15.

2 Born-Haber Cycle
15.2.1 Define and apply the terms lattice enthalpy, and electron affinity 15.2.2 Explain how the relative sizes and the charges of ions affect the lattice enthalpies of different ionic compounds The relative value of the theoretical lattice enthalpy increases with higher ionic charge and smaller ionic radius due to increased attractive forces 15.2.3 Construct a Born-Haber cycle for group 1 and 2 oxides and chlorides and use it to calculate the enthalpy change 15.2.4 Discuss the difference between theoretical and experimental lattice enthalpy values of ionic compounds in terms of their covalent character.

Born-Haber Cycle
A series of hypothetical steps and their

enthalpy changes needed to convert elements to an ionic compound and devised to calculate the lattice energy. Using Hesss law as a means to calculate the formation of ionic compounds

Born-Haber Cycle Steps

1. Elements (standard state) converted

into gaseous atoms 2. Losing or gaining electrons to form cations and anions 3. Combining gaseous anions and cations to form a solid ionic compound

Step 1: Atomisation
The standard enthalpy change of

atomisation is the H required to produce one mole of gaseous atoms Na(s) Na(g) Hoat = +109 kJmol-1

 NOTE: for diatomic gaseous elements,

Cl2, Hoat is equal to half the bond energy (enthalpy) Cl2(g) Cl(g) Hoat = E (Cl-Cl) Hoat = (+242 ) Hoat = +121 kJmol-1

Step 2: Formation of gaseous ions

Electron Affinity Enthalpy change when one mole of gaseous atoms or anions gains electrons to form a mole of negatively charged

gaseous ions.
Cl(g) + e- Cl-(g) Ho = -364 kJmol-1

For most atoms = exothermic, but gaining a 2nd electron is endothermic due to the repulsion between the anion and the electron

Becoming cations
Ionisation energy

Enthalpy change for one mole of a gaseous element or cation to lose electrons to form a mole of positively charged gaseous ions

Na(g) Na+(g) + e-

IE1= +494 kJmol-1

Lattice Enthalpy
Energy required to convert one mole of

the solid compound into gaseous ions. NaCl (s) Na+(g) + Cl-(g) Holat = +771kJmol-1 It is highly endothermic We cannot directly calculate Holat , but values are obtained indirectly through Hesss law for the formation of the ionic compound

Calculations
Calculate the lattice energy of NaCl(s)

using the following: (kJmol-1)

Enthalpy of formation of NaCl = - 411 Enthalpy of atomisation of Na = +109 Enthalpy of atomisation of Cl = +121 Electron affinity of Cl = - 364 Ionisation energy of Na = + 494

Enthalpy of atomisation + electron

affinity + ionisation = enthalpy of formation + lattice energy

Magnitude of Lattice enthalpy

The greater the charge on the ions, the

greater the electrostatic attraction and hence the greater the lattice enthalpy Ex: Mg2+ > Na+ The larger the ions, then the greater the separation of the charges and the lower the lattice enthalpy VICE VERSA

Trends
Holat
MgO NaCl KBr 3889 771 670

Change from NaCl

Increased ionic charge -----Larger ions

Use of Born-Haber Cycles

Empirical value of Holat is found using

Born-Haber cycle. Theoretical value of Holat can be found by summing the electrostatic attractive and repulsive forces between the ions in the crystal lattice.

Compound
NaCl KBr KI AgCl

Empirical value Theoretical value 771 766

670 632 905 667 631 770

Agreement
Usually there is good agreement

between empirical and theoretical values If there isnt good agreement

Implying that the description of the compound as ionic is inappropriate There could be a significant degree of covalent character in the bonding (EN difference less than 1.7) Presence of covalent character leads to an increase in Holat