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When I took high school chemistry many years ago, considerable effort was spent on teaching us to compute oxidation states of atoms in various compounds, following a set of rules that looked somewhat arbitrary to me at the time. As far as I remember, we were never told what benefits (other than passing tests) knowledge of oxidation states would give us.

They were used as part of a convoluted procedure for "balancing redox reactions", but I never saw an example of that where it wouldn't give the same results simply to require that the number of nuclei of each element, as well as the total charge, must be the same on both sides of the reaction, and solve the resulting linear Diophantine equations.

Nevertheless, the concept must be useful other than for setting homework exercises -- I see encyclopedias and other sources use much space on classifying compounds based on the oxidation state of this atom or that. Still I don't recall seeing any case where the oxidation states are used for anything (other than computing other oxidation states).

What is this concept actually used for? Just a basic example or two where knowing the oxidation states helps produce a meaningful prediction.

It doesn't seem that "oxidation state" actually encodes any particular configuration change inside the atom that tends to be preserved across reactions. Or does it somehow require effort (energy?) to change an atom from one oxidation state to another? In which case, what actually changes?

Sorry if this is too basic a question. It may be something "everybody knows". I've tried looking e.g. at the Wikipedia article, but that too seems to be entirely focused on how to determine oxidation states and doesn't explain why one would desire to know them. And all the questions here seems similarly to be about determining the oxidation states, and it is left unsaid why the asker wants to know ...


Edit: I'm looking for applications of oxidation numbers, by which I mean rules, laws, tendencies, rules-of-thumb or the like of the general form:

When you have (condition that involves oxidation numbers) then (prediction that can be verified without knowing what oxidation numbers are).

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    I'm an organic chemist, and we rarely have to balance redox equations, thank God! We rarely have to balance ANY kind of equations, really, other than in a qualitative sense, because most organic reactions are quite messy and produce a host of byproducts and impurities which are only quantified when it's vital to know everything about the reaction and its mechanism and conditions. We do perform numerous oxidations and reductions, but we'll usually just use a slight stoichiometric excess of the redox agent and let the devil see to the details. – Gregg Robinson Oct 16 '16 at 16:13
  • I will offer you this bit of mnemonic, though, of the sort we pot-boilers are so fond of, and which my students all seem to find useful: "On the chemical jungle's floor, LEO the lion GERs his awful roar." It's a way of remembering that the loss of electrons is an oxidation (LEO), and the gain of electrons is a reduction (GER). Yes. Sometimes it just comes down to that. – Gregg Robinson Oct 16 '16 at 16:13
  • When I took Chemistry at UW-Milwaukee, they skipped the redox part entirely. Years later, when I was a teaching assistant at Princeton U, I was expected to teach redox numbers and states, and I was totally flummoxed. I had to learn it from scratch basically. What I am saying is that the emphasis on redox depends strongly on who is teaching the class and at what university. My opinion now is that redox is primarily useful in analytical and electrochemistry. In a general chemistry class, it should certainly be covered, but no more than one or two lectures. If you are a student and have a hard ti – Badger 1992 Aug 12 '22 at 05:06

9 Answers9

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Of course they are useful. Perhaps you have not come across them yet, but being able to determine the oxidation state of an atom allows us to understand the properties of chemicals and how redox reactions work.

Let's just give two very simple examples. There are tons more. (I don't even want to go into organometallic chemistry, where being able to determine the oxidation state is incredibly important.)


Potassium permanganate, $\ce{KMnO4}$, has manganese in a +7 oxidation state. This means that it would have an electronic configuration identical to the noble gas argon: $\mathrm{1s^2 2s^2 2p^6 3s^2 3p^6}$, and therefore its $\mathrm{3d}$ orbitals are empty.

Now, most transition metal compounds are said to be coloured because of so-called "d-d* transitions". However, this can only occur if the d orbitals are partially filled - if there are no electrons in the d orbitals, like in $\ce{KMnO4}$, then there are no d-d* transitions available.

As such, the intense purple colour of $\ce{KMnO4}$ has to be explained via a different mechanism. In this case, it is explained by ligand-metal charge transfer.


Moving to organic chemistry. Let's say you have an acyl chloride, $\ce{RCOCl}$, and you want to convert it to an aldehyde, $\ce{RCHO}$. If you calculate the respective oxidation states of the carbonyl carbons, you get +3 and +1 respectively.

So, that tells you what kind of reagent you need to effect this transformation: you need a reducing agent. Hydrogen gas, $\ce{H2}$, is one such example of a reducing agent. Why? Well, that's because of oxidation states again. $\ce{H2}$ has hydrogen in an oxidation state of 0, and when hydrogen forms a bond to carbon, it has an oxidation state of +1.

Oxidation states are key to understanding why redox reactions work and why certain species are reducing agents (e.g. $\ce{LiAlH4}$: H(-1)) and why others are oxidising agents (e.g. DMSO, $\ce{(CH3)2SO}$, in the Swern oxidation).

orthocresol
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  • Your first example seems to be one where you say that you would have been able to use oxidation states for something, except that it doesn't work in that case? – hmakholm left over Monica Oct 16 '16 at 11:01
  • For the second case: Of course if you want to take something that doesn't contain any H and make something that does, you will need to provide a H from somewhere. Of course, since the numbers add up to zero, if you have a reaction where one of the numbers increase, there must be other numbers that decrease. But so what? This would be equally true no matter which arbitrary rules you use to assign the numbers. You could assign them pseudo-randomly for each compound and this would still be true. – hmakholm left over Monica Oct 16 '16 at 11:04
  • First example: I am using oxidation states to show that something does not occur. Second example: All I can say is - if you say so. Also, please stop using all caps in your comments, it's not nice. – orthocresol Oct 16 '16 at 11:26
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    No, I don't "say so" -- I'm asking what distinguishes the particular numbers you get from the oxidation-number rules in utility from other numbers that you could get from different rules of the same general kind. In order to be able to conclude something from oxidation numbers, there must be a rule in play somewhere that says "if the oxidation numbers are such-and-such, then you can expect this-and-that" -- where "this-and-that" is not a statement about the oxidation numbers themselves. I haven't seen such a rule formulated and would like to see some. – hmakholm left over Monica Oct 16 '16 at 11:38
  • For example, if I want to turn RCOCl into RCHO, I can either get the hydrogen by supplying H2, or by having CH4 turn into CH3Cl in the same reaction. I guess wildly that the latter reaction doesn't happen, but is there a general rule using oxidation states that will predict for me that one of these reactions will happen and the other doesn't? What does that rule look like? – hmakholm left over Monica Oct 16 '16 at 11:43
  • There isn't such a rule, using oxidation states, that says RCOCl + CH4 -> RCHO + CH3Cl is not possible. – orthocresol Oct 16 '16 at 11:50
  • Okay, unlucky guess on my part then. Is there any rule, using oxidation states, that says such-and-such reaction will or won't happen? – hmakholm left over Monica Oct 16 '16 at 12:06
  • @HenningMakholm No.There is no rule as such. –  Oct 16 '16 at 17:08
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I would say the main relevance of oxidation states is qualitative, not quantitative. Sure enough, it is possible to give a detailed quantitative picture of redox reactions in terms of quantum chemistry without ever mentioning oxidation states, and oxidation states ultimately are an extremely simplified reflection of that picture. However, most chemists most of the time aren't at all concerned with the detailed quantum chemistry picture, because they are working at a significantly higher level of abstraction, and so the question about how an oxidation state translates to a binding energy (cf. the comments to Ivan Neretin's answer) just doesn't come up. (I see you have a Stack Overflow profile. Exaggerating the difference somewhat, I might say that such a question is akin to asking of someone writing a Java program what the program is doing with the x86 registries.)

Two accounts, already mentioned in various ways in other answers, of how oxidation states are qualitatively helpful:

  • Half-reactions (cf. Marcel's answer). They provide a clear picture of the key changes going on in a redox reaction, and they provide a basis for assigning oxidation and reduction potentials. Half-reactions, however, are an abstraction -- an abstraction which wouldn't be nowhere near as meaningful if they weren't interpreted in terms of oxidation states. For instance, in $\ce{3 e− + 2 H2O + MnO4- -> MnO2 + 4OH−}$ the locus of interest for someone thinking in terms of redox reactions is what is going on with the manganese atoms, and the fact that it is their oxidation state that changes, and not that of the hydrogen or oxygen atoms, reflects that. By the way, even though you don't have to use half-reactions to balance redox equations, it always was my preferred method, as it makes enough sense chemically that it makes it much harder to make silly arithmetical mistakes.

  • Classification of chemical species (cf. Ivan Neretin's answer). Oxidation states can give an approximate, but very useful, idea of some properties of chemical species, such as redox reactivity. For instance, -1 chlorine compounds can be nice and stable (think table salt, $\ce{Cl-}$), while +1 chlorine compounds tend to be quite strong oxidisers (think bleach, $\ce{ClO-}$). No wonder that occasionally species are named after their key oxidation state (cf. Marcel's answer).


If you want a more direct interpretation in terms of a physical property: the oxidation state loosely corresponds to electron density around an atom, relative to what it would be like if that atom was neutrally charged and isolated. You should not expect an actual formula for getting electron densities out of oxidation states (given how loose the correspondence is), nor to compare absolute electron densities around different atoms using oxidation states (given that the values are relative).

To get a better idea of what kind of correspondence I am talking about, picture a neutral chlorine atom. If an electron is added to its electron shell (thus resulting in a chloride anion, $\ce{Cl-}$, which has -1 charge), an increase in electron density happens. Now, suppose that, rather than simply getting an extra electron, the chlorine atom forms a bond with a neutral hydrogen atom, forming an $\ce{HCl}$ molecule. The situation is quite different from the first one, as the pair of electrons forming the covalent bond is shared by both atoms, in a way that can be accurately characterised in quantum chemical terms (molecular orbitals, etc.). Still, the bond is not symmetrical, but skewed towards the chlorine atom, so that the electron density around it is higher than it was in the neutral, isolated state, though lower than in the chloride anion case (and vice-versa for the hydrogen atom). The major simplification involved in assigning oxidation states is ignoring this subtlety: we say chlorine is in -1 oxidation state in both $\ce{Cl-}$ and $\ce{HCl}$. Finally, it is worth noting that adding an electron to the neutral chlorine atom promotes an electronic reconfiguration (cf. the part about permanganate in orthocresol's answer) which happens to lead to a very stable state (a noble gas electronic configuration). That explains why -1 chlorine compounds are relatively stable next to those with higher oxidation states ($\ce{Cl2}$, $\ce{ClO-}$, etc.), which tend to be powerful oxidisers.

The example illustrates how oxidation states are, from the perspective I am adopting here, an approximation (pretending all bonds are either fully symmetrical or fully skewed towards the most electronegative atom) of an approximation (using charges as proxies for electron density). Still, they are useful to the extent they:

  • Offer a simple model of electron transfer in redox reactions (and note that this is quite independent from all I said about electron densities: Faraday's work on electrochemistry, for instance, predates quantum mechanics and the discovery of the electron by several decades).

  • Can capture general trends among chemical species of an element, thus serving as basis for heuristics. Given the many layers of approximation involved, these are heuristics, and not hard rules (which explains why no one has given you hard rules here). To go beyond the heuristics, you have to look at the electronic configuration in each particular case, which, other than in very simple cases (such as $\ce{Cl-}$) is merely hinted at by the oxidation state.

duplode
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    Even qualitatively, it is frustratingly difficult to get anyone to explicitly state one of the rules you all keep telling me you use. What is the "what is going on with the manganese atoms" that you learn from oxidation states? Not the oxidation states themselves, but what does those numbers tell you about the reaction? Or about the manganese atoms? Anything that doesn't boil down to "knowing the oxidation states will tell you how the oxidation states change". – hmakholm left over Monica Oct 16 '16 at 20:05
  • @HenningMakholm I hadn't emphasised that because, at first, I didn't see it as the focus of your question. I have added a second part to the answer, which hopefully will make things clearer. – duplode Oct 16 '16 at 21:23
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Back when we were small and the computers were huge, math books for kids were full of tricks for quick mental calculation, like "to multiply x by 9, just multiply by 10 and subtract x" or "to find a square of a number that ends with 5, for example, 65, go like $6\cdot7=42$ and append 25". Well, the oxidation states are much like that. Sure, you may balance pretty much anything without them just as well, but we are used to do it our way.

Besides, knowing your oxidation states gives you a rough idea of what to expect from the compound. Will it oxidize everything, including my skin if it gets a chance? or will it be indifferent? or will it reduce everything, to the point of igniting spontaneously in air? will it react with such-and-such?

Ivan Neretin
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    "knowing your oxidation states gives you a rough idea of what to expect from the compound" -- how? You seem to claim that these values can be used to make predictions of something that is not ITSELF about oxidation states, but the examples you give ("will it oxidize everyting") are themselves in terms of oxidation states and do not seem to lead out of a closed world where the only "facts" you get are things about "oxidation states" themselves. – hmakholm left over Monica Oct 16 '16 at 10:53
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    You either have the reaction, or you don't. Say, $\ce{Mn^7+}$ is a strong oxidant, hence it belongs to the first category. It will oxidize your skin. This is a real, very palpable fact. It is not about oxidation states. It is about those nice brown spots on you palms which would stay for about a week. – Ivan Neretin Oct 16 '16 at 11:13
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    What is the rule you use to predict something from knowledge of oxidation states here? You seem to be claiming that you can conclude from oxidation states that a certain reaction will happen -- what is the rule for getting from "the oxidation states are such-and-such" to "such-and-such reaction is likely to happen"? – hmakholm left over Monica Oct 16 '16 at 11:18
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    Well, it's not much of a rule, but... Long story short, I know my elements and what oxidation states they "prefer" to be in; if they are in unusual states, then something is likely to happen. – Ivan Neretin Oct 16 '16 at 12:11
  • Are you getting at something like "here's a way to use oxidation numbers to estimate binding energies of a compound"? – hmakholm left over Monica Oct 16 '16 at 12:14
  • No, far from that. Everything I said is just qualitative. Moreover, it is about elements, not compounds. "In these conditions Fe is going to be +3" - that's a likely conclusion, for example. – Ivan Neretin Oct 16 '16 at 16:26
  • Well, then that's not the direction I'm looking for. I'm asking for the step where you go from "Fe is going to be +3" to a conclusion that's not about oxidation states. – hmakholm left over Monica Oct 16 '16 at 16:29
  • If you want a definitive conclusion, then go for quantitative things, like oxidation potentials and Gibbs energies. – Ivan Neretin Oct 16 '16 at 16:38
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    I just want some conclusion that's not about the oxidation states themselves. – hmakholm left over Monica Oct 16 '16 at 16:51
  • @HenningMakholm How about "Cu is going to be +2 therefore this compound should be black instead of red"? – user253751 Oct 16 '16 at 22:20
  • (Actually, scratch that, because you could also look at tell by whether you have Cu2O or CuO. But consider a solution instead where you have etiher Cu+ or Cu2+ ions) – user253751 Oct 16 '16 at 22:36
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Oxidation states are used for "electron bookkeeping". This is useful in redox reactions, where we need to know what species are oxidised and reduced. By extension, oxidation states are an important tool for determining reacting ratios.

For example:

$\ce{Zn(s) + Cu^2+(aq) -> Zn^2+(aq) +Cu(s)}$

$\ce{Cu: +2->0}$

$\ce{Zn: 0-> +2}$

Hence we know that zinc is oxidised, and copper is reduced. While this is obvious from the reaction equation, this will not be the case in "messier" redox reactions, and oxidation states help us understand what is going on.

They also allow us to distinguish between compounds by using oxidation numbers - for example it is the oxidation number that allows us to tell the difference between iron (II) oxide and iron (III) oxide.

We should keep in mind, though, that oxidation states are a purely theoretical concept, and do not actually exist as physical quantities. When we use oxidation states, we are essentially assuminig that all bonds have a purely ionic character - this is rarely the case.

PGnome
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Marcel
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  • This is another "how do I find them?" explanation that says nothing at all about "what do I use them for once I have found them?" – hmakholm left over Monica Oct 16 '16 at 09:50
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    I gave two examples of uses for oxidation states: differentiating between different compounds of the same two elements, and keeping track of electron transfer in redox reactions. – Marcel Oct 16 '16 at 10:14
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    "differentiating between different compounds of the same two elements" apparently mean that you use the oxidation states to know what the oxidation states are! That's not an application as far as I can see. Your "keeping track of electron transfer in redox reactions" d0esn't look like an application either. You write down those two extra lines under the reaction, but WHAT DO YOU GET OUT OF WRITING THOSE LINES? Again, the claimed benefit of knowing the oxidation states simply seems to be that now you can write them down -- what then? – hmakholm left over Monica Oct 16 '16 at 10:48
  • We distinguish between the compounds by using the knowledge that they have different oxidation states.

  • A change in oxidation states is the very definition of a redox reaction - hence we need oxidation states to keep track of what is happening in the reaction.

  • – Marcel Oct 16 '16 at 11:10
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    (2), yes, so saying "redox reaction" is not an answer to how one uses oxidation states to predict something that is not itself about oxidation states. Saying that "we need oxidation states to keep track of the oxidation states" is just tautological. I'm asking for an application where oxidation states makes a prediction where determining whether the prediction came true or not does not involve knowing anything about oxidation states. – hmakholm left over Monica Oct 16 '16 at 11:15
  • And (1) is again just a way to say "we need to know the oxidation states because otherwise we wouldn't know what the oxidation states are". – hmakholm left over Monica Oct 16 '16 at 11:15
  • (1) is a way of differentiating between compounds.

    I suggest you take a look at Orthocresol's answer, this is going nowhere. You seem to be under the impression that oxidation states are an intrinsic property of nature - this is not the case. They are simply a way we have invented for describing and understanding interactions that involve electron transfer.

    – Marcel Oct 16 '16 at 11:19
  • "a way of differentiating between compounds" -- again if the only thing the oxidation states tell you is that some compounds have some arbitary numbers attached to them and other compounds have other arbitrary numbers attached to them, then it's just a parlor game. Knowing what the oxidation states in different compounds are is not an application. An application would be something that allowed me to conclude a difference between the compounds that is not about oxidation states. – hmakholm left over Monica Oct 16 '16 at 11:23
  • Even if oxidation numbers had been arbitrary, which they are not (see Orthocresol's answer below), they are still a way of distinguishing between compounds of the same element. Hence they have an undeniable practical use - for example, farmers need to know whether the fertilizer they are using contains iron (II) oxide or iron (III) oxide. – Marcel Oct 16 '16 at 11:29
  • Wait, when you say "distinguishing", do you merely mean that oxidation numbers are used for naming compounds? – hmakholm left over Monica Oct 16 '16 at 11:35
  • In that specific case, yes. – Marcel Oct 16 '16 at 12:00