Free Energy of Dissolution

Chemistry: Cambridge International A Level, topic 1.7.9

Free Energy of Dissolution

Dissolution is an example of a spontaneous process that occurs without the requirement of energy from some external source. The free energy change (ΔG°) of dissolution depends on many factors.

Spontaneity

Spontaneity

  • The formation of a solution is an example of a spontaneous process.
  • This is a process that occurs under specified conditions without the requirement of energy from some external source.
  • The topic of spontaneity covered more thoroughly in the application of thermodynamics section.
Factors favoring dissolution

Factors favoring dissolution

  • Factors that favor, but do not guarantee, the spontaneous formation of a solution include:
  1. A decrease in the internal energy of the system, so an exothermic change.
  2. An increased dispersal of matter in the system.
  • This indicates an increase in the entropy of the system, which will be discussed in a later section.
  • Dissolution requires a favorable free energy change (ΔG°).
  • A reaction that is exothermic and increases dispersal of matter is more likely to be favorable.
Steps involved in dissolution

Steps involved in dissolution

  • The dissolution of a solution involves several steps including:
  • Overcoming solute-solute interactions in the substance to be dissolved.
  • Rearrangement of solute and solvent molecules.
  • Formation of solute-solvent attractions once the substance is dissolved.
  • The relative magnitudes of the energy changes associated with these stepwise processes determine whether the dissolution process overall will release or absorb energy.
Dissolving ionic compounds

Dissolving ionic compounds

  • Dissolution of an ionic compound involves:
  • Overcoming the electrostatic forces between the cations and anions of the compound (solute–solute).
  • Establishment of attractive forces between these ions and water molecules (solute–solvent), which is called solvation.
  • Hydrogen bonding between water molecules must also be overcome.
Endothermic vs. exothermic

Endothermic vs. exothermic

  • If the solute’s electrostatic forces are greater than the solvation forces, the dissolution process is endothermic.
  • This means the compound may not dissolve to an appreciable extent.
  • Calcium carbonate, the major component of coral reefs, is an example of an “insoluble” ionic compound.
  • If the solvation forces are much stronger than the compound’s electrostatic forces, the dissolution is exothermic and the compound may be soluble.
  • A common example of this type of ionic compound is sodium chloride.
Endothermic vs. exothermic 2

Endothermic vs. exothermic 2

  • Spontaneous solution formation is favored, but not guaranteed, by exothermic dissolution processes.
  • Some compounds dissolve endothermically. An example is ammonium nitrate (NH4NO3).
  • Endothermic dissolutions such as this one require a greater energy input to separate the solute species than is recovered when the solutes are solvated.
  • However, they are spontaneous nonetheless due to the increase in disorder that accompanies formation of the solution.

Test yourself on Free Energy of Dissolution

  • Why can an endothermic dissolution process still be spontaneous?

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