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

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Discussion Overview

The discussion centers on whether the electrode potentials of specific half-reactions are influenced by pH. Participants explore the implications of pH on the chemical balance of these reactions and their corresponding electrode potentials, with a focus on halogen and persulfate species.

Discussion Character

  • Debate/contested
  • Technical explanation

Main Points Raised

  • One participant questions if the half-reactions Br2+2e- -> 2Br-, Cl2+2e- -> 2Cl-, I2+2e- -> 2I-, and S2O8+2e- -> 2SO42- have electrode potentials that depend on pH.
  • Another participant suggests that while H+ or OH- ions are not included in the Nernst equation, pH may still affect the chemical balance and thus the electrode potentials.
  • A different participant cites a source indicating that redox potential for these reactions does not depend on pH.
  • It is noted that for the Cl2/Cl- couple, there is no pH dependence, as illustrated by the Pourbaix diagram, but the stability of aqueous Cl2 is limited at higher pH due to its reaction with water to form HOCl.
  • One participant concludes that while there is no pH dependence, the reaction does not occur at high pH, making the discussion less relevant.

Areas of Agreement / Disagreement

Participants express differing views on the influence of pH on electrode potentials, with some asserting no dependence while others highlight conditions under which pH may play a role. The discussion remains unresolved regarding the broader implications of pH on the reactions in question.

Contextual Notes

There are limitations regarding the assumptions made about the stability of certain species at varying pH levels, and the discussion does not fully resolve the mathematical implications of these reactions.

Dolphinsea14
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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-?
 
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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).
 

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