Ionic Bonding

Ionic “Bonding”
• Ikatan ionik?

• Pembentukan senyawa ionik

menguntungkan bila:
– Senyawa yang terbentuk punya
Ep < Ep atom pembentuknya
– Struktur yang diadopsi oleh
senyawa yang terbentuk punya
Ep rendah (stabil secara
termodinamika)
Ionic Bonding and Periodic Table
Good electron donors; big atoms; Good electron acceptors; small atoms;
on the left of the periodic table; on the right of the periodic table;
s1, s2 and d (transition) elements. p5 (p4).
Pembentukan senyawa ionik
Syarat pembentukan senyawa ionik:
Energi ionisasi untuk membentuk kation

Afinitas elektron dalam pembentukan anion

Energi kisi pembentukan kisi kristal menguntungkan

secara energetika

Penggolongan Senyawa Ionik

Senyawa ionik dibagi menjadi 4 golongan:
Seny. Ionik sederhana ex: NaCl, MgCl2, dll
Seny. Ionik mengandung kation sederhana dan anion poliatomik
ex: K2SO4, NaNO3
Seny. Ionik mengandung kation poliatomik dan anion sederhana
ex: NH4Cl
kation poliatomik dan anion poliatomik ex: NH4NO3
 Karakteristik Senyawa ionik
• Daya hantar listrik rendah
dalam keadaan padat, tapi
cukup tinggi dalam keadaan
lebur atau larut dalam pelarut
polar

• Titik lebur dan titik didih tinggi.

Mengapa?

• Mudah larut dalam pelarut

polar yang memiliki tetapan
dielektrik tinggi

• Umumnya keras tapi rapuh.

Mengapa?
 Karakter Ionik dan Elektronegativitas

Berdasarkan SPU, Atom dengan elektronegativitas rendah

merupakan donor elektron yang baik (cation formers), dan atom yang
sangat elektronegatif merupakan akseptor elektron yang baik (anion
formers).

Perbedaan keelektronegatifan >2 umumnya membentuk ikatan ionik,

sedangkan ΔEN <1 membentuk kovalen (delocalised MO’s).
 % Karakter Ionik dalam
Senyawa Biner
Perbedaan % Karakter Ionik Perbedaan % Karakter Ionik
Keelektronegatifan Keelektronegatifan
0,1 0,5 1,7 51
0,2 1 1,8 55
0,3 2 1,9 59
0,4 4 2,0 63
0,5 6 2,1 67
0,6 9 2,2 70
0,7 12 2,3 74
0,8 15 2,4 76
0,9 19 2,5 79
1,0 22 2,6 82
1,1 26 2,7 84
1,2 30 2,8 86
1,3 34 2,9 88
1,4 39 3,0 89
1,5 43 3,1 91
1,6 47 3,2 92
 Jari-Jari Ionik

Jari-jari ionik adalah perkiraan ukuran ion

dam suatu kisi kristal.

Jari- jari kation < atom induknya

Electrons are removed from the highest energy,

outermost orbitals. The remaining orbitals also
contract due to reduced electron-electron
repulsions.

Jari-jari anion > atom induk.

Electrons are added to the highest energy,

outermost orbitals, which expand due to
electron-electron repulsions.
 Entalpi Pembentukan Pasangan Ion
dalam Fasa Gas
• Tahapannya apa saja?
• Contoh: Pembentukan NaCl fasa gas
Kation: Na(g) → Na+(g)+ e ΔHEI = 495,8 kJ/mol
Anion : Cl(g) + e → Cl-(g) ΔHAE = -349,0 kJ/mol
Psg ion: Na+(g) + Cl-(g)→ NaCl(g) ΔHAE = -552,0 kJ/mol
Na(g) + Cl(g) → NaCl(g) ΔH = -405,2 kJ/mol
• Pembentukan MgO?
 Polarisasi dan Kovalensi

• Kasimir Fayan: Kation yang ukurannya

kecil mampu mempolarisasi awan
elektron anion sehingga bentuk ion
mengalami distorsi (polarisasi)

• Aturan Fayan:
– Muatan kation>>> ukuran kation<<<
sehingga polarisasi >>>
– Muatan Anion >>> ukuran anion >>>
sehingga polaisasi >>>
– Konfigurasi elektron dari kation

Polarisasi >>>> kovalensi >>>>

 Akibat-akibat Polarisasi
Perak Halida Ksp
• Kelarutan <<<<<
AgF Larut
AgCl 2 x 10-10
AgBr 5 x 10-10
AgI 8 x 10-10

• Titik didih dan Titik leleh <<<<<

Senyawa LiF LiCl LiBr LiI
Titik Lebur (0C) 845 605 550 449

• Panjang Ikatan <<<<<

Hidrasi Ion
Hidrasi ion





H2O
Tujuh sisitem kristal (7 tipe unit sel) menunjukkan sumbu dalam ruang dengan
panjang dan sudut sisi yang berbeda
 Struktur Senyawa Ionik
• Ion-ion diasumsikan sebagai bola-bola bermuatan yang tak
terkompresi dan tak terpolarisasi
• Ion-ion mengatur dirinya sedemikian sehingga dikelilingi oleh ion
lawan muatan sebanyak-banyaknya dan sedekat-dekatnya
• Rasio kation terhadap anion harus menggambarkan komposisi
kimiawi senyawa yang bersangkutan
• Kristal ionik dibangun oleh kisi-kisi yang tersusun atas ion positif
dan negatif sehingga gaya tarik antara ion-ion berlawanan maksimal
dan gaya tolak minimal
• Isomorfis: senyawa-senyawa yang mempunyai struktur kristal sama
• Polimorfis: senyawa senyawa yang dapat mengkristal membentuk
dua macam kisi yang berbeda
 Structures of Ionic Solids: NaCl and CsCl

Even though their formulas have one

cation and one anion, the lattices of
CsCl and NaCl are different.

The different lattices arise from the

fact that a Cs+ ion is much larger than
a Na+ ion.
Banyaknya kation yang mengelilingi
anion dengan jarak yang sama →
bilangan koordinasi
Structures of Ionic Solids: NaCl and CsCl
 Ionic Bonding
Because electrostatic attraction is not directional in the same way as is covalent
bonding, there are many more possible structural types. However, in the solid state, all
ionic structures are based on infinite lattices of cations and anions. There are some
important classes that are common and that you should be able to identify, including:

CsCl NaCl Zinc Blende

F F

Ca

Fluorite Wurtzite
And others…Fortunately, we can use the size of the ions to find out what kind of
structure an ionic solid should adopt and we will use the structural arrangement to
determine the energy that holds the solid together - the crystal lattice energy, U0.
 Structures of Ionic Solids: NaCl and CsCl
NaCl Structure
• Each ion has a coordination number of 6.
• Face-centered cubic lattice.
• Cation to anion ratio is 1:1.

CsCl Structure
• Cs+ has a coordination number of 8.
• Different from the NaCl structure (Cs+ is larger than Na+),
body-centered cubic lattice.
• Cation to anion ratio is 1:1.
 Structures of Ionic Solids: The NaCl Structure
Every sodium ion is surrounded by 6 chloride ions, and every chloride
ion is surrounded by 6 sodium ions in an octahedral arrangement.

Na+ and Cl- have very different ionic radii: 1.81 and 1.02 Å, respectively.

The larger Cl- ions are actually close packed in a face-centred cubic (fcc)
lattice, with smaller Na+ cations in the interstices (spaces) between them.

Close packing of anions is very common in ionic crystals.

The arrangement of the cations depends on their size.

 Structures of Ionic Solids: The NaCl Structure

The chloride ion fcc lattice is an example of closest packing,

where the anions are at their highest density.

Only small cations like Na+ can fit into the available interstices.

The maximum cation radius can be estimated from simple geometrical

considerations.

Na+ is a bit bigger than this. It just squeezes into the interstice.
 Structures of Ionic Solids: CsCl

Larger cations such as Cs+ (1.61 Å) cannot fit into these octahedral interstices,
and so cannot form an fcc lattice.

The ions pack in a different way, giving in this case a body-centred cubic
lattice.

The maximum cation radius for this lattice is

Once again, Cs+ is a bit too big according to this model,

but “squeezes” in the interstice.
 Struktur ZNS
CaF2

Rutil (TiO2) Perovskite

Struktur ZnS

Fluorit
dye-doped TiO2-SiO2 core-shell
composite microspheres
http://nanophotonics.spiedigitallibrary.org
/
 SEM image of ZnO nanorods
deposited by chemical bath
deposition (http://www3.nd.edu/)

ZnO micro-crystallites
Source: http://what-when-how.com/nanoscience-and-

nanotechnology/
 Jarak antar Inti

Jari-jari van der Waals?

Jari-jari kovalen?
Jari-jari ionik?
Rasio jari-jari ionik?
Energi kisi?
 Lattice Energy

The Lattice Energy is the energy change when gas phase ions combine to form
a crystal lattice.

Li+(g) + F-(g) → LiF(s), the lattice energy is -1050 kJ mol-1.

This denotes the energy change

accompanying the formation of
1 mole of LiF.

The negative value denotes that the energy

of the crystal lattice is lower than that of the
ions. This is the same idea as the negative
potential energy that binds a negative
electron to a positive nucleus.
 Lattice Energy
The energy of a crystal lattice is due only to electrostatic interactions between
the ions, so we can calculate it exactly by adding up all of the pairs of
interactions between ions as long as we know their distances.
 Lattice Energy

The next-nearest, next-next-nearest neighbour distances all depend only on the

geometry of the lattice (ie. Square, triangular, hexagonal…, which includes the
number of neighbours), and the nearest neighbour distance.

That is, Total Energy of the Lattice may be written as = -NAq1q2/(4πε0rAB) x A,

where A is the Madelung Constant, and q1 and q2 are the charges on the ions.

This allows us to draw some general conclusions about ionic crystals.

1. Lattice Energy depends on the sum of the anion and cation radii, rAB.
2. Lattice Energy depends on the arrangement of the ions, which is described by A.
 Lattice Energy

The Madelung constant measures the potential energy of an extended

crystalline arrangement of ions relative to a cation-anion pair.

A = Energy of the crystal/(q1q2/4πε0rAB) = Energy of the crystal/nearest neighbour energy

Because electrostatic interactions are long-ranged, the potential energy of a

crystal continues to decrease (become more negative) as more ions are added,
and thus favours crystal growth.
Thank You… .