2
$\begingroup$

The following information is mentioned in my textbook:

In the laboratory, a manganese(II) ion salt is oxidized by peroxodisulphate to permanganate.

$\ce{2Mn^2+ + 5S_2O_8^2- + 8H2O -> 2MnO4- + 10SO_4^2- + 16H^+}$

The manganese ion does get oxidized, but as the oxidation number of sulphur in $\ce{S_2O_8^2-}$ and $\ce{SO_4^2-}$ is the same, i.e., equal to +6, $\ce{S_2O_8^2-}$ doesn't seem to undergo reduction. For a redox reaction, both oxidation and reduction are necessary to occur simultaneously. But in this equation, only oxidation seems to be taking place.

I think it might have to do with the peroxy-bond in the peroxodisulphate ion, but I am not entirely certain. Is it because - oxidation state of two oxygens (of $\ce{S_2O_8^2-}$) on the reactant side is -1, while all the oxygen atoms on the product side have their oxidation state equal to -2, so there is a net reduction? Could anyone please confirm if my understanding is correct?

$\endgroup$
2
  • $\begingroup$ Review how the oxidation number is defined and you have your answer. // simple hint: Do you need any electrons to convert peroxodisulphate to sulphate ? Are peroxocompounds generally oxidation agents ? How is managed oxidation e.g. by hydrogenperoxide in oxidation number context ? $\endgroup$
    – Poutnik
    Aug 4, 2021 at 7:49
  • $\begingroup$ @Poutnik Thank you so much, I see it now; $\ce{S_2O_8^2^- + 2e^- -> 2SO_4^2-}$ - gain of two electrons, so reduction is indeed taking place $\endgroup$
    – Pal
    Aug 4, 2021 at 7:53

1 Answer 1

4
$\begingroup$

It seems OP understands Poutnik's rationalization on the reduction step, so this question does not need an answer. However, I feel it is not completed because OP's statement of:

[...] but as the oxidation number of sulphur in $\ce{S2O8^2−}$ and $\ce{SO4^2−}$ is the same, i.e., equal to +6, [...]

This statement is not quite true if you just do the calculations and conclude from that as OP initially did. For benefit of other novice chemistry readers, I think it is better to explain what's going on in this situation in detail.

Suppose the oxidation number of sulfur in peroxodisulphate ion $(\ce{S2O8^2−})$ is $\alpha$. Then if you do usual calculations, it is like:

$$ 2 \cdot \alpha + 8(-2) = -2 \ \Rightarrow \ \therefore \alpha = \frac{16 - 2}{2} = +7$$

This means there is a reduction happening. However, this calculation is also erroneous. Let's look at the Lewis structure of the peroxodisulphate ion, which is a particularly interesting one:

Lewis structure of the peroxodisulphate ion

The trick here is that you should be able to notice that $\ce{S2O8^2−}$ ion has two oxygen atoms that are bonded via a single bond, which is known as a peroxide linkage. This linkage will influence the average oxidation state of oxygen in $\ce{S2O8^2−}$ ion. The two oxygen atoms in peroxide linkage will have a $−1$ oxidation state, similar to the same oxidation state that oxygen has in all peroxides. The rest of oxygens in the anion have usual $−2$ oxidation state, which implies that the average oxidation state of oxygen in $\ce{S2O8^2−}$ ion is: $$\frac{6(-2) + 2(-1)}{8} = -\frac74$$ Thus, if we redo the calculations:

$$ 2 \cdot \alpha + 8(-\frac74) = -2 \ \Rightarrow \ \therefore \alpha = \frac{14 -2}{2} = +6$$

This did not imply a reduction when we look at the oxidation number of sulfur in $\ce{SO4^2−}$ ion. If it is $\beta$ in $\ce{SO4^2−}$, then, $$ \beta + 4(-2) = -2 \ \Rightarrow \ \therefore \beta = 8 - 2 = +6$$

Yet, if you know the Lewis structure of the peroxodisulphate ion, you would realize there is something going on for oxygen atoms in $\ce{S2O8^2−}$ ion, which cannot be explained by these calculations. Therefore, it is always better to conclude by the facts found using the redox half reactions. Consequently, I admit that I also prefer to do usual redox half reactions if I find no change in oxidation states doing usual calculations, because that gives no place to make erroneous calculations. Accordingly, for the reduction half reaction:

$$\ce{S2O8^2− + 2 e- <=> 2SO4^2- } \tag1$$

This is the reduction half reaction. The equation $(1)$ clearly indicates the $\ce{S2O8^2−}$ ion has undergone a reduction during the complete reaction. The corresponding oxidation half reaction would be:

$$\ce{Mn^2+ + 4H2O <=> MnO4- + 8H+ + 5 e-} \tag2$$

If you combine the equations $(1)$ and $(2)$ in order to cancel the electrons, you get:

$$\ce{2Mn^2+ + 8H2O + 5 S2O8^2- -> 2MnO4- + 16H+ + 10 SO4^2-} \tag3$$ This is the given equation. When you consider the Standard Electrode (Reduction) Potentials $(E^\circ)$ in aqueous solutions at $\pu{25 ^\circ C}$, you would find for reaction $(1)$ it is $\pu{2.01 V}$ and for reaction $(2)$ it is $\pu{-1.51 V}$ (oxidation potential). Thus, for the completed reaction $(3)$ at standard conditions, $E^\circ_\mathrm{Rxn} = 2.01 + (-1.51) = \pu{+0.50 V}$, implying it is spontaneous at standard conditions.

$\endgroup$
1
  • 2
    $\begingroup$ There were 4-5 minor grammar errors (probably typos or keyboard autocorrect) which I edited. Please rollback if the changes are not appropriate. $\endgroup$
    – TRC
    Aug 5, 2021 at 13:53

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service and acknowledge that you have read and understand our privacy policy and code of conduct.

Not the answer you're looking for? Browse other questions tagged or ask your own question.