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spontaneity

General ChemistryThermodynamicsGibbs free energy

Summary

A spontaneous process is thermodynamically favorable: it proceeds forward from the given conditions without continuous outside work. At constant T and P, this means ΔG < 0. Spontaneous does not mean fast, because rate is set by kinetics.

Detail

Meaning: A spontaneous process is thermodynamically favorable: it proceeds forward from the given conditions without continuous outside work. At constant T and P, ΔG < 0 is spontaneous, ΔG = 0 is equilibrium, and ΔG > 0 means the forward reaction is nonspontaneous (the reverse is spontaneous). If ΔH < 0 and ΔS > 0, ΔG < 0 at every temperature. If ΔH > 0 and ΔS < 0, ΔG > 0 at every temperature. The other two combinations depend on temperature.

Equation: ΔG = ΔH − TΔS, where ΔG is the Gibbs free energy change (J/mol), ΔH is the enthalpy change (J/mol), T is the absolute temperature (K), and ΔS is the entropy change of the system (J/(mol·K)).

On the MCAT: You are given the signs of ΔH and ΔS and asked whether a reaction is spontaneous at high or low temperature, or you find the crossover temperature T = ΔH/ΔS. If Q < Keq, ΔG < 0 and the reaction shifts forward. A galvanic cell has E°cell > 0. In biochemistry, coupling an unfavorable step to ATP hydrolysis can make the overall process spontaneous.

Common confusion: Spontaneous does not mean fast. Rate depends on activation energy, and a catalyst lowers that barrier without changing ΔG. Diamond turning to graphite is spontaneous but extremely slow.

Sources

  • Chemistry: The Central Science
  • Chemistry: Atoms First
  • General Chemistry: Principles and Modern Applications

Written for the MCAT and checked before it was published. For study reference only. Spotted an error? Let us know.

spontaneity: MCAT Glossary