together by an interlocking
pair of covalent bonds.
Covalent bonds, the sharing of one or more pairs of electrons in a region
of overlap between two or more atoms, are directional interactions as
opposed to ionic and metallic bonds that are nondirectional.

These interactions are directional in nature.

Compounds that form covalent network crystals include SiO2, C, Si, BN.

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.

42
 Ionic Crystals
Elemental Ions Ionic Bonding
Na and Cl Na+ and Cl- NaCl

e-

e- e-

Picking any Na+, the chloride ion could approach from any direction.
Ionic bonds are nondirectional – the electrostatic forces dominate.
Many salts form ionic crystals CsCl, CaF2, KNO3, and NH4Cl.

Charge-Dipole Interactions Dipole-Dipole Interactions

1/r3

1/r2

London Dispersion Interactions Hydrogen Bonding Interactions

43
 Molecular Structures
Solid CO2 (dry ice) is a Solid H2O (ice) has several
face-centered cubic array forms depending on P and T
of CO2 molecules

Type Structural Bonding Characteristics Examples

Unit
Ionic Cations Electrostatic, Hard, brittle, high alkali metal
and anions nondirectional m.p.; moderate halides
insulators, melts
are conducting
Extended Atoms Mainly covalent Strong, hard diamond,
covalent crystals high silica
array m.p.
Molecular Molecules Mainly covalent Soft crystals of ice, organic
between atoms in low m.p; large compounds
a molecule, van coefficient of
der Waals of H- expansion;
bonding between insulators
molecules
Metallic Metal Band model m.p. varies, good Fe, Al
atoms conductors

44
 Silicates – SiO2
SiO2 is polymorphic

Quartz

cristobalite

Silicates – Structural Classification

[SiO4]4- (discrete)
Olivines, garnets

[Si2O7]6- (disilicate)
not common, but
occur for Sc2Si2O7

[SiO3]2- (chains)
pyroxenes
[Si4O11]6- (dbl chains)
amphiboles (asbestos)

[Si4O10]4- ( layers)
mica, talc

[SiO3]n-2n (rings)
beryl (emerald)

[SiO4]4-/ [AlO4]5-
feldspars, zeolites

45
 Quasicrystals
ordered, but aperiodic

Penrose tiling

Born-Haber Cycle
By accounting for three energies (ionization energy, electron
affinity, and lattice energy), we can get a good idea of the
energetics of the enthalpy of formation of an ionic solid.

46
 Lattice Energy
The energy required to completely separate a mole of a solid
ionic compound into its gaseous ions; or the energy released
when ions (gaseous) form a crystal.

Coulombs’s Law The magnitudes of the charges on

the ions are Z+ and Z-.
(ion pair M+, X-)

e2 Z  Z e 2
E E
4 0 r 4 0 r
e is the electronic charge, 1.6×10-19 C
ε0 is the permittivity of vacuum, 8.854×10-12 F m-1

The energy due to the coulombic interactions in a crystal is

calculated for a particular structure by summing all the ion-pair
interactions, thus producing an infinite series.

NaCl

√3r0

2r0
√2r0

r0

From a Na+,
Six Cl- a distance of r0 e2 12 8 6 24
EC   (6     ....)
4 0 r 2 3 2 5
Twelve Na+ at a distance of √2r0
or
Eight Cl- at a distance of √3r0 e 2
6 12 8 6 24
EC   (     ....)
Six Na+ a distance of 2r0 4 0 r 1 2 3 4 5

47
 e2 6 12 8 6 24
EC   (     ....)
4 0 r 1 2 3 4 5
The term (series) inside the brackets is known as the Madelung
constant, A. For one mole of NaCl, the energy due to the coulombic
interactions is: 2
N A Ae
EC   NA = Avogadro’s number
4 0 r
Madelung constants have been computed for many of the simple ionic structures.

Structure Madelung Number of A/ν Coordination

Constant, A ions in formula
unit, ν
Cesium chloride, CsCl 1.763 2 0.882 8:8
Sodium chloride, NaCl 1.748 2 0.874 6:6
Fluorite, CaF2 2.519 3 0.840 8:4
Zinc Blende, ZnS 1.638 2 0.819 4:4
Wurtzite, ZnS 1.641 2 0.821 4:4
Corundum, Al2O3 4.172 5 0.835 6:4
Rutile, TiO2 2.408 3 0.803 6:3

Born exponent
Ions are not point charges, but consist of positively charged nuclei
surrounded by electron clouds.
-repulsion needs to be taken into account at small distances
B
repulsion can be expressed by: ER 
rn
where B is a constant and n (the Born exponent) is large
and also a constant.

N A AZ  Z  e 2 B Derivation N A AZ  Z  e 2  1 
L  EC  ER    n L 1  
4 0 r r in textbook 4 0 r  n 
Born-Landé Equation
Ion Type Constant
[He] 5 1.389 105 AZ  Z   1 
L 1  
[Ne] 7 r0  n
Calculate average (n),
[Ar] 9
e.g. RbCl is 9.5 r0 in pm, units of L are kJ/mol
[Kr] 10 (Average of 9 and 10)
[Xe] 12

48
 Notice the large dependence on 1.389  105 AZ  Z   1 
the charge of the ions: L 1  
r0  n
Multiply charged ions tend to have larger lattice energies.
It was noted by A.F. Kapustinskii that the Madelung constant
divided by the number of ions in one formula unit of the
structure (A/ν) was almost constant (0.88 to 0.80).
-A general equation can be developed to set up a general
lattice energy equation and use the resulting equation to
calculate the lattice energy of an unknown structure.

1.214  105 vZ  Z   1  Kapustinskii equations

L (kJ / mol )   1  
r  r (in _ pm)  n 
Considering all of the approximations, there is good agreement with values
obtained using a Born-Haber cycle, except with large polarizable ions.

It is not possible to measure lattice energy directly. Typically a

thermochemical cycle is involved, but not all of the data (electron
affinities, etc.) is necessarily available. Estimations are useful.
-Neil Bartlett used a similar approach to prepare XePtF6.

49