Experimental Method of Lattice Energy

Submitted to

Submitted by

07

01

2015

Page |1

INDEX
Serial

Name of the Topics

Page

01

Introduction of Lattice Energy

02

02

Factors Affecting Lattice Energy of a Crystal

03

03

Attraction & Repulsion in a Crystal

04

04

05

05

The Relationship between Lattice Energies and Physical

Properties
Determination of Lattice Energy

06

The Born-Haber Cycle

07

07

Born-Haber Cycle: Explanation with an Examples

08-13

06

Born-Haber Cycle for Sodium Chloride

Born-Haber Cycle for Cesium Fluoride
Born-Haber Cycle for Lithium Fluoride
08

Importance of Born-Haber Cycle

13

09

Applications of Lattice Energy Determination

13

10

Problem

14

Tables
Table 1

Selected Enthalpies of Sublimation at 298 K

Table 2

Selected Bond Dissociation Enthalpies at 298 K

10

Table 3

Summary of Reactions in the BornHaber Cycle for the

Formation of CsF(s)
Representative Calculated Lattice Energies

12

Experimental & Theoretical Lattice Energies in Kcal per

Mole

14

Table 4
Table 5

13

Reference of the Topics Studied

01. Textbook of Physical Chemistry by Samuel Glasstone
02. Solid State Chemistry and its Applications by Anthony R West
03. General Chemistry (9th Edition) by Darrell D. Ebbing & Steven D. Gammon
04. Essentials of Physical Chemistry by Arun Bahl, B.S. Bahl & G.D. Tuli
05. A Textbook of Physical Chemistry by K. K. Sharma
06. Inorganic Chemistry (2nd Edition) by Catherine E. Housecroft
07. Inorganic Chemistry by J.D. Lee
08. Wikipedia.org
09. Chemwiki.com

Page |2

Introduction of Lattice Energy

Lattice energy, also called lattice enthalpy, of an ionic solid/crystal is a measure of the
strength of bonds in that ionic compound. The positive and negative ion in an ionic crystal are
held together by electrostatic forces. The energy released when a crystalline solid forms from
ions is related to the lattice energy of the solid.
Lattice Energy is defined as:
The decrease in energy accompanying the process of bringing the ions, when
separated from each other by an infinite distance, to the positions they occupy in the
stable lattice.
The lattice energy is the change in energy that occurs when an ionic solid is separated
into isolated ions in the gas phase.
Another definition of the lattice energy is to regard it as the energy of formation of a given
quantity of the crystal, e.g., 1 mole, from gaseous ions. That is, from separated ions free from
any solvent. In this way it is seen that the lattice energy is the same in magnitude as, but
opposite in sign to, the energy of dissociation of the crystal. It follows, therefore, that the
greater the lattice energy, numerically, the greater the energy required to break up the crystal
into its constituent ions.
Greater the lattice energy, greater the strength of ionic bond. Lattice energy works
against the solution process, so an ionic solid with relatively large lattice energy is usually
insoluble.
After the formation of cations and anions separately, they combine to form ionic compound.

In this process, energy is released.

Generally, two elements bond ionically if the ionization energy of one is sufficiently small and
the electron affinity of the other is sufficiently large and negative. This situation exists between
a reactive metal (which has low ionization energy) and a reactive nonmetal (which has large
negative electron affinity). In general, bonding between a metal and a nonmetal is ionic. This
also explains why ionic bonding normally results in a solid rather than in ion-pair molecules.
A quantitative measure of the stability of any ionic solid is given by its lattice energy or lattice
enthalpy (L.E.).
Lattice Energy is used to explain the stability of ionic solids. Some might expect such an
ordered structure to be less stable because the entropy of the system would be low. However,
the crystalline structure allows each ion to interact with multiple oppositely charge ions, which
causes a highly favorable change in the enthalpy of the system. A lot of energy is released as
the oppositely charged ions interact. It is this that causes ionic solids to have such high melting
and boiling points. Some require such high temperatures that they decompose before they can
reach a melting and/or boiling point.

Page |3

Factors Affecting Lattice Energy of a Crystal

The value of lattice energy depends upon the following two factors:
(a) Size of the ions
In order to have the greater force of attraction between the cations and anions their size
should be small as the force of attraction is inversely proportional to the square of the
distance between them.
Because the ionic radii of the cations decrease in the order K+ > Na+ > Li+ for a given
halide ion, the lattice energy decreases smoothly from Li+ to K+. Conversely, for a given
alkali metal ion, the fluoride salt always has the highest lattice energy and the iodide
salt the lowest.

Figure 1: A Plot of Lattice Energy versus the Identity of the Halide for the Lithium, Sodium, and Potassium Halides

Lattice Energies of Alkali Metals Halides (kJ/mol)

Li+
Na+
K+
Rb+
Cs+

F1036
923
821
785
740

Cl853
787
715
689
659

Br807
747
682
660
631

I757
704
649
630
604

Page |4

Because lattice energy is inversely related to the inter-nuclear distance, it is also inversely
proportional to the size of the ions. This effect is illustrated in figure, which shows that lattice
energy decreases for the series LiX, NaX, and KX as the radius of X increases. Because r0 in
is the sum of the ionic radii of the cation and the anion (r0 = r+ + r), r0 increases as the cation
becomes larger in the series, so the magnitude of U decreases. A similar effect is seen when
the anion becomes larger in a series of compounds with the same cation.

(b) Charge on Ions

Greater the charge on ions greater will be the force of attraction between them and
therefore, greater will be the strength of the ionic bond.
Because the lattice energy depends on the product of the charges of the ions, a salt
having a metal cation with a +2 charge (M2+) and a nonmetal anion with a 2 charge
(X2) will have a lattice energy four times greater than one with M+ and X, assuming
the ions are of comparable size (and have similar inter-nuclear distances). For example,
the calculated value of U for NaF is 910 kJ/mol, whereas U for MgO (containing Mg2+
and O2 ions) is 3795 kJ/mol.
Lattice energies are highest for substances with small, highly charged ions.

Attraction & Repulsion in a Crystal

The stability of an ionic crystal depends on the balancing of at least three forces:
a. The electrostatic, or Coulomb, forces between the ions which give a resultant attraction
falling off with the square of the distance
b. Van der Waals forces of attraction diminishing according to the seventh power of the
distance. And,
c. Interatomic repulsive forces, falling off still more rapidly with distance.

Page |5

The result of the attractive and repulsive forces is to lead to an equilibrium position of
minimum potential energy, i.e., of greatest stability, as depicted in the figure below:

Figure 2: Potential Energy of Crystal Lattices (Shown for NaCl)

The r0, corresponds to the minimum, represents the equilibrium value of the ionic separation
in the stable crystal lattice. At all temperatures there will, however, be some thermal oscillation
about the equilibrium positions; in some cases rotation also occurs.

The Relationship between Lattice Energies and Physical Properties

The magnitude of the forces that hold an ionic substance together has a dramatic effect on
many of its properties. The melting point, for example, is the temperature at which the
individual ions have enough kinetic energy to overcome the attractive forces that hold them in
place. At the melting point, the ions can move freely, and the substance becomes a liquid. Thus
melting points vary with lattice energies for ionic substances that have similar structures. The
melting points of the sodium halides (Figure 3), for example, decrease smoothly from NaF to
NaI, following the same trend as seen for their lattice energies (Figure 1). Similarly, the melting
point of MgO is 2825C, compared with 996C for NaF, reflecting the higher lattice energies
associated with higher charges on the ions. In fact, because of its high melting point, MgO is
used as an electrical insulator in heating elements for electric stoves.

Page |6

Figure 3: A Plot of Melting Point versus the Identity of the Halide for the Sodium Halides. The melting points follow the same trend as
the magnitude of the lattice energies in Figure 1

The hardness of ionic materialsthat is, their resistance to scratching or abrasionis also
related to their lattice energies. Hardness is directly related to how tightly the ions are held
together electrostatically, which, as we saw, is also reflected in the lattice energy. As an
example, MgO is harder than NaF, which is consistent with its higher lattice energy.
In addition to determining melting point and hardness, lattice energies affect the solubilities of
ionic substances in water. In general, the higher the lattice energy, the less soluble a compound
is in water. For example, the solubility of NaF in water at 25C is 4.13 g/100 mL, but under
the same conditions, the solubility of MgO is only 0.65 mg/100 mL, meaning that it is
essentially insoluble.
High lattice energies lead to hard, insoluble compounds with high melting points.

Page |7

Determination of Lattice Energy

Ionic crystals may be regarded as regular 3D arrays of point charges. The forces that hold them
together are entirely electrostatic and may be calculated by summing all the electrostatic
repulsions and attractions in the crystal.
Lattice energy can be calculated from Coulombs law or an experimental value may be
obtained from thermodynamic data.

The Born-Haber Cycle

Direct experimental determination of the lattice energy of an ionic solid is difficult and not
reliable. However, this quantity can be indirectly determined from experiment by means of a
thermochemical cycle originated by Max Born and Fritz Haber in 1919 and now called the
BornHaber cycle. The reasoning is based on Hesss law of constant heat summation.
There are several important concept to understand before the Born-Haber Cycle can be applied
to determine the lattice energy of an ionic solid: Ionization Energy, Electron Affinity,
Dissociation Energy, Sublimation Energy, Heat of Formation, and Hess's Law.
Ionization Energy is the energy required to remove an electron from a neutral atom
or an ion. This process always requires an input of energy, and thus will always have
a positive value. In general, ionization energy increases across the periodic table
from left to right, and decreases from top to bottom. There are some exceptions,
usually due to the stability of half-filled and completely filled orbitals.
Electron Affinity is the energy released when an electron is added to a neutral atom
or an ion. Usually, energy released would have a negative value, but due to the
definition of electron affinity, it is written as a positive value in most tables.
Therefore, when used in calculating the lattice energy, we must remember to
subtract the electron affinity, not add it. In general, electron affinity increases from
left to right across the periodic table and decreases from top to bottom.
Dissociation energy is the energy required to break apart a compound. The
dissociation of a compound is always an endothermic process, meaning it will
always require an input of energy. Therefore, the change in energy is always
positive. The magnitude of the dissociation energy depends on the electronegativity
of the atoms involved.
Sublimation energy is the energy required to cause a change of phase from solid to
gas, bypassing the liquid phase. This is an input of energy, and thus has a positive
value. It may also be referred to as the energy of atomization.
The heat of formation is the change in energy when forming a compound from its
elements. This may be positive or negative, depending on the atoms involved and
how they interact.
Hess's Law states that the overall change in energy of a process can be determined
by breaking the process down into steps, then adding the changes in energy of each
step. The Born-Haber Cycle is essentially Hess's Law applied to an ionic solid.
The Born-Haber Cycle can be expressed by the general equation:

Page |8

Heat of formation = Heat of atomization + Dissociation energy + (sum of Ionization

energies) + (sum of Electron affinities) + Lattice energy
Note: In this general equation, the electron affinity is added. However, when plugging in a value,
determine whether energy is released (exothermic reaction) or absorbed (endothermic reaction) for
each electron affinity. If energy is released, put a negative sign in front of the value; if energy is
absorbed, the value should be positive.

Rearrangement to solve for lattice energy gives the equation:

Lattice energy = Heat of formation - Heat of atomization - Dissociation energy - (sum of
Ionization energies) - (sum of Electron Affinities)
General Born-Haber Cycle for the Formation of Metal Halide

Born-Haber Cycle: Explanation with an Examples

Born-Haber Cycle for Sodium Chloride
The Born-Haber Cycle is based on the first law of thermodynamics. This cycle involves the
formation of an ionic compound (crystal lattice) from the reaction of a metal (often a group I
or II element) with a non-metal.
To understand the concept of Born-Haber Cycle let us consider the formation of NaCl from
its constituents.
To obtain the lattice energy of NaCl, one think of solid sodium chloride being formed from the
elements by two different routes, as shown in Figure below.
Process I
In one route, NaCl(s) is formed directly from the elements, Na(s) and 1 2 Cl g . The enthalpy
change for this is H , which is 411 kJ per mole of NaCl.
Na (s) + 1/2 Cl2 (g)

NaCl (s) + H f0

Page |9

Figure 4: BornHaber cycle for NaCl

Process II
The second route consists of five steps:
1. Sublimation of Sodium
Metallic sodium is vaporized to a gas of sodium atoms. (Sublimation is the
transformation of a solid to a gas.) The enthalpy change for this process, measured
108 per mole of sodium.
experimentally, is
Enthalpy of sublimation is always positive because energy is required to sublime a solid.
Table 1: Selected Enthalpies of Sublimation at 298 K
Substance Hsub (kJ/mol)
159.3
Li
107.5
Na
89.0
K
80.9
Rb
76.5
Cs
324.0
Be
147.1
Mg
Ca
177.8
164.4
Sr
180.0
Ba
2. Dissociation of chlorine
Dissociation of mole of Cl2 (g) into 1 mole of separate gaseous chlorine, Cl(g) atoms.
It is the enthalpy of atomization of chlorine. The enthalpy change for this equals the
Cl Cl bond dissociation energy, which is 240 kJ per mole of bonds, or 120 kJ per mole
120 /
of Cl atoms. Therefore,
The H for this reaction, too, is always positive because energy is required to dissociate
any stable diatomic molecule into the component atoms.

P a g e | 10

Table 2: Selected Bond Dissociation Enthalpies at 298 K

Substance D (kJ/mol)
436.0
H2(g)
945.3
N2(g)
498.4
O2(g)
158.8
F2(g)
242.6
Cl2(g)
192.8
Br2(g)
151.1
I2(g)
3. Ionization of sodium
Sodium atoms are ionized to Na+ ions. The enthalpy change is essentially the first
496 per mole of Na.
ionization energy of atomic sodium, which equals
Energy is needed to ionize any neutral atom. Hence, regardless of the compound, the
enthalpy change for this portion of the BornHaber cycle is always positive.
4. Formation of chloride ion
The electrons from the ionization of sodium atoms are transferred to chlorine atoms.
The enthalpy change for this is the electron affinity of atomic chlorine, which equals
349 per mole of Cl atoms.

Electron affinities can be positive, negative, or zero. In this case, H is negative because
of the highly negative electron affinity of chlorine.
5. Formation of NaCl(s) from ions
The ions Na+ and Cl- formed in Steps 3 and 4 combine to give solid sodium chloride.
Because this process is just the reverse of the one corresponding to the lattice energy
(breaking the solid into ions), the enthalpy change is the negative of the lattice energy.
.
If U be the lattice energy, the enthalpy change for Step 5 is
Because it is the reverse of the equation used to define lattice energy and U is defined
to be a positive number, H5 is always negative, as it should be in a step that forms
bonds.
According to Hesss law:

P a g e | 11

In summing the equations, we have canceled terms that appear on both the left and right sides
of the arrows. The final equation is simply the formation reaction for NaCl(s). Adding the
enthalpy changes, we find that the enthalpy change for this formation reaction is 375
.
But the enthalpy of formation has been determined calorimetrically and equals 411 .
Equating these two values, we get:

,
,

,
Therefore, the lattice enthalpy of the formation of NaCl is 786kJ/mol.
Born-Haber Cycle for Cesium Fluoride
Lets use the BornHaber cycle to determine the lattice energy of CsF(s). CsF is a nearly ideal
ionic compound because Cs is the least electronegative element that is not radioactive and F is
the most electronegative element. To construct a thermochemical cycle for the formation of
CsF, we need to know its enthalpy of formation, Hf, which is defined by the following
chemical reaction:

Figure 5: The BornHaber Cycle Illustrating the Enthalpy Changes Involved in the Formation of Solid Cesium Fluoride from Its
Elements

P a g e | 12

The following steps are involved in the formation CsF from its constituents:
1. Sublimation of Cs
Cs s Cs g
Enthalpy of sublimation, H

76.5 kJ/mol

2. Ionization of Cs
Cs g Cs g
H
375.7 kJ/mol
Enthalpy of Ionization, H
3. Dissociation of F
1
F g F g
2
H
79.4 kJ/mol
Enthalpy of dissociation, H
4. Formation of Fluoride
F g F g
H
328.2 kJ/mol
Electron affinity of fluorine, H
5. Formation of CsF(s)
F g CsF s
Cs g
H
553.5 kJ/mol
Enthalpy of formation, H
According to Hesss law:
Hf = H1 + H2 + H3 + H4 + H5
Or, H5 = H1 + H2 + H3 + H4 Hf
Or, U = 76.5 kJ + 375.7 kJ/ + 79.4 kJ + (328.2 kJ) (553.5 kJ)
= 756.9 kJ/mol
Table 3: Summary of Reactions in the BornHaber Cycle for the Formation of CsF(s)

(1)
(2)
(3)
(4)
(5)

Reaction
Cs(s) Cs(g)
Cs(g) Cs + (g) + e
F2(g) F(g)
F(g) + e F(g)
Cs + (g) + F(g) CsF(s)
Cs(s) + F2(g) CsF(s)

Enthalpy Change (kJ/mol)

Hsub = 76.5
I1 = 375.7
D = 79.4
EA = 328.2
U = 756.9
Hf = 553.5

P a g e | 13

Born-Haber Cycle for Lithium Fluoride

Importance of Born-Haber Cycle

1. It is useful to determine the electron affinities which are otherwise difficult to determine
by other means.
2. It is useful in analyzing and correlating the stability of various ionic solids.
3. It also provides an explanation for why most metals fail to form stable ionic compounds
in low valence states, such as AlO, MgCl.
Applications of Lattice Energy Determination
1. Estimation of electron affinities
One of the most valuable applications of the lattice energy is to calculate the electron
affinities of halogen atoms, i.e., work required to remove an electron from a halogen
ion, since these can only be determined directly with some difficulty. Use is made of
the Born-Haber Cycle.
2. Fluoride affinities
3. Estimation of standard enthalpies of formation and disproportionation
Table 4: Representative Calculated Lattice Energies
Substance U (kJ/mol)
682
NaI
1971
CaI2
2293
MgI2
887
NaOH
2481
Na2O
755
NaNO3
10,602
Ca3(PO4)2
2804
CaCO3

P a g e | 14

Table 5: Experimental & Theoretical Lattice Energies in Kcal per Mole

The discrepancy between the experimental lattice energy and that calculated on the assumption
of purely ionic linkages increases as the valence partakes increasingly of covalent character.

Problem
Draw a Born-Haber cycle for the formation of RbCl to determine the lattice enthalpy of the compound
using the following data:
H

431 kJ

H
H

86 kJ

122 kJ

Solution:
Born-Haber Cycle for the formation of RbCl:

Figure 6: Born-Haber Cycle for RbCl

408 kJ
349 kJ

P a g e | 15

Given,
H

431 kJ

H
H

86 kJ

122 kJ

H
H

And, Lattice Energy (L.E.), H5 = U =?

According to Hesss law:
Hf = H1 + H2 + H3 + H4 + H5
Or, H5 = H1 + H2 + H3 + H4 Hf
Or, U = 86 kJ/mol + 122 kJ/mol + 408 kJ/mol + (349 kJ/mole) (431 kJ/mol)
= 698 kJ/mol
Therefore, Lattice energy for the formation of RbCl = 698 kJ/mol.

408 kJ
349 kJ