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I've been trying to find out as much as I can about peracetic acid, especially regarding its use as a sanitizer. In the Wikipedia entry it notes that

Peracetic acid is always sold in solution as a mixture with acetic acid and hydrogen peroxide to maintain its stability.

This is definitely born out by commercial examples: Loeffler Lerasept PAA (a sanitizer I've used before) lists 31% hydrogen peroxide, 17% peracetic acid, 16% acetic acid and 1% phosphonic acid among its ingredients.

But, my understanding was that mixing acetic acid and hydrogen peroxide makes peracetic acid. From the same Wikipedia article:

It forms upon treatment of acetic acid with hydrogen peroxide.

So my question is: what exactly keeps the excess hydrogen peroxide from reacting with the excess acetic acid to simply form more peracetic acid? Does the phosphonic acid inhibit this reaction? Is there something else not listed that does this? Or is it just some bit of chemistry I'm not aware of?

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The formation of peracetic acid from acetic acid and hydrogen peroxide is an equilibrium reaction and so in order for the peracetic acid to remain at a constant concentration as desired, acetic acid and hydrogen peroxide must also be present so that the reaction can be at equilibrium. $$\ce{CH3COOH + H2O2 <=> CH3COOOH + H2O}$$

what exactly keeps the excess hydrogen peroxide from reacting with the excess acetic acid to simply form more peracetic acid?

Nothing. The hydrogen peroxide reacts with the acetic acid to form peracetic acid and water but the peracetic acid and water also react to reform hydrogen peroxide and acetic acid. At equilibrium the rates of these reactions are equal and so the concentrations of the species do not change. At room temperature the equilibrium constant is somewhere around 2.5 (see references) which indicates that significant amounts of reactants and products are present, supporting the reasoning above.

The paper Chin J Proc Eng 2008 February, 8 (1), 35–41 has some data on the values of the equilibrium constant and the variation in concentration of peracetic acid formed.

Another value for the equilibrium constant on page vii of Unis, Melod (2010) Peroxide reactions of environmental relevance in aqueous solution. Doctoral thesis, Northumbria University.

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  • $\begingroup$ OK that makes sense. My understanding of chemistry is pretty basic, and I always seem to forget the whole equilibrium thing (which seems pretty vital, really). Would it be more accurate to say they simply "exist" together in solution, rather than being "sold together"? $\endgroup$ – Franklin P Combs Mar 13 '15 at 19:09
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But, my understanding was that mixing acetic acid and hydrogen peroxide makes peracetic acid

Exactly! But within the mixture, peracetic acid reacts back to hydrogen peroxide and acetic acid. With other words, the components are in an equilibrium.

\[ \ce{CH3COOH + H2O2 <=> CH3CO3H + H2O} \]

For disinfection purposes, these mixtures are sold as made. This is safe (and cheap) for both the manufacturer and the consumer. The fairly stable and safe to use, while concentrated solutions of peracetic acid tend to decompose - violently.

Phosphonic acid with a (first) pKa around two is the strongest acid within the mix. One might speculate that it is added to adjust the pH, keep more acetic acid protonated and therefore shift the reaction a bit more towards the peracetic acid.

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    $\begingroup$ Hallo Klaus, This "phosphonic" is a typo I assume. Phosphoric acid is a traditional additive to stabilize peroxides. (Presumably by masking iron impurities) $\endgroup$ – Georg Mar 13 '15 at 18:57
  • $\begingroup$ Hallo Georg, that really makes much more sense! Admittedly, I was struggling a bit to find an "explanation" for the phosphonic acid ;) $\endgroup$ – Klaus-Dieter Warzecha Mar 13 '15 at 18:58
  • $\begingroup$ I don't think it is a typo. See this MSDS, which contains both phosphoric and phosphonic acid. I think they use it as a metal chelator for acid cleaning products. $\endgroup$ – Franklin P Combs Mar 13 '15 at 19:04
  • $\begingroup$ @FranklinPCombs I'm not convinced, since that's a peracetic acid free mixture. Georg's explanation is very reasonable. Phosphoric acid is stable towards oxidation, strong enough to adjust the pH and cheap as dirt: Perfect for the manufacturer. $\endgroup$ – Klaus-Dieter Warzecha Mar 13 '15 at 19:17
  • $\begingroup$ OK I believe you. Thanks for the answer. Both being equally helpful, I had to accept the one that came in first. $\endgroup$ – Franklin P Combs Mar 14 '15 at 12:58

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