Lattice Energy

Lattice Structure of Ionic Compound

Ionic compound are
solid which are
arranged alternatingly
in a regular and
orderly cubic pattern
in three dimensions
with the same
orientation; unit cells
The three dimensional
array formed by the
unit cells of a crystal is
called lattice.

Lattice Structure of Ionic Compound

Formation of crystal lattice is depending on
the attraction between opposite ions in
achieving the highest stability
Higher attraction, higher stability, greater the
lattice energy

The ions will tend to organised to reach the

highest stability with a minimal repulsion
forces

Magnitude of Lattice Energy

Depends on two main factors
A) The charge on the ions
The greater the charge on the ions
Greater the attractions between the ions
Greater the lattice energy

B) The size of the ions/ distance between ions

small
The smaller the ions
Greater the attractions between the ions
Greater the lattice energy

Factors affecting lattice energy

It is highly affected by the size and
charge of the ions
Isoelectronic cations or anion:
charge, HLE more negative due to
higher charge denstiy
Cation or anions of the same group:
ionic radius, HLE less negative due to
lower charge density

 Effects
Melting point
the higher the lattice enthalpy,
the higher the melting point of an ionic compound

Solubility
solubility of ionic compounds is affected by the relative
values of Lattice and Hydration Enthalpies

Factors affecting lattice

energy
factor explained by the electrostatic
This

theory and calculated using Coulombs

Law
Force of attraction, F
F=k
where
q1 & q2 = charges on the ions
r = distance between adjacent ions
k = Coulomb constant

F when q1 or q2 OR r

Lattice Enthalpy Values

Cl Br F

O2-

Na+ -780 -742 -918 -2478

K+

-711 -679 -817 -2232

Rb+ -685 -656 -783

Mg2+ -2256

-3791

Ca2+ -2259

Smaller ions will have a greater attraction for each other because of their higher
charge density. They will have larger Lattice Enthalpies and larger melting points
because of the extra energy which must be put in to separate the oppositely charged
ions.
Na+

Cl

K+

Cl

The sodium ion has the same charge as a potassium ion but is smaller. It has a higher charge
density so will have a more effective attraction for the chloride ion. More energy will be
released when they come together.

Ionic character
No compound has 100% ionic character
This is because when ionic compound is
formed, the anion will tend to be attracted by
cation
This will cause the distortion of electron
density (cloud) of the ionic bond (polarisation)
The larger the distortion, it will lead to compounds
that are more covalent than ionic character

Ionic character
The degree of polarisation in is
determined by:
the charge density of cation
electron density of anion
ionic radius and charge of cation and
anion
CATION: charge, size, charge density,
polarising power
ANION: charge, size, electron density,
more easily to be polarised

Ionic character

Factor of size and charge of cation

The Thermal Stability of sblock

compounds
Elements in Group 1 and Group 2
form cation when react to form
compound
However the stability of compounds
varies based on:
Size of the cation
Charge density of the cation

The thermal stability of sblock

compounds
Thermal stability (TS) describes the stability
of the compounds
Referring as decomposition of the compound on
heating
usually endothermic: required to break chemical
bonds
Higher TS means higher T needed to decompose the
compound; compound is stable
Compounds more stable if the cation has bigger size

 Small cations: more charge packed into

a small volume of space; high charge
density
Bigger cations: charges spread over a
larger volume of space; low charge
density, cause less distortion to nearby
negative ions
Single charge polarize less than the
higher charge

The thermal stability of sblock

compounds

Lattice Energy
Also known as Lattice enthalpy
The electrostatic force of attraction that joins ions
together in a crystal lattice
Defined as energy released when one mole ionic
compound is form from its gaseous ions under
standard condition; Hlatt
aMb+(g) + bXa- (g) MaXb(s)
Mg 2+(g) + 2Cl-(g) -- MgCl2 (s)
Always exothermic; the larger the value the stronger
the ionic bond

Lattice Energy
cannot be determined directly but can be
calculated from the sum of related equations
with experimental values through Born-Haber
cycle
The experimental values includes:
Atomization of element to form 1 mol of gaseous
element
1st, 2nd,. ionization energy of gaseous metal atom
1st, 2nd,. electron affinity, Hea of gaseous nonmetal atom

Enthalpy change of atomisation and

electron affinity
Atomisation
Mostly dealt with the atomisation of element
enthalpy change when one mole of gaseous atoms is formed
from its element in its standard state under 298 K and 100 kPa
X(s) X(g)
Hat is always endothermic

Electron affinity
Most of the chemical behaviour influence by the ability to
accept electron(s)
First EA, Hea1:
enthalpy change when 1 mol of electron is accepted by 1 mol gaseous
atom to form 1 mol gaseous 1 anion under 298 K and 100 kPa
X(g) + e X(g)

Most of the 1st EA value is ve: exothermic]

F(g) + e F(g) Hea1 = 328 kJ/mol

Enthalpy change of atomisation and electron

affinity
2nd electron affinity, 3rd electron affinity
etc. are always endothermic
Reason: energy is required to overcome the
repulsive force between the anion and
(incoming) electron(s)
O(g) + e O(g)
Hea1 = 141 kJ/mol
O(g) + e O2(g)
Hea2 = +798 kJ/mol
O(g) + 2e O2(g)
H = +657 kJ/mol

Enthalpy change of atomisation and electron

affinity

Trend of Electron Affinity Across the Period

Born-Haber Cycles
Another type of enthalpy cycle to
calculate lattice energy of an ionic
compound
Involve several step to form gaseous
ions which then form the ionic
compound
Atomisation of the elements followed by
the conversion of gaseous atoms to ions

Born-Haber Cycles
Example: Determine the lattice energy of NaCl using
the data given.

1st H
IE f[Na(s)]
[NaCl(s)] = 411.2 kJ/mol
496
(kJ/mol)

Hat[Cl2(g)]
(kJ/mol)
H
[NaCl(s)] = H [Na(s)] + H

1st EA [Cl2(g)]
(kJ/mol)

121.7

[Cl2(g)]
+ HLE [NaCl(s)] + 1st IE [Na(s)]
+ 1st EA [Cl2(g)]
HLE [NaCl(s)] = Hf[NaCl(s)] (Hat [Na(s)]
+ Hat [Cl2(g)] + 1st IE [Na(s)]
+ 1st EA [Cl2(g)])
= 411.2 [107.3 + 121.7 + 496
+ (348.8)]
= 787.4 kJ/mol
f

Exercise: pg 87

at

at

Enthalpy

HatNa
[Na(s)]
(s) + Cl2 (g) NaCl (s)
107.3
(kJ/mol)

348.8

Born-Haber Cycles
By using the Born-Haber cycle, the theoretical
Hf can be calculated for substances that do
not exist (eg. NaCl2, MgCl, MgCl3)
This will help to explain why the lattice of the
compound does not form
This is due to a very large endothermic Hf
which indicate that the compound is unstable
to exist in such form

Standard enthalpy changes of

solution
heat released or absorbed when one
mole of ionic solid completely dissolves
in sufficient water to form a very dilute
solution under 298 K and 100 kPa;
Hosol
The more negative, the more soluble
Hsol = Hhyd Hlatt

Standard enthalpy changes of

Hydration
Standard enthalpy of hydration, Hhyd
energy change when one mole of a specified gaseous
ion dissolves in sufficient water to form a very dilute
solution under standard conditions
MY+(g) + mH2O MY+(aq)
Hhyd, 298 (cation)
XZ-(g) + mH2O MZ-(aq) Hhyd, 298 (anion)

Depend on the strength of attractive force of ions with

water (ion-dipole interaction)
Higher charge density of cation, higher |Hhyd, (cation)|
Smaller ionic radius, higher |Hhyd, (cation)|

Calculating enthalpy changes of

solution
Ionic solid

Hlatt

Hsol

Hhyd

Gaseous ions

Ions in
aqueous
solution

Calculating enthalpy changes of

solution

Example: Dissolving NaCl in water

Lattice energy: 776 kJ mol1

Enthalpy change of hydration: 771 kJ mol1

Hsol

NaCl(s)
Hlatt =
776 kJ mol1

Na+(aq) + Cl
(aq)
Hhdy =
771 kJ mol1

Na+(g) + Cl(g)

Calculating enthalpy changes of solution

Example: Dissolving NaCl in water

Hsol + Hlatt = Hhyd
Hsol = Hhyd Hlatt
= 771 (776)
Hsol [NaCl] = +5 kJ mol1

Solubility of ionic compound

Depending on HLE and Hhyd
Generally, the compound is soluble in
water when Hhyd>HLE
Sometime Hhyd<HLE yet the
compound still soluble; eg. NaCl