Padatan Ionik

Yuni Krisnandi
Aminah Umar

Departmen Kimia, Fakultas Matematika dan Ilmu Pengetahuan Alam

Universitas Indonesia
 Types of Solids

Amorphous Solids are solids that lack a regular three-dimensional

arrangement of atoms. They lack long-range structural order.

Crystalline solids have atoms/ions/molecules arranged in regular,

repeating patterns. They possess long-range periodicity.

•minimizes free energy of the atoms/ions/molecules

•the
unit cell is the smallest repeating structural unit that has the full crystal
symmetry

Types of crystalline solids:

• Ionic Crystals
• Covalent or Network Crystals
• Molecular Crystals
• Metallic Crystals
• Group VIII Crystals (frozen Noble Gases)
 The 7 Crystal Systems
All 3D crystals belong to one of 7 crystal systems.

Cubic
 Types of Cubic Lattices

There are three cubic Bravais lattices:

b a
Simple Cubic Body-Centered Cubic Face-Centered Cubic

• The lengths of the unit cell edges (a,b,c) are called lattice constants.

• For cubic crystals, a = b = c, so there is only one lattice constant (a).

 Contents of a Unit Cell
An important feature of the unit cell is the number of lattice points it
contains. Atoms/ions/molecules are often located at lattice points.

1
8  atoms   occupancy
8
+ 1 atom  1 occupancy
2 atoms in a
Body-Centered
Cubic cell

1 1
8  atoms   occupancy 8  atoms   occupancy
8 8
1 atom in a + 6  atoms  1  occupancy
Simple Cubic cell 2
4 atoms in a
Face-Centered
Cubic cell
Menghitung Atom Dalam Unit Sel 3D

• Fraksi atom yang menempati satu unit sel

untuk beberapa posisi dalam unit sel
 Contents of a Unit Cell

Consider sodium
chloride: rock
salt

Cl at corners: (8  1/8) = 1 Na at body centre = 1

Cl at face centres (6  1/2) = 3 Na at edge centers (12  1/4) = 3

Unit cell contents: 4(Na+Cl-)

 Types of Cubic Cells
Different cubic cells result from different packing of atoms.

r
r r

Simple Cubic Body-Centered Cubic Face-Centered Cubic

Atoms per Coordination

Unit Cell cell Number Lattice Constant Packing Fraction

2r
Simple Cubic 1 6 52%

4r
Body-Centered Cubic 2 8 68%
3

Face-Centered Cubic 4 12 2r 2 74%

 BCC
Simple Cubic (primitive)

a √3a = 4R
a = 4R/√3
a = 2R
FCC

4R = √2 a
a = 2R√2
Close-Packed Structures
HCP

CCP
Unit Cell of HCP and CCP
 Packing Efficiency

For FCC
a = 2r√2
Volume of a unit cell
V= a3 = (2r√2)3
Crystal Structures
(Ionic solids)
 Padatan Ionik
• Padatan ionik cenderung untuk memiliki struktur simetrik dengan close-
packed arrangement of atoms.
• Hal ini bergantung pada perbedaan size (radius) dari masing-masing
atom yang berinteraksi dan juga bilangan koordinasinya.
• Struktur yang paling diinginkan adalah ketika jarak antara kation dan
anion sedekat mungkin (attractive interaction), sedangkan jarak antara
anion-anion atau kation-kation adalah maksimal (repulsive interaction)
Common Structures of Ionic Solid

Descriptive Inorganic Chemistry, Third Edition

James E. House and Kathleen A. House
NaCl CsCl ZnS

Zinc blende
ZnS CaF2 TiO2

Wurtzite
ReO3

Descriptive Inorganic Chemistry, Third Edition

James E. House and Kathleen A. House
Struktur NaCl

Struktur type NaCl:

• Bilangan Koordinasi dari Na+ dan Cl- = 6
• Mengandung 4 atom Na dan 4 atom Cl dalam setiap unit
cell
• Atom Cl menempati lubang Oh dari lapisan Na dan
sebaliknya. Lubang Th kosong
 Struktur Fluorite, CaF2

Struktur Fluorite : fcc array, semua lubang-T diisi dengan anion.

Mengandung 8 atom F- dan 4 atom Ca untuk setiap unit cell
Bilangan Koordinasi untuk Ca2+ = 8
Bilangan Koordinasi untuk F- = 4
 Struktur Zinc Blende (ZnS)

Bilangan Koordinasi untuk Zn2+ = 4

Bilangan Koordinasi untuk S2- = 4
 Interstitial sites in CP Structures
A large number of ionic structures can be regarded as built of CP layers of anions
with the cations placed in interstitial sites

for every anion, there is 1 Octahedral site and 2 Tetrahedral sites

Octahedral Holes in CCP

coordinates:
of O holes
½,0,0
0,½,0
0,0,½
½,½,½

= O site
Tetrahedral Holes in CCP

T+ sites:
¾,¼,¼
¼,¾,¼
¼,¼,¾
¾,¾,¾

T- sites:
¼,¼,¼
¾,¾,¼
¼,¾,¾
¾,¼,¾
Type of Crystals
 CsCl Structure

Along the body diagonal, the Cs+ is touching the two Cl- ions on either end, so its length, d, is :

d = r- + 2r+ + r- = 2r+ + 2r-

Using Pythagoras's theorem, the length of the side and the body diagonal of a cube are related :

d2 = a2 + a2 + a2 = 3a2 = 3 x 4r-2 = 12r-2

d = 2r-√3
So,
2r- + 2r+= 2 r-√3
r+/r- = √3 – 1 = 0.732
https://scilearn.sydney.edu.au/fychemistry/prelab/e12_appendix.shtml
 NaCl Structure

As shown in the figure, along the cube edge, the Na+ is touching two Cl- ions,
so its length, a, is :

a = r- + 2r+ + r- = 2r+ + 2r-

To get as close to the cation as possible, the anions must touch along the diagonal of a face
of the cube. The diagonal has length, d, where :

d = r- + 2r- + r- = 4r-
Using Pythagoras's theorem, the length of the side and face diagonal of a cube are related :

d = a2 + a2 = 2a2
d = √2 a
4r-= √2 (2r+ + 2r-)
https://scilearn.sydney.edu.au/fychemistry/prelab/e12_appendix.shtml
r+/r- = √2 – 1 = 0.414
Structures of Ionic Solid

# kation = # anion

1.69 0.98 0.74

1.81 1.81 1.90

0.93 0.54 0.39
CsCl
NaCl
Lattice Energy (Energi Kisi)
 Energi Kisi (Lattice Energy)

• Energi kisi meningkat dengan meningkatnya

muatan ion.
• Juga meningkat dengan menurunnya ukuran ion.
 Energi Kisi dari Kristal Ionik
Energi kisi dari kristal ionik adalah energi yang dibebaskan
ketika ion-ion dari jarak yang tak terhingga berdekatan
membentuk kristal ion.
q  q  e2 Z  Z 
E 
40 r 40 r

e 2 Z  Z  6 e 2 Z  Z 12 e 2 Z  Z  8 e 2 Z  Z  6 e 2 Z  Z  24
Ec      ...
40 r 40 r 2 40 r 3 40 r 4 40 r 5

e2 Z 2 12 8 6 24
Ec   (6      ...)
40 r 2 3 4 5

e 2 Z 2 AN A
Ec   A = Madelung Constant
40 r NA = Avogadro’s number
 Konstanta Madelung

Tipe Struktur A
CsCl 1,7627
NaCl 1,7476
Wurtzit (ZnS) 1,6413
Zincblende (ZnS) 1,6381
Fluorit (CaF2) 2,5194
Rutil (TiO2) 2,408
Cadmium Iodida (CdI2) 2,355
 Energi Kisi dari Kristal Ionik

• Energi tolakan menurut Born

B
Erepulsion  n Ketika ion-ion berdekatan terdapat energi tolakan, meskipun
Ion-ion tersebut berbeda muatan (interaction of e clouds)
r

• B dan n konstanta yg ditentukan secara experimen

atau dapat diprediksi secara teori.
Energi Kisi dari Kristal Ionik

e 2 Z 2 AN A B
Ug    n
Ion-ion repulsive energy 40 r r

Binding energy
e 2 Z 2 AN A 1
Ug   (1  )
Attractive energy
40 r0 n
 Siklus Born-Haber
The Born-Haber cycle is an approach to analyze reaction energies.
• Formation of ionic compound from gaseous ions (exothermic), or, the energy
to break the ionic compound into gaseous ions (endothermic process)
• Can be imagined as the series of component reaction as individual steps for
compound.
 Energi Kisi
DHfo = S + 1/2 D + I + E - Ug
Ug = S + 1/2 D + I + E – DHfo
DHfo => Entalpi pembentukan standar
- Bisa endotermik maupun exotermix
I => Energi Ionisasi
- Proses endotermix
- Selalu positif
E => Electron Affinity
- Proses exotermix
- Selalu negative
S => Entalpi sublimasi
- Proses endotermix
- Selalu positif Descriptive Inorganic Chemistry, Third Edition
D => Energi pemutusan ikatan James E. House and Kathleen A. House

- Proses endotermix
- Selalu positif
Ug => Energi Kisi (lattice energy)
 Energi Kisi
• Bagaimana menghitung entalpi kisi?
• Entalpi kisi ditentukan melalui entalpi data
menggunakan siklus Born-Haber
 Entalpi standar dekomposisi senyawa
menjadi unsur-unsurnya = - entalpi standar
pembentukan senyawa dari unsur-unsurnya
 Entalpi pembentukan kisi = - entalpi kisi
SIKLUS BORN-HABER
UNTUK
NATRIUM KLORIDA
kJ
+800

+700

+600

+500

+400

+300

+200
Na(g) + 1/2 Cl2(g)
+100
Na(s) + 1/2 Cl2(g)
HNa= +107kJmol-1
0

-100

-200

-300
Atomisation of sodium
-400
kJ
+800

+700

+600

+500

+400

+300
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g)
HCl = +121kJmol-1
+100
0 Na(s) + 1/2 Cl2(g)

-100

-200

-300
Atomisation of chlorine
-400
kJ
+800
Na+(g) + Cl(g)
+700
ee- -e-
+600 e-e-
+500 e- -
e -
+400 e -
HNa+ = +502kJmol-1 ee-
+300 e-
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g)
+
+100
0 Na(s) + 1/2 Cl2(g)

-100
Ionisasi pertama dari Na
-200

-300

-400
kJ
+800
Na+(g) + Cl(g)
+700

+600
HCl - = -355kJmol-1
+500

+400
Na+(g) + Cl-(g)
+300
Na(g) + Cl(g)
+200

+100
Na(g) + 1/2 Cl2(g) - e-
0 Na(s) + 1/2 Cl2(g)

-100

-200
Afinitas elektron pertama dari Cl
-300

-400
kJ
+800
Na+(g) + Cl(g)
+700

+600

+500

+400
Na+(g) + Cl-(g)
+300
Na(g) + Cl(g)
- + -
+200 + - +
Na(g) + 1/2 Cl2(g)
+100 - + -
0 Na(s) + 1/2 Cl2(g)

-100

-200 Hf = -411kJmol-1

-300 Pembentukan (formation) NaCl(s)

-400
NaCl(s)
kJ
+800 Siklus Born-Haber
Na+(g) + Cl(g)
+700 ∆HNa + ∆HCl + ∆HNa+
+600
(-) ∆Cl- (-) ∆Hf + ∆L = 0
+500
ENTALPI KISI UNTUK NaCl
+400 ∆HL = - ∆HU
Na+(g) + Cl-(g)
+300 = - 786 kJmol-1
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g) - + -
+100
+ - +
0 Na(s) + 1/2 Cl2(g)
- + -
-100

-200
HU =- 786 kJmol-1
-300

-400
NaCl(s)
 Latihan Soal
1. Tentukan berapa jumlah kation dan anion untuk setiap unit cell
dibawah ini dan berilah nama dari senyawa tersebut !
2. Berapa bilangan koordinasi untuk kation dan anion-nya?
Logam dan Alloy
 Logam dan Alloy
• Ikatan yang terjadi adalah ikatan logam
– Definisi ikatan logam?
– Konsekuensi dari terdapatnya ikatan logam?
– Daya hantar panas dan listrik?
– Reaksi?

• Alloy???
 Ikatan Logam
 Logam adalah suatu zat yang terdiri “Electron Sea Model”
dari ion-ion positif, berada di dalam
crystal lattice dengan elektron
(valence electron) yang bergerak
secara bebas di dalam crystal lattice
tersebut.

 Elektron tersebut bertindak sebagai

cohesive force yang menyebabkan
atom-atom logam tersebut bersatu
dan membentuk Ikatan logam.

 Ikatan Logam : adalah ikatan yang

dihasilkan karena adanya kombinasi
antara gaya elektrostatik antara
elekron dengan nukleus yang
bermuatan positive.
 Ikatan Logam
Strength of Metallic Bond :
Varies considerably among different metals since
the mobile electrons are responsible for the bonding
in metal.

Na < Mg < Al
[Ne] 3s1 [Ne] 3s2 [Ne] 3s2 3p1

The bond becomes stronger

 Ikatan Logam
Characteristic Properties of Metals:
• Electrical Conductivity
good conductors of electricity (electrons are free
to move, and can be displaced in a given direction
if voltage is applied.

• Heat Conductivity
good conductors of heat (mobile electron easily
absorb heat energy and increase the vibrational
motion, allowing for heat transfer.
 Ikatan Logam
Characteristic Properties of Metals:
• Ductile (stretched) and Malleable (deform)
Metal can be easily drawn into wires or forced to be
pressed into sheet.

Like balls bearing oil

The electron render the repulsive
interaction among the cations.
 Ikatan Logam
Characteristic Properties of Metals:

• Metallic Lustre
Metal are shiny in appearance, which is due to the
fact that the mobile electron readily absorb light
falling upon them and move to higher energy
level. When they fall back to their original position
they emit radiation.
 Model Orbital Molekul

Model “sea of electron” tidak

menjelaskan kecenderungan-
kecenderungan yang teramati
misal titik leleh, titik didih,
panas fusi, etc.
– Model orbital molekul
mengusulkan bahwa sifat-sifat di
atas meningkat dengan
meningkatnya jumlah elektron
valensi.
 Model Orbital Molekul
Sc = [Ar] 3d1 4s2

Ti = [Ar] 3d2 4s2

V = [Ar] 3d3 4s2

Cr = [Ar] 3d4 4s2

Mn = [Ar] 3d5 4s2

Fe = [Ar] 3d6 4s2

Zn = [Ar] 3d10 4s2

 In the transition metal, the bond is getting weaker as we fill the antibonding orbital.
 Weaker bonds between atoms lead to metals with lower melting and boiling points,
lower heats of fusion, lower hardness,and so forth.
 Model Orbital Molekul

kecenderungan ini dapat

dijelaskan dengan pita energi
yang dibuat oleh sejumlah
besar orbital-orbital molekul
yang terbentuk ketika atom-
atom logam berikatan satu
sama lain.
 Model Orbital Molekul
Pembentukan Pita Energi:
1. Pita Konduksi
2. Pita Valensi
 ALLOY
• Definisi : campuran 2 jenis logam/elemen atau lebih
Tujuan : untuk meningkatkan kualitas logam seperti
kekuatan, kekerasan dan daya tahan terhadap korosi
Contoh:
– Perunggu  paduan dari tembaga (Cu) dan Timah
(Sn), biasanya Sn < 20%
• Kegunaan:
– Alat-alat berat, perkakas rumah tangga, restorasi gigi
• Proses: Logam-logam dicampurkan dalam keadaan
cair (liquid), T >1000oC kemudian dibiarkan mengeras
(solidifikasi) pada suhu yang lebih rendah
 JENIS-JENIS ALLOY

1. Binary alloy  alloy yang dibentuk dari 2

jenis logam
2. Solid solution alloy
a. Substitusional solid solution  see on
Atkins&Shriver
b. Interstisial solid solution biasanya interaksi
dari logam dan nonlogam (H, B, C, N)
c. Intermetallic compound (MgZn2, Cu3Au)
3. Eutectic alloy
 Substitusional and Interstisial Alloys

1. The atomic radii of the elements are within about 15 per cent of each other.
2. The crystal structures of the two pure metals are the same; this similarity
indicates that the directional forces between the two types of atom are
compatible with each other.
3. The electropositive characters of the two components are similar; otherwise
compound formation, where electrons are transferred between species,
would be more likely
 Intermetallic Alloys

The structures are often unrelated to the parent structure

 Eutectic Alloy

• Kedua logam pembentuk alloy bercampur dengan baik ketika

berada dalam keadan cair.
• Tetapi tidak saling melarutkan ketika berada dalam keadaan
padat.
• Diamati dengan mikroskop: terlihat dua lapisan logam yang dapat
dibedakan. http://www.rmutphysics.com/charud/scibook/crystal-structure/eutectic%20alloys.htm
 Sifat-sifat Padatan
• Sifat-sifat mekanik
– Metals/Alloys, e.g. Titanium for aircraft
– Cement/Concrete Ca3SiO5
– 'Ceramics', e.g. clays, BN, SiC
– Lubricants, e.g. Graphite , MoS2
– Abrasives, e.g. Diamond , Quartz (SiO2) , Corundum

• Sifat listrik
– Metallic Conductors, e.g. Cu, Ag...
– Semiconductors, e.g. Si, GaAs
– Superconductors, e.g. Nb3Sn, YBa2Cu3O7
– Electrolytes, e.g. LiI in pacemaker batteries
– Piezoelectrics, e.g. a Quartz (SiO2) in watches
 Sifat-sifat padatan
Magnetic Properties
• CrO2, Fe3O4 untuk teknologi rekaman

Magnetite – Fe3O4
• Optical Properties
– Pigments, e.g. TiO2 in paints
– Phosphors, e.g. Eu3+ in Y2O3 is red on TV
– Lasers, e.g. Cr3+ in Al2O3 is ruby
– Frequency-doubling of light, e.g. LiNbO3
• Catalysts
– Zeolite ZSM-5 (an aluminosilicate)
– Petroleum refining - methanol octane
• Sensors
– Oxygen sensor, e.g. ZrO2/CaO solid solution
 Daftar Pustaka

1. Atkins & Shriver, Inorganic Chemistry, 5th edition, Oxford, 2010

2. Brown, LeMay, Bursten, and Murphy, “Chemistry The Central Science”,
12th eds, Pearson Educational International, 2010