Structures &

Energetics of
metallic and
ionic solids
(Inorganic Chemistry)

Wirawan Ciptonugroho
Chemistry Education
Sebelas Maret University
Literature
1. C. A. Housecroft and A. G. Sharpe (2012) Inorganic Chemistry, Pearson, England

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Packing of sphere

Closed pack arragement

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 Cubic closed packing (ccp)

Hexagonal closed packing (hcp)

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A-B-A A-B-C

12 coordination number

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Unit cell

4r
a

Cubic closed packing/face-centred cubic (fcc) hcp

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Interstitial holes

Octahedral hole > tetrahedral

Octahedral configuration

Reduced sphere size

Tetrahedral configuration

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Non close packing arrangement

a?

Simple cubic Body centre cubic (bcc)

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Problem
❑ show that in a simple cubic lattice:
a. There is one sphere per unit cell
b. 52% of volume of unit cells is occupied

Each sphere contributes 1/8 fraction occupying

the unit cells, as this unit cell consists of 8 (1/8
sphere)s hence: 1 sphere per 1 unit cell

r 2r

Packing efficiency = vol sphere in unit cell/vol. unit cell

r = 1x (4/3 π r3)/(2 r)3 = 0.52

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Exercise 1
❑ show that for fcc contains 4 complete spheres

❑ if the radius of sphere in fcc is r, prove that the cell edge length is r √8

❑ prove that the packing efficiency of fcc is 74%

❑ show that in the bcc arrangement of sphere, a unit cell contains two complete
spheres

❑ confirm that packing efficiency in bcc is 68%

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Polymorphism in metals
❑ Some metals have more than one type of crystal

❑ i.e. Sc has hcp (ɑ) at room temp. and changes to bcc (β) at 1610 K

❑ Sn at 25 °C has β phase (white) upon cooling to 13 °C it slowly alters to ɑ (grey)

At 25 °C < 13 °C
cooling

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Phase diagram of Fe as a function of p and T

Exercise 2

1. What will happen if iron is heated to 900 K at

constant pressure of 1 bar?
2. In general, bcc type of crystal forms at high
temperature (transformed from closed packed at low
temperature), what will happen with the density
during the phase change?

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Metallic radius

Metallic radius = f (coordination number)

Exercise 3
1. Determine the metallic radius of K at 1 atm and 25 °C
(bcc, 8 coordination number)
1. Find the metallic radius of ɑ-Sn? At 1 atm and 25 °C
2. Estimate the metallic radius of Na (rNa) at 25 °C and 1 atm

rCN-8/rCN-12 = Rel. rad. 8/Rel. rad. 12

rCN-8 = Rel. rad. 8/Rel. rad. 12 x rCN12 = 227.95 pm
1 pm = 10-12 m
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Alloy
❑ alloy is a mixture of two elements (metal) which can create a completely different
property with the individual element.
i.e.: carbon steel

The second atom should

be similar in size
Example:
1. Sterling silver for cutlery

Substitutional alloy interstitial alloy

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Semiconductor
l
D

𝜌×𝑙
𝑅=
𝐴

Resistivity as a function of temp for various metals Resistivity as a function of temp for various semiconductor

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Molecular orbital of simple Li atom (1s22s1)

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 P-type n-type

Partially occupied,
conductor Overlapping, conductor
semiconductor

Band gap Ga-dopped As-dopped

Si Si

e- defficient e- rich
isolator Higher energy increase the population of electron
in the valence band

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Ionic radius

e-

Na Na+ + e-

e-

F-
e- + F

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Coordination of cation

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NaCl crystal structure

NaF, NaBr, NaI, NaH, halide dari Li, K dan Rb, CsF, AgF, AgCl, MgO, SrO, BaO
MnO, CoO, NiO, MgS, CaS, SrS, BaS

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CsCl structure

CsBr, CsI, TlBr, TlCl, NH4Cl (25 °C), NH4Br(25 °C)

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Fluorites structures

CaF2 ZnS

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ZnS blende structure: diamond type network

O
Si

Diamond structure Zinc blende Β-cristobalite silica

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Rutile structure (TiO2)

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Wurtzite (another polymorph of ZnS blende)

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Layer structure

❑ MX2 crystals form this layer structure (M=metal

& X=halogen)
❑ CdI2 is a typical example
❑ Having ABAB arrangement (hexagonal close packing)
❑ Extended lattice → stacked sandwich
❑ Van der Waals force operates between sandwich
❑ other examples: MgBr2, MgI2, CaI2, iodides of d-block

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Lattice energy (Coloumbic attraction)
❖ Coloumbic attraction between isolated pair
Z+ Z-
M X M X

r
Mz+(g) + Xz- (g) → MX(g)

❖ Change in internal energy (ΔU, in Joule) due to the formation of ionic pair from the gaseous constituents:

e : charge of electron (1.602 × 10-19 C)

z+ : modulus of positive charge
z- : modulus of negative charge
ε0 : vacuum permitivity (8.854 × 10-12 F/m)
r : Internuclear distance between ion

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 Each M+ (in this case Na+) is surrounded by:

NaCl with FCC crystal arrangment

Can you imagine??

So the change of internal energy

It is compliacated, don’t worry

Madelung constant (A) is there to
save you

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 L : Avogadro number
A: Madelung constant which depends on the
crystal structure

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Madelung constant for different types of crystal structure

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Born-Lande equation (a correction of Coulombic attraction
based on electrostatic model)
Where,
B: repulsion coefficient
n: Born exponent

Coloumbic attraction & repulsion simplified Electron & nucleus repulsion in a crystal lattice during
into the equation applying Madelung constant the assembly from the gaseous elements
(Born force)

When dΔU/dr = 0, the above expression can be rewritten to:

Born – Lande equation

r0 is determined from the experiment using X-ray diffraction data

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Born-Meyer equation (a refinement from Born – Lande)

Born - Meyer model modifies LB/rn term from Born-Lande and replaces it with e-r/ρ leading to the following expression:

Where,
ρ : constant expressing crystal compressability

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Born exponent for various ions

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Born-Haber cycle

(appendix 10)
(appendix 10) (appendix 8)

(appendix 9)

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Experimental (thermochemistry) vs calculation (electrostatic model)
Layer structure
Of CdI2

Van der Waals force

Born-Meyer Born-Haber
(theoretical/cal (experimental)
culation) Born-Meyer Born-Haber
ΔU (kJ/mol) - 761 - 783 (theoretical/cal (experimental)
culation)
They fit well ΔU (kJ/mol) - 1986 - 2435
A good agreement is also observed for:
Alkali metal – halides & group 2 metal - fluorides Significant difference

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 Thanks!

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Appendix 8

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Appendix 8 (contd.)

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