Lecture 25-27

CH2101-Inorganic Chemistry 2101

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy
Dense, ordered packing

r
Energy
typical neighbor
bond length
r

typical neighbor
bond energy
Dense, ordered packed structures tend to have
lower energies.
2

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of:

-metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Noncrystalline materials...

Si

Oxygen

atoms have no periodic packing

occurs for:

-complex structures
-rapid cooling

"Amorphous" = Noncrystalline

noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
3

Crystal Structures
How can we stack atoms to minimize empty
space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

4

Close Packed Circles?

Close Packed Circles!

Close Packed Circles!

What is percent area filled for each case??

area of circle
Area of triangle
1 2
r

% Area filled = (2r )( 3r ) 2 3 90.7

2

Area of circle
Area of square

% Area filled = r2/(2r)2 = 78.5

Area of circle = r2 Area of triangle = bh/2 Area of square = l2

Three-Dimensional Packing

At start all sites equivalent Filled hollows Empty Hollows

After placing first atom in second layer, two sites now present

Three-Dimensional Packing

At start all sites equivalent Filled hollows Empty Hollows

After placing first atom in second layer, two sites now present

Three-Dimensional Packing

A site

C site

When placing atoms in third layer, we have two choices

Similar to forming second layer, we can only choose 1 site.

Three-Dimensional Packing

A site
Filling the A site gives an ABABABAB packing pattern
Resulting in hexagonal close packing (hcp)

Three-Dimensional Packing

C site
Filling the C site gives an ABCABCABC packing pattern
Resulting in cubic close packing (ccp)

13

http://www.youtube.com/watch?v=Rm-i1c7zr6Q

https://www.youtube.com/watch?v=Rm-i1c7zr6Q
https://www.youtube.com/watch?v=cAOD940oqF4

3.5 Nonclose-packed structures

Not all elemental metals have structure based on close-packing and
some other packing patterns use space nearly as efficiently.
Even metals that are close-packed may undergo a phase
transition to a less closely packed structure when they are heated
and their atoms undergo large-amplitude vibrations.

Non-close-packing: simple cubic and body centred cubic

arrays

Unit cells of (a) a simple cubic lattice and (b)

a body-centred cubic lattice.

The least common metallic structure is the primitive cubic (cubic-P)

structure , in which spheres are located at the lattice points of a primitive
cubic lattice, taken as the corners of the cube. The coordination
number of a cubic-P structure is 6.

One form of polonium (-Po) is the

only example of this structure among
the
elements
under
normal
conditions.

Body-centred
cubic
structure
(cubic-I or bcc) in which a sphere is
at the centre of a cube with spheres
at each corner
Metals with this structure
have a coordination number
of 8
Although a bcc structure is less closely
packed than the ccp and hcp structures (for
which the coordination number is 12),

R=r, they are both same

Atomic Packing Factor (APF):SC

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
APF for a simple cubic structure = 0.52
atoms
unit cell

a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell
Chapter
23 3 -

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 8e.

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell

Chapter
24 3 -

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF

2a

Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
Chapter
26 3 -

R=r, they are both same

Volume for a cube = a3 = 1.21 x e-28 m3

Rock Salt Structure

Highlighting the close-packed
planes
A
C
B

Rock Salt Structure

highlighting the two
interpenetrating fcc
lattices

Bonding in TiO
Several of the 3d
monoxides illustrate
high conductivity that
decreases with
temperature.
TiO and VO

TiO adopts the rocksalt

structure (NaCl).

Bonding in TiO
The titanium atoms
are close enough to
form a conduction
band.
Overlap of t2g
orbitals of the metal
ions in neighboring
octahedral sites.
Illustrated for dxy
orbitals.

Ionic Bonding
Cesium chloride structure
8:8 coordination
Primitive Cubic (52% filled)
e.g. CsCl, CsBr, CsI, CaS

Rutile structure
6:3 coordination
Body-centered cubic (bcc)
(68% filled)
e.g. TiO2, GeO2, SnO2, NiF2

Nickel arsenide structure

6:6 coordination
hcp
e.g. NiAs, NiS, FeS, PtSn

Rock Salt structure

6:6 coordination
Face-centered cubic (fcc)
e.g. NaCl, LiCl, MgO, AgCl
You can determine
empirical formula for a
structure by counting the
atoms and partial atoms
within the boundary of the
unit cell (the box). E.g. in
the rutile structure, two of
the O ions (green) are
fully within the box and
there are four half atoms
on the faces for a total of
4 O ions. Ti (orange) one
ion is completely in the
box and there are 8 eighth
ions at the corners; this
gives a total of 2 Ti ions in
the cell. This means the
empirical formula is TiO2;
the 6:3 ratio is

Perovskite - An Important Class of Cubic Mineral

StrontiumTitanateSrTiO3
Srincellcenter:1
Sr

+2

Ti+4
O-2

Titaniumoncell
Corners:8x1/8=1
Oxygenoncell
Edges:12x1/4=3

Perovskite - An Important Class of Cubic Mineral

StrontiumTitanateSrTiO3
Sroncell
Corners:8x1/8=1
Sr+2 Titaniumincellcenter:1
Ti+4 Oxygenoncellfaces:
6x1/2=3
O-2

Occupation of Octahedral Holes

three blue atoms on bottom
three purple atoms on top

Typically, close-packed spheres are anions and species filling

tetrahedral and octahedral holes are cations

Occupation of Tetrahedral Holes

one blue atom on bottom
three purple atoms on top

Tetrahedral and Octahedral Holes

Two views of tetrahedral hole

Two views of octahedral hole

38

Point Defects
Interstices in FCC structure.
(a) Octahedral void. (b)
Tetrahedral void.

Interstices in the BCC

structure. (a) Octahedral
void. (b) Tetrahedral void.

Interstices in the HCP

structure. (a) Octahedral
void. (b) Tetrahedral void.

Look for the Td and Oh holes

Interstices in FCC structure.
(a) Octahedral void. (b)
Tetrahedral void.

Spinel Structures.
CFT aids in understanding the arrangements of metal ions in
spinel structures(AB2O4)
The spinel is a MIXED METAL OXIDE with a general formula
(M2+)(M3+)2(O2-)4..
Spinel is MgAl2O4
Many compounds adopt this type of structure.
The basic structure is a FCC lattice of O2anions.
How does CFT help us understand this
Structure?
Cations occupy tetrahedral and octahedral
holes.

Spinel (garnet) MgAl2O4

AB2O4 - normal
A: M2+ (Fe, Mg)
B: M3+ (Al, Fe, Cr)

C.2: Spinels
---- normal spinel cubic close packed anion arrangement
The unit cell contains eight FCC oxygen subcells in a
cubic array. Hence it has 32 octahedral (1/2 occupied)
interstices and 64 tetrahedral interstices (1/8 occupied).
** where all of the B atoms occupy octahedral sites and all of
the A atoms occupy tetrahedral sites
Highly refractory compound suitable for structural and
optically transmitting applications.
---Soft magnetic ferrites used as inductors, transformer cores,
and read/write heads for magnetic storage media.

Spinels (regular and inverted)

Spinel, MgAl2O4, is a rare gemstone that was used to imitate rubies.
The structure has face-centered cubic symmetry, and is a little
heavy to understand. The general formula is AB 2O4. The oxygens
form an fcc lattice. The A cations occupy tetrahedral holes, and the
B cation occupy octahedral holes. It then follows that 1/8 of the
tetrahedral holes are occupied, and 1/2 of the octahedral holes.
The first way to think of the spinel structure is the array of Al
atoms. They sit on the corners of tetrahedra which share corners
infinitely in 3 dimmensions, an array known as a Kagome net

Now we add the Mg atoms

As we said above, the Mg atoms sit in tetrahedral

holes, so lets show the MgO4 tetrahedra.

ke this is a very simplified representation of the spinel for your underst

There are two types of spinel structures:

In normal spinel the 8 A cations occupy 8 tetrahedral sites (out
of the 64 available sites) and the 16 B cations occupy 16
octahedral sites (out of the 32 available sites).
Normal = A [B]2 O4 e.g. Mg [Al]2 O4
In inverse spinel, 8 of the B cations occupy the 8 tetrahedral
sites, while 8 A cations and 8 B cations are distributed over the
16 occupied octahedral sites.
Inverse = B [A0.5 B0.5]2 O4e.g. Fe [Fe0.5 Ti0.5]2 O4
Some important minerals with the spinel structure are
magnetite Fe3O4 - Fe3+[Fe2+,Fe3+]O4
chromite FeCr2O4 - Fe2+[Cr3+]2O4
spinel
MgAl2O4 - Mg2+[Al3+]2O4

Inverse-spinels
To summarize all of the A and half of the B atoms (in AB2O4) occupy the octahedral
sites and the other half of the B atoms occupy the tetrahedral sites
NOTE: A and B cations could be completely disordered over the
octahedral and tetrahedral sites.
The exact distribution of the metal atoms is influenced by : a number of
factors including ionic size, charge, and the crystal field stabilization
energy

The degree of disorder in the cation distribution is

represented by the factor , which is the fraction of B cations
at tetrahedral sites.

=0 specifies an ideal normal spinel. =1/2 specifies an ideal inverse

spinel. Intermediate values indicate some degree of disorder.

Spinel structures and CFT

Normal Spinal Structure.
M2+ is tetrahedral, M3+ is octahedral Example: (Mg2+)T(2Al3+)O(O2-)4

Ionic Bonding
The ratio of the radii of the ions in a salt can allow us to predict the type of
arrangement that will be adopted. The underlying theory can be attributed to the
problem of trying to pack spheres of different sizes together while leaving the least
amount of empty space. The size of a cation (the smaller sphere) that can fill the hole
between close packed anions (the larger spheres) can be calculated using simple
geometry. The ratio of the radii can give a rough estimate of the coordination number
of the ions which can then be used to predict the structural arrangement of the salt.
Coordination number 2
3
4
6
8

A
C

r+/r-

< 0.155

0.155
-0.225

0.225
-0.414

0.414 0.732

> 0.732

structure

covalent

covalent

ZnS

NaCl

CsCl

B = (AC2+ BC2)={(a)2+ a2}=2a

AD = (AB2+ BD2)={(2a)2+ a2}=3a

Spinel structures and CFT

Normal Spinal Structure.
M2+ is tetrahedral, M3+ is octahedral Example: (Mg2+)T(2Al3+)O(O2-)4
Inverse Spinal Structure.
M2+ is octahedral M3+ is tetrahedral and in the remaining
octahedral holes Example: (Fe3+)T(Fe2+,Fe3+)O(O2-)4

This later example is magnetite or Fe3O4.

Fe3O4 (Fe2+, 2Fe3+, 2O2-)

Fe0 is d8

Note the O2- is a weak field ligand. (Fe is H.S.)

What are the electron configurations of the Fe ions?dxy, dyz, dxz

dx2-y2, dz2

Fe

2+

3/5 o

eg

OR

2/5 o

T
3/5 T

t2g
dxy, dyz, dxz

2/5 T

dx2-y2, dz2

eg

Mn3O4 Spinel Structure.

Mn3O4 (Mn2+, 2Mn3+, 4O2-)
Electron configurations are .. ?

dxy, dyz, dxz

dx2-y2, dz2
3/5 o

eg

OR

2/5 o

T
3/5 T

t2g
dxy, dyz, dxz

2/5 T

dx2-y2, dz2

b) Defect-spinels such as -Al2O3 (thermal decomposition of

Al(OH)3) and -Fe2O3
**same framework as the spinel, but some of the
octahedral sites that would normally be occupied are vacant.
There are 8/3 Al vacancies per unit cell, with respect to the
ideal spinel.
DEFECT-SPINEL FORMULA:

(Al8+3)T[Al40/3V8/3]OO32, where the V stands for a vacancy

Writing the formula of spinels

Normal spinel
** If all of the cations A are in the tetrahedral sites, (A),
and all of the B cations are in octahedral sites, [B], the
formula is written (A)[B2]O4
** Example: (Ti)[Zn2]O4
Inverse spinel
** If all of the A cations are in the octaheral sites, [A],
and the B cations are distributed over the remaining
octaheral and tetrahedral sites, (B) and [B], the formula is
written (B)[AB]O4
**Example: (Zn)[TiZn]O4

Imperfections in Solids
All crystalline solids possess
imperfections.
Crystal growth occurring at many sites
causes boundaries to form.
Vacancies and self-interstitials
Substitutions
Dislocations

Defects in Ceramic
Structures
Frenkel Defect
--a cation is out of place.

Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect:

from W.G. Moffatt, G.W.

Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. 1, Structure,
John Wiley and Sons, Inc., p.
78.

Frenkel
Defect

~e

Equilibrium concentration of defects

QD / kT

Interstitial solid solution: carbon in -iron.

The carbon atom is small enough to fit with
some strain in the interstice (or opening)
among adjacent Fe atoms in this important
steel structure.

But the interstitial solubility is quite low since the size mismatch of the site to
the radius of a carbon atom is only about 1/4

Ionic Crystals
Overall electrical neutrality has to be maintained
Frenkel defect
Cation (being smaller get displaced to interstitial voids
E.g. AgI, CaF2

Schottky defect
Pair of anion and cation vacancies
E.g. Alkali halides

Other defects due to charge balance

If Cd2+ replaces Na+ one cation vacancy is created
Defects due to off stiochiometry
ZnO heated in Zn vapour ZnyO (y >1)
The excess cations occupy interstitial voids
The electrons (2e) released stay associated to the interstitial cation

 FeO heated in oxygen atmosphere FexO (x <1)

Vacant cation sites are present
Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ Fe3+ + e
For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions provides the 2 electrons required by excess oxygen

Imperfections in Metals

What are the outcomes if impurity (B) is added to

Solid
host
(A)?solution of B in A (random distribution of point
defects)

OR
Substitutional solid
solution.
(e.g., Cu in Ni)

Interstitial solid
solution.
(e.g., C in Fe)

Solid solution of B in A plus particles of a new

phase (usually for a larger amount of B)
Second phase particle
-- different composition
-- often different structure.
69

Hume - Rothery Rules

The Hume-Rothery rules are basic
conditions for an element to dissolve in a
metal, forming a substitutional solid
solution.
1. The atomic radius of the solute and solvent
atoms must differ by no more than 15% (r <
15%).
2. The solute and solvent should have similar
electronegativities.
3. Same crystal structure for pure metals.
4. Maximum solubility occurs when the solvent
and solute have the same valence. Metals with
lower valence will tend to dissolve metals with70

Substitutional Solid Solution Example:

Copper and Nickel
Element

Cu
C
0.046
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn

Atomic Crystal Electro- Valence

Radius Structure nega(nm)
tivity
0.1278
0.071
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

FCC

FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP

1.9
2.5

1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6

1
3
2
3
2
2
2
2

Interstitial Solid Solution

Carbon forms an interstitial solid solution
when added to iron; the maximum
concentration of carbon that can be added
is roughly 2%.
The atomic radius of the carbon atom is
much less than that of iron (0.071nm vs
0.124 nm).
For interstitial solid solutions, the HumeRothery rules are:
1. Solute atoms must be smaller than the pores
in the solvent lattice.
2. The solute and solvent should have similar
72
electronegativity.

Random, substitution solid solution can

occur in Ionic Crystalline materials as well.
Here shown---- NiO in MgO.
The O2 arrangement is unaffected. The
substitution occurs among Ni2+ and Mg2+
ions.

A substitution solid solution of Al2O3 in MgO is not as

simple as the case of NiO in MgO. The requirement
of charge neutrality in the overall compound
permits only two Al3+ ions to fill every threeMg2+
vacant sites, leaving oneMg2+ vacancy.

Iron oxide, Fe1xO with x 0.05, is an example of

a nonstoichiometric compound. Both Fe2+ and
Fe3+ ions occupy the cation sites, with one Fe2+
vacancy occurring for every two Fe3+ ions present.

Rationalization of Structure of
Crystalline Solids
Predicting coordination number from
radius ratio (r+/r-).
A hard sphere treatment of the ions.
Treats bonding as purely ionic.
Simply, as the M+ ratio increases, more
anions can pack around it.

Thermodynamics of Ionic Crystal

Formation
A compound tends to adopt the crystal
structure corresponding to lowest
Gibbs energy.
M+(g) + X-(g) MX(s)
G = H - TS,

Lattice enthalpy
MX(s) M+(g) + X-(g)HL (standard molar
enthalpy change)
Currently, we are interested in lattice
formation.

Ionic Solids
Lets find the energy required to transfer an electron
from Na to Cl and then to form a NaCl molecule
To remove an electron from Na (ionize the atom) one
needs to spend 5.14eV

Na + 5.14eV Na+ + e When a Cl atom captures an electron, 3.62eV of energy is

released

Cl + e- Cl- + 3.62eV

Ionic Solids
In solid, Na+ and Cl- are brought together at the
distance r0 2.51 [ = 10-10m = 0.1nm]
The total energy is lowered due to the Coulomb
attraction
1 e2

The result is -5.73 eV

4 0 r

Thus when a NaCl molecular unit of NaCl solid

is formed the following occurs
Na + 5.14eV Na+ + eCl + e- Cl- + 3.62 eV
Cl- + Na+ NaCl + 5.73 eV
Na + Cl NaCl + 4.21 eV

The Born-Haber
Cycle
A special
thermodynamic
cycle that includes
lattice formation as
one step.
The cycle has to
sum up to zero if
written
appropriately.
Write down values
for KCl.

The Born-Haber Cycle

A discrepancy between this value
and the real value may indicate the
degree of covalent character.
We have assumed Coulombic
interactions between ions.
The actual values for KCl and MgBr2 are
701 and 2406 kJ/mol (versus 720 and
2451).

Lattice Enthalpy Calculations

(explanations were done on board)

Considering only Coulombic contributions

The electrostatic potential energy between
each pair.
z A zB e2

U
d 0 4 o
zA, zB = ionic charges in electron units
d0 = distance between ion centers
e = electronic charge
4o = permittivity of a vacuum
e2/ 4o = 2.307 10-28 J m

Calculation would be performed on each

cation/anion pair (nearest neighbor).

Lattice Enthalpy
Calculations
A more accurate equation depicts the
Coulombic interactions over the entire
N Ae 2 z A z B
crystal.

U
4 o

d 0

NA = Avogadros constant
A = Madelungs constant, value specific to a
crystal type (in table). This is a sum of all the
geometric factors carried out until the
interaction become infinitesimal.

Lattice Enthalpy
Calculations
Repulsions between ions in close
d
proximity term.
d*
U N A Be

B = constant (will cancel out when finding the

minimum)
d*= compressibility constant, ~ 30 pm

Combining terms

N Ae z A z B
U
A N A Be d *
4 o d
2

Lattice Enthalpy
Calculations
Finding the
minimum energy
dU/dd = 0

N A z A zBe2
d *
U
1
A
4 o d
d

A negative of this
value may be
defined as the

How H2 Gets Activated?

Something worth mentioning that I forgot to teach earlier while
doing MO theory!

How H2 Gets Activated?

Dr. Gregory Kubas

Los Alamos National Lab, USA

The Kubas Complex, W(CO)3(P-iPr3)2(H2), which shows that hydrogen

can bind to transition metal
complexes, has been called the most
important development in inorganic

Cy-cyclohexyl