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Kevin Wright

Why is bromine produced at the anode when aqueous sodium bromide undergoes electrolysis?

David Frigault  Follow

This is how I see it:

In the electrolysis of NaBr, water is reduced at the cathode. This occurs because water is more easily reduced than are sodium ions. This is reflected in their standard reduction potential.

At cathode reduction of water occurs:

$$\ce{2H2O(l) + 2e- -> H2(g) + 2OH-(aq)}$$

And hydrogen gas is produced

At the anode, where oxidation occurs, the standard oxidation potential of water is –1.23 volts, while that for bromide ions is -1.07 volts.

The production of bromine itself has a negative electrode potential.One of the half-reactions must be reversed to yield an oxidation.

$$\ce{Br^2- -> Br2 + 2e-}~~~~~~~ Eº -1.07$$

Remember that when one reverses a reaction, the sign of Eº (+ or –) for that reaction is also reversed.

This means that bromide ions are more easily oxidized than water.

It is important to note: When current begins to flow, the distribution of ions around the electrodes changes, and the equilibrium electrode potentials no longer accurately apply.

I think other factors also apply;

  • Concentration
  • Temperature
  • Nature of ions

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Jacquelin Page  Follow
The electrode potential for the reduction of water is -0.83V whereas for H+ ions, it is 0.00V. As such, shouldnt Hydrogen ions be reduced? Also, why are you considering the +1.23V reaction of water rather than the +0.40V one?More
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Joseph Schachner  Follow
Why is water reduced at the cathode? Shouldnt it be Hydrogen ions since they have an electrode potential of 0 V? Also, could you write the reaction in which water is reduced? The 1.23V reaction I know has Oxygen being reduced, not water.More
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John Wright  Follow
I added the equation showing reduction of water at cathodeMore
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Jorge Roman  Follow
And where are you generating the hydrogen ions from in the first place? Please show the reaction that you are referring to. Also read Ivan Neretins comments they essentially answer your additional questionsMore
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Jackie Howe Janssen  Follow
The hydrogen ions come from the water present H2O <---> H+ +OH-More
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