LATTICE ENERGY

BY MEHRUNNISA QAISAR
SHORT NOTES

 Lattice energy is the enthalpy change when 1 mole of an ionic compound is formed from its gaseous ions under standard
conditions.
■ it is the gaseous ions that combine to form the ionic solid
■ the lattice energy is always exothermic: the value of H latt is always negative, because the definition specifies the bonding
together of ions, not the separation of ions.
 The standard enthalpy change of atomisation, H at, is the enthalpy change when 1 mole of gaseous atoms is formed from its
element under standard conditions.
 A Born–Haber cycle is a particular type of enthalpy cycle used to calculate lattice energy.
 We can determine the lattice energy of a compound if we know:

■ its enthalpy change of formation.

■ the enthalpy changes involved in changing the elements from their standard states to
their gaseous ions.
SHORT NOTES

 The Born–Haber cycle as an energy level diagram

 To draw the cycle you:

■ start by putting down the elements in their standard state on the left-hand side
■ add the other enthalpy changes in the order of steps 1 to 4 shown in Figure 19.4
■ complete the cycle by adding the enthalpy change of formation and lattice energy.
 SHORT NOTES
 Factors affecting the value of lattice energy

1. As the size of the ion increases, the lattice energy becomes less exothermic, for ions with similar charges a lower charge density results in weaker
electrostatic forces of attraction in the ionic lattice
2. The lattice energy becomes more exothermic as the ionic charge increases, for ions of similar size, the greater the ionic charge, the higher the charge
density. This results in stronger ionic bonds being formed.
 the positive charge on the cation in an ionic lattice may attract the electrons in the anion towards it. This results in a distortion of the electron cloud of
the anion and the anion is no longer spherical which is known as ion polarisation.
 The ability of a cation to attract electrons and distort an anion is called the polarising power of the cation
 The degree of polarisation of an anion depends on:

■ the charge density of the cation

■ the ease with which the anion can be polarised – its polarisability.
 An anion is more likely to be polarised if:

■ the cation is small

■ the cation has a charge of 2+ or 3+
■ the anion is large
■ the anion has a charge of 2– or 3–.
SHORT NOTES

 The thermal stability of Group 2 carbonates and nitrates

1. The more positive the enthalpy change, the more stable the carbonate relative to its oxide and
carbon dioxide.
2. the further down the group, the higher the temperature required to decompose the carbonate
3. the carbonate ion has a relatively large ionic radius so it is easily polarised by a small highly charged cation
4. the Group 2 cations increase in ionic radius down the group: Mg2+ < Ca2+ < Sr2+ < Ba2+
5. the smaller the ionic radius of the cation, the better it is at polarising the carbonate ion
6. so the degree of polarisation of the carbonate ion by the Group 2 cation follows the order Mg2+ > Ca2+ > Sr2+ > Ba2+
7. the greater the polarisation of the carbonate ion, the easier it is to weaken a carbon–oxygen bond in the carbonate and form carbon
dioxide and the oxide on heating
 A similar pattern is observed with the thermal
decomposition of Group 2 nitrates
 SHORT NOTES
 The enthalpy change of solution, ΔHsol, is the energy absorbed or released when 1 mole of an ionic solid dissolves in sufficient
water to form a very dilute solution.
■ the symbol for enthalpy change of solution is ΔHsol
■ the symbol ‘aq’ represents the very large amount of water used
■ enthalpy changes of solution can be positive (endothermic) or negative (exothermic)
■ a compound is likely to be soluble in water only if ΔHsol is negative or has a small
positive value; substances with large positive values of ΔHsol are relatively insoluble.
 The enthalpy change of hydration, ΔHhyd, is the enthalpy change when 1 mole of a
specified gaseous ion dissolves in sufficient water to form a very dilute solution.
■ the symbol for enthalpy change of hydration is ΔHhyd
■ the enthalpy change of hydration is always exothermic
■ the value of ΔHhyd is more exothermic for ions with the same charge but smaller
ionic radii, e.g. ΔHhyd is more exothermic for Li+ than for Na+
■ the value of ΔHhyd is more exothermic for ions with the same radii but a
larger charge, e.g. ΔHhyd is more exothermic for Mg2+ than for Li+ .
 SHORT NOTES
 The solubility of Group 2 sulfates decreases as the radius of the metal ion increases.
■ Smaller ions (with the same charge) have greater enthalpy changes of hydration
■ so the enthalpy change of hydration decreases (gets less exothermic) in the order Mg2+ > Ca2+ > Sr2+ > Ba2+
■ this decrease is relatively large down the group and it depends entirely on the increase in the size of the cation, as the anion is unchanged (it is the sulfate ion in
every case).
■ Lattice energy is greater if the ions (with the same charge) forming the lattice are small
■ so the lattice energy decreases in the order Mg2+ > Ca2+ > Sr2+ > Ba2+
■ the lattice energy is also inversely proportional to the sum of the radii of the anion and cation
■ the sulfate ion is much larger than the group 2 cations
■ so the sulfate ion contributes a relatively greater part to the change in the lattice energy down the group
■ so the decrease in lattice energy is relatively smaller down the group and it is determined more by the size of the large sulfate ion than the size of the cations.
■ the lattice energy of the sulfates decreases (gets less exothermic) by relatively smaller values down
the group
■ the enthalpy change of hydration decreases (gets less exothermic) by relatively larger values down the
group
■ so applying Hess’s law, the value of ΔH —O sol gets more endothermic down the group
■ so the solubility of the Group 2 sulfates decreases down the group.
ENTROPY AND GIBBS FREE ENERGY
BY MEHRUNNISA QAISAR
 ENTROPY
 Entropy is a measure of the dispersal of energy at a specific temperature.
 Entropy can also be thought of as a measure of the randomness or disorder of a system.
 The higher the randomness or disorder, the greater the entropy of the system.
 A system is the part under investigation.
 The system of magnesium reacting with sulfuric acid in a test tube to form magnesium sulfate and hydrogen releases energy to the surroundings.
 The surroundings include:
■ the solvent (in this case water)
■ the air around the test tube
■ the test tube itself
■ anything dipping into the test tube (e.g. a thermometer)
 Changes that tend to continue to happen naturally are called spontaneous changes
 Chance and spontaneous change reactions involve diffusion, in which the movement of particles depend upon probability and chance and they simply move because there is
a high probability of it happening due to the energy in the particles present.
 To make any comparison of entropy values fair, we must use standard conditions. These standard conditions are the same as those used for ΔH:
■ a pressure of 10^5Pa
■ a temperature of 298K (25 °C)
■ each substance involved in the reaction is in its normal physical state (solid, liquid or gas) at 105Pa and 298K
 Standard molar entropy is the entropy of one mole of substance in its standard state. The values of all standard molar entropies are positive
 ENTROPY
 Gases generally have much higher entropy values than liquids, and liquids have higher entropy values than solids.
 Simpler substances with fewer atoms have lower entropy values than more complex substances with a greater number of atoms.
 For similar types of substances, harder substances have a lower entropy value.
 For a given substance the entropy increases as a solid melts and then changes to a vapour.
 When a solid changes to a liquid:
■ the regularly arranged lattice of particles close together in the solid changes to
■ an irregular arrangement of particles, which are close together but rotate and slide over each other in the liquid.
 When a liquid changes to a vapour:
■ the irregular arrangement of particles in the liquid which are close together and rotating changes to
■ an irregular arrangement of particles, which are free to move around rapidly because they are far apart from each other.
 If there is a change in the number of gaseous molecules in a reaction, there is likely to be a significant entropy change.
 The more gas molecules, there are, the greater is the number of ways of arranging them and the higher the entropy.
2N2O5(g) 4NO2(g) + O2(g)
 we should expect an increase of entropy of the system because there are a greater number of moles of gas molecules in the products (5 molecules) than in the
reactants (2 molecules). In addition, there are two different product molecules but only one type of reactant molecule.
N2(g) + 3H2(g) 2NH3(g)
 we should expect a decrease in the entropy of the system because there is a reduction in the number of gas molecules as the reaction proceeds.
 ENTROPY CALCULATIONS
 We can use entropy values to predict whether a chemical reaction will occur spontaneously or not.
 The total entropy change involves both the system and the surroundings.
 If the total entropy change increases, the entropy change is positive, e.g. ΔS total is +40 JK–1mol–1 . The reaction will then occur spontaneously. We say that the
reaction is feasible.
 If the total entropy change decreases, the entropy change is negative, e.g. ΔS total is –40 JK–1mol–1. The reaction is then not likely to occur.
 Note that:
1. We need to take account of the stoichiometry of the equation (as we did in calculations involving ΔH).
2. When looking up entropy values in tables of data, we need to choose the data for the correct state, solid, liquid or gas.
 The entropy change of the surroundings is calculated using the relationship:
 Where:
■ ΔH reaction is the standard enthalpy change of the reaction
■ T is the temperature in kelvin. At standard temperature, this value is 298K.
 Note:
1. When performing calculations to find ΔS surroundings the value of ΔH reaction in kJmol–1 should be multiplied by 1000. This is because entropy changes are
measured in units of joules per kelvin per mole.
2. The negative sign in front of ΔH reaction is part of the equation and not the sign of the enthalpy change. If the enthalpy change is negative, the whole –ΔH /T term
becomes positive.
 At the position of equilibrium the total entropy change of the forward reaction equals the total entropy change of the backward reaction, and under standard
conditions the overall entropy change is zero.
 GIBBS FREE ENERGY
 In determining whether a chemical reaction is likely to be spontaneous we use the quantity Gibbs free energy change, ΔG. The Gibbs free
energy change is given by the relationship:
 We can also write the expression without having to consider the entropy changes of the surroundings:
 Where T is the temperature in kelvin
 To make any comparison of Gibbs free energy values fair, we must use standard conditions.
 The standard molar Gibbs free energy of formation is the free energy change that accompanies the formation of one mole of a compound
from its elements in their standard state
 The symbol for standard molar Gibbs free energy of formation is ΔG —O f . The units are kJmol–1
 For a reaction to be spontaneous, ΔS total must be positive. Thus If the value of ΔG is negative.
 If the value of ΔG is positive, the reaction is not spontaneous.
 standard Gibbs free energy change of formation of an element is zero
 The standard Gibbs free energy change of reaction is the Gibbs free energy change when the
amounts of the reactants shown in the stoichiometric equation react under standard conditions to
give products. The reactants and products must be in their standard states
 Gibbs free energy change can be thought of as part of the enthalpy change that is needed to
GIBBS FREE ENERGY

 The method of calculating Gibbs free energy change of

reaction uses an energy cycle
 To calculate the Gibbs free energy change of
reaction from an energy cycle like this, we use
the following procedure:
■ write the balanced equation at the
top
■ draw the cycle with the elements at
the bottom
■ draw in all arrows making sure that
they go in the correct directions
■ calculate ΔG reaction = ΔG2 – ΔG1
taking into account the number of moles of
reactants and products.
 GIBBS FREE ENERGY
 Gibbs free energy of formation is a measure of the stability of a compound.
 The more negative the value of ΔG f , the greater the stability of the compound.
 It is unlikely to decompose. If ΔG f is positive.
 the compound is likely to be unstable with respect to its elements.
 The Gibbs free energy change of reaction is also a measure of the feasibility of a reaction.
 Reactions with negative values of ΔG reaction are likely to be feasible (spontaneous).
 Those with positive values are less likely to be spontaneous.

■ When a system is in chemical equilibrium and the amounts of products and reactants balance, the value of ΔG reaction is zero (ΔG
reaction = 0).
■ The products predominate if the value of ΔG reaction has a fairly low negative value, e.g. –10 kJmol–1.
■ The reactants predominate if the value of ΔG reaction has a slightly positive value, e.g. +10 kJmol–1.
■ The reaction can be regarded as complete if the value of ΔG reaction is high and negative, e.g. –60 kJmol–1.
■ The reaction can be regarded as not being feasible (spontaneous) at all if the value of ΔG reaction is high and positive, e.g. +60
kJmol–1.