1.7.9

Free Energy of Dissolution

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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.

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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.
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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.
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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.
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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.
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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.
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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.

Jump to other topics

1Physical Chemistry

1.1Atoms, Molecules & Stoichiometry

1.2Atomic Structure

1.3Chemical Bonding

1.4States of Matter

1.5Chemical Energetics

1.6Electrochemistry

1.7Equilibria

1.8Partition Coefficient

1.9Reaction Kinetics

2Inorganic Chemistry

3Organic Chemistry & Analysis

3.1Introduction to Organic Chemistry

3.2Hydrocarbons

3.3Halogen Derivatives

3.4Hydroxy Compounds

3.5Carbonyl Compounds

3.6Carboxylic Acids & Derivatives

3.7Nitrogen Compounds

3.8Polymerisation

3.9Analytical Techniques

3.10Organic Synthesis

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