Energetics –

Enthalpy Calculations – Solutions

 Enthalpy Calculations – Solutions
Dissolution of Ionic Compounds
• When an ionic solid dissolves, the following processes occur:

1. Lattice
Dissociation
NaCl (s) Na+ (g) + Cl– (g)
– ΔHlatt

 2. Hydration or
ΔHhyd




Overall: ΔHsol
Solvation
Dissolution

Na+ (aq) + Cl– (aq)



Thus, ΔHsol = – ΔHlatt + ΔHhyd

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 Enthalpy Calculations – Solutions
Enthalpy of Solution
• Recall: Standard Enthalpy of Solution ( ΔHsol ) [aka Heat of Solution] is


the enthalpy change when 1 mole of a solute dissolves in a solvent to
form an infinitely dilute solution under standard conditions
• E.g. NaCl (s) + water  Na+ (aq) + Cl– (aq); ΔHsol = +4 kJ mol


–1

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 Enthalpy Calculations – Solutions
Lattice Dissociation
• When an ionic solid dissolves, the following processes occur:
1. Lattice Dissociation
– The ions separate from each other
– This is an endothermic process because bonds are being broken
– This process has an enthalpy change (lattice dissociation energy)
equal in magnitude but opposite in sign to lattice energy

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 Enthalpy Calculations – Solutions
Lattice Energy
• Recall: Lattice Energy ( ΔHlatt ) is the enthalpy change when 1 mole


of an ionic solid is formed from its gaseous ions under standard
conditions
• E.g. Na+ (g) + Cl– (g)  NaCl (s);


ΔHlatt = –787 kJ mol–1
• All lattice energies are negative since bonds are being formed. No
bonds are being broken.
• Recall that since lattice energy is a measure of the strength of
interionic attraction, the magnitude of the lattice energy increases
– as the size of the ion decreases and
– as the charge on the ion increases

• Lattice Dissociation Energy has the same magnitude but opposite

sign to Lattice Energy as defined above
NaCl (s)  Na+ (g) + Cl– (g);


ΔHlattice dissociation = +787 kJ mol–1

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 Enthalpy Calculations – Solutions
Hydration or Solvation
2. Hydration or Solvation
– The separated ions become surrounded by water molecules
(hydration) or other solvent molecules (solvation)
– This is an exothermic process because bonds are being formed
with solvent molecules
– The total enthalpy change (enthalpy of hydration) for this
process is equal to the sum of the enthalpies of hydration for
the cations and the anions

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 Enthalpy Calculations – Solutions
Enthalpy of Hydration
• Recall: Standard Enthalpy of Hydration ( ΔHhyd ) is the enthalpy


change when 1 mole of gaseous ions is completely hydrated in
water to infinite dilution under standard conditions

• E.g. The enthalpy of hydration of NaCl is the sum of the enthalpies

of hydration of the cation and the anion:

Na+ (g) + water  Na+ (aq);


ΔHhyd = –406 kJ mol–1
Cl– (g) + water  Cl– (aq);


ΔHhyd = –377 kJ mol–1
• Thus, overall:
Na+ (g) + Cl– (g)  Na+ (aq) + Cl– (aq);

ΔHhyd = –783 kJ mol–1

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 Enthalpy Calculations – Solutions
Sign of ΔHsol


• The sign of ΔHsol depends on whether the energy released upon
hydration or solvation is greater or less than the energy that needs
to be absorbed for lattice dissociation
• If ΔHlatt > ΔHhyd , then


– ΔHsol is positive


– the dissolution is endothermic

– Energy must be supplied to dissolve the ionic solid
– The container will feel cool to touch


• If ΔHhyd > ΔHlatt , then

– ΔHsol is negative


– the dissolution is exothermic

– Energy is released when the ionic solid dissolves
– The container will feel warm to touch
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 Enthalpy Calculations – Solutions
Sign of ΔHsol

– ΔHlatt


endothermic
NaCl (s) Na+ (g) + Cl– (g)

ΔHhyd




ΔHsol = – ΔHlatt + ΔHhyd

+ve if ΔHlatt is greater exothermic
–ve if ΔHhyd is greater
Na+ (aq) + Cl– (aq)

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 Enthalpy Calculations – Solutions
Sign of ΔHsol – Example: NaCl

– ΔHlatt


–(–787 kJ mol–1)
NaCl (s) Na+ (g) + Cl– (g)
Or +787 kJ mol–1

ΔHhyd




ΔHsol = – ΔHlatt + ΔHhyd

= –(–787 kJ mol–1) + (–783 kJ mol–1) –783 kJ mol–1
= +4 kJ mol–1
Na+ (aq) + Cl– (aq)

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