Lattice Energy

Lattice Energy
Energy given out when ions of opposite charges come together to form a crystalline lattice.
Arises from the electrostatic force of attraction of oppositely charged ions when the
crystalline lattice is formed.
Enthalpy change when 1 mole of an ionic compound is formed from its gaseous ions under
standard conditions.
Internal energy change when 1 mole of an ionic compound is formed from its gaseous ions
at 0K.
 Symbol - ΔHөlatt
Always exothermic because the definition specifies the binding of ions. Bonding of ions is
always exothermic.
 The larger the ΔHөlatt value, the more stable the lattice.
 Can be determined by using Born-Haber cycle.
Enthalpy Change of Atomisation
 Enthalpy change of atomization is the enthalpy change when 1 mole
of gaseous atoms is formed from its element under standard
conditions.
 Symbol, ΔHөat. The value is always positive (endothermic). Energy
needed to break the bonds holding the atoms in the element
together.
 Electron Affinity
 Energy change occurring when a gaseous non-metal atoms accepts on electron.
 Symbol, ΔHөea.
 May have more than one electron affinity depending on the charge of the element.
First electron affinity (ΔHөea1) is the enthalpy change when 1 mole of electrons is added to 1 mole of
gaseous atoms to form 1 mole of gaseous 1- ions under standard conditions. It is always exothermic
i.e negative.
 Eg; Cl(g) + e-  Cl- (g) ΔHөea= -348 kJmol-1
Second electron affinity (ΔHөea2) (ΔHөea1) is the enthalpy change when 1 mole of electrons is added
to 1 mole of gaseous 1- ions to form 1 mole of gaseous 2- ions under standard conditions. Second
and third ΔHөea are always endothermic i.e the values are positive.
It is always endothermic because electron is added to an ion which is already negative. Therefore, it
must overcome the repulsion. In order to overcome the electrostatic repulsion energy, energy must
be added in. Thus, it is endothermic.
Eg; O(g) + e-  O- (g) ΔHөea1 = -141 kJmol-1
Eg; O-(g) + e-  O2- (g) ΔHөea1 = +798 kJmol-1
Born-Haber cycles
 Enthalpy cycle used to calculate lattice energy.
 Eg; Steps:
1. Change other state (liquid and solid)
to gas. (ΔHөat)
2. Change the gaseous element(s) to
their respective charge (positive).
(ΔHөi1)
3. Change the gaseous element(s) to
their respective charge (negative).
(ΔHөea1)
4. Addition of these values = ΔHө1.
5. Δhөlatt = ΔHөf – ΔHө1
Examples
Calculate the lattice energy for sodium chloride given that:
ΔHөf [NaCl] = -411 kJmol-1
ΔHөat [Na] = +107 kJmol-1
ΔHөat [Cl] = +122 kJ mol-1
ΔHө11 [Na] = +496 kJmol-1
ΔHөea [Cl] = -348 kJmol-1
Born-Haber Cycle. Energy Level Diagram
 Eg; Lattice energy of NaCl.
Steps :
1. LHS – Elements in their
standard state.
2. Change the standard state
to gas i.e. ΔHөat(cation) (going
up).
3. ΔHөie  ΔHөat(anion)  ΔHөea
(endo) ΔHөlatt (endo)
4. Final  Product in standard
state.
Born-Haber Cycle of MgCl
• ΔHөi1 [Mg] = +736kJ/mol
• ΔHөi2 [Mg]= +1450kJ/mol
• ΔHөat [Cl] = +122kJ/mol
• ΔHөea1 [Cl] = -348kJ/mol
• ΔHөf [MgCl2] = +736kJ/mol
• Δhөat[Mg] = +148kJ/mol
Born-Haber Cycle of Al2O3
• ΔHөi1 [Al] = +577kJ/mol
• ΔHөi2 [Al]= +1820kJ/mol
• ΔHөi3 [Al]= +2470kJ/mol
• ΔHөat [Al] = +326kJ/mol
• ΔHөea1 [O] = -141kJ/mol
• ΔHөea2 [O] = +798kJ/mol
• ΔHөat[O] = +249kJ/mol
• ΔHөf [Al2O3] = -1676kJ/mol
Factors affecting the value of lattice energy
1. SIZE OF IONS
 ION size INCREASES, lattice energy become LESS EXOTHERMIC i.e
INCREASES. (both anions and cations)
 CATION  going down the group SIZE INCREASES  lattice energy LESS
EXOTHERMIC.
 ANION  going down the group SIZE INCREASES  lattice energy LESS
EXOTHERMIC.
 STATEMENT : NaF has a less exothermic lattice energy than LiF
 REASONS : SAME IONIC CHARGE have lower charge density as their
radius is larger. The charge spreads out over a large volume. LOWER
CHARGE DENSITY results in WEAKER ELECTROSTATIC FORCES of attraction
in the ionic lattice. Thus, Na+ has lower charge density compared to Li+.
 Factors affecting the value of lattice energy
2. CHARGE OF IONS
 ION CHARGE INCREASES, LATTICE ENERGY BECOMES MORE EXOTHERMIC
 Example : LiF and MgO
 Explanation :
1. Both have the same arrangement of ions in the lattice structure.
2. Both cations of Li+ and Mg2+ have similar sizes.
3. Both anions of F- and O2- have similar sizes.
4. The physical difference between LiF and MgO is the ionic charge.
5. Doubly charged of Mg2+ and O2- ions attract each other more strongly compared
to singly charged Li+ and F-.
6. For ions WITH SIMILAR SIZES, THE GREATER THE IONIC CHARGE, THE HIGHER
THE CHARGE DENSITY, STONGER IONIC BONDS FORMED AND LATTICE ENERGY
INCREASES.
 ION POLARISATION
 ION POLARISATION – Attraction of electrons in the anion towards cation due to the positive charge of
cation in an ionic lattice. This causes distortion of the electron cloud of the anion and is no longer spherical.
 POLARISING POWER of cation – Ability of a cation to attract electrons and distort an anion.
 POLARISABILITY – the ease with which the anion can be polarized.
 Factors affecting ion polarization Small and highly charged
1. Charge density of cation cation e.g Fe 3+
can attract
electrons and distort a larger
2. Polarisability
anion to such an extent that
 Anion is likely polarized if : the bond formed has a
1. Cation is small considerable amount of
2. Cation has charge of +2 or +3 covalent character.
3. Anion is large
4. Anion has charge of 2- or 3-
 Many ionic compounds have some covalent character due to polarization.
 Many covalent compounds have some degree of charge separation i.e polar due to bond polarization.
 Thermal Stability of Group 2 CO3 and NO3
 G2 carbonates decomposes to oxides and CO2 upon heating.
 Example : CaCO3 (s)  CaO(s) + CO2(g) , ΔHөr
 The more positive the enthalpy change, the more stable the carbonates compared to its oxide
and CO2.
 The further down the group, the higher the temperature required to decompose the
carbonates.
 Thus STABILITIES OF CARBONATES INCREASES DOWN THE GROUP.
 Carbonate ion has large ionic radius so it is easily polarised by a small highly charged cation.
Going down G2, ionic radius increases. The smaller the ionic radius, the better at polarising
carbonate ion. The greater the polarisation of carbonate ion, the easier to weaken a carbon-
oxygen bond in the carbonate and form CO2 and the oxide upon heating. Thus, less stable.
 Similar pattern is observed with G2 Nitrates.
The difference in the stability of G2 carbonates can be analysed by comparing Born-Haber cycles
between CaCO3 and CaO. The unequal changes in the lattice energies between CaCO3 and CaO
results in increasing thermal stability.
Enthalpy changes in solution
 Enthalpy change of solution ΔHөsol  Energy absorbed or released when 1 mole
of an ionic solid dissolves in sufficient water to form a very dilute solution.
Example :
MgCl2(s) + aq  MgCl2(aq) OR MgCl2(s) + aq  Mg2+(aq) + 2Cl- (aq)
ΔHөsol = -55kJ/mol
 aq  very large amount of water used
 ΔHөsol can be endo or exo.
 A compound soluble in water only if ΔHөsol is negative or has a small positive
value. Large positive values are relatively insoluble.
 Enthalpy changes of hydration
 Enthalpy change when 1 mole of a specified gaseous ions dissolves in sufficient
water to form a very dilute solution.
 ΔHөhyd is always exothermic.
ΔHөlatt [NaCl] = -788kJ/mol and ΔHөsol = +3.9kJ/mol.
 Where does the energy needed to separate the ions come from?
 Answer : Strong attraction between the ions and the water molecules.
 Ionic solid dissolves in water, bonds are formed between water molecules and the
ions. These bonds are called ion-dipole bonds.
 Water is polar molecule. δ- Oxygen atoms in water molecule attracted to cation in
the ionic compound and δ+ hydrogen atoms in water molecules are attracted to the
anion in the ionic compounds.
 Energy released in forming ion-dipole bond compensate the energy that must be
put in to separate the anions and cations that are bonded together in crystal
lattice.
 ΔHөhyd more exothermic for ions with the same charge but smaller ionic radii.
(ΔHөhyd ↑ going up the group)
 ΔHөhyd more exothermic for ions with the same radii but larger charge. (ΔHөhyd ↑
charge increases)
Calculating enthalpy changes in solution
 ΔHөlatt + ΔHөsol = Δhөhyd
 ΔHөhyd  Addition of both ΔHөhyd (cat) and ΔHөhyd (ani)
Question
Draw the enthalpy cycle, energy level diagram and determine the
enthalpy change of solution of NaF.
ΔHөlatt = -902kJ/mol
ΔHөhyd [Na] = -406kJ/mol
ΔHөhyd [F] = -506kJ/mol
The solubility of Group 2 Sulfates
 Solubility decreases as the radius of the metal ion increases i.e. going
down the group.
 Lattice energy of sulfate decreases down the group.
 Smaller ions (with the same charge) have higher ΔHөhyd. Thus, going up
G2, the ΔHөhyd increases. ΔHөlatt also increases going up G2.
 Lattice energy is inversely proportional to the sum of the radii of the
anion and cation.
 Sulfate ion is much lager than G2 cations. Thus, it contributes a greater
part to the change in the lattice energy down the group compared to the
lattice energy of G2.