The Student Room Group

Electrode Potentials

I tried these questions on Redox Equilibria; ELECTRODE POTENTIALS and I just wanna know if the answers are correct

QUESTION:
“Show whether disproportionation will occur in the following cases under standard conditions”
a) VO2+ = VO2+ and V3+
b) MnO2 = MnO4- and Mn2+

MY ANSWERS: (the = signs represent equilibrium arrows)

a) VO2+ = VO2+ and V3+

using the equations:
VO2+ + 2H+ + e- = V3+ + H2O (E = +0.34V)
VO2+ + 2H+ + e- = VO2+ + H2O (E = +1.00V)

Which then makes;
V3+ + H2O + VO2+ + 2H+ + e- = VO2+ + 2H+ + e- + VO2+ + H2O

Simplified down to:
V3+ + VO2+ = 2VO2+

And the E nought value for this is 1.00 (-0.34) = +1.34V

So the answer for a) is that a disproportionation reaction is feasible, but it is the exact opposite reaction than the one thought to occur (in the question);
Instead of
VO2+ = VO2+ and V3+
We have
V3+ + VO2+ = 2VO2+

b) MnO2 = MnO4- and Mn2+

using the equations
MnO2 + 4H++ 2e- = Mn2+ + 2H2O (E = +1.23V)
MnO4- + 8H+ + 5e- = Mn2+ + 4H2O (E = +1.51V)
MnO4- + 4H+ + 3e- = MnO2 + 2H2O (E = +1.70V)

(I used the first one and the third one, and multiplied them accordingly so the number of electrons were equal)

Which then makes:
3Mn2+ + 6H2O + 2MnO4- + 8H+ + 6e- = 3MnO2 + 12H+ + 6e- + 2MnO2 + 4H2O

Simplified down to:
3Mn2+ + 2MnO4- + 2H2O = 5MnO2 + 4H+

And the E nought value for this is 1.70 1.23 = +0.47

So once again the answer for b) is that a disproportionation reaction is feasible, but it is the exact opposite reaction than the one thought to occur (in the question):
Instead of
MnO2 = MnO4- and Mn2+
We have
3Mn2+ + 2MnO4- = 5MnO2

Are these right? (thanx for reading this btw)
Reply 1
for (b), if the reverse reaction is feasible then the forward reaction will have the negative of the E0 value and not be feasible. I don't think the back reaction is disproportionation either. So for (b), disproportionation is not feasible. I think.. I have only skimmed it
Reply 2
mik1w
for (b), if the reverse reaction is feasible then the forward reaction will have the negative of the E0 value and not be feasible. I don't think the back reaction is disproportionation either. So for (b), disproportionation is not feasible. I think.. I have only skimmed it


hang on if the backward reaction is +0.47 then it must be feasible (unlike forward reaction)
Reply 3
Yes, so the back reaction is feasible, but the question is asking you about the forward reaction isn't it. The E0 value of that is -0.47 and so the reaction they are asking you about will not happen.