IKATAN IONIK

Ikatan ionik : ikatan yang terjadi antara ion positif dan ion
negatif karena interaksi elektrostatik

Terjadi apabila terdapat atom yang mempunyai energi
ionisasi kecil dan bertemu dengan atom yang mempunyai
afinitas elektron besar selisih EN sangat tinggi

Kekuatannya sangat tergantung pada ukuran ion dan
muatan ion semakin besar ukuran ion, ikatan ionik
semakin lemah dan makin tinggi muatan ion, makin kuat
ikatannya

r
q q
U
2 1
=
Contoh :
Na Na
+
+ e
-
Cl + e
-
Cl
-
Na
+
+ Cl
-
Na
+
Cl
-

Mg Mg
2+
+ 2e
-
O + 2e
-
O
2-
Mg
2+
+ O
2-
Mg
2+
O
2-

Al Al
3+
+ 3e
-
O + 2e
-
O
2-
2 Al
3+
+ 3O
2-
(Al
3+
)
2
(O
2-
)
3
The compounds with more 50% ionic character are
normally considered to be ionic solids.
-
Catatan :
1. Apabila selisih ukuran antara kation dan anion cukup
besar untuk memungkinkan terjadinya persinggungan
anion-anion atau kation-kation, maka ikatan ionik
antara ion akan diperlemah oleh tolakan persinggungan
tersebut
Jika kation relatif besar maka akan terjadi
kontak antar kation
Jika anion relatif besar maka akan terjadi
kontak antar anion
-
+
+
+ +
+ +
- -
- -
- +
(a) (b)
2. Kristal ionik yang mengandung anion kompleks cenderung
untuk lebih mudah terurai apabila kation tersebut memiliki
kemampuan yang tinggi untuk menarik elektron dari anion.
Ukuran kation makin kecil, makin mudah mempolarisasi.

MA M
+
A
-
M
+
A
-

kovalen kov polar ionik

Jika kemampuan kation untuk menarik elektron dari anion
makin kuat maka ikatannya makin lemah.

Makin besar kemampuan kation untuk menarik elektron, akan
meningkatkan karakter kovalen

Contoh : CaCO
3
dan BaCO
3
r Ca
2+
< Ba
2+
sehingga Ca
2+
memiliki kemampuan menarik
elektron anion CO
3
2-
lebih besar daripada Ba
2+
, akibatnya
polarisasi Ca
2+
> Ba
2+
, sehingga CaCO
3
lebih mudah terurai
Sifat-sifat senyawa ionik
1. Pada keadaan padatan, senyawa mempunyai
konduktivitas sangat rendah, sedangkan dalam
fasa cair/larutan, mempunyai konduktivitas tinggi.
Contoh :
Secara teoritis, NaCl dalam padatan mengandung banyak ion
sehingga mampu menghantarkan listrik yang baik, tetapi faktanya
ion-ion terikat secara kuat sehingga tidak dapat bebas bergerak
oleh karena itu konduktivitasnya mendekati 0 (sangat rendah).

Jika padatan NaCl dilarutkan dalam air maka ion (+) dan (-) akan
berdiri sendiri-sendiri sehingga dapat menghantarkan listrik
dengan baik konduktivitas menjadi tinggi
2. Mempunyai titik lebur tinggi

Karena ion (-) dari Cl tidak hanya berinteraksi dengan salah satu
ion (+) dari Na tapi ion (-) dari Cl berikatan ke segala arah shg
ikatan Na
+
dengan Cl
-
menjadi semakin kuat shg energi untuk
memutus ikatan Na
+
Cl
-
menjadi semakin besar t.l tinggi
Ikatan ionik ke segala arah sehingga memperkuat interaksi antar
ion.



Contoh : titik lebur dari beberapa garam Na
Anion : F
-
Cl
-
Br
-
I
-
Titik leleh : 1268 1073 1023 924
+
- + -
-
+
+ -
+ - + -
+
-
+
-
+
+
-
-
+
3. Keras dan britle

Keras : padatan tersusun secara kompak dari senyawa ionik
yang sudah tidak dapat dimampatkan lagi. Kekerasan naik
dengan menurunnya jarak antar ion dan naiknya muatan ion.
britle : permukaannya mudah rontok (mripil)
Contoh : LiF NaF
M-X (pm) : 202 231
kekerasan : 3,3 3,2

4. Mudah larut dalam pelarut polar (pelarut yang
mempunyai tetapan dielektrik tinggi, contoh : air)

Tetapi tidak semua zat yang larut dalam pelarut polar adalah
ionik

Lithium-Fluoride
structure
ENERGI IKATAN DALAM PADATAN
IONIK
ENERGI KISI

Adalah :
~ energi yang diperlukan untuk
mengubah 1 mol senyawa ionik padatan
menjadi ion-ionnya dalam fasa gas
~ energi yang dilepaskan apabila ion (+)
dan (-) dalam keadaan gas berubah
menjadi padatan.
Evaluation of lattice energy
Experimentally
Born-Haber cycle
Theoretically
Born-Mayer equation
Kapustinskii equation
1 2
-
A
L
H
is the standard molar enthalpy change accompanying the formation
of a gas of ions from an ionic solid
) ( ) ( ) ( g X g M s MX
+
+
The disruption of a lattice requires energy and it is, therefore, an
endothermic process
This means that Lattice Enthalpies are always positive and the most stable
crystal structure of a compound is the structure with the greatest lattice
enthalpy under prevailing conditions
Dalam padatan/kristal ionik terdapat 2 jenis
energi :
1. E
tarikan
muatan berlawanan E
coulomb
2. E
tolakan
muatan sama E
repulsion


berlaku untuk 2 ion

Karena padatan terdiri dari banyak ion maka :
z = muatan ion
A = tetapan Madelung
r 4
z z
c
E

+
=
c
r 4
z Az
c
E

+
=
c
Energi tolakan dari Born :

B = tetapan Born
n = eksponen Born

Energi kisi = U

U = E
c
+ E
r

- + karena tandanya
berlawanan maka dalam kurva U vs r akan di
dapat harga U minimal pada r tertentu
n
r
r
B
E =
At large inter nuclear distances (right side of graph) there is no
overlap of electron clouds. This state is designated with PE = 0.
As the nuclei approach each other (moving to the left on the
graph), the atoms become stabilized due to sharing of their
electron with the other atom. We see the PE decrease in this
region.
The minimum on the curve corresponds to the optimized
balancing of attraction (nuclear-electron) and repulsion (nuclear-
nuclear and electron-electron). The energy at the minimum is
the bond strength which represents the amount that the
molecule is stabilized over the free atoms. If you want to break
the bond, you need to supply that much energy. The inter
nuclear distance at this minimum is the bond length for that
molecule.
If the nuclei are brought any closer together, the nuclear-nuclear
repulsion dominates and the PE for the molecule shoots up.
At large inter nuclear distances (right side of graph) there is
no overlap of electron clouds. This state is designated with
PE = 0.
0
1 n 2
1 n 2
0
2
n
0
2
r c
n4
r e Z AZ
B
0
r
nNB
r 4
e Z ANZ
dr
dU
r
NB
r 4
e Z ANZ
U
E E U
+
+
+
+
=
= =
+ =
+ =
Pada U minimal U=U
0
dan r=r
0
sehingga :
)
n
1
1 (
r 4
e Z ANZ
U
0
2
=
+

Pers. BORN-LANDE
n tergantung pada konfigurasi elektron ion yang
bersangkutan
Harga n untuk kristal ionik selalu > 1
Tabel harga n

Konfigurasi e ion n
2 (He)
10 (Ne)
18 (Ar)
36 (Kr)
54 (Xe)
5
7
9
10
12
Contoh :

Na
+
Cl
-
11
Na : 1s
2
2s
2
2p
6
3s
1
Na
+
: 1s
2
2s
2
2p
6
e = 10
Konfigurasi e Na
+
= konf. e Ne sehingga n
Na
+
= 7
17
Cl : 1s
2
2s
2
2p
6
3s
2
2p
5
Cl
-
: 1s
2
2s
2
2p
6
3s
2
2p
6
e = 18
Konfigurasi e Cl
-
= konf. e Ar sehingga n Cl
-
=
9

Jadi, n untuk NaCl = (7+9)/2 = 8



+
-
-
+
-
+ -
+
+
-
+
-
r\3
r\6
r\2
r\5
r
+ +
+
+ -
-
-
-
Cl
-
Na
+
-
+ - +
+ - +
+ - -
+ - -
+ - -
+ + -
The Madelung constant, A,
depends on the relative
distribution of cations and
anions in the structure
MENCARI HARGA A


r
A
coul
E
A
r
e
Ecoul
r r r
r
e
Ecoul
coul E coul E coul E coul E Ecoul
r
coul E
r
coul E
r
coul E
r
e
coul E
z z
e
e e e
e
e
e
0
2
0
2
0
2
0
2
0
2
0
2
0
2
4
4 4 4
4
4
4
.....)
2
6
3
8
2
12
6 (
.....)
2
6
3
8
2
12
6 (
4
2
......
2
6
3
8
2
12
4
2
6
..........
4 3 2 1
2
6
4
3
8
3
2
12
2
4
2
6
1
1
0
0
0
tc
tc tc tc
tc
tc
tc
tc
tc
tc
=
+ + =
+ + =
+ + =
+ + + + =
+ =
=
+ =
=
= =
+
for NaCl
6Cl
-
at a distance r

12 Na
+
at r2
8 Cl
-
at r3
6 Na
+
at 2r
A = Madelung constant
r
z z e
r
e
E
0
2
0
2
4 4 tc tc
+
= =
Giving its dependence on large contribution coming from
nearest neighbours,
the Madelung constant increases with coordination number
Structure type A Coordination
numbers
ZnS blende 1.638 4, 4
NaCl 1.748 6, 6
CsCl 1.763 8, 8
Tipe struktur kristal ionik
NaCl LiCl, KBr, RbI, AgCl,
AgBr, BeO, MgO, CaO, SrO, BaO
ZnS (blende) CuCl, CuBr, CuI,
AlP, SiC, BeS, CdS, HgS, ZnO
ZnS (wurtzite) AgI, ZnO, NH
4
F,
AlN
CsCl CsBr, CsI, TlCl, TlBr
THEORETICAL EVALUATION OF THE LATTICE ENERGY
Born-Mayer Equation:
it shows the dependency of the lattice enthalpy from the structure
A
d
d
d
e z z N
H
B A A
L
|
|
.
|

\
|
= A
0 0 0
2
1
4tc
Constant Madelung the is A
r r d
pm) (34.5 constant a is d
m C J 10 1.112 4
) m C J 10 (8.854 vacuum the of ty permittivi the is
C) 10 (1.602 charge l fundamenta the is e
anion and cation of charges the z and z
number s Avogadro' the is N
0
1 - 2 1 - 10 -
0
1 - 2 1 - 12 -
0
19 -
B A
A
+
+ =
=

t
) (
-1
mol J
The use of the Born-Land equation requires the knowledge of the
structure of the compound (Madelung constant)
If the structure of the compound is not known, or the Madelung
constant is not available, the Kapustinskii equation can be used to
calculate the lattice energy
|
|
|
.
|

\
|
|
.
|

\
|

+
+

+
+
+

= A
r r
r r
z z
L
H
5 . 34
1
5
10 214 . 1 v
The Kapunstinskii Equation
) (
-1
mol kJ
sign) the (without anion and cation of charges the are and
formula chemical the in ions of number the is
distance) anion - (cation radii ionic the of sum the is
z z

(pm) r
-
-
+
+
+
v
r
The enthalpy of a given chemical reaction is constant, regardless of the
reaction happening in one step or many steps.
Hesss Law
EXPERIMENTAL EVALUATION OF THE LATTICE ENERGY
Born - Haber Cycle: a closed path of steps (reactions), which include the
lattice formation of the compound MX from its constituent ions
We need to define all the quantities included in a Born-Haber cycle
The standard enthalpy of decomposition of a compound into its elements in
their reference states is the negative of its standard enthalpy of formation
-
-
A +
A +
H - X(s) M(s) s MX
H MX(s) X(s) s M
f
f
) (
) (
Likewise the standard enthalpy of lattice formation from the gaseous
ions is the negative of the lattice enthalpy
- +
- +
A +
A +
L
-
L
-
H - MX(s) g X g M
H g X g M s MX
) ( ) (
) ( ) ( ) (
For a solid element, the standard enthalpy of atomisation
-
A H
atom
is the standard enthalpy of sublimation
-
A H M(g) s M
sub
) (
For a gaseous element, the standard enthalpy of atomisation
is the standard enthalpy of dissociation
-
A H 2X(g) g X
dis
) (
2
The standard enthalpy for the formation of ions from their
neutral atoms is the enthalpy of ionisation (for the
formation of cations) and the electron-gain enthalpy (for
the formation of anions)
- +
A + H (g) e (g) M g M
ion
-
) (
-
A + H (g) X (g) e g X
eg
-
) (
The value of the lattice enthalpy can be calculated from
the requirement that the sum of the enthalpy changes
round a complete cycle is zero
Sublimation of
K(s)
+ 89
Ionisation of K(g) + 425
Dissociation of
Cl
2
(g)
+ 244
Electron gain by
Cl(g)
- 355
Formation of
KCl(s)
- 438
) /(
-1
mol kJ H A
-1 -1
mol kJ 719 mol kJ ) 355 122 425 89 438 ( = + + + + = A
-
L
H
The lattice energy is equal to -x
0
* * * * *
= A A + A + A + A
L eg ion sub f
H H H H H
Only one chlorine atom from Cl
2
(g) is used to produce
KCl and therefore half of the dissociation energy of Cl
2
is
used
Formation of an Ionic Solid
1. Sublimation of the solid metal
M(s) M(g) [endothermic]
2. Ionization of the metal atoms
M(g) M
+
(g) + e
-
[endothermic]
3. Dissociation of the nonmetal
1/2X
2
(g) X(g) [endothermic]
4. Formation of X ions in the gas phase:
X(g) + e
-
X
-
(g) [exothermic]
5. Formation of the solid MX
M
+
(g) + X
-
(g) MX(s) [quite exothermic]

Sublimation of Li
Ionization of Li
Dissociation of F
2
Electron affinity
of F
Formation
of solid
Why does the reaction stop at NaCl?
Why doesn't it keep going to form NaCl
2
or NaCl
3
?

The lattice energy would increase as the charge on the
sodium atom increased from Na
+
to Na
2+
or Na
3+
. But
to form an Na
2+
ion, we have to remove a second
electron from the sodium atom, and the second
ionization energy of sodium (4562.4 kJ/mol) is almost
10 times as large as the first ionization energy.
The increase in the lattice energy that would result
from forming an Na
2+
ion can't begin to compensate
for the energy needed to break into the filled-shell
configuration of the Na
+
ion to remove a second
electron.
The reaction between sodium and chlorine therefore
stops at NaCl.
LATTICE ENERGIES FOR ALKALI METALS
HALIDES
The bond between ions of opposite charge is
strongest when the ions are small.
The lattice energies for the alkali metal halides
is therefore largest for LiF and smallest for CsI.

) ( Energy Lattice
2 1
r
Q Q
k =
Ionic Sizes
Arrange the following ionic
compounds in order of increasing
lattice energy: LiCl, NaCl, MgCl
2


1. NaCl < LiCl < MgCl
2

2. LiCl < NaCl < MgCl
2

3. MgCl
2
< NaCl < LiCl
Correct Answer:
1. NaCl < LiCl < MgCl
2

2. LiCl < NaCl < MgCl
2

3. MgCl
2
< NaCl < LiCl
Lattice energy depends
on size of the ions and
their charges. MgCl
2

has the highest lattice
energy because it has a
more positive cation.
LiCl is higher than NaCl
because the interatomic
distance between
cation and ion is
shorter.
LATTICE ENERGIES OF ALKALI METALS HALIDES
(KJ/MOL)

F
-
Cl
-
Br
-
I
-

Li
+
1036 853 807 757
Na
+
923 787 747 704
K
+
821 715 682 649
Rb
+
785 689 660 630
Cs
+
740 659 631 604
LATTICE ENERGIES FOR SALTS OF THE OH
-
AND
O
2-
IONS
The ionic bond should also become
stronger as the charge on the ions
becomes larger.
The lattice energies for salts of the
OH
-
and O
2-
ions increase rapidly as
the charge on the ion becomes larger.
LATTICE ENERGIES OF SALTS OF THE OH
-
AND
O
2-
IONS (KJ/MOL)

OH
-
O
2-

Na
+
900 2481
Mg
2+
3006 3791
Al
3+
5627 15,916
SIFAT KRISTAL IONIK BERDASARKAN ENERGI
KISI
Kelarutan padatan ionik dalam pelarut polar
dan non polar
Titik leleh dan titik didih padatan ionik
Stabilitas padatan ionik
LATTICE ENERGIES AND SOLUBILITY
Whether a given ionic solid is soluble or insoluble in a
polar (ionic) or non-polar solvent depends two factors
viz, (a) lattice energy of the ionic solid, and (b)
hydration energy of ionic solid.
The lattice energy of a salt gives a rough indication of
the solubility of the salt in water because it reflects the
energy needed to separate the positive and negative ions
in a salt.
Higher is the magnitude of hydration energy , greater
will be the tendency of the ionic solid to break into ions
in water and then to get hydrated by H
2
O molecules and
consequently the solubility of the solid will increase.
Apabila energi hidrsi lebih besar daripada
energi kisi, padatan ionik akan larut dalam
pelarut polar dan sebaliknya.
Padatan ionik tidak dapat larut dalam pelarut
nonpolar seperti benzena, CCl
4
, selama ion-
ion padatan ionik tidak berinteraksi dengan
molekul pelarut membentuk ion-ion terhidrat.
SOLUBILITY RULES IONIC SOLIDS IN WATER
Ionic solids (or salts) contain positive and
negative ions, which are held together by the
strong force of attraction between particles
with opposite charges. When one of these
solids dissolves in water, the ions that form
the solid are released into solution, where
they become associated with the polar
solvent molecules.

H
2
O
NaCl(s) Na
+
(aq) + Cl
-
(aq)
We can generally assume that salts
dissociate into their ions when they dissolve
in water. Ionic compounds dissolve in water if
the energy given off when the ions interact
with water molecules compensates for the
energy needed to break the ionic bonds in
the solid and the energy required to separate
the water molecules so that the ions can be
inserted into solution.

Solubility is a result of an interaction between
polar water molecules and the ions which make up
a crystal. Two forces determine the extent to which
solution will occur:
Force of attraction between H
2
O molecules
and the ions of the solid
This force tends to bring ions into solution. If this is the
predominant factor, then the compound may be highly
soluble in water.
Force of attraction between oppositely
charged ions
This force tends to keep the ions in the solid state. When it
is a major factor, then water solubility may be very low.

Sodium and potassium salts are soluble in water
because they have relatively small lattice energies.
Magnesium and aluminum salts are often much
less soluble because it takes more energy to
separate the positive and negative ions in these
salts.
NaOH is very soluble in water (420 g/L), but
Mg(OH)
2
dissolves in water only to the extent of
0.009 g/L, and Al(OH)
3
is essentially insoluble in
water.

CONTOH :
a. LiCl, LIBr, NaCl, NaBr larut dalam air karena
energi hidrasinya lebih besar daripada energi
kisinya.
E hidrasi : LiCl = 883, LiBr = 854, NaCl= 775, NaBr = 741
E kisi : LiCl = 840,1 LiBr = 781,2 NaCl= 770,3 NaBr = 728,4
b. KCl, KBr, KI tidak larut dalam air karena energi
hidrasinya lebih kecil daripada energi kisinya.
E hidrasi : KCl = 686, KBr = 657, KI= 619,
E kisi : KCl = 701,2 KBr = 671,1 KI=632,2
LATTICE ENERGIES AND THE STRENGTH OF THE
IONIC BOND
The strength of the bond between the ions of
opposite charge in an ionic compound depends
on the charges on the ions and the distance
between the centers of the ions when they pack
to form a crystal.
An estimate of the strength of the bonds in an
ionic compound can be obtained by measuring
the lattice energy of the compound.
Greater is magnitude of lattice energy of the
ionic solid, greater is the stability of the ionic
solid.