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Things I Won't Work With

Things I Won’t Work With: Peroxide Peroxides

Everyone knows hydrogen peroxide, HOOH. And if you know it, you also know that it’s well-behaved in dilute solution, and progressively less so as it gets concentrated. The 30% solution will go to work immediately bleaching you out if you are so careless as to spill some on you, and the 70% solution, which I haven’t seen in years, provides an occasion to break out the chain-mail gloves.
Chemists who’ve been around that one know that I’m not using a figure of speech – the lab down the hall from me that used to use the stuff had a pair of spiffy woven-metal gloves for just that purpose. Part of the purpose, I believe, was to make you think very carefully about what you were doing as you put them on. Concentrated peroxide has a long history in rocketry, going back to the deeply alarming Me-163 fighter of World War II. (Being a test pilot for that must have taken some mighty nerves). Me, I have limits. I’ve used 30% peroxide many times, and would pick up a container of 70%, if I were properly garbed (think Tony Stark). But I’m not working with the higher grades under any circumstances whatsoever.
The reason for this trickiness is the weakness of the oxygen-oxygen bond. Oxygen already has a lot of electron density on it; it’s quite electronegative. So it would much rather be involved with something from the other end of the scale, or at least the middle, rather than make a single bond to another pile of electrons like itself. Even double-bonded oxygen, the form that we breath, is pretty reactive. And when those peroxides decompose, they turn into oxygen gas and fly off into entropic heaven, which is one of the same problems involved in having too many nitrogens in your molecule. There are a lot of things, unfortunately, that can lead to peroxide decomposition – all sorts of metal contaminants, light, spitting at them (most likely), and it doesn’t take much. There are apparently hobbyists, though, who have taken the most concentrated peroxide available to them and distilled it to higher strengths. Given the impurities that might be present, and the friskiness of the stuff even when it’s clean, this sounds like an extremely poor way to spend an afternoon, but there’s no stopping some folks.
Any peroxide (O-O) bond is suspect, if you know what’s good for you. Now, if it’s part of a much larger molecule, then it’s much less likely to go all ka-pow on you (thus the antimalarial drugs artemisinin) and arterolane, but honestly, I would still politely turn down an offer to bang on a bunch of pure artemisinin with a hammer. It just seems wrong.
But I have to admit, I’d never thought much about the next analog of hydrogen peroxide. Instead of having two oxygens in there, why not three: HOOOH? Indeed, why not? This is a general principle that can be extended to many other similar situations. Instead of being locked in a self-storage unit with two rabid wolverines, why not three? Instead of having two liters of pyridine poured down your trousers, why not three? And so on – it’s a liberating thought. It’s true that adding more oxygen-oxygen bonds to a compound will eventually liberate the tiles from your floor and your windows from their frames, but that comes with the territory.
These thoughts were prompted by a recent paper in JACS that describes a new route to “dihydrogen trioxide”, which I suppose is a more systematic name than “hydrogen perperoxide”, my own choice. Colloquially, I would imagine that the compound is known as “Oh, @#&!”, substituted with the most heartfelt word available when you realize that you’ve actually made the stuff. The current paper has a nice elimination route to it via a platinum complex, one that might be used to make a number of other unlikely molecules (if it can make HOOOH in 20% yield, it’ll make a lot of other things, too, you’d figure). It’s instantly recognizable in the NMR, with a chemical shift of 13.4 for those barely-attached-to-earth hydrogens.
But this route is actually pretty sane: it can be done on a small scale, in the cold, and the authors report no safety problems at all. And in general, most people working with these intermediates have been careful to keep things cold and dilute. Dihydrogen trioxide was first characterized in 1993 (rather late for such a simple molecule), but there had been some evidence for it in the 1960s (and it had been proposed in some reactions as far back as the 1880s). Here’s a recent review of work on it. Needless to say, no one has ever been so foolhardy as to try to purify it to any sort of high concentration. I’m not sure how you’d do that, but I’m very sure that it’s a bad, bad, idea. This stuff is going to be much jumpier than plain old hydrogen peroxide (that oxygen in the middle of the molecule probably doesn’t know what to do with itself), and I don’t know how far you could get before everything goes through the ceiling.
But there are wilder poly-peroxides out there. If you want to really oxidize the crap out of things with this compound, you will turn to the “peroxone process“. This is a combination of ozone and hydrogen peroxide, for those times when a single explosive oxidizing agent just won’t do. I’m already on record as not wanting to isolate any ozone products, so as you can imagine, I really don’t want to mess around with that and hydrogen peroxide at the same time. This brew generates substantial amounts of HOOOH, ozonide radicals, hydroxy radicals and all kinds of other hideous thingies, and the current thinking is that one of the intermediates is the HOOOOO- anion. Yep, five oxygens in a row – I did not type that with my elbows. You’ll want the peroxone process if you’re treated highly contaminated waste water or the like: here’s a look at using it for industrial remediation. One of the problems they had was that as they pumped ozone and peroxide into the contaminated site, the ozone kept seeping back up into the equipment trailer and setting off alarms as if the system were suddenly leaking, which must have been a lot of fun.
What I haven’t seen anyone try is using this brew in organic synthesis. It’s probably going to be a bit. . .uncontrolled, and lead to some peroxide products that will also have strong ideas of their own. But if you keep things dilute, you should be able to make it through. Anyone ever seen it used for a transformation?

85 comments on “Things I Won’t Work With: Peroxide Peroxides”

  1. Pete says:

    Not just the strength of the O-O bond but the strength of the C=O bond? Good to see the Me 163 Komet mentioned. I think the Graf Spee’s range finder was in one of the slides I used when I visited Vertex in July last year.

  2. Anonymous says:

    We breath triplet oxygen *O-O*
    Singlet oxygen O=O is very reactive and is used in pericyclic reactions.

  3. Project Osprey says:

    Wikipedia lists has a page on it under Trioxidane

  4. Cato the Elder says:

    Coincidentally, “Oh, @#&!” is its SMILES formula

  5. Hap says:

    @2: I thought triplet oxygen does have a double bond (sort of) – the Lewis structure doesn’t quite accurately represent the species, and the bond energy of O2 from Wikipedia is 498 kJ/mol (119 kcal/mol) which is much higher than the standard O-O bond energy (35 kcal/mol?), so representing it as .O-O. isn’t really accurate, either.

  6. Wavefunction says:

    $^@@!**, %$#)))((*@
    That was SMILES for “Awesome post”.

  7. D. C. Sessions says:

    Anyone ever seen it used for a transformation?

    You mean, besides from “lab” to “ruin?”

  8. SP says:

    I remember a talk by Sharpless where he said how in the early days of asymmetric epoxidiation development he needed some strong H2O2. So we went over to JPL and got some high end stuff, I forget if he said 95% or 99%, and drove it back to his lab- to make sure it didn’t spill or rattle around, he drove with the container held between his knees. Fortunately he didn’t end up having to change his name from Sharpless to —-less.

  9. newnickname says:

    Story Synthesis, anyone? Cyclic triperoxides decompose thermally to a mixture of cyclic hydrocarbon and lactone (with loss of CO2). Useful for making large rings. If it doesn’t blow up first.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 1968, 90(3), 817-818. and several others that followed.
    For those wanting to use 100% (or anhydrous) H2O2, consider alternatives like R3SiOOSiR3, H2O2-DABCO complex, H2O2-urea complex, etc.

  10. Yancey Ward says:

    Two chemists walk into a bar. The first says, “Can I have a glass of H2O.”
    The second chemist says “Can I have a glass of water too.”
    The first chemist broke down in tears – his assassination attempt had failed.

  11. John Wayne says:

    Using ozone and hydrogen peroxide is the classic way to oxidatively cleave an olefin and oxidize any of the resulting aldehydes to carboxylic acids. This may not count because this is usually portrayed as a one pot, two step reaction. Anybody ever toss an olefin and hydrogen peroxide in the ozone generator?
    When I was a graduate student I was told that one of Criegee’s students died when he injected an ozonide into a GC and it exploded. Seems like a good story to get graduate students to be careful, but I’m not sure if it is true.

  12. Anonymous says:

    Why not polymeric oxygen? Are there ANY conditions (e.g., high pressure, low temperature) under which that would be stable?

  13. NJBiologist says:

    “There are apparently hobbyists, though, who have taken the most concentrated peroxide available to them and distilled it to higher strengths.”
    Would these hobbyists be the same guys trying to come up with something they could put in a water bottle and sneak past the TSA, or are there less criminal hobby purposes for concentrated hydrogen peroxide?

  14. Simon Higgins says:

    If you’re talking crazy military applications of peroxide, how about the Royal Navy’s concentrated peroxide/diesel submarine project in the 1950’s? At one time, they held the world submarine speed record (this was slightly before USS Nautilus). They were known as the Explorer class. Naturally, with the usual apt RN lower-deck humour, they were known by the sailors as the Exploders.

  15. Hap says:

    I assume the public hobbyists are looking to do smaller versions of the X-Prize rockets, but I don’t know.

  16. Anonymous says:

    How do people usually dispense peroxides, such as HOOH or tBuOOH? I’ve only used them a couple times myself, and I remember transferring some to a vial using a glass pipette, and then measuring it out from the vial using a syringe, so as to not introduce any metal from the syringe needle directly into the reagent bottle. I’m not sure whether that’s the standard protocol, or whether it was paranoid overkill on my part?

  17. anchor says:

    @ 16- No,you are not a paranoid. I myself did it exactly the way you described. The name of the game is “respect” the reagent. In my days, I would fire polish the pipette (to smooth out those rough edges). But these days, you can those plastic pipettes which is fine. Never underestimate the reagents!

  18. A Nonny Mouse says:

    Once distilled t-BuOOH to get 100%; first year of my PhD and nobody told me not to. Managed to get some 80% peroxide as a gift from some company or other.
    Urea:hydrogen peroxide is my favourite which I used to make Bis-TMS peroxide (Synlett, 1990ish).

  19. John Schilling says:

    Coincidentally, my IR&D project for doing stability, materials compatibility and gas solubility measurements on 98% hydrogen peroxide was just approved last week.
    It’s going to be a fun year. Though the one that really scares me is the 12.5% solution of acetylene in liquid nitrous oxide; that one I almost did turn down. But we’ve got a nice new wet chemistry lab in a concrete bunker, shame to let it go to waste…

  20. Anonymouse says:

    Rocketry of various and insane stripes. I saw an article about a rocket belt builder in Mexico City who was distilling 99% in his back yard. Ive read that 95%+ is actually more stable then the 70-95 range stuff, but anyone that has 10s (or 100s! yipe!) of liters of that stuff in his backyard is both insane and a menace.

  21. NJBiologist says:

    @15 Hap, 20 Anonymouse–Thank you. That’s still scary, but more in a call-the-fire-department way than a call-homeland-security kind of way. If that’s any better.

  22. Hap says:

    It depends if they live next to you or rent your house, I guess.

  23. Chris Croy says:

    The most popular synthesis of Ecstasy used to involve a performic/peracetic oxidation of an alkene which calls for concentrated H2O2. I believe it was usually concentrated by freezing. While also heinously illegal, at least they weren’t trying to make it go boom.

  24. Anonymous says:

    #18: In the process of making bis-TMS peroxide I made the peroxide-DABCO complex in grad school.
    Org. Syn. 1997, 74, p. 84.
    To dry the solid I put it on the rotovap but must have had my heating bath too hot. The other person in my bay ended up with glass in his back when the flask blew up!

  25. John Schilling says:

    @13 et al: It isn’t just amateurs who use hydrogen peroxide in rocketry, and unfortunately some of the professionals have to “roll their own” as well. The only remaining supplier for rocket-grade peroxide (in the US at least) has a policy of only selling to government contractors. Of which club, fortunately, my present employer is a member.
    98% peroxide does seem to be about as safe an oxidizer as you can find for rocket use. Liquid oxygen and nitrous oxide also have their proponents, and all three have hazards that absolutely must be respected. But I’ve never heard of any injuries among even the amateur rocket-builders using the stuff. And among professionals, hydrogen peroxide was the propellant of choice for the only certified rocket-propelled commercial airliner.
    Amateurs forced into the peroxide-manufacturing business, that’s another matter, and there have been several catastrophes there. Basically, 98% H2O2 and 2% H2O is reasonably safe, whereas 98% H2O2 and 2% concentrated sludge is very much not. So if you start with 70% H2O2 and a still, you can see how things might go wrong. If they do, you won’t likely get to the point of loading the resulting brew into a rocket.
    Compare old-style black powder. Incredibly useful, and recruits with a few weeks of training could handle the stuff in the field. But the powder mills kept blowing up with disturbing regularity.
    Hydrogen peroxide peroxide, I hadn’t heard of before today. I think I will compare that to nitroglycerine. Unfavorably.

  26. davin says:

    Nice! I want to play around with this and see what organic transformations it can do!

  27. Fred the Fourth says:

    Re: ME-163 and “mighty nerves”:
    One of the test pilots for the ME-163 was a diminutive german lady named Hannah Reitsch.
    My father had the pleasure of hearing her address the Society of Experimental Test Pilots (probably about 1970). He relayed to me her description of a “hard landing ” (euphemism alert), and the bit where she was seen calmly making notes as the rescue crew drove up to pry her out of the cockpit… while the corrosive, explosive, and (IIRC) hypergolic fuels leaked out into the immediate neighborhood. Fun times.
    Say, don’t most of your entries under “Things I Won’t Work With” include mention of contemporary german chemists? Must be something in the water…

  28. MLB pitcher and Medicinal Chemist says:

    I wonder if Derek Lowe considered pitching to Barry Bonds and Sammy Sosa is like working with hydrogen peroxide.

  29. Alan Miller says:

    So does this mean that you have no interest in trying out the “Dragonfly” helicopter that’s powered by “readily available commercial-grade liquid diluted to around 50 to 70 percent”? It only goes through about 11 gallons/hour, stored in plastic tanks on each side of the pilot and siphoned up and out to the catalyst rockets at the end of the rotor blades.
    After all, I’m sure the seals aren’t going to leak a fine mist of peroxide over the pilot, and there’ll never be a crash that breaks those tanks open.

  30. Anonymous BMS Researcher says:

    Yep, that German rocket fighter must have been exciting to fly all right: Wikipedia says “the cockpit was unpressurized, the operational ceiling was limited by what the pilot could endure for several minutes while breathing oxygen from a mask, without losing consciousness. Pilots underwent altitude-chamber training to harden them against the rigors of operating in the thin air of the stratosphere without a pressure suit. Special low fiber diets were prepared for pilots, as gas in the gastrointestinal tract would expand rapidly during ascent.”

  31. Nick K says:

    #11 John Wayne: That sounds like a very useful transformation, and a lot easier than the von Rudloff method of cleaving an olefin to an acid (periodate and catalytic ruthenium tetroxide).
    It’s worth pointing out that the molozonide, the first intermediate in the Criegee mechanism of ozonolysis, has three oxygens in a row. Of course, it’s unstable and immediately dissociates to a carbonyl and a carbonyl oxide which then recombine to give the isolable ozonide. Has anyone ever observed the molozonide?

  32. t.f. says:

    I’m surprised h2o2 makes your list, even in high concentration. I used to follow some of the amateur rocketry efforts using peroxide. Check out the material safety video armadillo aerospace made in 2001 after securing a commercial supplier for 98% peroxide :
    Leather bursting into flame is startling, but its not nearly the same level of whoof! as liquid O2. (Does liquid O2 make the will-not-touch list?)
    Fun John Carmack quote: “cotton is good, because it will soak through and give you peroxide itch long before it will combust.”

  33. Wolf Baginski says:

    Hydrogen peroxide was the staple of British rocketry up until the 1960s. The explanation I heard was that it was used by the German rocket scientists who escaped the Russians, and the USA didn’t want. So there was the high-speed submarine, and various attempts at jet+rocket fighters, and the home-grown British space program.
    With the peroxide decomposing into steam and oxygen, British rocketry was very nearly running on steam engines, which almost seems right. By Steam to the Stars!
    Er, sorry…
    Anyway, we did launch a satellite with this tech, and it’s still up there, and British boffinry seemed relatively comfortable with concentrated hydrogen peroxide.
    And Morris dancing.

  34. sepisp says:

    Triplet oxygen might be best described as a “triple minus single” bond. Three electron pairs in a bonding orbital and one in an antibonding orbital.
    But, oxidative transformations should be used more often. They’re cheap.

  35. Anonymous says:

    I am not a working laboratory chemist, other than by matrilineal descent, and I therefore take great care to listen to the wisdom of my betters…
    Whic includes the warning that *the* most dangerous thing an ordinary high-school chemistry teacher will encounter – or (say) a public-health lab technician doing the same reactions, day in, day out – might discover, is a jar of hydrogen peroxide with a fading label at the back of a store cupboard, closed and forgotten for decades.
    It might just have a bit of a gas buildup, and a stuck stopper.
    It might, or so I have been warned, contain HOOH and a crazy mixture of H’s and O’s in combinations that you couldn’t or wouldn’t have drawn with a crayon when you were six years old.
    Some of them are photosensitive – I’m guessing that’s superoxygenated contaminants – but all of it’s shock sensitive. Vibration sensitive. Closing-the-cupboard-door sensitive.
    I could, of course, be misinformed about Hydrogen Peroxide – twice by chemists, and once by a member of the Leicestershire Fire Service. And I risk starting another ‘”Sand won’t save you now” thread if you all start volunteering stories of the worst thing that you could discover at the back of the bottom shelf, where no-one ever looks, in a storeroom that’s been there for decades.

  36. oldnuke says:

    Every time I see xxxxxxx peroxide I hear “Warning Will Robinson, Warning, Warning” in my head until proven otherwise.
    Seeing a structure with a lot of nitrogen and little else elicits the Monty Pythonesque, “Run Away, Run Away”.
    And when fighting a nitrocellulose fire, “white smoke stay and fight, brown smoke run away”.
    All of which have resulted in me retaining all of my limbs. Although my ears have been ringing for the past forty years… gr

  37. MJS says:

    #8. The chemist driving with the container of conc H2O2 between his knees reminds me of the story about the radiation safety lecture. The speaker said that radium dial watches were slightly dangerous. Someone in the audience took off his radium dial watch and put it in his pocket.

  38. Nick K says:

    I remember many years ago reading about a drag car which was powered entirely by the decomposition of high-test hydrogen peroxide. There was no actual fuel. Instead, the hydrogen peroxide was forced through a platinum sponge into a nozzle, whereupon it decomposed into steam and oxygen, plus a lot of heat.

  39. RM says:

    Since peroxides are stabilized by attaching something larger than hydrogen to them, I imagine the same would hold for HOOOH. Given the excess of electrons on the oxygens, a powerful EWG might do the trick …
    so how about trinitrophenyl?

  40. Anonymous BMS Researcher says:

    “It depends if they live next to you or rent your house, I guess.”

  41. gippgig says:

    I’ve been wondering about stericly stabilized peroxides. For example, attach a peroxide to the “inside” carbons of phenanthrene and it would be almost impossible for it to decompose. Something like this might at least partially stabilize trioxides. Anyone know if anybody has studied this?
    To change the subject, if you annoy a bombardier beetle it pumps hydrogen peroxide and hydroquinone into a combustion chamber and blasts you with the exhaust. Yes, nature invented the liquid-fueled rocket engine (and laser and electric motor and nuclear reactor and ….)

  42. Anonymous says:

    #39. So an explosive stabilized with another explosive (picric acid)?

  43. Anonymous says:

    @32 t.f.
    Note that H2O2 on its own doesn’t actually make his list. Its HOOOH and higher that he’s saying he won’t touch.

  44. sepisp says:

    #41 gippgig: I don’t think that’s a good idea. That’s a molozonide, and they decompose pretty fast. The usual pericyclic route is not available, but I could draw a mechanism with the usual electron pushing that would decompose it nevertheless. It’s not a good idea to put that many aromatic electrons next to a very-soon-to-be carbonyl oxide + peroxide anion. The carbonyl oxide is a resonance structure of an aromatic carbocation with a ketone to stabilize, so you can essentially select any carbon to become a cation. Most likely, it will be the inner quaternary carbon that reacts with the peroxide to give a five-membered ring. This will then decompose, to give a phenol and another carbonyl oxide, which breaks the C-C bond between the ketone and the inner quaternary carbon to give an acylium ion. This can be captured by any resident nucleophile; in water, a hydroxide, to give a carboxylic acid.
    I don’t think there’s any realistic way to stabilize a molozonide. You’d want a substituent that is neither polarizable nor charged, which is kind of a have the cake and eat it too.

  45. MiddleO'Nowhere says:

    So the obvious next step (for one of those German groups that’s always messing about with high energy compounds) is to make the fluorine analog,FOOOF.
    Trade name: Whoomp! There it was!

  46. Rocketmensch says:

    @27 Fred: A professional rocket engineer I knew recalled a talk he’d attended in the ’60’s. The speaker showed a slide of the ME-163 and explained that it used propellants so hazardous that 50% of the time, it was on fire by the time it landed.
    At this point, a elderly man in the back of the audience stood up and shouted, with a strong German accent, “That is a lie! That is vile English propaganda! It did not land on fire more than one time in three!”

  47. newnickname says:

    @23 “concentrated H2O2. I believe it was usually concentrated by freezing.” H2O2 solutions (3 – 30%) decompose at a rate of, maybe, 1% per month at room temp, I think.
    Some chemists store their 30% H2O2 in the fridge (approx 4 C) to slow the decomp. The problem is that even at fridge temps, you can start to freeze out the high conc H2O2 zones. I’ve seen fridge “ice” in 500 mL plastic H2O2 bottles but I don’t know if it was wet-ice or conc-H2O2-ice. I don’t want to know. I steer clear.
    NEVER store 30% H2O2 in the -20 freezer!
    Personally, I NEVER even store H2O2 in the 4 C fridge because I consider it a potential hazard. When using 30%, I decant some into a vial or beaker, use what I need and pour the remainder down the drain with running water. I never put ANYTHING into a bottle of 30%, not even a plastic pipet. I only pour OUT from the bottle.
    I can’t find the story on-line but I kind of recall a chem lab at Kentucky or Kansas (one of those K-states, I think) that blew up in the late 70s while they were trying to make 100% H2O2 (by lit procedures). The explosion blew off a corner of the building and I think that there were deaths.

  48. dave w says:

    #13 – yes, there are non-criminal hobby applications for fairly concentrated (85-95%) H2O2: I was (a few years back) involved in an amateur rocket project that used this as a monopropellant (decomposed by a metallic silver catalyst to steam and oxygen).
    The trick to getting things to work reliably is that the peroxide must be quite free of phosphate ion, which “posions” the catalyst surface. (Once we figured that out, it was “no wonder our results so far have been so consistently inconsistent” – one time the motor would fire nicely, and then the catalyst would lose activity, and the next firing attempt would just spray undecomposed peroxide!)

  49. Fergal says:

    If we’re in HOOOOO territory, we may as well talk about a O6 ring.
    I’m too lazy to look it up so i’ll ask here – is there any mention of it in the literature. Presumably theoretical…
    I wonder if a flip from boat to chair conformation would be enough to remove your fingers?

  50. Fergal says:

    Aargh. My apologies…

  51. dave w says:

    #47: the eutectic mixture of H2O2 and H2O is just under 60% H2O2 and freezes at around -55 deg. C at that concentration. So freezing a solution of lower concentration will result in a slush of water-ice and a liquid phase of enriched H2O2 concentration.
    (Freezing solid H2O2 from a higher-concentration solution is one of the preferred ways of preparing high-purity H2O2…)
    Also, in my experience even the “strong” stuff isn’t THAT scary to handle – not quite as bad as e.g., conc. HN03… similar precautions apply: don’t get it on you (and have rinse water available to wash it off if you do), DONT’t get it in your eyes, avoid mixing with combustible/reducing substances: it’s less aggresively corrosive to skin than HNO3 (a brief exposure, rapidly rinsed, will leave an itchy white spot, rather than an instant hole), and if it does start oxidizing stuff, there isn’t any NO2 produced as a reaction product.

  52. Anonymous says:

    #38 Nick – that’s how Bloodhound SSC’s (1000 mph land speed car) hybrid rocket engine is going to work as well:

  53. pjcamp says:

    Blowing the roof off the Science Shack doesn’t count as a transformation?

  54. Scott says:

    I’ve been meaning to ask, are “interesting and exciting” chemicals like those on the list of things Derek Lowe won’t work with how chemists get the accounting department to approve new lab equipment?
    “Reason for need: previous unit destroyed during experimental accident, current replacement type is now X”

  55. Syn-Thesis says:

    In my PhD-Lab, we could borrow the 90% H2O2 from the other organic working group in the building, who were located five floors down from us.
    In order to obtain the (about 1 l) bottle, you were given a stern lecture about how not to contaminate the bottle, not to use a syringe when taking out the liquid, and other survival stuff. The bottle would be placed into a bucket and put into the elevator by the poor grad student in charge of the H2O2 and sent up. Of course, there was a sign attched to the bucket “Do not enter! Chemical transport!” and you had to jog up back to your floor to get it out of the elevator when it arrived. We used to call this game “chemists’ Russian roulette” and always wondered if it would go “bang” on the way.

  56. poose says:

    Although I’ve never had the pleasure of working with the hyperconcentrated peroxides, I have worked with H2O2 in the 35% range.
    The application was making kid’s 250ml “drink boxes” (for fear of getting sued, I’ll leave the exact manufacturer of said equipment out of it) and it was an aseptic process, the product was heat pasteurized and the packaging material sterilized in a 2m deep tank of peroxide, rocket motor strength, heated to about 120F. The forming of the box was done in a heat-sterilized cabinet and filled/sealed in a continuous process.
    The “problem” arose when one of the immersion tanks formed a hairline crack in one of its welds, and over about an eight-week time period everyone turned into either a blond or (strangely) a redhead. The filler room became all but uninhabitable. They eventually caved and replaced the tank-about $45,000 as I remember…
    What I remember most about those heady days was an open container of hydraulic oil on the filler-room desk. It wasn’t an infrequent problem to encounter a wayward drop of peroxide, and you wouldn’t notice anything until your skin would blister and burn-since hands were the most affected, plunge in into the oil. Killed the reaction immediately.

  57. poose says:

    addendum-yes, I realize 35% ain’t quite “rocket fuel”, but it will work in platinum-bed thrusters as I recall.
    The stuff still sucked to work with.
    An on the “how do you transport it” front? In Polyethylene (LDPE, I think) 50-gallon casks with half-inch thick walls and a hefty deposit on their return (about $100/ea back in 1988). We went through two/week in a three-filler operation.

  58. Anonymous says:

    #29 I just hope that “commercially available liquid” is peroxide and not Hydrazine.

  59. cr says:

    @ Nick K #38
    “I remember many years ago reading about a drag car which was powered entirely by the decomposition of high-test hydrogen peroxide.”
    They still are:

  60. Dr.Methyl says:

    Hey I remember I asked for H2O2 in an organic lab, and a chemist gave me a bottle of what the called “solid hydrogen peroxide”, nobody really knew what it was but they told me to dilute the tablets into water to reach the correct concentration. Now I think that was probably H2O2/urea complex.
    You mentioned the FOOOF and Id like to point out that is the MOST EVIL chemical I’ve heard of ! It was mentioned in a security book along with a lot of odd explosives and toxics materials such as mercury petazolides for example. It was written than FOOOF can disproportionate to FOOOOF and FOOF, yes you correctly read FOOOOF with a chain of 4 Oxygen !!!! It was written that a less than 5% (or maybe 2%) of this compound at less than -100°C in liquid inert gas (Argon I guess) react explosively with a lot of compound including NITROGEN (which is known as inert) where liquid pure fluorine gives no reaction at these temperature. I dont need to mention that everybody learned at school that fluorine is the most powerful oxidiser known to man. Hey hey this stuff is totally insane and its name fits well : FOOOOF !!

  61. Hugh says:

    Here is a paper regarding O3F2:
    Good heavens!

  62. Glen says:

    Around twenty years back I was doing engineering work at a nuclear power plant. The supply department consolidated into a fine new warehouse. About 6 months later someone noticed that the HazMat area had a neatly stacked pile of Hydrazine (used as O2 scavenger). The adjacent stack was equally neat drums of high strength hydrogen peroxide.
    We were fortunate that our forklift drivers had been very careful.

  63. eyesoars says:

    “It’s going to be a fun year. Though the one that really scares me is the 12.5% solution of acetylene in liquid nitrous oxide; that one I almost did turn down. But we’ve got a nice new wet chemistry lab in a concrete bunker, shame to let it go to waste…”
    Yeek. That should scare you, at least if you’re handling more than milligrams at a time. A lot of people died understanding how to safely handle acetylene, and people still do occasionally. The largest university near me had an incident with a welding tank where the welder cut his C2H2 line, and took out more than half the university’s phone system for an extended period (including that of the hospital).
    What temperatures and pressures are the mixture stored at?
    I keep thinking of Derek’s comments regarding small, energetic molecules, and how enthalpy tilts things pretty steeply… you’ve got all those nice N2O molecules plus all those C2H2 molecules, that would be ever so happy to make the transition to N2, H2O, and CO/CO2, all in a nice not-very-far from stoichiometric mix.
    I’m sure it would make a more-than-adequate explosive mixture for mining.

  64. Mark says:

    Well, I’m one of those amateur rocket scientists that has flown rockets powered by H2O2 (35-50%) and unleaded gasoline (pressurized by dry ice). The H2O2 is commercially available (even has it) and is labeled as “food grade”… yum! It’s main use is sterilizing commercial kitchens.
    Around 1998-2000 Beal Aerospace developed a commercial launch vehicle capable of reaching geosynchronous orbit that ran on kerosene and 98% H2O2, pressurized with helium… no moving parts. The H2O2 was catalytically decomposed and the kerosene was injected into the combustion chamber causing a hypergolic reaction.
    One propellent that I won’t work with…
    Oh, and don’t forget the Air Force engine that ran on fluorine and liquid hydrogen…
    I suspect that the EPA might frown on the exhaust products of either of those propellents.

  65. Calli Arcale says:

    Hydrogen peroxide . . . well, if you want a crazy example of lunatic things people do with it, there are people who think it’s a great way to cure diseases. And I don’t mean using it topically as an antiseptic (which isn’t recommended anymore as it’s pretty hard on human tissues, even at wimpy OTC dilutions). It’s called “oxidative therapy” and it’s frankly shocking more people haven’t been killed by it. But here’s one who was:
    Katherine Ann Kurtz-Bibeau sought treatment for multiple sclerosis from a quack in South Carolina (who did later lose his medical license for this and other looniness). He told her she had an undiagnosed infection and prescribed intravenous 3% H2O2. I am not kidding. She died five days later.

  66. Hairy says:

    @ Poose #56,57 : People of certain ethnicity bleach to non blond hair colors.
    The ethnic majority Japanese, for example, get this very vivid orange-red.

  67. Harry Buttcrack says:

    Hydrogen Peroxide causes instant blood clotting, that poor lady probably died from some kind of stroke.

  68. Anon says:

    In fact, not only singlet oxygen is reactive. The triplet one we’re breathing is reactive as well, as should be expected for a biradical. That’s why medical treatment with higher concentrations of oxygen in the breathing gas can damage the lung tissue.

  69. JB says:

    I never knew the stuff we like to breathe could be so nefarious. Maybe it gets its rebellious nature from sitting next to nitrogen, its shamelessly explosive cousin, in the periodic table…? And when the two get together, as in polynitrocubanes—well, they ought to be quarantined at the Trinity Site and banned from human conversation.
    You’re the best, buddy. Keep it up!

  70. Ed says:

    High-test hydrogen peroxide is used as part of bi-propellant combustion engines for torpedoes. The Russians used it, with some bad side effects, such as in the Kursk, and the Swedish Navy has used it with fewer side effects for several decades.
    During WW2, the Germans tried it for submarine propulsion (the Walther engine) and the [British] Royal Navy tried it in a prototype submarine, the HMS Graph.
    I’m rather glad the USN didn’t go down that route. I’m not far from a major maker of submarines, and having truckloads or trainloads of high-test hydrogen peroxide going through my neighborhood does not feel me with a warm fuzzy feeling.

  71. David Brodbeck says:

    Re #38: I think you’re thinking of Turbonique, which made all kinds of crazy Wile E. Coyote-esque stuff, including a monopropellant turbine-powered “rocket axle” for dragsters.

  72. Heteromeles says:

    I ran through quite a lot of 30% H2O2 in grad school running soil particle analyses. You have to get the organic carbon out of the sample so that you can determine the percents of sand, silt, and clay (particles of different size classes, for the non soils scientists), and the standard procedure is to boil the sample in 30% H2O2. We went through a bunch of beakers (nothing like stirring sand in a beaker full of boiling peroxide to make the pyrex break), but no one got more than a few holes in their sleeves. Fortunately.

  73. aairfccha says:

    @Ed: The British also built HMS Explorer and Excalibur to test HTP based propulsion, those apparently were quickly renamed Exploder and Excruciator. The Black Knight and Black Arrow rockets also used HTP as oxidizer.

  74. Joshua Belanger says:

    Ok, why do I keep seeing the oxygen we breathe referred to as a triplet? Admittedly I’m a layman when it comes to chemistry, but last I heard, the molecular oxygen gas we breath is O2. That’s two atoms. Ozone is O3, obviously made of three atoms. So why do people keep calling the stuff we normally breath a triplet when it’s only a pair of oxygen atoms? (Not to say we don’t sometimes inhale ozone, but it’s not the stuff we live on.)

  75. tangent says:

    @Joshua, tl,dr “triplet” is a technical term of quantum mechanics. Which I can’t give a solid explanation of, but here’s a programmer’s shot at it:

    Two electrons jointly have four basic spin states, of which three (“triplet”) have total spin 1, and one (“singlet”) has spin 0. O2 is unusual in that its lowest-energy configuration is triplet. (Singlet oxygen would set us all on fire, so this works out well for us.)

    In Lewis structure, triplet oxygen has an unpaired electron on each atom, i.e. two electrons in antibonding molecular orbitals.
    Singlet oxygen (two on left) versus triplet (on right) molecular orbital population:
    I believe these two electrons are the ones we’re talking about the spin states of, but I can’t honestly even approximate an explanation of why those orbital populations mean triplet and singlet…

  76. a says:

    The triplet refers to the spin state of the electrons on each of the oxygen atoms, rather than referring to the number of atoms (O2 is best represented as two oxygen atoms separated by a single bond with an unpaired electron of each oxygen, instead of a double bond between the atoms): if the two electrons have the same spin, it is a “triplet state”, if the two electrons have opposite spins, it is a “singlet state”

  77. Isidore says:

    Here’s a graphical illustration of the triplet-singlet oxygen molecule:

  78. Joshua Belanger says:

    I know electron bonds are how atoms form molecules, but I’m pretty sure spin doesn’t vary its direction within a particle type. For example, neutrinos always have a spin that runs opposite to their linear momentum, making them “left-handed.” Only an anti-neutrino has a “right-handed” spin. Something doesn’t add up to the reply given by “a” up above, as, logically, electrons should all also spin one direction, and only positrons should spin the other way. (I also know about how spin 1 and spin 1/2 particles, which is a fascinating bit of science in and of itself, with a spin 1 particle being a particle that rotates 360 degrees before it returns to its initial orientation, but a spin 1/2 particle has to rotate 720 degrees to do the same thing.)

    Of course, none of this explains why quantum mechanics terminology is getting used in the comments on a chemistry blog instead of referring to the two states of oxygen mentioned as unexcited and excited O2.

  79. tangent says:

    Hey, meaning this politely, are you looking to learn some QM or to get people to stop talking about it? If we could take one or the other.

    In the case of O2, a chemist is interested in what the structure of the unexcited state is, which happens to be unusual and has big implications for how O2 acts chemically. Chemistry is quantum.

    There is only one kind of electron with one intrinsic spin, but an electron can be oriented in space, and specifically we find the spin orientation can be ‘up’ or ‘down’ here. Analogously a spinning ball can have its spin axis oriented various ways. The same spinning ball can be oriented so it is right-handed as seen from the top, or left-handed. And two identical spinning balls can be oriented with “same spin” or “opposite spin”.

    When you see people write about orbital electrons being spin +1/2 or -1/2, that orientation is what the sign is denoting. (And yes, quantum spin is bizarre that only two relative orientations are measurable.) I do think it’s a little sloppy to call “intrinsic spin” and “relative spin” by the same term, but that’s what you’re seeing there.

  80. tangent says:

    FYI, the handedness you mentioned for neutrinos is not their spin, it’s the relative orientation of their spin and their momentum, called helicity. Neutrinos and anti-neutrinos both have the same spin, in fact, but the helicity is negated.

    Helicity varies according to your frame (imagine throwing a right-handed spiral pass, and then how it looks while you chase after it at twice its speed), and an object at rest doesn’t have helicity defined. Spin on the other hand is frame-invariant.

  81. Joshua Belanger says:

    Ok, those replies explain much. I’m not actually in the sciences for a career, whether chemistry or physics (most chemistry I’ve done is high school chem my senior year, about 17 years ago), but I’ve always found them fascinating. I could have phrased that comment about how it doesn’t explain why QM terminology is being used far better than I did. I meant it in a questioning sense, not a shut discussion down sense. As for the neutrino thing, chalk that up to one more screw-up on in the “science” and scientific terminology from the Deep Space Nine episode “Rivals.” At one point in that ep, Jadzia Dax says that the spin of the neutrinos in the vicinity of the station is wrong because they are all left-handed, but I remember it being pointed out in some forums right around that time that neutrinos are always left-handed, and to have the opposite handedness, some of the particles would have had to be anti-neutrinos. What that forum post missed was correcting the term spin to helicity, apparently. Fascinating, the things I get to learn just indulging my curiosity (and getting a few laughs from the TIWWW and HNtDI categories) on this blog. And don’t ever worry about informing me I’m wrong. That’s part and parcel of true science. One often makes a discovery that either only opens up more questions, or shows that the scientific community actually knows a lot less on a subject than they thought they did. Astrophysics, based on some of my reading, is particularly prone to the latter.

  82. The Me-163 Komet was indeed a horrific threat to foe and friend alike, The Germans called the high-test peroxide “T-stoff”, accounts I’ve read describing it as being inclined to dissolve flesh or even cause what was essentially spontaneous human combustion. Pilot injuries must have been almost too awful to contemplate. And not just test pilots; the thing actually saw combat, if for a mercifully brief period. It may even have the rather singular distinction for a weapon of being responsible for more losses to its own side than to its enemy’s. With a swept tailless wing and speeds within sight of the transonic, the Me-163 was sometimes said to be an aircraft far ahead of its time. Infinitely far, one may hope.

  83. James says:

    I know most present here are chemists rather than aeronautical engineers, but the great drawback of the Komet was not the pilot-dissolving Stoff (they had quite a lot of experience handling the stuff by that point) but the lethal landing characteristics and the inexperience of the pilots.

  84. Tom says:

    The words singlet doublet & triplet come historically from the line spectra of the compounds. (one two or three spectral lines)
    This classification dates from a time before QM and was one of the early successes of quantum mechanics.

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