Do these half-reactions have electrode potential that depends on pH?

Join the discussion
Ask a follow-up here, or get your own question answered by working scientists, mathematicians and engineers — people, not an autocomplete.
Real named experts · corrections over time · the nuance an AI answer skips
4 replies · 3K views
Dolphinsea14
Messages
2
Reaction score
0
Do following half-reactions have electrode potential that depends on pH? I know H+ or OH- ions wouldn't be included in Nernst equation for these, but would pH affect chemical balance in these reactions, and therefore electrode potentials?
Br2+2e- -> 2Br-
Cl2+2e- -> 2Cl-
I2+2e- -> 2I-
S2O8+2e- -> 2SO42-?
 
Chemistry news on Phys.org
Yes. You can google the Pourbaix diagrams for these species to find the dependence.
Dolphinsea14 said:
I know H+ or OH- ions wouldn't be included in Nernst equation for these, but would pH affect chemical balance in these reactions, and therefore electrode potentials?
This isn't quite true. At least for the halides, in water one of the stable species that is formed in highly oxidizing conditions is hypohalite, which entails reaction between the halide and water.
 
Cl2-Cl- electrode potential.png

I found this in a book (Inorganic Chemistry by Shriver and Atkins). It seems redox potential in these cases doesn't depend on pH.
 
Ok, yes for the Cl2/Cl- couple specifically, there is no dependence on pH. You can see this on the Pourbaix diagram for chlorine as a horizontal line at low pH and high voltage (it's easier to see in the bromine diagram):
1567778959911.png

But it's kind of a weird statement to make, because aqueous Cl2 is not stable above pH 2 or so. It reacts with water to form HOCl, which gets deprotonated at high pH to give hypochlorite. Note that the redox potential for Cl-/hypochlorite is dependent on pH.
 
In other words: there is no dependence on pH, just the reaction doesn't occur when the pH is high enough (so whole discussion becomes a moot).