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 Hess’s 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 ΔH required to
produce one mole of gaseous atoms
• Na(s)  Na(g) ΔHoat = +109 kJmol-1
• NOTE: for diatomic gaseous elements, Cl2,
ΔHoat is equal to half the bond energy
(enthalpy)
• Cl2(g)  Cl(g) ΔHoat = ½ E (Cl-Cl)
ΔHoat = ½ (+242 )
ΔHoat = +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) ΔHo = -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) ΔHolat =
+771kJmol-1
• It is highly endothermic
• We cannot directly calculate ΔHolat , but values
are obtained indirectly through Hess’s 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
ΔHolat Change from NaCl

MgO 3889 Increased ionic charge

NaCl 771 ------

KBr 670 Larger ions

 Use of Born-Haber Cycles
• Empirical value of ΔHolat is found using Born-
Haber cycle.
• Theoretical value of ΔHolat can be found by
summing the electrostatic attractive and
repulsive forces between the ions in the
crystal lattice.
Compound Empirical value Theoretical value

NaCl 771 766

KBr 670 667

KI 632 631

AgCl 905 770

 Agreement
• Usually there is good agreement between
empirical and theoretical values
• If there isn’t 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 ΔHolat