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

In summary, the half-reactions for Br2+2e- -> 2Br-, Cl2+2e- -> 2Cl-, I2+2e- -> 2I-, and S2O8+2e- -> 2SO42- show a dependence on pH, as seen in the Pourbaix diagrams. However, for the Cl2/Cl- couple specifically, there is no dependence on pH due to its instability in aqueous solutions with a pH above 2. While the Nernst equation does not include H+ or OH- ions, pH can affect the chemical balance in these reactions and therefore the electrode potentials.
  • #1
Dolphinsea14
2
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-?
 
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  • #2
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.
 
  • #3
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.
 
  • #4
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.
 
  • #5
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).
 

1. What is an electrode potential?

Electrode potential is the measure of the tendency of an electrode to gain or lose electrons. It is an important factor in determining the direction and rate of a chemical reaction.

2. How does pH affect electrode potential?

pH can affect electrode potential by changing the concentration of hydrogen ions in the solution. This can alter the charge on the electrode surface and therefore impact its ability to gain or lose electrons.

3. Are all half-reactions affected by pH?

No, not all half-reactions are affected by pH. Only those involving ions that can gain or lose protons are affected by changes in pH. For example, the reduction of oxygen gas is not affected by pH, but the reduction of hydrogen ions is.

4. Can electrode potential be calculated for half-reactions with pH-dependent electrode potential?

Yes, electrode potential can be calculated for half-reactions with pH-dependent electrode potential. This can be done by using the Nernst equation, which takes into account the effect of pH on electrode potential.

5. How can pH be controlled in order to manipulate electrode potential?

pH can be controlled by adding acids or bases to the solution. By changing the pH, the concentration of hydrogen ions can be altered, which in turn affects the electrode potential of the half-reaction. This can be useful in controlling the direction and rate of a chemical reaction.

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