Topic 12 – Entropy and energetics

A spontaneous process will proceed on its own without any external influence Eg:- diffusion
Some exothermic reactions as well as endothermic reactions are spontaneous.

Exothermic and endothermic reactions

NH3 and HCl react together at room temperature to form a white solid NH4Cl. This reaction is an
exothermic as well as a spontaneous reaction.
The product has less energy than the reactants. Hence, product is more energetically stable than the reactants

Decomposition of N2O4 is an example for an endothermic reaction. If we place some N2O4 in a sealed
container at room temperature, some of it will decompose to form NO2. The product has more energy than
the reactants. Hence, product is less energetically stable than the reactants. Eventhough the product is less
energetically stable; this reaction is also a spontaneous reaction.

Hence, the driving force for a spontaneous reaction cannot be the formation of more energetically stable
products. There should be another factor that determines whether a given reaction is spontaneous or not.
That factor is entropy.
Entropy (S)
Entropy is a measure of disorder of the particles.
It tells you the number of ways that particles can be arranged and the number of ways that the energy can be
shared out between the particles.
The more disordered the particles are, the higher the entropy is. A large, positive value of entropy shows a
high level of disorder.
Entropy is dependent on the following factors.
1) Temperature:
As the temperature of a substance increases, the particles gain energy and their motion also increases.
Higher temperatures therefore increase the disorder of the particles (entropy increases).

2) State of matter:
Entropy increases with change of state.

3) Number of particles:
Entropy increases when the number of particles increases.
The more particles you’ve got, the more ways they and their energy can be arranged.
Eg:- N2O4 (g) 2NO2 (g) Entropy increases because the number of moles increases.

4) Dissolving a solid
Dissolving a solid increases its entropy — dissolved particles can move freely as they’re no longer held in
one place. Example: Dissolving ammonium nitrate crystals in water results in an increase in entropy:

* The entropy of a substance can only be zero at zero kelvin and this assumes a perfectly ordered crystal
(perfect crystals). A perfect crystal is one in which the internal lattice structure is the same at all times. In
other words, the particles are fixed and are not moving in any way.
* Substances are actually more energetically stable when there’s more disorder. So particles will move to try
to increase their entropy.
Total entropy
Standard entropy (S0) is the entropy of a substance at standard temperature (298 K) and pressure (100 kPa).
The unit of entropy is JK-1mol-1
The total entropy change for a physical or chemical process can be given by the following equation.
ΔS total = ΔSsystem + ΔSsurroundings

The ‘surroundings’ are the container, air and solvent. Δssurroundings is calculated using the expression:

ΔH = enthalpy change of the reaction (J mol–1)

T = temperature in kelvin

‘System’ is the species that are taking part in a reaction. ΔSsystem is calculated using the expression:

If Δstotal is positive, the reaction is thermodynamically feasible (thermodynamically spontaneous).

Eventhough a given reaction is thermodynamically feasible, it does not say that the reaction will occur or
not. This is because some reactions have a high activation energy
Questions
Effect of temperature on feasibility
If the reaction involves an increase in entropy of the system (∆Ssystem is +ve), then increasing temperature
will make the -∆H/T have a smaller magnitude and it will more likely that ∆Stotal will be positive and more
likely that the reaction occurs

If the reaction involves a decrease in entropy (∆Ssystem is -ve) then increasing the temperature make it more
less likely that ∆Stotal will be positive because the -∆H/T will have a smaller magnitude and will be less
likely to compensate for the negative ∆Ssystem. It will be less likely for the reaction to occur.

Question and answer

Calculate the ∆Stotal for the change of water into ice at 5 0C and -5 0C.

At 5 0C:
∆Ssystem = (47.9 – 69.9) = -22.0 JK-1mol-1
−6010
∆Ssurroundings = - = +21.6 JK-1mol-1
278

∆Stotal = -0.4 JK-1mol-1

Total entropy change is negative. Hence the change is not thermodynamically spontaneous.
At -5 0C:
∆Ssystem = (47.9 – 69.9) = -22.0 JK-1mol-1
−6010
∆Ssurroundings = - = +22.4 JK-1mol-1
268
∆Stotal = +0.4 JK-1mol-1
Total entropy change is positive. Hence the change is thermodynamically spontaneous. The water will
freeze.

Free Energy
The tendency of a process to take place is dependent on three things — the entropy, the enthalpy, and the
temperature.
When you put all these things together you get the free energy change, ∆G.
∆G tells you if a reaction is feasible or not — the more negative the value of ∆G, the more feasible the
reaction.
For feasible reactions ∆G must be negative or zero

∆H = enthalpy change (in J mol–1)

T = temperature (in K)
∆Ssystem = entropy change of the system (in J K–1 mol–1)
The units of ∆G is often Jmol-1

When ∆G = 0, the reaction is just feasible. So the temperature at which the reaction becomes feasible can be
calculated by rearranging the equation like this:
∆H – T ∆Ssystem = 0
Feasible Reversible Reactions
An equilibrium constant is a measure of the ratio of the concentration of products to reactants at equilibria
for a reversible reaction at a specific temperature.
Reactions with negative ∆G, and so are theoretically feasible, have large values for their equilibrium
constants — greater than 1.
Reactions with positive ∆G, and so not theoretically feasible, have small values for their equilibrium
constants — smaller than 1.
This relationship is represented by the equation:

R = gas constant, 8.31 J K–1 mol–1

T = temperature (in K)
ln K = the natural log of the equilibrium constant

Questions
Standard lattice energy (∆LEH0)
The enthalpy change when 1 mole of an ionic solid is formed from its gaseous ions under standard
conditons.
The standard lattice energy is a measure of ionic bond strength. The more negative the lattice energy, the
stronger the bonding.
E.g. out of NaCl and MgO, MgO has stronger bonding

Standard enthalpy change of atomisation (∆atH0)

The enthalpy change measured at standard conditions when 1 mole of gaseous atoms is formed from the
element in its standard state.

First electron affinity (1st EA)

The enthalpy change when 1 mol of electrons are added to 1 mol of neutral gaseous atoms to form 1 mol of
gaseous 1- ions.

The first electron affinity is exothermic for atoms that normally form negative ions because the ion is more
stable than the atom and there is an attraction between the nucleus and the electron.
First Electron affinity values will become less exothermic as you go down Group 7 from chlorine to iodine
because the atoms get bigger and have more shielding. So it becomes less easy to attract electrons to the
atom to form the negative ion.

Second electron affinity (2nd EA)

The enthalpy change when 1 mol of electrons are added to 1 mol of gaseous 1- ions to form 1 mol of
gaseous 2- ions.

The second electron affinity for oxygen is endothermic because it takes energy to overcome the repulsive
force between the negative ion and the electron being added.

Standard enthalpy change of formation (∆f H0)

The enthalpy change when 1 mole of the compound is formed from its elements under standard conditions.
First ionisation energy (1st IE)
The enthalpy change to remove 1 mole of electrons from 1 mole of gaseous atoms to form 1 mole of gaseous
1+ ions.

Second ionisation energy (2nd IE)

The enthalpy change to remove 1 mol of electrons from 1 mol of gaseous 1+ ions to form 1 mol of gaseous
2+ ions.

Factors affecting the magnitude of lattice energy

1. The sizes of the ions:
The smaller the ionic radii of the ions involved, the more exothermic (more negative) the lattice energy.
Smaller ions have a higher charge density and their smaller ionic radii mean that the ions can sit closer
together in the lattice. Both these things mean that the attractions between the ions are stronger
Eg:- The lattice enthalpies become less negative down any group. e.g. LiCl, NaCl, KCl, RbCl

2. The charges on the ion:

The higher the charge on the ions, the more energy is released when an ionic lattice forms. This is due to the
stronger electrostatic forces between the ions.
More energy released means that the lattice energy will be more negative.
Lattice energies for compounds with 2+ or 2– ions (e.g. Mg2+ or S2–) are more exothermic than those with 1+
or 1– ions (e.g. Na+ or Cl–).

Born-Haber cycle
The lattice energy cannot be determined directly. We calculate it indirectly by making use of changes for
which data are available and link them together in an enthalpy cycle called the Born -Haber cycle.
Questions
Theoretical and experimental lattice energy
There are two ways to work out a lattice energy:
• the experimental way — using experimental enthalpy values in a Born-Haber cycle
• the theoretical way — doing some calculations based on the purely ionic model of a lattice.

To work out a theoretical lattice energy, you assume that all the ions are spherical and have their charge
evenly distributed around them — a purely ionic lattice. Then you work out how strongly the ions are
attracted to one another based on their charges, the distance between them and so on. That gives you a value
for the energy change when the ions form the lattice.

Why Theoretical lattice energy and Born Haber (experimental) lattice energy differ?
For any one compound, the experimental and theoretical lattice energies are usually different. How different
they are tells you how closely the lattice actually resembles the ‘purely ionic’ model used for the theoretical
calculations.
The more the covalent character the bigger the difference between the experimental and theoretical lattice
energy values.
When a compound has some covalent character- it tends towards forming giant covalent structure. So the
lattice is stronger than if it was 100% ionic.
In a sodium halide, e.g. NaCl, the cation, Na+, has only a small charge (+1) so it can’t really pull electrons
from the anion towards itself — so the charge is distributed evenly around the ions (there’s almost no
polarisation).
That’s why the theoretical calculations of lattice energy match the experimental ones so well for sodium
halides.
However, the magnesium halides don’t fit the ionic model quite so well, because charge isn’t evenly
distributed around the ions — the cation, Mg2+, has a bigger charge (+2), so it can pull electrons from the
anion towards itself a bit, polarising the bond.
In general, the greater the charge density of the cation , the poorer the match will be between experimental
and theoretical values for lattice energy.

Polarisation
The covalency in bonding is caused by polarisation of the anion by the cation.
Polarisation results in distortion of the electron density within the anion, resulting in a higher electron
density near the cation.

When 100 % ionic the ions are

Anion is polarized. The theoretical and
spherical. The theoretical and the born
the experimental Born Haber lattice
Haber lattice enthalpies will be the
enthalpies will differ.
same.

The polarising power of cation increases when

• the positive ion is small High charge density of the cation
• the positive ion has high charge
Eg:- The charge density of Mg2+ is larger than Na+. This results in greater polarisation of the Cl- in MgCl2
than in NaCl. Hence, MgCl2 shows more covalent character than NaCl.

The polarizability of an anion increases when

• the anion is large
• the anion has high charge
Eg:- I- ion is more easily polarised than F- ion. Hence, AgI shows more covalent character than AgF.

Pauling values can be used to work out how polar a covalent bond is.
The greater the difference in electronegativity, the greater the shift in electron density, and the more polar
the bond. Bonds are polar if the difference in Pauling electronegativity values is more than about 0.4.

Questions

Dissolving
When a solid ionic lattice dissolves in water these two things happen:
1) The bonds between the ions break — this is endothermic. The enthalpy change here is the opposite of the
lattice enthalpy. It also increases the entropy of the system (more disorder) due to increased number of
particles.

2) Bonds between the ions and the water are made — this is exothermic. The enthalpy change here is called
the enthalpy change of hydration. The negative ions are attracted to the δ+ hydrogens on the polar water
molecules and the positive ions are attracted to the δ - oxygen on the polar water molecules (ion-dipole
interaction). The entropy of the system decreases due to water molecules becoming more ordered as they
arrange themselves in an orderly manner around the positive and negative ions.

The enthalpy change of solution is the overall effect of these two things.
Enthalpy change of solution (∆solH)
Enthalpy change when one mole of an ionic solid dissolves in water to form an infinitely dilute solution.
(dissolve in large amount of water to ensure that the dissolved ions are well separated and do not interact
with one another)

Enthalpy change of solution cannot be determined experimentally.

∆solH can be either negative or positive.

Enthalpy change of hydration (∆hydH)

Enthalpy change when one mole of gaseous ions is completely hydrated by water (infinitely diluted).

Hydration enthalpies are exothermic.

The two things that can affect the lattice energy can also affect the enthalpy of hydration. They are the
- size
- charge of the ions
E.g. Fluoride ions have more negative hydration enthalpies than chloride ions
a magnesium ion is smaller and more charged than a sodium ion, which gives it a much more negative
enthalpy of hydration

Questions
Relationship between ∆solH, ∆hydH and ∆LEH

Question and answer

Draw an energy level diagram to show the relationship between ∆solH, ∆hydH and ∆LEH of NaCl salt when
dissolved in water.

Why some ionic solids are soluble and some are insoluble?
The solubility of an ionic solid is determined by the total entropy change for the solid.

According to this equation, the solubility of the solid depends on the following factors.
a) ∆Ssystem
b) ∆solH
c) Temperature
If ∆Stotal is positive, then the ionic solid will dissolve in water. The process is said to be thermodynamically
spontaneous.