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Discuss the factors, ΔH, ΔS and ΔG for spontaneous and non-spontaneous processes.

OR 

What can be said about the spontaneity of reactions when 

(1) ΔH and ΔS are both positive 

(2) ΔH and ΔS are both negative 

(3) ΔH is positive and ΔS is negative 

(4) ΔH is negative and ΔS is positive.

1 Answer

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For a spontaneous or a non-spontaneous process,

ΔH and ΔS may be positive or negative (ΔH < 0 or ΔH > 0; ΔS < 0 or ΔS > 0). 

But ΔG must decrease, 

i.e., ΔG < 0. 

If ΔG > 0, 

The process or a reaction will definitely be non-spontaneous. 

This can be explained by Gibbs equation, 

ΔG = ΔH – TΔS.

(1) If ΔH and ΔS are both negative, then ΔG will be negative only when TΔS < ΔH or when temperature T is low. Such reactions must be carried out at low temperatures.

(2) If ΔH and ΔS are both positive then ΔG will be negative if, TΔS > ΔH; such reactions must be carried out at high temperature.

(3) If ΔH is negative (ΔH<0) and ΔS is positive (ΔS>0) then for all temperatures ΔG will be negative and the reaction will be spontaneous. But as temperature increase, ΔG will be more negative, hence the reaction will be more spontaneous at higher temperature.

(4) If ΔH is positive, (ΔH > 0) and ΔS is negative (ΔS < 0), ΔG will be always positive (ΔG > 0) and hence the reaction will be non-spontaneous at all temperatures.

This can be summarised in the following table :

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