Lattice Energy

1. First definition:
The lattice energy is the energy required to break apart an ionic solid and convert its
component atoms into gaseous ions. This definition causes the value for the lattice energy to
always be positive, since this will always be an endothermic reaction.

2. Second definition:
The other definition says that lattice energy is the reverse process, meaning it is the energy
released when gaseous ions bind to form an ionic solid. As implied in the definition, this
process will always be exothermic, and thus the value for lattice energy will be negative. Its
values are usually expressed with the unit kJ/mol.

3. 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 favourable 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.

4. Lattice enthalpy is a measure of the strength of the forces between the ions in an ionic solid.
The greater the lattice enthalpy, the stronger the forces. Those forces are only completely
broken when the ions are present as gaseous ions, scattered so far apart that there is
negligible attraction between them.

5. Example:

For sodium chloride, the solid is more stable than the gaseous ions by 787 kJ mol-1 and that is
a measure of the strength of the attractions between the ions in the solid. Remember that
energy (in this case heat energy) is given out when bonds are made, and is needed to break
bonds.
So lattice enthalpy could be described in either of two ways:
A) You could describe it as the enthalpy change when 1 mole of sodium chloride (or whatever)
was formed from its scattered gaseous ions. In other words, you are looking at a downward
arrow on the diagram. In the sodium chloride case, that would be -787 kJ mol-1.
B) Or, you could describe it as the enthalpy change when 1 mole of sodium chloride (or
whatever) is broken up to form its scattered gaseous ions. In other words, you are looking at
an upward arrow on the diagram. In the sodium chloride case, that would be +787 kJ mol-1.
 The lattice dissociation enthalpy is the enthalpy change needed to
convert 1 mole of solid crystal into its scattered gaseous ions. Lattice
dissociation enthalpies are always positive.

The lattice formation enthalpy is the enthalpy change when 1 mole of

solid crystal is formed from its scattered gaseous ions. Lattice
formation enthalpies are always negative.

Factors affecting lattice enthalpy

The two main factors affecting lattice enthalpy are the charges on the ions and the ionic radii (which
affects the distance between the ions).
The charges on the ions
Sodium chloride and magnesium oxide have exactly the same arrangements of ions in the crystal
lattice, but the lattice enthalpies are very different.

You can see that the lattice enthalpy of magnesium oxide is much greater than that of sodium
chloride. That's because in magnesium oxide, 2+ ions are attracting 2- ions; in sodium chloride, the
attraction is only between 1+ and 1- ions.

The radius of the ions

The lattice enthalpy of magnesium oxide is also increased relative to sodium chloride because
magnesium ions are smaller than sodium ions, and oxide ions are smaller than chloride ions.
That means that the ions are closer together in the lattice, and that increases the strength of the
attractions. You can also see this effect of ion size on lattice enthalpy as you go down a Group in the
Periodic Table. For example, as you go down Group 7 of the Periodic Table from fluorine to iodine,
you would expect the lattice enthalpies of their sodium salts to fall as the negative ions get bigger -
and that is the case:
Attractions are governed by the distances between the centres of the oppositely charged ions, and
that distance is obviously greater as the negative ion gets bigger.
And you can see exactly the same effect as you go down Group 1. The next bar chart shows the lattice
enthalpies of the Group 1 chlorides.

Note: To save anyone the bother of getting in touch with me to point it out, it's not strictly fair to
include caesium chloride in this list. Caesium chloride has a different packing arrangement of ions in
its crystal, and that has a small effect on the lattice enthalpy. The effect is small enough that it doesn't
actually affect the trend.
Standard atomisation enthalpies

The standard atomisation enthalpy is the enthalpy change when 1

mole of gaseous atoms is formed from the element in its standard
state. Enthalpy change of atomisation is always positive.

You are always going to have to supply energy to break an element into its separate gaseous atoms.
All of the following equations represent changes involving atomisation enthalpy:

Notice particularly that the "mol-1" is per mole of atoms formed - NOT per mole of element that you
start with. You will quite commonly have to write fractions into the left-hand side of the equation.
Getting this wrong is a common mistake. This is because the definition says that 1 mole of gaseous
atoms formed, thus the right hand side of the equation will not have number more than one.

What is standard atomisation enthalpy?

The enthalpy of atomization for a certain temperature is the heat you have to provide at
constant pressure to separate the atoms of an element. It requires an element (like Li in
metallic form and Cl2 in biatomic form or S8 and so on).

Lattice energy is the energy necessary to separate ions in an ion lattice. To calculate it you
have to sum the entalpies of atomization of the two elements in gaseous form, the
enthalpy of vaporisation of any element not in vapour form, the enthalpies for ion
formation (first ionization energy for the cation and electron affinity for the anion).

The general idea is that since enthalpy change at constant pressure is equal to the change
in internal energy, to calculate the energy of a process (formation of a lattice from
elements in the most stable forms) you can sum the enthalpy change of any path that
brings you to the desired result from the starting condition.

An example: you have Na (s) at standard condition, to atomize it you just have to separate
the metallic bonded molecules. So the atomization enthalpy is the sum of the enthalpies
of fusion and vaporisation. You get Na (g) and you have complete atomization.

At standard condition you have Cl2 (g), a diatomic gas, for atomization you dont need to
form a gas if you are at standard condition. So the enthalpy of atomization per mole
correspond to the bond energy of Cl2 (you just need to provide enough energy to break
the bonds)

The sum of the previous enthalpies is the total energy needed to obtain single atoms from
Na (s) and Cl2 (g). To form a lattice you need ions. So you must separate electrons from
Na (first ionization energy). Electrons must be added to Cl (and this releases energy since
Cl has negative electron affinity). Sum these two changes with the previous ones and to
form a lattice you just need to form the bonds, which is also exothermic.
Electron Affinity
1. Energy of an atom is defined when the atom loses or gains energy through chemical reactions
that cause the loss or gain of electrons. A chemical reaction that releases energy is called an
exothermic reaction and a chemical reaction that absorbs energy is called an endothermic
reaction. Energy from an exothermic reaction is negative, thus energy is given a negative sign;
whereas, energy from an endothermic reaction is positive and energy is given a positive sign.
An example that demonstrates both processes is when a person drops a book. When he or
she lifts a book, he or she gives potential energy to the book (energy absorbed). However,
once the he or she drops the book, the potential energy converts itself to kinetic energy and
comes in the form of sound once it hits the ground (energy released).

2. When an electron is added to a neutral atom (i.e., first electron affinity) energy is released;
thus, the first electron affinities are negative. However, more energy is required to add an
electron to a negative ion (i.e., second electron affinity) which overwhelms any the release of
energy from the electron attachment process and hence, second electron affinities
are positive.

3. Example:
First Electron Affinity (negative energy because energy released):

Second Electron Affinity (positive energy because energy needed is more than gained):

First Electron Affinity

Ionization energies are always concerned with the formation of positive ions. Electron
affinities are the negative ion equivalent, and their use is almost always confined to elements
in groups 16 and 17 of the Periodic Table. The first electron affinity is the energy released when
1 mole of gaseous atoms each acquire an electron to form 1 mole of gaseous -1 ions. It is the
energy released (per mole of X) when this change happens. First electron affinities have
negative values. For example, the first electron affinity of chlorine is -349 kJ mol-1. By
convention, the negative sign shows a release of energy.
When an electron is added to a metal element, energy is needed to gain that electron
(endothermic reaction). Metals have a less likely chance to gain electrons because it is easier
to lose their valance electrons and form cations. It is easier to lose their valence electrons
because metals' nuclei do not have a strong pull on their valence electrons. Thus, metals are
known to have lower electron affinities.

Example 1: Group 1 Electron Affinities

This trend of lower electron affinities for metals is described by the Group 1 metals:

Lithium (Li): 60 KJ mol-1

Sodium (Na): 53 KJ mol-1
Potassium (K): 48 KJ mol-1
Rubidium (Rb): 47 KJ mol-1
Cesium (Cs): 46 KJ mol-1

Notice that electron affinity decreases down the group.

 When non-metals gain electrons, the energy change is usually negative because they give off
energy to form an anion (exothermic process); thus, the electron affinity will be negative. Non-
metals have a greater electron affinity than metals because of their atomic structures: first, non-
metals have more valence electrons than metals do, thus it is easier for the non-metals to gain
electrons to achieve a stable octet and secondly, the valence electron shell is closer to the
nucleus, thus it is harder to remove an electron and it easier to attract electrons from other
elements (especially metals). Thus, non-metals have a higher electron affinity than metals,
meaning they are more likely to gain electrons than atoms with a lower electron affinity.

Example 2: Group 17 Electron Affinities

For example, non-metals like the elements in the halogens series in Group 17 have a higher electron
affinity than the metals. This trend is described as below. Notice the negative sign for the electron
affinity which shows that energy is released.

Fluorine (F) -328 kJ mol-1

Chlorine (Cl) -349 kJ mol-1
Bromine (Br) -324 kJ mol-1
Iodine (I) -295 kJ mol-1
Notice that electron affinity decreases down the group, but increases up with the period.

Non-metals vs. Metals

To summarize the difference between the electron affinity of metals and non-metals:

Metals: Metals like to lose valence electrons to form cations to have a fully stable octet. They
absorb energy (endothermic) to lose electrons. The electron affinity of metals is lower than that
of non-metals.
Non-metals: Non-metals like to gain electrons to form anions to have a fully stable octet. They
release energy (exothermic) to gain electrons to form an anion; thus, electron affinity of non-
metals is higher than that of metals.
Patterns in Electron Affinity
Electron affinity increases upward for the groups and from left to right across periods of a periodic
table because the electrons added to energy levels become closer to the nucleus, thus a stronger
attraction between the nucleus and its electrons. Remember that greater the distance, the less of an
attraction; thus, less energy is released when an electron is added to the outside orbital. In addition,
the more valence electrons an element has, the more likely it is to gain electrons to form a stable octet.
The less valence electrons an atom has, the least likely it will gain electrons.

Electron affinity decreases down the groups and from right to left across the periods on the periodic
table because the electrons are placed in a higher energy level far from the nucleus, thus a decrease from
its pull. However, one might think that since the number of valence electrons increase going down the
group, the element should be more stable and have higher electron affinity. One fails to account for the
shielding affect. As one goes down the period, the shielding effect increases, thus repulsion occurs
between the electrons. This is why the attraction between the electron and the nucleus decreases as
one goes down the group in the periodic table.

As you go down the group, first electron affinities become less (in the sense that less energy is evolved
when the negative ions are formed). Fluorine breaks that pattern, and will have to be accounted for
separately. The electron affinity is a measure of the attraction between the incoming electron and the
nucleus - the stronger the attraction, the more energy is released. The factors which affect this
attraction are exactly the same as those relating to ionization energies - nuclear charge, distance and
screening. The increased nuclear charge as you go down the group is offset by extra screening electrons.
Each outer electron in effect feels a pull of 7+ from the center of the atom, irrespective of which element
you are talking about.

Question and Answer:

Why is energy released when an electron is added to a neutral atom?

Energy is not always released when an electron is added to an atom. It depends on the kind of
atoms.
Energy is released when electronegative atom attains a more stable state by accepting electrons.
Stable states have less energy when compared to other states and this difference in energy is
released when an atom accepts an electron.
It actually requires energy to add an electron to an electropositive atom which has an extra
shell of electrons which makes it unstable. To add another electron, we would have to
overcome the repulsion due to the already present electrons on the valance shell and hence
energy would have to be supplied rather than being released.