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

Hess’s Law
The enthalpy of a given chemical reaction is constant, regardless of
the reaction happening in one step or many steps.

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

M ( s)  X(s)  MX(s) f H
MX ( s )  M(s)  X(s) - f H
 Likewise the standard enthalpy of lattice formation from the
gaseous ions is the negative of the lattice enthalpy

MX ( s )  M  ( g )  X - ( g ) H L
M  ( g )  X - ( g )  MX(s) - H L

For a solid element, the standard enthalpy of atomisation atomH
is the standard enthalpy of sublimation


M ( s )  M(g)  sub H
For a gaseous element, the standard enthalpy of atomisation
is the standard enthalpy of dissociation

X 2 ( g )  2X(g)  dis H 
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)

M ( g )  M  (g)  e - (g)  ion H 

X ( g )  e - (g)  X  (g)  eg H 

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
 H /( kJ mol -1 )

Sublimation of + 89
K(s)

Ionisation of K(g) + 425

Dissociation of + 244
Cl2(g)

Electron gain by - 355

Cl(g)

Formation of - 438
KCl(s)
 The lattice energy is equal to
-x
  f H *   sub H *   ion H *   eg H *  H L*  0

H L  (438  89  425  122  355) kJ mol -1  719 kJ mol -1

Only one chlorine atom from Cl2(g) is used to

produce KCl and therefore half of the dissociation
energy of Cl2 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
1/2X2(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]
 Electron affinity
Dissociation of F2 of F

Ionization of Li

Formation
of solid
Sublimation of Li
Why does the reaction stop at NaCl?
Why doesn't it keep going to form NaCl2 or NaCl3?

• The lattice energy would increase as the charge on

the sodium atom increased from Na+ to Na2+ or
Na3+. But to form an Na2+ 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 Na2+ 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.

Q1Q2
Lattice Energy  k ( )
r
Ionic Sizes
Arrange the following ionic
compounds in order of increasing
lattice energy: LiCl, NaCl, MgCl2

1. NaCl < LiCl < MgCl2

2. LiCl < NaCl < MgCl2

3. MgCl2 < NaCl < LiCl

 Correct Answer:

1. NaCl < LiCl < MgCl2

Lattice energy depends
on size of the ions and
2. LiCl < NaCl < MgCl2 their charges. MgCl2
3. MgCl2 < NaCl < LiCl 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 O2- 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 O2- ions increase rapidly as
the charge on the ion becomes
larger.
Lattice Energies of Salts of the OH- and O2-
Ions (kJ/mol)

　 OH- O2-

Na+ 900 2481

Mg2+ 3006 3791
Al3+ 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 H2O molecules and
consequently the solubility of the solid will increase.
• Apabila energi hidrasi lebih besar daripada
energi kisi, padatan ionik akan larut dalam
pelarut polar dan sebaliknya.
• Padatan ionik tidak dapat larut dalam pelarut
nonpolar seperti benzena, CCl4, 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.
 H2O
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 H2O 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.