Does a high +∆G mean that the reaction is irreversible (and equilibrium cannot be attained) or that the reaction lies to the right?

2 Answers
Jan 27, 2018

A positive value of ∆G indicates that the reaction is not spontaneous in the direction written, A high value of Keq indicates the equilibrium lies to the right.

Explanation:

Reactions are spontaneous when the change in free energy (∆G)is negative. (spontaneous does not imply rate, only favored direction).
Since ∆G = ∆H- T∆S, reactions tend to be favored if the change in enthalpy (∆H) is negative (exothermic reaction, goes to lower potential energy), and the change in entropy (∆S) is positive (system increases in disorder,)
If ∆H is negative and ∆S is positive, the reaction is spontaneous at all temperatures.
If ∆H is positive and ∆S is negative, the reaction is never spontaneous.
If both ∆H and ∆S are negative the reaction may be spontaneous at low temperatures, but when T∆S becomes greater than ∆H, reaction will no longer be spontaneous.
If both ∆H and ∆S are positive, the reaction will become spontaneous when T∆S exceeds ∆H.

Jan 27, 2018

I think you've got it mixed up.

Large positive DeltaG indicates a nonspontaneous reaction (i.e. the reverse direction is very fast), which is irreversible in the REVERSE direction, not forward direction.

Equilibrium reactions necessarily have DeltaG = 0, so equilibria cannot lie to either side AND be irreversible at the same time.

[You may want to read this for further discussion on irreversibility.](https://socratic.org/questions/for-a-spontaneous-process-in-an-isolated-system-the-change-in-entropy-is-positiv#532832)


Consider the deviation of the change in Gibbs' free energy DeltaG from standard state:

DeltaG = DeltaG^@ + RTlnQ

  • First of all, reactions that have positive DeltaG are necessarily nonspontaneous, and therefore, the forward direction is easily reversed.

Thus, the reactants have a really hard time reaching a dynamic equilibrium (where r_(fwd) = r_(rev)), whatever the size of bbQ happens to be, since the reverse rate is much larger than the forward rate, i.e. r_(fwd) "<<" r_(rev).

  • Second, all spontaneous reactions are irreversible... in the forward direction. Therefore, DeltaG must be negative for irreversible forward reactions. In that case, r_(fwd) ">>" r_(rev).