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What This Here Compound Needs Is Some Hydrogen Peroxide

As an organic chemist, I am willing to deal with the occasional bang or kapow in the lab, as long as things don’t get too out of hand. You’re supposed to know enough to be on guard against the sorts of compounds most likely to do that and be ready for them in case they decide to make the thermodynamic cliff dive all of a sudden. That said, like most chemists, I don’t actually sit around thinking up ways to make things blow up, so reading the energetic-materials literature is always an interesting experience – it’s a world where people are happily walking up the same staircase that everyone else is frantically sliding down.

Take this paper from Jean’ne Shreeve’s group at Idaho, a lab that has certainly given us all some alarming compounds over the years. If you or I (’cause we’re sensible, right?) look at a well-known crater-maker like dinitropyrazolopyrazole, we’ll probably decide that it has pretty much all the nitrogens it needs, if not more. But that latest paper builds off the question “How do we cram more nitro groups into this thing?”, and that’s something that wouldn’t have occurred to me to ask. Saying “this compounds doesn’t have enough nitro groups” is, for most chemists, like saying “You know, this lab doesn’t have enough flying glass in it” – pretty much the same observation, in the end. The way to stuff in more nitros, in case you’re wondering, is to hang hemiaminals off the NH groups and then nitrate those. (Edit: or, as shown at right, make the N-amino compounds and nitrate that). Why not? Round-bottom flasks, rota-vaps, and balances aren’t supposed to last forever, right?

shreeve-compound

The nitrated nitros shown in the paper are less thermally stable than the starting material – who’da thunk – although from reading the experimental section, it appears that Shreeve’s group – who definitely know what they’re doing in this field – did not experience any explosions while making them. The Supporting Information does mention that you definitely want to avoid any operations that involve scratching or scraping the solid products. Solid advice, that, and I can guarantee that the very thought has given any experienced chemist reading this part the shivers. Yeah, digging those last bits off the outer rim of the sintered-glass funnel to increase the yield is definitely not recommended here.

That paper, though, bracing though it is for people who like their glassware unpulverized and their eardrums intact, is not the only eyebrow-raiser that’s shown up recently in Angewandte Chemie. Try this paper out, from the Matzger group at Michigan. It’s on the delightful hexanitroisowurtzitane compound (CL-20) that I wrote about here. Now, if you complain that this one doesn’t have enough nitro groups in it then there’s something wrong with you, but apparently there are still those who look at this structure and say “Dang, not explosive enough”. Recall that this is the compound whose cocrystal with TNT is actually less dangerous than the pure starting material itself, and yeah, I know that sounds like the guy at the pet store packing a starved Komodo dragon into the carrier with your new dog, just to calm him down some. But there it is.

cl-20

Making this compound even worse by nitrating it further isn’t practical, though, even by the expansive definition of “practical” that obtains in this field. It’s already nitrated to hell and gone by most standards anyway, and the classic methods, which involve forgiving reagents like hot red fuming nitric acid, are not enough. So how do you make it more dangerous? (I know that’s kept me up at night).

Well, the chemists in the crowd will be familiar with compounds forming hydrates – those are when one or more molecules of water crystallize along with a compound. It’s something that you have to think about (for example) when you’re formulating a drug candidate, because the hydrate will have different properties than the original substance (melting point, solubility, stability), and it might be better, might be worse. Hydrates of CL-20 are known, but as the paper points out, why wouldja do such a thing, because dousing the crystal’s unit cell with water just hurts all its properties from a blowing-stuff-up (BSU) perspective. (My acronym, not theirs).

The crystal’s unit cell looks like it could accommodate something else, though, so why not. . .anhydrous hydrogen peroxide? So I have to congratulate these folks; they’ve managed to combine two of my Things I Won’t Work With entries into the same flippin’ substance. All you have to do is take the hexanitroisowurtzitane, which you have to have military connections to get ahold of apparently, or at least I should hope so, and some 98% hydrogen peroxide, no thank you, and co-crystallize from acetonitrile. This is apparently the first time anyone’s done this “peroxate” solvate trick with any energetic material, and no doubt others in the field are slapping their heads while reading this paper – gently, though, so as not to set off the stuff next door.

The experimental section of the paper is worth a read, and again, you can tell that Matzger’s group has good technique because everyone made it intact to the writing of the manuscript. There are pictures of the crystals themselves, which are very nice, until you realize that they’re plotting to blow you into the ceiling crawl space at the first opportunity. It says that “no unplanned detonations were encountered” during the work, which is a nice distinction. For most of us in the lab, every detonation has a spontaneous zing to it, a je ne sais quoi that you really just have to experience, because words are insufficient. It expands your horizons while it expands your fume hood, and if the sensation is not to your taste, you may find yourself expanding your employment possibilities to, say, a relaxing job wrangling Komodo dragons for the better class of pet store. I might consider that myself if I had to repeat this paper – I don’t want any CL-20 (pretty sure about that), I don’t want to handle any 98% hydrogen peroxide (very sure about that indeed), and once I’ve crystallized the two together, which is the sort of thing most people would consider a very unfortunate accident, I most definitely do not want to take the powder X-ray diffraction spectrum of the stuff by “finely grinding and packing the material” into a sample holder. Who the hell got to be the first person to try that, and what were they wearing while they did it?

I’d be dressed up like the first person to set foot on Venus, I can tell you (“That’s one. . .small. . .step for a foolhardy moron. . .”) and while I picked up the mortar and pestle (assuming my suit allowed me that much mobility) and muttered a brief prayer to Cthulhu (edit: spelled his name wrong; I’m toast now), I’d be thinking that if I’d only planned my career with more attention that I could be wrestling a hungry carnivorous six-foot lizard instead. Mom always wanted me to go into reptile-wrangling, should have listened while I had the chance. . .

122 comments on “What This Here Compound Needs Is Some Hydrogen Peroxide”

  1. robbbbbb says:

    Things I Won’t Work With is always the best column on this blog.

    1. Martin says:

      I agree, I got a good laugh out of this, but i all honesty, wouldn’t a new substance that didn’t explode vigorously at sub 100C temperatures, but was /violently/ exothermic with tremendous energy above that threshold be very valuable? Especially if it decomposed into simple constitutes like atmospheric nitrogen, water vapor, etc?

      1. Sam says:

        Less so than you might think. I short; we have plenty of ways to blow stuff up these days. Additional explosive power isn’t a massive priority from a practical stand point because you can just use more bangy stuff. New explosives need to really earn their keep to replace existing ones, and even then existing explosives will blow the crap out of everything that needs exploding anyway and there’s already a crap ton of it out there in stockpiles.

        Also, and as this article and a lot of others about high-energy materials make clear; these things are typically unstable in a variety of terrifying ways and we have no reason to suspect that any new ones will break that pattern. It’s interesting research and expands our knowledge about lots of things; and of course you never know what will actually become important in the future, but right now there’s not many non-research sectors crying out for more explosive power.

        Some industries would like it, if it’s cheaper and equally practical, but there’s nothing that people are looking at and thinking ‘If only we had slightly more boom…”

        1. AKA the A says:

          Things like shaped charges on anti-tank missiles would greatly benefit from more bang in the same volume and weight… bigger/heavier warhead means you need a bigger rocket to get it the same distance… bigger missile = heavier missile = the ATGM squad being more pissed that they have to lug it around
          If you give the missile even more armor defeating capability (because apparently being capable of punching through the equivalent of 1.5m (yes, meters) of hot rolled steel is starting to not be enough these days).
          Not sure if the same would apply to explosive reactive armor.

          But nobody sane will trade ofr +50% chance of armor penetration if it also means +50% chance of accidentally blowing up if you manage to trip while carrying said missile on your back 😀

        2. loupgarous says:

          Matzger’s group did some work with co-crystals of CL-20 and HMX for Livermore, which ought to tell you one fun thing they had in mind – they are obviously looking for more efficient things to make “insensitive high explosives” from. One of the go-to IHEs used to in thermonuclear weapon primary stages is a mixture of HMX and Viton plastic.

          Matzger et al decided to go the TNT-CL20 co-crystal one better, and co-crystallized the beta-phase of HMX with CL-20. No earth-shattering ka-boom ensued; in fact the co-crystal was about as stable as boring old beta-HMX, but half again as powerful an explosive.

          When you’re making MIRVed warheads for, say, ICBMs, every ounce saved counts, so if you can reduce the weight of the explosive lenses in the primary some, you’ve done a good thing right in time for the new, improved ICBM that the US Air Force wanted even before they got a Commander-in-Chief who thinks that’s an amazing idea.

  2. SirWired says:

    Yay! Another Things I Won’t Work With!

    I’m not a clinician, I’m not a chemist, just somebody who vaguely recalls hints of high school AP Chemistry twenty years ago, and these entries always leave me in stitches.

    If these ever get collected into an e-book, I’m totally buying a copy the day it’s released!

    1. Captain Ned says:

      Sir Wired:

      I come at this from the same level of knowledge. I have learned over the years, though, that more nitrogen is never a good thing

      1. David says:

        Or…”always a good thing”?

        It’s all about perspective..

      2. tango_uniform says:

        “More Nitrogen” is to inorganic chem as “More Cowbell” is to sketch comedy.

        We got to make nitrocellulose, gunpowder and ammoniumtriiodide (the precipitate dried on paper towels and whacked with a yardstick for fun) in my AP Chem class back in the early ’80s. Our instructor was famous for his “Learn or Burn!” methods.

        1. Jennifer Monroe says:

          If only I’d gone to college on time, before all those pesky “safety” (read: let’s make chemistry less interesting) regulations were decided upon! Alas! I redeemed myself only by working with a group determined to handle the hottest radioactive environmental samples in a lab that was destined to be decommissioned (before it was decided that we were a new reality show called Lab Wars, in which a bunch of apparently expendable chemists were dropped into a junk yard and told to build a hot lab from the rubble).

          That said, I’d still not work with these materials, though I left that job to raise children, and frankly, the radioactive stuff was less frightening. This is the first time I’ve read your column, and I’m in love. I think it might be time to get back in the field and start BSU.

      3. Aidan the Gravel Inspector says:

        I have learned over the years, though, that more nitrogen is never a good thing

        One of my SCUBA diving friends had a problem with the gas mixes in his rebreather a couple of years ago which spiked to a PPO2 (partial pressure of oxygen) of nearly 1.8 bar while he was demasking and changing over to his bailout bottle. He definitely thought that “more nitrogen” was a good thing.
        Our local hyperbaric chamber supervising physician recommends keeping PPO2 below 1.5 if you can and a ceiling of 1.6 ; at 1.8 you’re running a high risk of oxygen convulsions which have a well-earned reputation for tearing muscles and dislocating joints. This is not good at depth.

        1. Derek Lowe says:

          I have to admit, I had never heard of oxygen convulsions. And yeah, that sounds like the last thing you need on a technical dive. . .

        2. Scott says:

          *wince*

          I would not want a PPO2 anywhere near 1 bar even at sea level, if I could avoid it!

          Was bad enough when the folks on the sub cranked up the O2% early Saturday mornings… Going from ~19% to 21% is enough to wake everyone up.

    2. Baylink says:

      I provided the title one blog and several years back:

      Sand Won’t Save You This Time:
      Chlorine Trifluoride, and other delightful chemical compounds I want no part of.

      🙂

  3. Curious Wavefunction says:

    “This is the compound whose cocrystal with TNT is actually less dangerous than the pure starting material itself”

    That’s like a person whose combination with Jeffrey Dahmer is less sinister than either of the two.

    More Things I Won’t Work With please, especially with all the madness around us these days.

    1. Zak says:

      Secondary explosives popular for commercial and military applications are fairly insensitive, usually requiring something else (a primary explosive) to be exploded in contact or close proximity before they can explode. TNT in particular is known for its insensitivity.

      1. Aidan the Gravel Inspector says:

        A different friend blew half his hand off trying to steam the TNT out of a shell which had spent some decades rotting in a bombing range. But it probably wasn’t the TNT that detonated, but some reaction product between soil acids, TNT, copper, zinc, tin (i.e. brass-ish) and whatever made up the primary explosive.
        Now there’s a research project : what are these sensitive decomposition products?

  4. Anon says:

    Has anyone tried co-crystallizing Hitler with Trump?

    1. Hap says:

      Really? You Godwinned a “Things I Won’t Work With”?

      1. Anon says:

        Sure. What’s the difference between “things I won’t work with” and “people I would never trust with nuclear launch codes”?

        1. fajensen says:

          The “football” is just a prop anyway. We know this is so because Bill Clinton lost “the biscuit” for three months – “the biscuit” supposedly being the part with the codes written on it – without the US air force losing it’s bowel contents over not being able to nuke something or everything, should the occasion merit.

          Trust The System, it is quite resilient to be able to last for 200 years. If the US system was easily subverted, derailed or even destroyed by any crackpot who happens to become president, the US would have been a straight-up dictatorship or a failed state like Somalia well before we were born – and Trump and Hillary wouldn’t exist .

      2. Not Godwin says:

        Due to the current political climate Godwin’s Law has been suspended indefinitely. From the Wikipedia entry for Godwin’s Law:

        In December 2015, Godwin commented on the Nazi and fascist comparisons being made by several articles on Republican presidential candidate Donald Trump, saying that “If you’re thoughtful about it and show some real awareness of history, go ahead and refer to Hitler when you talk about Trump. Or any other politician.”

    2. qvxb says:

      The Hitler-Trump co-crystal should be less dangerous. Only Hitler served in the military.

    3. Amorphous solid says:

      macmillan and baran

    4. loupgarous says:

      Naw. The Obama-Clinton co-crystal gave us ISIS and Russian expansionism, so we decided co-crystallization of power-hungry morons was a bad idea.

      1. Pennpenn says:

        “so we decided co-crystallization of power-hungry morons was a bad idea.” So why in the name of tortured metaphors do we have Donald “Elemental Ego” Trump and Mike “I will burn this state to burn the gays” Pence as an alternative?

        Also, if you think that Russian expansionism was bad under Obama you ain’t seen nothin’ yet, given (for starters) Trump’s stated desire to ditch NATO and also his apparent fondness for Putin.

        Also leaving aside the fact that ISIS basically grew out of the prison camps set up under Bush Jnr, do you honestly think the situation is going to get any better with a president who will persecute and punish people just for being muslims? As if that wouldn’t drive millions to ISIS’s arms, which is what America certainly doesn’t need and exactly what ISIS has said they want. They want a war between Islam and the rest of the world, and people like Trump are dancing to their tune.

    5. Aidan the Gravel Inspector says:

      I first read this as “co-crystallise Hiliary with Trump”.
      There’s a horrible image for the poor woman.

  5. David Borhani says:

    Derek, why don’t you post chemical pictures anymore?

    1. Derek Lowe says:

      No time on the train this morning – let me see if I can drop one in now that it’s lunchtime. . .

    2. Mike says:

      His ChemDraw ran out of Ns.

      1. Scott says:

        More like, “His ChemDraw said, “hell no, waaaaay too many Ns in that!””

        And huzzah, another fun entry in the Things I Won’t Work With category.

      2. David says:

        There was a picture…but it exploded.

  6. b says:

    Now there’s a word I can’t say I’ve ever come across before in the chemical literature: explosophore. You learn something new every day.

    1. Sili says:

      It’s ever expanding.

  7. dave w says:

    Hmmm… even before you add the weird nitro stuff, any soluble organic solvent (e.g. acetonitrile) mixed with H2O2 is a potentially explosive mixture. Peroxide itself isn’t on my “won’t work with” list, but I would avoid mixing it with something like that.

  8. Isidore says:

    I wonder if the standard student medical and life insurance premiums apply to members of these research groups.

  9. oldnuke says:

    And who wants to be the brave soul to pop that tube into the NMR or into the FT-IR?

    Just how much excitement can you take in one day? To use Clint’s phrase, “Do you feel lucky punk?”.

  10. p says:

    These research groups could own YouTube if they decided to go that way.

  11. Li Zhi says:

    Interesting. I think long ago Derek suggested Ignition! by John D. Clark ( a free download, I thought it was public domain, but I’m no longer sure of that) which was entertaining to me and should be required reading for chemists with an interest in explosives or rocket propellants, imho. There are other issues with doing dangerous work at academic labs. “Free consent” by the indentured servants who are grad students seems to me to be a clear problem. I’m sure there’ll be some who say they (should have) known what they were getting into, but isn’t that the same argument you could use about going up for a nightcap? Does “unplanned” mean “unscheduled”? I mean, we have plans for retaliating after a nuclear strike on NYC, don’t we? Expected, scheduled, and planned (for) are 3 different things. I wonder if any invited to participate refused?

    1. Karl says:

      It appears that Ignition! can be found at e.g.

      https://library.sciencemadness.org/library/books/ignition.pdf

      Friends and family raised eyebrows when I scored a “real” hardback copy for $135 — worth it, for me. It’s one of the top two or three funniest technical books I’ve ever read.

      1. metaphysician says:

        Is it just me, or is that PDF seriously borked?

        1. ground says:

          Looks like it’s been run through an enigma machine.

        2. Stuart says:

          The PDF works for me, but not in a browser window – I had to download it and open it in a “proper” PDF viewer (Preview, on OS X, in my case) before I could see much more than the first two photos and their captions.

        3. Snoopy says:

          It opened for me, no problems. But I’ve long since turned off the PDF functionality in my browsers, and download to Foxit Reader.

        4. Steven Leach says:

          The pdf is a series of pictures of the pages in the book, nothing more

      2. Home says:

        Highly highly recommend Ignition! Just great writing, great thinking, and full of nitrated laughs.

    2. Jaybee says:

      I am 99% sure Ignition!(gotta love the ! in the title) is not public domain. But it has been out of print for so long that you are harming nobody at all by copying it. One might question the utility of copyright laws that protect works no one will publish.

      1. Aidan the Gravel Inspector says:

        One might question the utility of copyright laws that protect works no one will publish.

        (Waiting for ISIS Publishing Co to step up to the … launchpad?

  12. Gene says:

    “Now we mix the happy little H2O2 into the CL-20 and watch the crystals form (from a distance).”

    Apologies to Bob Ross

  13. MA says:

    Fun stuff. And remember, CL-20 would fall under the category of energetic materials I would personally consider “not that bad.”

    We used to do some work on explosive cocrystals — the observed phenomenon of a more insensitive material when combined was not at all uncommon. We once saw two materials that alone were bad news, but when cocrystallized you could handle like any other organic white powder.

    1. Eric says:

      You snorted it?

  14. Bob says:

    I recall when I was an undergraduate and working in a lab as basically a pair of hands to make intermediates for the grad students I had occasion to do some reactions with Osmium tetroxide as well as 98% Hydrogen peroxide. (NOT AT THE SAME TIME!!!!!!). The grad student insisted I go to the library first and read everything I could find about the safe handling of these things and I did so. Consequently I was scared to death and VERY CAREFUL. After a few iterations, though, I lost my fear of the Hydrogen Peroxide, but, luckily never got sloppy enough to pay for it. I even entertained thoughts of reproducing in a controlled (!!!!???) manner the explosions I had read about. Better sense prevailed and my chemistry career was not cut short.

    1. Michael says:

      There would certainly be no shame in having a healthy fear of both. Mistakes made with 98% H2O2 will usually simply blow you up; the associated crater occupying where your fume hood and laboratory once stood will certainly liven up a dull afternoon. As to the relentlessly foul Osmium Tetroxide, at least it gives you a warning by blinding you before it kills you. A healthy fear of both is a good thing…I on the other hand will pass.

  15. CMCguy says:

    I can imagine the phrase “no unplanned detonations” as the theme of those in military/contractor research groups working on explosives and munitions since the trick is not so much to generate stuff that can decompose or react with excess energy but to have the materials do so precisely when one wants that.

    1. Jim Hartley says:

      Great name for a rock band.

      1. Phil says:

        I think “The Unplanned Detonations” works best.

      2. wlm says:

        Almost as good as “Rapid Unscheduled Disassembly”

      3. tangent says:

        No Unplanned Detonations is surely a Culture ship name.

        1. Not A Chemist says:

          Agreed 🙂

  16. asoc says:

    Go home nitrogen, you’re drunk.

  17. Hap says:

    So now CL-20 can clean your wounds as it delivers them? That must have comforted the people working with the cocrystal.

  18. Mike Andrews says:

    Hurrah! Another TIWWW! And a lovely one, too: adding Yet More Oxygen to hexanitroisowurtzitane, as if it weren’t already sitting balanced on the knife-edge lip of the potential well. Not only an earth-shattering KaBOOM!, but also an enhanced excess of reddish-brown fumes. What could be better, for some unusual values of “better”?

    I do so very much look forward to the TIWWW articles. This one is in no way a disappointment, particularly to labware vendors.

  19. Thomas says:

    2,5,8-triazido-s-heptazine seems a beauty too. But it is flat.

  20. Lev says:

    > you can tell that Matzger’s group has good technique because everyone made it intact to the writing of the manuscript

    That’s a perfect example of survival bias… hmmm, yes indeed.

    1. HFM says:

      *Mon Mothma voice* Many undergrads died to bring us this information…

    2. Curious Wavefunction says:

      Hopefully there are no von Stauffenbergs on that list.

  21. Xiao Bu says:

    I feel like this paper could be improved by either photos of videos of the group detonating vials of the stuff out in the parking lot. I actually checked the SI to see if there was anything like this.

  22. Jeff Strunk says:

    I’m no chemist but I would be curious to know how this stuff stacks up against Azidoazide Azide, C2N14. There’s a bit about it starting at 3:00 in this SciShow YouTube video.
    https://www.youtube.com/watch?v=ckSoDW2-wrc

    1. SirWired says:

      Much of that video (though not the Azidoazide Azide) appears to be a blatant rip-off of this very blog.

      1. Vampyricon says:

        I wouldn’t call it ripping off as they linked back here.

  23. Humble Scrivener says:

    I laughed until I cried. When will the TIWWW book be published?! I’m waiting for it as (im)patiently as I once waited for new volumes of Stephen R. Donaldson’s Second Chronicles.

  24. wlm says:

    What a bunch of slackers! Surely if water and hydrogen peroxide for co-crystals, they should have tried hydrazine!

    1. Ksr15 says:

      If they were feeling REALLY lucky, they could have tried crystallizing it with tetraflurohydrazane. That would have been exciting!

  25. Hano3s says:

    I’ve encountered a few Komodo dragons in the wild and I would say about 15 feet was close enough. I would much rather crystallize hexanitroisowurtzitane with hydrogen peroxide than wrangle one of those beasts. Brrrr.

  26. Druid says:

    I would like all practical synthetic organic, inorganic and organometallic chemists to have to use or make something explosive, and something very toxic, on the very small scale of course, as part of their education – earning their stripes. That way I know they have what it takes to work in a dangerous place – a chemistry lab. Everyone else is an accident waiting to happen.

    1. HawkeyeState says:

      My father-in-law still has the photo of him holding his face shield when he won that month’s Wise Owl award from Diamond Alkali*. He got his name on a few patents before he became a process chemist in the 60s for a group working on the Apollo project – strangely enough, not in propellants, but in avionics. Absolutely everyone working with him or under him got all kinds of safety training.

      *For more about the history of Diamond Alkali in Northern Ohio, a nice little piece about resorts and old spaces: http://www.clevescene.com/cleveland/badlands/Content?oid=1501842

  27. enl says:

    “even by the expansive definition of “practical” that obtains in this field”

    I must remember this…

  28. Earl Boebert says:

    Way, way back in the bad old Cold War days I was assigned to a project that required me to take an in-house course in fuze (detonator) engineering. The instructor began with the following:

    “If you tell me the ordinance absolutely positively must detonate when you want it to, I can handle that.

    “If you tell me the ordinance absolutely positively must *not* detonate when you *don’t* want it to, I can handle that as well.

    If you tell me you want both, we need to talk.”

    Fascinating business.

  29. loupgarous says:

    Speaking of another wonderful term Derek’s given us, “Satan’s kimchi,” the wonderful folks at India’s High Energy Materials Research Laboratory (their Pune laboratory) have given us an appreciation of their experience with making dinitrogen pentoxide and how they’ve been using it to make CL-20 and even more interesting things.

    Just in case the world needed less stable shit, and more ways to make it.

    1. Mark Thorson says:

      50 grams/batch. Enough to be interesting, but probably not enough to bring the building down. There are some chemists who have a certain idea of “fun”, and they seem to exist everywhere there are chemists.

      1. loupgarous says:

        That article was dated 2005. Since then, the Pune lab has issued press releases claiming they’re making CL-20 in quantity, so apparently they’ve scaled that synthesis up successfully. Since (going by how they run nuclear power plants) India’s a little more forgiving on the “health and safety” thing than OSHA and EPA are here, they might not have some of the constraints US manufacturers of CL-20 do.

      2. loupgarous says:

        Looking over that abstract, the wild and crazy guys at HEMRL Pune sure do know how to party – adding ozone to dinitrogen tetroxide (a rocket fuel oxidizer which vies with another favorite on this blog, chlorine trifluoride and its shy, not-so-popular cousin perchloryl fluoride for popularity as a mixer with UDMH for spacecraft upper stages) isn’t my idea of “getting the party started” (or a synthesis amenable to large-scale production), but those pukka sahibs at Pune are hardier partiers than we.

  30. Anon says:

    Back in school days, I used to try making nitroglycerin in my parents’ garage, but never succeeded. The stuff always used to overheat and “explode” (rapidly break down) during synthesis, filling the garage with brown fumes which I had to waft out before my folks got back from work.

    1. dwywit says:

      “Back in school days, I used to try making nitroglycerin in my parents’ garage”

      Are you me? I tried that once, but only had access to school-lab-grade HNO3 and H2SO4. Pre-internet, research sources were my parents’ copy of the Worldbook Encyclopedia, and another forgotten encyclopedia at the local library. Approximately 50ml of proto-nitroglycerin decomposed rapidly in a volcano-like fashion, leaving a smoking patch on the roof of the garage.

      My friend and I washed everything down with the garden hose, and the only evidence we left were a couple of irregular clean patches on the roof and floor, immediately above and below the site of the volcano.

      I had better luck with traditional gunpowder. Good times.

      1. Anon says:

        Glad I’m not the only nutter. Later on I tried to make VX nerve gas. I didn’t do any analytical chemistry on the product, but guess I failed at making that, too, since I’m still around to talk about it. Perhaps there is some natural selection for crappy chemists? Anyway I ended up doing protein engineering. 🙂

        1. loupgarous says:

          Roach problem in the dorm? Can’t think of too many other practical applications for VX – that don’t involve uncomfortable discussions with the authorities afterward.

          Now, nitrogen triiodide is fun at parties, and literally “bathtub chemistry” (the bathtub’s a good place for the reaction, actually, because you’ll want to flush all the stuff you made it in with water liberally afterwards – or experience a “porcelain storm” later.

          We used to put the wet crystals in door locks… then retreat FAR down the dorm hallway for the detonations and swearing.

          1. Anon says:

            Yes, I skipped the “why am I doing this?” step, the “how do I explain why I’m doing this?” step and the “what the hell do I do with the stuff if I do manage to make it?” step before I got on with trying it anyway. Probably not very smart in retrospect, but I had just seen The Rock. 🙂

          2. Mark says:

            We had a roach problem in our dorm and our solution was to spray them with Right Guard deodorant and set them on fire… they burn green. After over-liberally dousing one and setting the not-so-liitlle bugger ablaze, it ran under my friend’s bed. But the overspray from the Right Guard had landed on his bed spread. Flaming roach + bedspread soaked in flammable pit spray = fun for all. Beer helps…

            Oh, and roaches make for a decent make-shift vacuum chamber gauge. At a certain pressure (can’t remember the value) their wings fold out. Keep pumping the critter down and it flops on it’s back. Keep going and the wings fold back in. Bring up the pressure and the process reverses. You can pump them down several times before they break.

      2. Leonard says:

        Nitroglycerin is actually easy to do at home. Back when I was kid (communist Poland) the biggest problem was to actually get hold of quality glycerin as it was always mixed with some contaminant. I had no problem finding acids even as a kid as they were used for many puproses by general population.

    2. fajensen says:

      I had a school friend who blew up his parents garage with Nitro. Took him a year to pay for the new one too. The trick is: Small batch, plenty of cooling, adding the Nitric acid slowly and having some methylated spirit at hand to dissolve the nitro in so it doesn’t blow up in your pocket.

      Now, This was back in the days (1980’s)when we had actual, effective, terrorist cells all over the place in Europe which the police were dealing with – none of this overblown “War On X”-bullshit, so of course no one got nicked just for a little fun with explosives.

    3. loupgarous says:

      The informal literature on mixed-acid nitration of anything generally stresses ice baths for the reaction vessel, and/or controlling the addition of acid to whatever you’re nitrating (or peroxidating in the case of The National Molecule of Palestine, TATP) to keep that temperature down.

  31. loupgarous says:

    During Derek’s last deliberations on CL-20 and its cocrystals (he mentioned the curious phenomenon that CL-20 becomes tamer co-crystallized with TNT, which actually has precedent going back to “ednatol” and other TNT co-crystalline entities around WW2) in “Things I Won’t Work With”, I’d posted this paper from Matzger’s group describing their creation of a 2:1 co-crystal of CL-20 and β-HMX,

    Quoting from the abstract: “The cocrystal consists of a 2:1 molar ratio of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), a powerful explosive too sensitive for military use, and HMX. A predicted detonation velocity 100 m/s higher than that of β-HMX, the most powerful pure form of HMX, was calculated for the cocrystal using Cheetah 6.0. In small-scale impact drop tests the cocrystal exhibits sensitivity indistinguishable from that of β-HMX. This surprisingly low sensitivity is hypothesized to be due to an increased degree of hydrogen bonding observed in the cocrystal structure relative to the crystals of pure HMX and CL-20. Such bonding is prevalent in this and other energetic cocrystals and may be an important consideration in the design of future materials. By being more powerful and safe to handle, the cocrystal presented is an attractive candidate to supplant the current military state-of-the-art explosive, HMX.”

    I wonder if the increased hydrogen bonding in the CL-20 – β-HMX co-crystal didn’t, perhaps raise hopes that anhydrous H2O2 might also make a kindler, gentler beast out of CL-20.

    Apparently that didn’t happen. They got more detonation velocity out of one of their peroxysolvates of hydrated α-CL-20 than from ϵ-CL-20, and about the same sensitivity.

    That in itself may vindicate the hopes voiced in Matzler et al’s CL-20 – β-HMX co-crystal article that hydrogen bonding in co-crystals adds stability to CL-20, because intuitively, shoving a peroxyl radical in the same crystal with CL-20 seems a lot like lighting a short fuse – but “no unplanned detonations were observed.” A record that, say, Klapötke’s group might envy in one of their projects.

    Thanks for giving us more brisant chuckles, Derek! Always nice to read another “Things I Won’t Work With” from you!

  32. David Edwards says:

    Ah, another “Things I Won’t Work With” entry, and long overdue too!

    Derek, you always seem to sparkle with particular vigour when writing entries for this section. Though hopefully the effervescence won’t turn into detonation, as is very likely with some of the compounds you’ve covered here 🙂

    As an aside, you might want to look at the font settings for your blog. Only commas and full stops are indistinguishable even on my high resolution monitor, which makes for some interesting parsing of the comments.

    Meanwhile, back to the kaboom … I have to say, it takes a truly special sort of mentality to think of making co-crystals of HNIW and anhydrous hydrogen peroxide. I was almost expecting it to be a Klapotke product … or is his lab working on a co-crystal of HNIW and anhydrous hydrogen azide? Could be interesting if so given that I live close enough to Germany to see the mushroom cloud when it detonates – the English Channel might not be enough separation to shield UK residents from the Munich shrapnel if that’s what they’re planning … or even worse, a co-crystal with a 1:1 mix of hydrogen azide and cyanogen azide, even assuming such a combination is possible without propelling bits of the lab all the way from Germany to Iceland …

    Klapotke’s lab isn’t so much the place where nitrogen is drunk, more spaced out on angel dust, to borrow a previous commenter’s entry. I harbour suspicions that the lab’s next project involves making a cage compound, trapping some C2N14 inside a polynitro prism, then nitrating the prism just for the giggles. Or should I not be giving them ideas like this through your blog? 😀

    1. fajensen says:

      ” I harbour suspicions that the lab’s next project involves making a cage compound, trapping ”
      Hmm, couldn’t one perhaps be trapping some Actinides in such a molecular cage, for adding some additional colours to the chemical excitement?

      1. Anon says:

        Cool, Nano-Fireworks!

      2. David Edwards says:

        I suspect trapping something like a plutonium atom in such a cage would require all sorts of national security hoops to be jumped through, though if Klapotke receives an invite to Los Alamos or Lawrence Livermore, it might be something he’d try. Though I dread to think of what use such a crazy substance would be put to …

        1. loupgarous says:

          The odd-numbered actinides only do the voodoo they do do so well when their atoms are suddenly smacked together hard enough that a really fast nuclear chain reaction happens.

          Placing an actinide inside a cage that lets go in a really brisant manner could have some unpredictable effect (if you do that trick with the heavier transuranics, there are researchers saying the outer-shell electrons act in ways you wouldn’t think they would).

          But it’d mainly make sure that when the highly explosive cage decided to dive off the thermodynamic cliff (thanks, Derek!) the actinide would be more than far enough from other actinides in the same batch of that compound to just be heavy metals, not fissiles.

  33. Daen de Leon says:

    Derek, thank you. This is wonderful stuff. In the next book?

    1. Donal maloney says:

      At the old Schering-Plough we were accused of insubordination for not using hydrogen peroxide/ Iron(111) as a mild cheap oxidant to replace the excellent Vanadyl(acac) tert-butylhydroperoxide. Ref. K.B. Sharpless , Aldrichimica Acta. Vol.12,No 4. page 63.Is it any wonder that Merck took us over!

  34. Kent G. Budge says:

    Hexanitroisowurtzitane: Already looks rather overoxidized to me. Rather than overoxidize it even more with peroxide, I’d have added some powdered aluminum or maybe fuel oil.

    By remote control from a different continent.

    1. loupgarous says:

      There appears to have been method to Matzger’s madness. He not only got away with co-crystallizing CL-20 2:1 with β-HMX, but making enough to do sensitivity tests with – and discovering it was as stable as the β-HMX itself. In the abstract to the paper where Matzger et al describe that fear of derring-do the authors say “This surprisingly low sensitivity is hypothesized to be due to an increased degree of hydrogen bonding observed in the cocrystal structure relative to the crystals of pure HMX and CL-20. ”

      Well, if you’re looking for a handy way to add a little “oomph” to CL-20 which has hydrogen in abundance to bond with, hydrogen peroxide is hopping up and down going “Pick me! Pick me!!!” If it was going to blow up, it would have done so right in the reaction vessel, after all…

      It’s hard to argue with the “no unplanned detonations occurred” part of the paper. That’s more than, say, the guys in Munich and Wuppertal can say of the spicy azides they’re cooking up (some with US Army funding, perhaps in hope that something a touch greener than lead azide can be tamed to sit quietly in cartridge primers until woken up by the firing pin of a rifle).

      The fact that hydrogen peroxide can be made to share a crystal with CL-20 at all, and that it’s not much more sensitive than ϵ-CL-20 may mean that Matzger and his people are on to something. It’s almost a worst-case test of their hypothesis that hydrogen bonding has power to soothe the savage breast of CL-20.

      1. Ivan Bushmarinov says:

        Any compound forming hydrates forms isostructural “peroxates” as well. It is a quite well-known fact in the crystallographic community — however, Matzger must have arrived to the conclusion independently, since he did not cite any relevant papers.

        1. loupgarous says:

          I guess I ought to have been clearer and said “The fact that hydrogen peroxide can be made to share a crystal with CL-20 without causing an immediate detonation… “

  35. Ivan Bushmarinov says:

    Dear Derek,

    This post is somewhat incomplete without the glorious TTTO, tetrazino-tetrazine 1,3,6,8-tetraoxide (C2N8O4), recently made and studied by my colleagues! (doi:10.1002/anie.201605611 — published this July in ANIE).

    1. loupgarous says:

      Congratulations on starting with 2,2-bis(tert-butyl-NNO-azoxy)acetonitrile and not creating a new skylight over your reaction vessel!

    2. loupgarous says:

      And. quoting from someone quoting the Angewandte Chemie article

      ” One of the critical practical requirements its sensitivity to thermal or mechanical treatment. “In the preliminary experiments, it did not detonate when rubbed in an agate mortar, but exploded in unglazed porcelain one,” the authors wrote on their initial studies.”

      Yes, I think we have a winner, Derek!

  36. CF says:

    It could be worse — you could have misspelled Hastur’s name… aw, *&^%$#!….

  37. jon gray says:

    Thank you, Derek! Been waiting for a TIWWW for awhile!

  38. AMorro says:

    My love for your writing is like Klapötke’s love for nitrogen groups.

  39. not a chemist says:

    OK, if they can stuff hydrogen peroxide into this, why not something like….dioxygen difluoride?

    Try this somewhere far from Chicago. Maybe Hangzhou would be far enough.

  40. David Edwards says:

    I’ve just had an evil thought that will make Derek shudder. 🙂

    Step 1: solve the problem of synthesising hydrazine tetraazide.

    Step 2: make a peroxide co-crystal with it.

    Of course, Step 1 above will be the toughest part, but I think Klapötke may already be working on this. If it’s possible to make tetrabromohydrazine, then reacting it with neat hydrazoic acid should do the trick, unless of course the mechanism that works with cyanogen bromide doesn’t work with this other compound. Though how stable the reaction product will be is anyone’s guess.

  41. Michel says:

    The ‘Things I Won’t Work With’-articles make for some of the best reads on the whole Internet. Seriously.

  42. Jim says:

    Sundance: “Think ya used enough Nitrogen there Butch?”

  43. Steven Leach says:

    Wonderful wonderful read as i was sent back to my days of working with picric acid, metallic Sodium and various gases like SiF4
    Just imagining all “planned” experiments set me into uncontrolled chuckles

  44. NotOnTwtr says:

    Hunter S. Thompson may have called this “Bad Craziness”. (One of his trademark taglines.) I have had a colleague literally blow himself to smithereens scaling-up a batch of product containing (just only!) ammonium nitrate. I was not available to help stop or contain his dangerous practice(s) unfortunately. Not Recommended!!

  45. charlesfreck says:

    This reminds me, there’s an acronym in hobby high power rocketry called a RUD, which stands for Rapid Unscheduled Disassembly. It would happen sometimes when for example an ammonium perchlorate based fuel grain inside a solid fuel motor has a flaw in its casting….. RUD….

    There’s another one I like, a kinetic core sample, which is when a rocket fails to deploy its parachute and returns to the ground in ballistic fashion, usually sans nosecone.

  46. Brian Skinn says:

    I propose classifying all energetic materials cocrystallized with H2O2 as ‘perdetonates’.

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