Reaction Feasibility (CIE A Level Chemistry)

• The Gibbs equation can be used to calculate whether a reaction is feasible or not

ΔG^θ = ΔH_reaction^θ - TΔS_system^θ

• When ΔG^θ is negative, the reaction is feasible and likely to occur
• When ΔG^θ is positive, the reaction is not feasible and unlikely to occur

• The feasibility of a reaction can be affected by the temperature
• The Gibbs equation will be used to explain what will affect the feasibility of a reaction for exothermic and endothermic reactions

Exothermic reactions

• In exothermic reactions, ΔH_reaction^θ is negative
• If the ΔS_system^θ is positive:
  • Both the first and second term will be negative
  • Resulting in a negative ΔG^θ so the reaction is feasible
  • Therefore, regardless of the temperature, an exothermic reaction with a positive ΔS_system^θ will always be feasible

• If the ΔS_system^θ is negative:
  • The first term is negative and the second term is positive
  • At high temperatures, the -TΔS_system^θ will be very large and positive and will overcome ΔH_reaction^θ
  • Therefore, at high temperatures ΔG^θ is positive and the reaction is not feasible
  • The reaction is more feasible at low temperatures, as the second term will not be large enough to overcome ΔH_reaction^θ resulting in a negative ΔG^θ

• This corresponds to Le Chatelier’s principle which states that for exothermic reactions an increase in temperature will cause the equilibrium to shift position in favour of the reactants, i.e. in the endothermic direction
  • In other words, for exothermic reactions, the products will not be formed at high temperatures
  • The reaction is not feasible at high temperatures

Summary of factors affecting Gibbs free energy for exothermic reactions

If ΔH ....	And if ΔS ....	Then ΔG is	Spontaneous?	Because
is negative < 0 exothermic	is positive > 0 more disorder	always negative < 0	Always	Forward reaction spontaneous at any T
is negative < 0 exothermic	is negative < 0 more order	negative at low T positive high T	Dependent on T	Spontaneous only at low T TΔS < H

Endothermic reactions

• In endothermic reactions, ΔH_reaction^θ is positive
• If the ΔS_system^θ is negative:
  • Both the first and second term will be positive
  • Resulting in a positive ΔG^θ so the reaction is not feasible
  • Therefore, regardless of the temperature, endothermic with a negative ΔS_system^θ will never be feasible

• If the ΔS_system^ꝋ is positive:
  • The first term is positive and the second term is negative
  • At low temperatures, the -TΔS_system^θ will be small and negative and will not overcome the larger ΔH_reaction^θ
  • Therefore, at low temperatures ΔG^θ is positive and the reaction is less feasible
  • The reaction is more feasible at high temperatures as the second term will become negative enough to overcome the ΔH_reaction^θ resulting in a negative ΔG^θ

• This again corresponds to Le Chatelier’s principle which states that for endothermic reactions an increase in temperature will cause the equilibrium to shift position in favour of the products
  • In other words, for endothermic reactions, the products will be formed at high temperatures
  • The reaction is therefore feasible

Summary of factors affecting Gibbs free energy for endothermic reactions

If ΔH ....	And if ΔS ....	Then ΔG is	Spontaneous?	Because
is positive > 0 endothermic	is negative < 0 more order	always positive > 0	Never	Reverse reaction spontaneous at any T
is positive > 0 endothermic	is positive > 0 more disorder	negative at high T positive low T	Dependent on T	Spontaneous only at high T TΔS > H