Consider the general case of a redox couple which involves the participation of H
+ or OH
-:
A: Ox + ne
- + nH
+ Red + nH
2O
B: Ox + ne
- Red + nOH
-What is the difference in ΔG between these reactions? (Hint: set up a Hess's law cycle involving the reaction H
+ + OH
- H
2O) You will find that ΔG is more negative for A than B, and thus E° is more positive for A.
Thus for redox reactions involving the ionisation of water, the oxidising agent is more strongly oxidising in acidic than in basic solution, and reducing agents are more strongly reducing in base.
Now sometimes (especially with transition metals) there are several possible lower oxidation states, and the species formed can vary with pH. This complicates the picture, but the situation is essentially that outlined above. You might express it by saying that the oxidation state diagram is rotated anticlockwise in acid compared to base, and the minimum may come in a different place; see attached diagram.