Sciencemadness Discussion Board

Isopropyl alcohol and hydrogen peroxide

hkparker - 28-5-2011 at 18:36

A friend recently asked me what the reaction between isopropyl alcohol and hydrogen peroxide would be. I said either the alcohol would oxidize to an aldehyde then maybe a carboxylic acid, or an organic peroxide would form, but I cant be sure which (leaning more toward the nasty organic peroxide). He says he searched around the web and didn't find much, so I was wondering if anyone knew what would happen. I've been thinking about trying this experimentally in mg quantities.

bbartlog - 28-5-2011 at 18:51

I don't think these will react appreciably without catalysis or maybe forcing conditions. But I could be wrong.

Magpie - 28-5-2011 at 21:09

Isopropyl alcohol is 2-propanol. It can't form a 3 carbon aldehyde or carboxylic acid. It might form acetone however, a ketone.

hkparker - 29-5-2011 at 09:09

Quote: Originally posted by Magpie  
Isopropyl alcohol is 2-propanol. It can't form a 3 carbon aldehyde or carboxylic acid. It might form acetone however, a ketone.


Ah, I'm sorry Magpie, I was copying from the oxidation path of ethanol, different story when there is another carbon there. Still a bit new in organic. Following that same mechanism though, I can see why ketone formation is likely. I will give it a try, I'm just still wondering about organic peroxides.

Magpie - 29-5-2011 at 09:34

Hey, don't worry about it. You're doing fantastic work for your young age.

There are several ways to prevent peroxides as discussed in this forum. I add BHT (butylated hydroxy toluene, IIRC). I put this in my diethyl ether and THF at ~200ppm.

hkparker - 29-5-2011 at 10:05

Thank you, I really appreciate it. I've read a bit about avoiding peroxides when I make ether, but unfortunately I don't have any BHT. I might still give this a try in such small quantities it doesn't matter, and see if I can smell some acetone being produces.

simba - 31-5-2011 at 17:13

If the reaction between IPA and hydrogen peroxide truly yields acetone than one should take care when doing the reaction, because an excess of hydrogen peroxide could react with the acetone forming acetone peroxide, which is highly explosive.

I don't think the reaction between acetone and hydrogen peroxide occurs expontaneously, but anyway, I would take care when doing it though.

hkparker - 31-5-2011 at 17:16

Thats a good point, though that reaction requires an acid catalyst. Also, TATP forms only at low temperature, otherwise the even more unstable (but less powerful) Diacetone Diperoxide forms.

Jor - 1-6-2011 at 07:31

To be sure, do this reaction on a small scale! So half a mL of both reactants for example. You don't want acetone peroxide or CH3CH(OOH)CH3 to form, if this is possible. I'm sot sure.

ScienceSquirrel - 1-6-2011 at 07:53

A quick Google shows a lot of alcohol oxidations using hydrogen peoxide but they seem to use transition metal catalysts, try "hydrogen peroxide alcohol oxidation".
Also hydrogen peroxide is a very weak nucleophile so I doubt it will form a hydroperoxide.

hkparker - 1-6-2011 at 08:35

Ill be trying it on a very small scale, thanks.

Thank you SS, your search did turn some results. I'll try this reaction uncatalyzed first then see where I can go from there.

The WiZard is In - 3-6-2011 at 13:04

Quote: Originally posted by hkparker  
A friend recently asked me what the reaction between isopropyl alcohol and hydrogen peroxide would be. I said either the alcohol would oxidize to an aldehyde then maybe a carboxylic acid, or an organic peroxide would form, but I cant be sure which (leaning more toward the nasty organic peroxide). He says he searched around the web and didn't find much, so I was wondering if anyone knew what would happen. I've been thinking about trying this experimentally in mg quantities.

I find no info on isopropyl alcohol reacting w/ H2O2, there is
however, an oblique reference indicating that the combination
high strength H2O2 and IP may have explosive properties.

Byda 90% H2O2 and ethanol with 100 ppm Fe+++ catalyst yields (50% of theory) acetic acid.

ES Shanley & FP Greenspan
Highly Concentrated Hydrogen Peroxide [90%] :
Physical and Chemical Properties
Industrial and Engineering Chemistry 39 [12] 1536-43
December, 1947.


djh
----
The explosion removed the windows,
the door and most of the chimney.
It was the sort of thing you expected in
the Street of Alchemists. The neighbours
preferred explosions, which were at least
identifiable and soon over. They were better
than the smells, which crept up on you.

Terry Pratchett

Magpie - 3-6-2011 at 16:25

The Google entry for this article:
http://pubs.acs.org/doi/abs/10.1021/j100339a051
hints that there is a way.

"Oxidation of 2-Propanol Using Hydrogen Peroxide in Place of Dioxygen. .... catalyst on the :"

Interesting...

MagicJigPipe - 3-6-2011 at 20:15

If you read the first part of this article you will notice that it mentions some researchers who studied the photochemical and thermal initiation of this reaction and cites both. If you can give me a direct link to the online article I might be able to get you the .pdf (alternatively, try the references section on this forum).

Radiation-induced oxidation of 2-propanol by hydrogen peroxide in aqueous solutions

Abstract:
The radiation-induced oxidation of 2-propanol by hydrogen peroxide in neutral deaerated aqueous solution has been investigated. 2-Propanol is oxidized to acetone, and hydrogen peroxide reduced in stoichiometrically equivalent high yields. The yields are independent of hydrogen peroxide concentration in the range 5 × 10−2 to 10−3 M and linearly dependent on alcohol concentration in the range 0.13 to 1.05 M. The reaction yields increased with decreasing dose rate.The results are explained by a chain mechanism in which initiation occurs via H-atom abstraction from 2-propanol to form either (CH3)2ĊOH (1) or CH3 CHOH ĊH2 (2). 1 reacts with H2O2 in a chain propagating reaction2 may abstract the α hydrogen from the parent alcoholor undergo bimolecular termination. A lower limit of 53 ± 101mole−1 s−1 is estimated for the rate constant for this radical conversion reaction.


Attachment: Radiation-induced oxidation of 2-propanol by hydrogen peroxide in aqueous solutions.pdf (381kB)
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Verdict

makeaccount - 5-3-2017 at 09:13

Verdict=?

I mixed to create a sterile solution that would hopefully kill bacteria and viruses and other saty things. Does it? Or does it react into some dangerous different thing?
(I just leave it in an open container @ room temp)

AJKOER - 5-3-2017 at 15:10

OK, H2O2 and transition metals, or H2O2 and radiation, are both paths to hydroxyl radical formation.

So the methods mentioned could actually be hydroxyl radical assisted paths. Interestingly, in place of H2O2 one can, at least theoretically in this case, use air/O2 in the presence of an acid, the usual transition metal employed in this synthesis and a small amount of a reductant, like citrate or ascorbate or a bit of both.

Theory also suggest employing HOCl, in place of H2O2, and an appropriate transition metal in an analogous Fenton-type reaction.

If the purpose is to disinfect, my recollection is that the paths I suggested are capable of so doing and likely the existing basis of disinfecting sprays and the like.

[Edited on 5-3-2017 by AJKOER]

Melgar - 6-3-2017 at 07:41

Of course, H2O2 and isopropanol are both capable disinfectants on their own, so that would probably hold true of a mixture of the two as well. H2O2 could probably oxidize isopropanol into lactic, pyruvic, and acetic acid via radical pathways, which then might catalyze the formation of acetone peroxides. Granted, this would take a long time, but it seems plausible enough to warrant not storing such a mixture.

tsathoggua1 - 6-3-2017 at 13:34

Whilst it is rare and by no means anything like as much of a risk of it happening, I have read that it is possible for propan-2-ol to peroxidize in storage to form an explosive organoperoxide. You might wish to be careful with deliberately adding H2O2 to iPA.

http://www.sigmaaldrich.com/chemistry/solvents/learning-cent...

Note that propan-2-ol is specifically mentioned, as being capable of forming explosive organoperoxides that in the case of iPA are 'significantly less volatile than the solvent itself' and warns that evaporation and concentration can (as ethers are well known for when being stripped) increase the concentration of the peroxide. And it also states that multiple openings of containers of 'most group B solvents' can result in 'significant and dangerous peroxide concentration'

Although admittedly, the references I've heard to actual explosions from iPA perodizing (no, I do mean isopropanol, not diisopropyl ether, which is a bugger, I prefer to keep the latter in sealed metal cans under pressure (indeed fractionation, after first testing for peroxidation, and doing it under inert gas of diisopropyl ether-based car starting fluid is almost preferable, since that way the DIPE is kept out of reach of O2 and light, and the metal can should provide transition metal ions to retard peroxidation should it not, similarly to keeping some copper wool or wire in EtOEt?

Of course it means fractionating from EtOEt and toluene, heptane and acetone is present also, although the acetone can be removed with H2O) but diisopropyl ether is one of relatively few solvents that rather give me the willies

Quick question-EtOEt should be tested at least yearly, DIPE every 3 months minimum, how often should one ideally test THF?

gaztonbidefranck - 8-9-2018 at 09:47

Hello, i join this topic for my first reply on this forum.
So i have found this document how to produce hydrogen peroxide from isopropyl alcohol.


Attachment: burgess2007.pdf (678kB)
This file has been downloaded 617 times

Alkoholvergiftung - 8-9-2018 at 21:52

Isopropylalkohol and very deluted hydrogenperoxyd was used to produce hydrogenperoxyd and Aceton throught Reflux Destillation. They heat the mix to 75 C and the Alkohol breaks up into acetenon and H2O2 without the deluted hydrogenperoxyd it only breaks to Aceton and water.