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Chemical Storage, Good and Not So Good

Back to science! I will admit that my Twitter feed is going to be rather more politicized than usual for some time to come, but this is not a political site, and thank God for that. I have to say, it certainly brings in the comments and the traffic, but that’s not my goal in life.

A reader sent along a query that’s about as far from current events as possible, and I think that a lot of us are in the mood for some of that. It’s about storing reagents. I know that a lot of labs, and even whole departments, especially in academia, often just go straight alphabetical. The question was not so much whether that makes sense or not, but whether or not it can lead to very incompatible things being crammed in right next to each other.

I think that a lot of places use a “modified alphabetical” system, though, where the run of normal-ish reagents are stored by name, and more reactive stuff is moved out over to the side. Strong acids, strong bases, reactive gases – these traditionally have their own storage cabinets anyway, and there are also places that separate out strong oxidizers and/or strong reducing agents as well. Then you have the whole room temperature versus fridge versus freezer storage issue as well, which also tends to separate out the more reactive stuff into the colder compartments. (In my own experience, it’s cold storage in the labs, which is definitely necessary, that does more than anything else to randomize the attempts to track reagents department-wide).

Individuals and individual labs, naturally, sometimes evolve their own systems. From an organic chemistry viewpoint, there’s a lot to be said for a whole cabinet that’s nothing but primary and secondary amines, for example, or a whole box of isocyanates or carboxylic acids. Synthon-based storage tends to get hard to manage after a while, especially with multiple functional groups, but it can be very convenient. And since it’s based on chemical reactivity right from the start, it tends to get around the incompatible storage problem by definition. This is how things tend to get sorted out under my own hood, on a project-by-project basis.

If you have a completely bar-coded system, though, which you really need to if you’re actually going to be able to track everything, then you don’t have to store alphabetically at all, or by any system other than something tied to the number on the bottle. Organizing them by bar-code would work fine, except you’re almost certainly going to have things that shouldn’t be sitting next to each other, so the sort-out-the-reactives techniques mentioned above are usually employed. That way, when you search for some reagent, its location comes back first as “Acid shelf”, “Oxidizer cabinet” or whatever.

That’s only going to work, though, if people actually put the flippin’ bottles back in the right flippin’ places, and there you have the weak link of every single reagent storage system: the flippin’ chemists. We suck at this. Everybody’s just going to borrow the bottle of the ortho-fluoro intermediate for just a few minutes and then bring it right back. Well, tomorrow, definitely tomorrow. Maybe Monday – I had to set up the reaction again to make more. And so on. No one ever gets around to noting exactly which chemicals are wandering around like this, no matter how many scanners you install or how spiffy the software might be. The only solution I’ve seen, and I’ve seen it implemented many times, is a periodic scan-down of everyone’s bench, hood, and fridge to locate where everything actually is, for at least a little while, as opposed to who had it three months ago. This works pretty well, but it also means that you have to have a staff that does nothing else, which is hard to arrange in many academic departments – the time-is-money attitude in the company labs ensures that people are hired to do just that job, though.

So here’s a question to finish off with: what’s the worst/stupidest/most potentially catastrophic chemical storage you’ve had the displeasure of seeing? I think my own might have been when I came across about half a kilo of chromium trioxide baking in an open dish in a drying oven, the same one that people dumped solvent-soaked glassware into regularly. Or maybe it was the moment during my first year of grad school, studying at a little cubicle in an unused lab, and looking up to see that there was an old kilo jar of benzidine next to my head. No, scratch that one, at least it was in a sealed container. The worst I can think of at the moment happened to a colleague of mine years ago in a biology department. A notice had come out to everyone about old peroxide-forming reagents needing to be disposed of, especially in the non-chemistry labs. The biology lab head involved read this, noted the part about possible crystalline peroxide formation, went over to a cabinet and rummaged around for an elderly can of diethyl ether in the far back corner, and then shook it next to their ear to see if it sounded like had deposited any solid. My colleague who witnessed this bold analytical technique reported to me that it was the first time they’d ever felt the hairs on their head actually lifting up in panic, and also reported that they never wanted to experience that sensation again, if that could be arranged.

Update: I’ve heard from my source for this incident! Their comment was “You make me sound a lot more polite than I was at the time.” Much shouting and exchange of Anglo-Saxon vocabulary took place after the audiometric assay, as one can well understand.

190 comments on “Chemical Storage, Good and Not So Good”

  1. A Nonny Mouse says:

    I am told the story of someone who started a PhD in the Boston area (late 1970s) and went to clean up his bench space which had not been used in a long time. He happened to find a kilo of amphetamine which was converted to the sulphate which covered the living expenses for the duration of his time there.

    Having looked on Google maps, I see that the laboratory has not yet been swallowed up by MIT.

  2. Ivan Bushmarinov says:

    I heard a story about a professor who was offered a lab at Wien University in the 50s, on the condition that he sorts out the storage of solvents. Essentially, it meant that he had to deal with a room full of drums filled with old diethyl ether, some of them neglected since WWII, with nice big crystals on the bottom. In a historic building in the middle of a densely populated city.

    The solution was to construct a system (mostly consisting of copper tubes to increase sturdiness and exclude the possibility of sparks) for careful mixing of the old solvent with peroxide-free one and subsequent controlled burning of the mix. The lab building still stands.

  3. Project Osprey says:

    Sometimes grouping similar compounds can lead to unexpected hazards, the classic example being concentrated nitric and acetic acids. Most people would store them in the same cabinet without a second thought but if they were to actually mix you’d get a fairly nasty fire (potentially very nasty depending on the other things in the cupboard).

    Most strong acids are actually incompatible, in so much as they’ll react together to make something worse than the sum of their parts.

    1. Falanx says:

      The majority of strong mineral acids behave just fine. They become extremely aggressive to other things you put in mixtures of them – nitrating mixtures and aqua regia, I’m looking at you – but otherwise, reasonably well behaved.

      1. Nicholas Yee says:

        Or strong(ish) Lewis Acids. My old environmental chem prof who was known to, cough, embellish, but I don’t think a man is under oath while trying to find stories to keep a class of 20 something’s attention for more than five seconds, told a story of a research gone wrong in an old lab in the 80s involving an unfortunate mixture of HF and SO³ that managed to wreck some havoc.

  4. enl says:

    It has been 20 years since I was near a bench (semiconductor fab for a while when it was still wet, and doing electronics for a research group at MGH), and the only bad one I recall was nitric acid stored on a bench about a meter from a south facing window. Maybe 500ml bottles, clear glass. It tends to get a bit angry in those conditions. Words came from above to the person responsible.

    Only other thing that comes to mind is the carefree (by the standards today) way organic solvents (methylene chloride, carbon tet, benzene, etc) were handled in the semiconductor lab.

    1. Dave says:

      Don’t be daft. We never used Carbon-Tet like that. Instead, we used Trichloroethylene to clean the spaghetti sauce stains off our blue ties and white shirts (while we were wearing them, of course!). And, after all, Trichloroethylene has to be safer than Carbon-Tet, since TCE has one less Chlorine atom than Carbon-Tet; right?

      https://en.wikipedia.org/wiki/Trichloroethylene

      P.S. And, I’m serious about that comment about using it to clean the spaghetti sauce stains off ties/shirts. We used to get it in one gallon cans.

      1. MTK says:

        Well, PERC, percholoroethylene, is the solvent used at most dry cleaners so its not surprising that trichloroethylene would work also.

        1. Falanx says:

          Seeing as even now it’s still used as a vapour cleaning solvent in electronics and aerospace metalwork..

      2. oldnuke says:

        I still have a couple of cans of Freon TF — it is great for getting spots out of my shirts.

        Hopefully it is enough to last me another 18 months until I retire. 🙂

      3. Chad Irby says:

        When I was in the Air Force (long ago), we carried spray cans of “trike” along to clean contacts on electronics.

        Do you know that, if you squirt someone with trichloroethylene, it’s really, really cold?

        1. Some idiot says:

          Yep… I also know (from personal experience) that when someone fills your lab coat pocket with liquid nitrogen (while you are wearing it) that gets pretty cold too…

        2. Nick K says:

          Dichloromethane under the watchstrap – cold and extremely painful!

      4. Roland Smith says:

        Years ago the mechanics in our machine shop would dip their hands in the vapor degreaser filled with tri to clean their hands if they were really greasy.

        A decade or so earlier (before my time) in the same company the floor of the polyester/epoxy/phenolic resin laboratory tended to get sticky. So every Friday afternoon they would upend a 25 liter can of solvent on the floor to brush the sticky stuff off and wash it down the drain.

        The same building used to house the laboratory of a bakelite plant. The cellar still had a distinctly chemical smell decades after they stopped producing it.

      5. Highwater says:

        My dad used to wash grease off his hands with TCE… the whole area downhill of the plant he worked at is contaminated with the stuff.

  5. AndrewD says:

    There was a story told at one company I worked for, that, when they cleared out a disused chemical storage celler they found a cache of improvised antitank weapons, several(unfuzed) hand grenades and a few kilo’s of TNT dating back to WW2. It was believed that they were made for the local Home Guard unit.

    1. Falanx says:

      Except, that didn’t happen at UK schools, at all. Well done Gizmodo, and by extension Guardian. It happened at Colleges, and we tend to make a distinction, even if recently several more schools have assimilated six form colleges for what used to be post-school age students.

      1. Deborah says:

        A friend, however recently related an incident from his wife’s schooldays:

        “arkady did this as well at age 13, but the school was worried a’s electronics would blow up. this is because a designed them as part of something intended to blow up: a timing circuit for detonating nitroglycerin. a had previously made nitroglycerin, at school at age 12 1/2, after watching a TV show about how to make nitroglycerin as a step to making dynamite, which was the aim at the time. the chem lab had nitric acid, so a made nitroglycerin. took 4kg of fuller’s earth to make it into dynamite to school! a made the nitroglycerin. teacher worked out what a had made, and called the bomb disposal squad to dispose of the, er, two pints of nitroglycerin a had made in the school chemistry lab. the nitroglycerin was taken out to the playing field and the school got a new long jump pit. a didn’t realise till later (a) just how much trouble they’d caused the school (b) that they were quite possibly personally responsible for uk school kids not having access to actual nitric acid.”

        Moral: be careful what you store openly in school labs!

        (From here: https://reddragdiva.dreamwidth.org/598193.html)

  6. As a librarian, I can sympathize with the problem of “returned to _where_?” People put books back in the wrong place on the shelf all the time — shelvers make errors, untrained patrons jam them back in the closest available slot, and some students put the book they want to read in a Sekrit Place on the shelf known only unto them instead of checking it out…

    The only solution that works is to regularly check the shelves and put anything in the wrong place back in the right place. At least we don’t have to worry about Hayek and Marx giving off sparks when shelved next to each other.

    1. Roger rabbit says:

      Marx should be stored with the potent APIs for its ability to cause brain cancer, especially in the youth!

      1. Nick K says:

        Fortunately, Marxism is the only brain disease one can grow out of.

  7. steve says:

    Back in graduate school people were still using ether to anesthesize animals. It got to the point where different graduate students each had their own bottle so about a dozen open ether bottles with plastic caps were left in a refrigerator in the animal prep room. Luckily it was over Thanksgiving weekend when no one was around but when people came in Monday morning it was clear that there was an explosion that occurred with such force that it blew the door off of the refrigerator and embedded it in the cinder block wall facing it.

    1. Helianthus says:

      In a similar vein, my highschool teacher in physics/chemistry told us us about a fridge with 2 ether bottles in it.
      As the story goes, one day, the fridge (well, most of it) was found one floor above its usual place.
      Maybe he was exaggerating for effect. I’m not exactly interested in finding out by myself.

  8. Anthony says:

    Freon (I don’t remember which one) with a boiling point somewhere between nighttime low temperature and daytime high, in a 55-gallon drum with a tap, outdoors. It wasn’t really dangerous, not even potentially so, but it’s impressive to come to work in the morning and see a steel 55-gallon drum pinched in half the way you might do to a soda can.

  9. Anonymous says:

    After all these years, whenever I need a potassium salt in our alphabetically arranged inorganic cabinet, I start at “K”.

  10. Jacob says:

    Oh, my! When I was an undergraduate, someone discovered a jar of picric acid, complete with metal cap, sitting cheerfully on a windowsill in a lab.
    I still remember watching the bomb squad setting it off in a big steel drum out on the lawn in front of the chemistry building. It made quite an impressive thump.

    1. UudonRock says:

      I was cleaning an old storage room and uncovered a very rusty and forgotten acid cabinet dating back to the 1970’s. There were multiple glass bottles of acetic acid and one 500g metal topped bottle of picric acid. It had crystalized. I remember not breathing as I slowly backed out of the room. We had to get a bomb squad to remove it…
      Bad as that was there was, years before I had worked at a plating facility. There were major renovations taking place and the decision was made to temporarily house some of the larger containers of nitric and hydrochloric acid (multiple 50 gallon industrial barrels) in a storage area used for the R&D labs. They decided to stack them on top of each other a shelving unit that was directly above our organic storage cabinet. Several techs, engineers and I collectively requested some other arrangement rather politely or we would have to shut down the plant and call OSHA and the EPA. We could never figure out who came up with that bright idea…

      1. Ontario for some reason used to provide picric acid as standard stock in high school chem labs. At some point during the Disco Era, the powers that be decided that was a bad idea and ordered schools to discontinue using picric acid. For some reason, a number of teachers decided not to dispose of the picric acid. Instead, they just put the bottles at the back of the chem store lockers.

        Some years later the obvious issues with this manifested. Cue various high schools getting visits from the bomb squad…..

        1. I bet Derek expected me to tell the story of how I knocked a jar labeled picric acid across a room, The good news is that nobody else was endangered because the room I was in was designed to contain explosions and conflagrations safely. Because it was where they stored corrosive and explosive materials.

        2. You Arewrong says:

          They used to provide it because people were aware of its actual properties. Now nobody works with it so supposed scientists deal in superstitions about its sensitivity.

          It is explosive, but not sensitive, regardless of dryness or crystallinity.

          Our bottle is from the 40s, we use it regularly and store it dry. We have run BAM impact and friction testing on it, demonstrating similar sensitivity compared to TNT, only slightly higher). Old literature on picric acid collaborates our data. Only in the last 15-20 years has this myth about highly sensitive dry picric acid propagated. Always by people who have never handled it.

          Biggest danger about picric acid is that it is very toxic.

          1. DHC says:

            Isn’t the danger of picric acid more related to it forming metal picrate salts when stored for a long time with metal?

          2. you arewrong says:

            @ DHC

            Yes, that can be an issue with certain metals. However iron picrate forms a 6-hydrate even less sensitive than picric under ambient conditions. Only a few metals form anhydrous picrates capable of going off from a twist of the cap, and those are things like lead, silver, thallium.

            Molten picric + metals is really bad though. Sensitivity of molten explosives goes up.

            But an ancient bottle of dry picric with a plastic cap, my colleagues and I laugh so hard when people freak out over this. Only way dry picric is an explosion risk is if you make a habit of storing detonators in it.

          3. Colintd says:

            In the 80’s I was at school and we disposed of the school’s old picric acid out in the cadet force range by burning probably 1Kg+ on concrete slab. No detonation, just a fierce fire.

            I was 17 at the time and allowed to help, given that I’d proved my care when we made rockets and other pyrotechnics.

            We also used open mercury jars with glass tubes to measure the transpiration pressure of plants.

            Them were the days….

          4. dan says:

            The biggest danger of picric acid is that it ruins the reputation of chemistry.

            Of course the bomb squad will blow it up with more explosives, so a big kawoom is guaranteed.
            Makes news every time, always with the same people involved: Clueless chemistry teacher, apologetic headmaster, ‘expert’ on chemical dangers, concerned parents, guy from the bomb squad which obviously needs more funding, and a nice video of a big explosion.

            The end result is that educational chemistry gets more and more regulated, to a point, that schools can’t even do experiments that where included in chemistry sets when we were young.

            I wish people would create less of a hysteria about picric acid, here is a video that shows how it reacts
            https://www.youtube.com/watch?v=fA3gqrzjef0

            As long as there is any water in the bottle, it is NOT EVEN CLASSIFIED AS AN EXPLOSIVE. Moistened picric acid has its own UN number (UN 3364) and is only classified as a flammable solid.

            I have never heard of any explosion, even though picric acid used to be very common as a stain for microscopy, and probably every high school biology lab had many bottles drying out in the sun.

            IMHO, a trained chemist should be able to dispose of a small quantity inconspicuously and thereby do chemistry a big favor.

          5. Getheren says:

            Picric acid not an explosive? Er, try telling that to the people of Halifax, NS.

            In December 1917, the munitions ship *Mont Blanc* was entering the harbour there, when it was rammed by another ship and caught fire. TNT was a significant portion of its load, true, but most of the rest was picric acid, both wet and dry. The picric acid barrels on the deck merely burned (with reports of exotically-coloured flame); but the picric acid confined below decks did in fact detonate with the TNT. The resulting festivities obliterated a sizable proportion of the city — in fact, it remained the largest human-caused explosion in history until nuclear weapons came along, and the largest non-nuclear explosion till PEPCON.

            Perhaps at small scales its toxicity is its main danger, but get enough of it together in a confined space and add energy, and it will in fact do some brutally spectacular things.

    2. Skippy says:

      Another picric acid story, I remember finding a old jar of the stuff sitting on a shelf in inorganic lab during undergrad. Most scared I’ve ever seen a TA or professor get. Thankfully it was “only” about 20 grams of the stuff so the bomb squad got rid of it by very slowly opening the jar in a 5 gallon bucket of water and letting it dilute itself to harmlessness.

  11. Kevin says:

    Conc HCl and neat sulphuric acid stored next to each other is very common and very unwise. I am always surprised by how few chemists realise what happens if you mix them.

    1. Mister B. says:

      Ho dear !
      I will correct that immediatly ! Thanks for that !

    2. Semichemist says:

      This would be an appropriate time to tell us why that’s unwise?

      1. Carl says:

        It makes a reagent called Aqua regia, latin for ‘kings water’, as it can dissolve gold and platinum. It also is highly oxidizing and belches orange fumes consisting of chlorine gas and nitrosyl chlroride that you really don’t want to breathe in.

      2. Carl says:

        Sorry, Aqua regia is HCl and nitric acid. Mixing HCl and sulfuric acid basically dehydrates the HCl and spews out HCl gas. Also not good to breathe in.

      3. anon the II says:

        Adding 12 M HCl to sulphuric acid is a great way to get a nice stream of dry HCl gas if done slowly.

        If done rapidly, replace “stream” with “blast” and remove “nice”.

  12. myma says:

    An anecdote from not in the lab: my grandfather in his retirement he had a sizable vegetable garden in the backyard. Years pass, house is sold, some years later the other grandmother buys the same house, its back in the family. We open up grandpa’s garden shed out back and there is a nice bottle of DDT sitting there. Right next to it was a sizable bottle of Chlordane.

  13. NHR_GUY says:

    Throughout my career I have experienced many types of inventory/tracking systems. What I have found is that regardless of the type of inventory/tracking systems in use, they are only as good as the people using them.

    1. Make the Inventory Great Again says:

      Explains why are fancy inventory system is completely non-functional: our department is full of deplorables!

  14. MTK says:

    Do large pharma companies have automated chemical storage, retrieval, and inventory systems. I’m imagining something like large hospitals have in their pharmacies or that large warehouses use.

    The system barcodes, tares, dates, and stores every bottle. A chemist “orders” a chemical, the robotic system than retrieves it, puts it a box, which the chemist picks up. Upon return the chemist places the bottle in some sort of queue where the automated system reads the barcode, weighs it, and returns it to its designated place.

    Sorry if this is a stupid question, but I haven’t worked at a large pharma in over a decade.

    1. Mister B. says:

      Back to my time at GSK, the automat was a dedicated quatuor of technicians.

      It worked really nice and they always had funny stories about chemicals ! Plus, they were able to tell you immediatly if the desired compound was “good enough” by checking the bottle first. Good time with them !

    2. RM says:

      There’s a thought: drone delivery of chemicals. Put in your order on the computer, and a drone is dispatched from the central storage facility with the bottle. — Just imagine all those quadcopters zipping down the hallways, flying overhead.

      1. Some idiot says:

        Presumably with flashing lights and a siren when it is transporting the ethanethiol…

    3. CFaulkner says:

      I’ve heard Apotex (Canadian generics) uses a system like this. Have to believe it’s used elsewhere.

    4. OldLabRat says:

      Yep, most Pfizer sites used to have such a system, as did some other pharma lab sites.

    5. simpl says:

      The chemical production site I knew best had no computerised dispensing system, but of course, solvent tanks, fork-lift pallets, and many different rooms, including cooled rooms, nitrogen flooding, etc. Volume was tens of thouands of tons.
      Something touched on in the comments as a lab-scale horror, prolonged storage, was a no-no for most goods, including most of the intermediates, rather just-in-time planning. They were delivered straight to the producing area storage bays, who were experienced in their material assortment. Low inventory pleased the finance guys, too.

  15. CMCguy says:

    Having taken part in many lab clean outs, from High School, College and Industry sites, indeed have seen many incompatibles stored side-by-side mostly strong oxidizing agents and readily oxidized or flammable agents that spawned head shake (hands often already twitching). However the worst hazard IMO, where encountered in all situations, are those “WTF” samples that have obscured, missing labels or bottles with an original label crossed out an illegible name. Frequently these where shoved way back in shelves or cabinet, covered with dust so knew old vintage. In few cases tried an NMR or other quick techniques (careful dissolution small sample in water or organic) to guide but mostly double bagged and placed in waste drums filled with vermiculite.

  16. will says:

    Back in my grad days we had a solvent stills for the usual suspects (DCM, THF, EtO2 and tol). The ethers were distilled over sodium, and the others over calcium hydride. They were typically left running all the time, and serially connected via water condensers. One night, somehow one of the condensers developed a crack, and filled all four stills completely with water. Since the stills were under Ar or N2, no fire; i guess the crack must have been small enough that the water added in at a slow enough rate to avoid a detonation.

    There was a whole slew of gunky solids at the bottom of each pot; which was a study in terror as we cleaned up.

  17. ChemE says:

    Not mine personally, but I have heard to good ones. The first was from my department chemical stockroom just before a big EPA audit. They found a 1 gallon wax lined glass bottle of HF that hadn’t moved from its bottom shelf since probably 1965. Someone dug up an MSDS sheet for it, and promptly craped themselves. That stockroom had undergrads in steel toe boots walking around it on a regular basis, making for some really ugly nightmares. The other was a local science museum which had been given someones chemical collection. When a chemist was hired, the first thing they had to do was catalog it. That resulted in an immediate bomb squad call, for multiple old mason jars of picric acid.

    As a question, what does happen when you mix Conc HCl and neat sulfuric acid? Its just going to evolve HCl gas right?

    1. Falanx says:

      Yes. The water content of the acid will be consumed by the sulphuric, and off comes little clouds of dry neat HCl, assuming you add it very gently.

  18. Magrinho says:

    That’s an easy one – I still get chills thinking about it.

    As a post-doc, we were tasked with lab cleanout and we came across a sealed vacuum tube containing diethyl ether. On the walls was a thin coating of potassium metal. Or so it was written faintly in pencil on a crumbling paper tag. That jived with a researcher who had been there 20 years earlier.

    We left it.

  19. Tom Mc says:

    When I was a PhD student I ordered a bottle of 2.5 M nBuLi in hexanes from our internal stores. I went to collect it and the guy behing the counter picked it up from the shelf, flipped it up into the air, caught it and slammed it down on the counter. Looking really pleased with himself, he said ‘there you go!’ expecting a round of applause or something. My colleague and I just looked at each other, shook our heads in disbelief and left with the BuLi before he could do anything else stupid with it.

    It was only a 100 mL bottle playing catch with it; not a good idea.

  20. charlesj says:

    Many years ago as a kid, my brother stole a jar of bromine from the high school lab, to add to his element collection. He hid it in a drawer in his bedroom dresser, which was later put into storage without checking the contents. When he came to reopen the drawer some years later, the metal handles fell off – the inside parts having been converted to powder, presumably FeBr3.

  21. BK says:

    This happened while I was in grad school, circa 2007 ish. The building manager had to clean up an abandoned lab of a prof who either didn’t get tenure or who retired (I forget exactly) with the director of undergrad labs. The building manager grabbed an unlabeled bottle of something with his bare hands and there was some residue on the outside of the bottle and this stuff stained the skin that came into contact with the bottle a purple/black color. A month or so later, he had to be put on dialysis and a few months later, he died from it. They later found out it was some gold compound that I completely forget what exactly it was.

    1. David says:

      Do you think you can find out, what kind of gold compound it was? I would be very interested in it.
      I am currently working with gold complexes. While cytotoxicity has been shown for some gold complexes in literature, they are most of the time considered to be not highly toxic. They are often being sold as green, less toxic transition metal complexes, which, considering the cytotoxicity, can’t be the whole truth.

      Or did they toxicity stem from the ligand itself (eg gold cyanide is fairly common)? Purple-black color hints to gold complexes gone bad, purple and black are the typical colors for that.

      1. Lisa says:

        I’m with you on this one, David. I’ve worked fairly extensively with gold and it’s generally quite benign – patients taking auranofin can have 10 micro molar serum gold concentrations with little ill effect. Seems unlikely that the gold itself would be able to kill someone so quickly.

  22. loupgarous says:

    When I was a kid on south Louisiana, every public high school chem lab in the state had a supply of picric acid. In a metal can. A rusty one, because the scope for preparing picrates in high school chemistry is mercifully narrow.

    Fast forward ten-twelve years. Someone discovers one of these little hand grenades and instead of prying the rusted threads of the cap open, wisely whistles in the state police explosives disposal unit. Who then went on a state-wide tour (64 parishes in Louisiana, almost all with at least one high school chemistry lab. The larger cities, like New Orleans, Shreveport, Baton Rouge, Lake Charles and Lafayette have several).

    1. Ken says:

      I like that in Wikipedia, the sentence “Bomb disposal units are often called to dispose of picric acid if it has dried out” has eight footnotes.

      1. loupgarous says:

        That might be something I need to look at. Eight sources for a simple assertion may be inappropriate, but I guess we’re going to chew that over on the talk page. That’s the sort of gray area whole page-long arguments in article talk pages are made of.

  23. OldLabRat says:

    Another in the cleaning an old lab genre. Getting ready to move to a new site, I was asked to see if there was anything worth taking in an old store room. Upon opening a cabinet on the back wall, there was a bottle of hydrazine next to a bottle of perchloric acid, both with plenty of water droplets on the outside of the bottles. On the shelf below was an old wooden box with a bottle of 90% H2O2. I’ve never left a room more carefully and quickly. It was impressive to see the bomb squad remove and detonate the H2O2. Definitely a once in a lifetime experience.

    1. Derek Lowe says:

      Storing hydrazine next to perchloric acid takes either a keen sense of humor, or an utter lack of knowledge of chemistry. Impressive.

      1. OldLabRat says:

        The store room dated from an era when fume hoods were wooden with lead bench tops; smoking was allowed in the lab in the presence of solvents. A bit more casual approach to safety. The facility had lab techs that had a broad range of chemistry knowledge.

        1. Dan says:

          Heck, way back when some procedures **recommended** smoking in the lab.

          Apparently it (or so it was thought) sensitizes you to the smell of HCN.

    2. lol wut says:

      Nice story but they did not detonate your 90% peroxide as it is incapable of sustaining a detonation on its own without being intimately mixed with a fuel.

      1. Nick K says:

        Are you sure about that? I remember reading that TATP (triacetone triperoxide, the explosive used in several recent terrorist attacks in Europe) decomposes explosively to acetone and oxygen. No actual combustion takes place.

        1. lol wut says:

          Having worked on the determination of explosive ranges of 90% peroxide with organic fuels, including personally inserting the detonator into 90% peroxide and pushing the button myself, I am certain.

        2. OldLabRat says:

          Yep. An explosion is defined by the velocity of the wave front generated by the expanding gas(es). Rapid burning is a very common way to generate the gases, but isn’t the only way.

        3. Nick K says:

          Correction: TATP decomposes acetone and OZONE, not oxygen.

  24. Anon says:

    Surely it depends on how many compounds (things) you have to store. If all you have are francium metal and conc. sulphuric acid, and you put them in alphabetical order, then they will be right next to each other. But so they will if you put them in reverse alphabetical order. Or in random order. That is, unless you keep them apart. Duh.

    Anyway, the whole point of putting each compound in its own separate container, is that you can carry and store them where you like. Except in a furnace.

    I don’t understand the point of this question. Does it matter?

    Trump is more interesting.

    1. Derek Lowe says:

      There are other blogs for Trump, and how.

    2. loupgarous says:

      The point is that some reagents, like picric acid, must be stored in solution, because they become temperamental and violent explosives when dry and crystalline – but left in storage, they often do dry out, because (say) high school chemistry teachers just don’t get around to dusting off their reagent shelf every year and checking the picric acid to see whether it’s dried out from reagent grade to bomb grade.

      Other reagents, especially the acids, attack their containers over time. Hydrofluoric acid’s especially bad about that. So a reagent shelf, unless reasonable (and sometimes Levitical) precautions are taken, can consist of compounds which react to either combust, detonate, or form compounds ranging in toxicity from insidiously carcinogenic to virulently lethal.

      Chemistry sets used to be much more interesting than they are today. A well-to-do relative sent young, elementary school-aged me her son’s old Gilbert Chemistry Set, its metal case nicely corroded from some of the goodies it contained. Among them were a test tube (corked but not sealed) with pitchblende, which the chemistry set manual said was nice to watch glow in the dark. Fortunately, by that time I knew about radon, and to keep the tube corked.

      All this discussion assumes good will, or at least absence of malice, on the part of everyone concerned. Graham Young the inspiration for the movie “The Young Poisoner’s Handbook”, is an example of what can happen when reagents fall into the hands of someone determined to use them badly.

      1. Noni Mausa says:

        “Chemistry sets used to be much more interesting than they are today. ”

        Apparently so, according to an anecdote of my ex-husband’s. As a youth, he tells me, he would make mercury fulminate, and paint the liquid under the rockers of his father’s rocking chair. Good times, good times…

        1. loupgarous says:

          I have to admit, I was wary of making fulminates, but indulged in the next higher grade of explosive prankery as a college undergrad – nitrogen triiodide (and yes, I know, if you’re making it by the anhydrous ammonia-iodine route, you wind up with – if you did it right – a 1:1 composition of ammonia and nitrogen triiodide). Kept wet and cold with excess ammonia, this stuff was kind-of sort-of stable enough to shove inside key locks. Then, after it warmed and dried… it wasn’t stable at all.,, jiggling the door said lock was attached to or inserting a key would be enough to cause a detonation.

          You didn’t want to get any on you, or let it dry on any of the things you made it in or handled it with, for obvious reasons. I lived in a dorm, and waited until everyone was asleep to make my batches on the shower stall floor, then flush everything with water.

          But I wasn’t the guy Campus Security wanted – that was the fellow whose idea of fun was flushing packets of calcium carbide in the plumbing of the dorms in Tiger Stadium – somehow he figured out how to detonate the acetylene given off. Some LSU football fans got an unanticipated shower courtesy of this guy’s calcium carbide bomb and the sewage lines.

          Good times, indeed.

          1. Gene says:

            And if you take small lumps of the compound and scatter them wet onto an Arizona high school football field before The Big Game, you can delay the game a full day for the field to be rolled and all the lumps detonated.

            Not that *I* ever took part in anything like that…

  25. Barry says:

    a colleague relates that he was an undergrad when it came time to clean out the cellar of the old chemistry building. The cost of proper disposal of the benzene was appalling. It vanished, a pint at a time, into one of the professors’ cars’ gas tanks. But there was that bottle of greenish liquid with the ground-glass stopper and the hand-written “nitroglycerine” label. For that, they called the local fire department, which quickly escalated to the bomb squad, which brought the parade of military vehicles. The suspect bottle emerged from the building strapped to a stretcher between two men in body armor. It was explained that–as a suspected bomb–it would be wrapped in a weighed quantity of plastic explosive, set on a steel plate in an open field, and the plastic detonated. The damage to the steel plate attributable to the plastic being know, any damage above and beyond would be attributed to the suspicious bottle. It did impressive damage to that steel plate.
    Perhaps someone else on this list will recount the events of January 2.

  26. Dieter Weber says:

    The classic “clear liquid in an unlabeled wash bottle”. It was HF.

    1. Elizabeth says:

      In my old metallurgy lab in grad school, there was an incident of a wash bottle with HF sharpied on the side. (We did indeed use HF and aqua regia in that lab with some frequency, as they are useful etchants for aluminum alloys.)

      It turned out to be the work of a grad student who was tired of having his acetone stolen several times a week. But it did cause a great deal of consternation and a meeting and lecture about labeling for everyone in the lab.

  27. Curious says:

    Just out of curiosity, suppose somebody with limited chemistry knowledge had inherited a 1/4 pound metal bottle labeled “Ether Squibb, for anesthesia, Copper Protected” that looked like it dated to about the 1960s. Suppose that bottle had been being used as a decorative accent in somebody’s parent’s house. And imagine that that bottle seemed to be basically full of some relatively light liquid, and had an intact metal seal on the top of it.

    What would that person be best advised to do with said bottle if one did not want to learn too much about organic peroxides?

    Asking for a friend.

    1. loupgarous says:

      Depends on the theme your friend’s going for.

      “Aftermath of an Explosion” might be the visual effect if over a hundred grams of medical-grade ether continues to be used as a decorative accent or, really, as anything but the centerpiece of a preventative detonation by your local police bomb squad.

    2. Concerned for the hypothetical parents says:

      Someone can correct me if I’m wrong, but in plain language, that bottle may now be filled with what is effectively a primary (sensitive) explosive.

      Basically, over time, stored ethers form peroxides. Peroxides in high concentrations are fairly explosive. Combine that with highly flammable ether in a sealed container, and it’s basically a bomb.

      As far as the “Copper Protected” bit, they’re referring to the fact that a small quantity of copper was added to the ether to prevent the formation of peroxides. However, over the time scale mentioned, that copper may have been used up, meaning that the aforementioned explosive condition may be developing anyway.

      I’d call the fire department and be VERY descriptive. Also I wouldn’t hang out in that room. Or house.

      1. exGlaxoid says:

        The old metal cans of ether were soldered shut and quite well protected from air. I used some of those cans, which were decades old at a place I worked years ago that had gotten them free from a school or university. They were peroxide free when we opened them and used them up. As much as I agree that some reagents go bad, some are stored in a way to preserve them well, Just as come canned goods can last decades without going bad.

        I also remember people putting waste benzene in to their gas tank, cleaning their hands with benzene or DCM, and many other scary things. Some of them are now 88, 91, or 95 years old and doing fine. Perhaps some of the fear is overrated, just like for picric acid.

        My favorite example of brilliant storage was the waste company cleaning out chemicals from a now closed R & D bldg, where they took all of the chemical bottles to dispose of into one lab and piled them in stacks 2 feet high, all completely mixed up, with bottles of BuLi, Hg, sodium azide, acids, and many others randomly heaped into huge piles on a bench. That was one of the only times I almost ran out of a lab. I did tell the Dept head that if OSHA had walked in, it would become a criminal case for him.

        And the time someone had a summer intern do the inventory scan, and they were handling the bottles of phosgene in toluene like a soda bottles and balancing them precariously on a cart while scanning the other bottles in the fridge. I did stop them and correct that issue by saying that someone who knew some chemistry should be doing that job.

        1. Gilbert Pinfold says:

          Both Mom and Dad were analytical chemists. Growing up in Central NJ, we lit our grill and burned our paper trash using benzene purchased in gallon cans at the local hardware store. We even had a gas chromatograph in the basement. Dad would buy thinner for model airplane paint in tiny, expensive bottles, and determine its composition on the GC, and mix big batches from bulk solvents. Ah, the olden days…

  28. Rock says:

    Back in grad school in the 80’s, our group had an auxiliary lab which contained some equipment including an old permanent magnet NMR that no one used as well as a brand new IR spectrometer. Within that room, separated by a door was our lab chemical stockroom. There was no air conditioning in that space and often the window was kept open to provide some fresh air (very old building). On a particularly rainy and humid day I walk in to get a chemical, and see fumes coming out of an old metal can on the top shelf. Inspection of its contents proved it to be dimethyl dichloro silane, and that 90% of the volume was gone (along with most of the cap) presumably converted to HCl. Now remember earlier how I said we had that nice new IR instrument? Well we previously had the service people in there multiple times for issues. Each time it was the same thing: the mirror coating on one of the concave lenses was corroded. We then finally figured out why……

  29. anon says:

    I’m in an academic lab – one of the organic groups sorts by number of carbons. I’m in a physical chem group. Before sorting anything, we first write down the appropriate Hamiltonian.. then we sort it alphabetically, with separate areas for strong oxidizers, organic vs inorganic acids, etc.

    1. BK says:

      In grad school, my advisor preferred to have all chemicals stored by number of carbons from C-0 all the way up to C-15, then after that, it was C-infinity. In each C#, it was further alphabetized with smaller bottles in the front and larger in the back, generally. We kept a reasonably up-to-date inventory with names, location, size of bottle, vendor, and CAS numbers (with URL inserted to direct to the vendor, i.e. sigma or acros, etc),

  30. NJBiologist says:

    Test substance sent to a toxicology CRO–Nalgene bottle of clear liquid, no label, no client name, just a return address that looked residential. The last I heard, three week’s effort had not turned up any other information.

    1. Sudaka says:

      was the return address from Syria or North Korea?

      1. NJBiologist says:

        Somewhere near Atlanta, if I recall correctly.

        Working at a tox CRO exposes you to many highly educated consumers, and a handful of genuinely bewildering people.

  31. Anon says:

    Definitely for me it’s a CDCl3 100mL bottle that was filled to the brim with nitric acid. The thing was stored under the bench and naturally got tipped over. An NMR bottle cap can’t handle nitric acid so it started leaking through onto the cotton lining the cabinet, smoking as it did so…

  32. Anon says:

    I joined a biochem lab at the University of Michigan in the 1990s, and there on one of the open shelves was a large jar containing a kilo of yellow uranium acetate, which I verified with a Geiger counter. At my first group meeting I asked if it was safe to have sitting around and just got lots of blank stares like “who the hell are you?”. So I just shut up and didn’t go anywhere near it.

    1. Derek Lowe says:

      For electron microscopy, I assume?

      1. Anon says:

        I hope, as it was on an open shelf accessible to anyone who walked in without any security.

        1. Hold (U)r Horses says:

          Honestly it’s not that bad as depleted uranium is 1) non-fissile, and 2) an alpha emitter. It is pretty poisonous, however, as most heavy metals are…

          1. Dave says:

            Careful… alpha emitters are very nasty if they get inside you. If the heavy metal poisoning doesn’t kill you, the radiation will.

          2. aairfccha says:

            Even natural Uranium is mostly U-238 with a half-life of 4.47 billion years and the 0.7% U-235 is not that active either (704 million years). Recovered uranium is a different issue as it has at one point been in a reactor.

          3. loupgarous says:

            Natural uranium (or depleted uranium that’s not been irradiated in a reactor), having a half-life in geological time, isn’t much more radiotoxic than potassium in food like bananas.

            While K-40’s radiation emissions don’t involve alpha rays, its beta emissions at 1,33 MeV are over twice as energetic as strontium-90’s – but since Sr-90’s half life is 26.79 years, it emits them much more often either natural/depleted uranium or potassium, and it’s a radiotoxin implicated in elevated rates of bone cancer (it is absorbed in bone in the same way calcium is).

          4. Falanx says:

            Uranium has far greater chemical toxicity than its radiological profile would ever cause. It causes severe renal damage, probably because of its similarity to molybdenum or vanadium to biological structures, in much the same way cadmium is toxic because of its similarity to zinc and magnesium to biological entities, and that organism’s attempt to substitute them.

    2. Ed says:

      One of my college frat brothers was noted for the odd tech-related items he tended to have: the very first personal computer (this was in 1972).

      And a nice jar of uranium salts, in a leaded, orange plastic container.

  33. MA says:

    Back at old my old position, I found an acetone wash bottle during a lab cleanup full of a mysterious pale yellow liquid. Someone has sharpied in “NOT” above “Acetone,” but there were no other identifying marks…

  34. nastywoman says:

    Not as scary as some others but still an interesting find while cleaning out a very old chemistry stockroom during grad school. A large plastic bottle only labeled with a handwritten “K”. Looked like it used to contain a liquid (mineral oil probably) but had dried out to just be the solid. The sides of the bottle were completely sucked in. Was probably more than 30 years old.

  35. Me says:

    We had the army come down to GSK Harlow and do a controlled explosion on a bottle of picric acid with crust around the top.

    Fun times!

    Other storage paradigms: boronic acids section, stannane section, oversized bottles, ‘locked’ section.

    Also remember hearing a related story about how Gilbert Stork nearly blew himself up once by cooking a steak on his hot plate and scraping the fat into a nitric acid bin. Lots of black smoke coming out of it, presumably due to nitration of glycerine 🙂

  36. SD says:

    A post-doc left our group and with his departure a gift to our lab. On his bench was a desiccator with dry-rite turned a bright turquoise color and reagents inside. A lab member noted that he had said this was very dangerous but no one in the group knew anything about it (labels on the bottles were not readable). After contacting said postdoc, as I am the lab safety coordinator, I found out that there was a solution of trimethylphosphine in THF leaking out causing the dry rite color change. Additionally there was a melting plastic container of KH suspension also in this desiccator. There proceeded to be a long day of removing the chemicals safely behind a blast shield and luckily no incident but a lot of stress.

  37. Design Monkey says:

    Well, nothing especially horrible comes to mind, although it depends of point of view (nothing is especially horrible, if it has not yet blown up/set fire/poisoned everything around).

    Some funny cases

    – 5 x 20 kg Red_Al metal cans, who were rusting in unheated warehouse for god only knows how many years.
    – a couple each of lecture bottles of ethylene oxide and HF, kept in approximately the same conditions
    – various sloppinesses of variable degree with mercury manometers and broken thermometers, too many to count
    – various ancient organomercury and organoarsenic compound bottles in forgotten nooks and crannies. Sure, they went out of fashion long time ago, but, uhm?
    – people trying to throw out Cd-Hg Weston reference cells into common trash
    – Boring “oxide shelf”, large bottles. Iron, aluminium, zinc, copper, cobalt, cobalt, cobalt, hey, what’s that one with label mostly fallen off? Have fun, that’s half a kilo of THALLIUM oxide. Make thermite accidentally from that?

    1. Design Monkey says:

      On the other hand, finding a little bottle of Trypaflavine manufactured by Bayer, still with label, stating I.G. Farbenindustrie, was cool. History!

  38. John Campbell says:

    In my first job at a lab in central London waste solvent was disposed of by pouring into a large trough on the roof and allowing the ventilation outlet to evaporate the solvents. This worked well until the fire brigade arrived to put out a fire. No one in the building had noticed but a man walking across Waterloo Bridge had seen thick black smoke coming from the roof. Luckily little damage occurred but they were never allowed to use the trough again. The next place I worked had a pit 6 ft deep cut into a permeable chalk soil. Periodically solvent waste and unwanted chemicals were thrown in and set on fire. The fumes carried over to a children’s hospital nearby. Happy days!

  39. UudonRock says:

    The lab that I was working for at the time, and it was an academic lab, had been inundated over the years with donated materials from the multitude of local chemical manufacturers and R&D labs that dotted the countryside. The sheer volume of indicators we had was astounding. Among the other pleasant surprises I encountered while cleaning out the mystery stockroom were a combined 12kg of uranyl acetate and more raw sodium, potassium and lithium than anyone should ever possess. Fortunately the metals still had plenty of mineral oil on them. On the brighter side we did find a stock pile of roughly 15kg of silver nitrate, almost half a liter of chloral auric acid and a supply of platinum crucibles and quartz cuvettes. It was a very impressive haul if I do say so.

  40. kyosce says:

    Odd storage? Well, my father was a chemist and towards the end of his life quite a hoader since he grew up during the Depression. Had a big shed back of the house the former owner had used as an auto body shop. Dad used to cruise garage sales and buy stuff he thought was useful. That shed was so full one had to walk through narrow canyons of piled up “stuff”. When he passed on my siblings and I pitched in to help my mother clean everything up. Rented one of those huge construction dumpsters and a tent. Everything going to trash went in the dumpster (we filled three) and everything going to auction went in the tent. Then there was that third catagory; chemicals. By law these can’t go in the trash. And who the heck am I going to sell them to? Fortunately, where I live we have have a hazardous waste disposal facility that is free to residents.

    I took six full vanloads of chemicals over to those guys.

    Had a long talk with them and their supervisor when I showed with that first van full of chemicals. Managed to explain the situation and assure them I was not dumping waste for some company or cleaning out my designer drug lab in the basement. Since I’m also a chemist, so I also assured them I wasn’t going to transport anything likely to cause unpleasant surprises. (They weren’t going to come pick anything up. Apparently local law says I have to bring it to them or I have to pay for disposal.) The highlight was his extrordinary collection of (mostly banned) pesticides and herbicides from the 50’s and 60’s. But Dad was reasonably careful; there weren’t any ethers or explosion hazards like dinitrophenylhydrazine or picric acid. He did have a pound of sodium in mineral oil and a pound of bromine. Lots of acids and bases, solvents, and salts. Some phosphorus compounds. The cases of freons and 20 L tin of benzene earned a few extra questions at the hazmat station, mostly because I think the techs actually knew what those were. Remember that all of this was stored in cardboard boxes and cabinets in a crowded shed in someone’s back yard. Imagine a fire . . .
    Eventually it all got cleaned up and life moved on. In the end I was amazed to see what chemicals one could buy in the past as an average consumer.

    1. Falanx says:

      You’d be amazed what you can *still* buy off EBay…

  41. Anonymous says:

    The main topic is Storage but that blurs with safety. I’ve got comments on both.

    1. The storage regulations are often ambiguous, ridiculous or contradictory. “Keep oxidizers here; acids there; etc.” So many compounds have so many properties that they cannot be uniquely categorized. Many Safety Officers do not have anything more than basic chemistry training and try to enforce rules the consequences of which they do not understand.

    2. I always stored chemicals in smaller bins, such as plastic shoe box sized bins. A large storage cabinet becomes completely jumbled up when searchers start moving things around. When split into smaller boxes, the boxes become jumbled but mostly still localized to their correct vicinity. (And if a bottle should break, the mess in contained in the smaller bin.)

    3. Bretherick’s Handbook of Reactive Chemical Hazards (current = 7th Ed) is a MUST HAVE reference to REAL hazards. If you’re lucky, you’re institution has online access. (See “Can of Beans” entry. See the entry that says ~”Nitric Acid plus Alcohol = Rocket Fuel. I saw the aftermath of several explosions caused when non-chemists were cursorily trained to do HNO3 chemistry.)

    4. David R. Burfield, the guy who taught us how to dry solvents in an important series of papers, also had a paper on removing peroxides from ether and storage of ethers. A few indicator mol sieves (the blue ones with, I assume, CoCl2), will slowly but efficiently break down peroxides in ether. My “shelf” bottles of ether for extraction and TLC always had a few blue Mol Sieve in them. (Your ether will become “wet” with EtOH and H2O from the breakdown so don’t count on keeping anhydrous ether anhydrous with indicator Mol Sieve.)

    Deperoxidation of ethers. A novel application of self-indicating molecular sieves.
    David R. Burfield, J. Org. Chem., 1982, 47 (20), pp 3821–3824
    DOI: 10.1021/jo00141a003

    5. I found a big (4L) bottle of di-isopropyl ether in a storage cabinet. (iPr)2O is worse than Et2O for forming hazardous peroxides. Waste disposal took it away for us.

    Down the hall there was an explosion and we all went to help. Everyone was OK but there was some minor lab damage. A POST-DOC(!) had put a can of ether on top of a drying oven and it went ka-boom. (He went on work very successfully at Merck.)

    Ether usually ships with stabilizer, such as BHT. I have been thru both situations of having no stabilizer and too much stabilizer. I extracted by product and the crude NMR showed more ether peroxides than product! My product was unstable and various attempts to recover it failed. On another occasion, I extracted my product and I was surprised to see huge Ar-H and CH3 peaks swamping everything out. On both occasions, I confirmed the bad ether and reported to the stockroom that they should pull those batch numbers to protect others from the same problem. I routinely “spot test” most of my ethers on KI-starch paper before doing anything important.

    6. Storage of nBuLi. nBuLi is stable at room temp. You can even reflux it (I forget – Et2O? PhH?) for long periods without decomposition. However, nBuLi is LIGHT SENSITIVE. I think that more nBuLi degrades from condensation going in and out of cold storage than when kept at rt under a light protective cover (such as an inverted can).

    7. Mercury storage – An electrochem prof retired and the new guy started cleaning up the old lab. Found a small puddle of Hg. Others came in to help. They pulled out old benchwork and found more puddles of Hg underneath! And more and more! I guess they were unintentionally “storing” their Hg in those places. The university soon decided that the lab needed a major HazMat cleanup and refurb.

    8. I knew a guy who stored his purified reagents using code names on the labels (to deter pilfering and contamination). I thought he was nuts … until co-workers starting pilfering and contaminating my purified solvents and reagents. Nevertheless, I never resorted to code names.

    9. Many reagents do better or protect surrounding bottles from their own “leakage” when stored as bottle-in-a-bottle (or jar). Get a small cheap flint glass jar, sprinkle X on the bottom and put the smaller bottle of reagent in the jar. X depends on the reagent: bicarb for acid fume leakers, desiccant for moisture sensitive compounds, etc.

    I have lots more stories and advice. I will try to post more later.

    1. A Nonny Mouse says:

      As for mercury;

      We were strapped for cash when I was doing my PhD (even at a very reputable institution) and I dropped a couple of stirrer bars down the sink and so decided to take the panel off the cupboard to retrieve them (which was there from 1920!) and found that the water went into a trough before going into the (open) drain. I managed to fish out about 20 stirrer bars, but there was about a 1 inch layer of mercury at the bottom. I then took the rest of the panels off and each of the troughs had layers of mercury at the bottom but I did recover about 200 stirrer bars.

  42. Anonymous Researcher snaw says:

    One of the places where I have worked, the most memorable slide from the Lab Safety Training session depicted what was left of a lab where somebody had stored volatile solvents in a fridge that wasn’t approved for that. There’s a reason why you’re supposed to store volatile liquids in an expensive special fridge that has been designed and built so as to prevent solvents reaching places where electrical sparks might occur.

  43. Simon Higgins says:

    On starting a postdoc in a lab in Leeds in the mid-80’s, I found a large ampoule of strychnine in a drawer of my bench. I don’t know why it was there; this was an organometallic chemistry group. When I was in Oxford a few years later, a new mains power supply was being installed, and the workers digging the cable trench uprooted a bunch of old bottles. It turned out that these contained organoarsenic compounds from the WW1 era that had been ‘disposed of’- by burying them by the lab door! But my worst personal disposal problem was inheriting a thf still which had used NaK as the drying agent.

  44. Chad Irby says:

    “We need to carefully dispose of this pound of sodium metal!”

    “How about a good-sized lake and a very large slingshot?”

    (Yes, this did actually happen)

    1. loupgarous says:

      The US Army did the same thing, but on the grand scale, in 1947 . Drums and drums of sodium metal rolled down a cliff into an alkaline lake, machine-gunned once they hit water, and the violent reaction between sodium and water (evolving all that hydrogen as the sodium oxidized) did the rest. Explosively.

    2. John Campbell says:

      By the aforementioned Roger Burfield if I remember right, in Malaysia.

      1. Derek Lowe says:

        The Burfield and Smithers papers – first chemistry papers I every photocopied, back when I was an undergrad in the early 1980s. . .

    3. Delivery McGee says:

      My college chemistry teacher told a story of when she was a student, she was staying late working on a titration on the third floor while a couple of other students were helping clean out the storage room. They found a hefty hunk of sodium, and disposed of it by tossing it in the duck pond next to the building. Ruined whatever my teacher was working on when she jumped at the explosion, and they had to pay for a couple of first-floor windows.

    4. Ed says:

      I recently met Ken Roy (the NSTA’s science lab safety compliance advisor) at a CSTA conference.

      He told me about a group disposing of a largish amount of sodium by the pond method. This involved floating the sodium out in a raft that was supposed to sink a safe (?) distance off-shore.

      It didn’t; it sunk roughly immediately. Unfortunately, the appropriate directions weren’t given to the nearest spectators (turn around and run away), and the resulting “whoomp” resulted in 5 people going blind.

  45. poorbuthappy says:

    In our labs in Sheffield we always had an open gas flame for coffee and tea and I used to run large open chromatography columns eluting with a 50/50 mix of ethanol and benzene a meter away… those were the days!

    I do remember the time my wife asked me to do some operations involving cyanogen bromide late on a Friday evening when we had forgotten that the fume hoods had been switched off and had to go for a pint to take away the woozy feelings…

  46. Delivery McGee says:

    Not so much storage, but still a fun anecdote that freaks out the people that don’t know of such things:

    When my father was in the Army in Vietnam, they’d burn C4 when they were out of camp stove fuel. [cue the civilians gasping in terror because he was BURNING a HIGH EXPLOSIVE and all the other veterans/people who took chemistry classes chuckling at them]

    When I mentioned this on another forum, somebody said it was horribly toxic, but looking it up it’s just RDX, synthetic rubber, and mineral oil, which being just hydrocarbons and nitrogen would seem to burn fairly inoffensively. Well, and a tiny bit of lead chromate dye, but when you’re so far out in an active war zone that you’re burning plastique to heat your rations, you’re more worried about lead poisoning of the ballistic variety.

    1. Ed says:

      My father served on PT boats in the USN during WWII, a few feet from torpedoes. He said they never worried about the TNT in the warheads (several hundred pounds of it), as he had seen tracer bullets go through it with no effect. On the other hand, he said they tended to be very cognizant of the torpedoes’ air storage cylinders. This was in the days before fracture mechanics, and the cylinders would, on occasion, react to bullets in the same sort of way a well-filled balloon reacts to a pin…..

      1. Mark Thorson says:

        My organic professor (James Cason) worked on explosives during WW2, and he said you could beat TNT on an anvil with a hammer and it would not explode. You could shoot TNT bombs with rifle bullets and they would not explode. You could drop a TNT bomb 100 feet onto a concrete runway and it would not explode. With a single detonator you could only set off something like 200 lbs of TNT (I don’t remember the exact number), and if you tried to set off more than that the rest would blow around as dust. If you wanted a bigger bomb, you’d blend it with some amount of RDX and then you could make it as big as you like.

      2. Mark Thorson says:

        An interesting bit about torpedo oxidizer tanks during WW2 is that one of the reasons Japan had the best torpedoes (longer range, larger warhead, faster speed, less visible trails) was that everybody else used compressed air. They used pure oxygen.

      3. Mike Andrews says:

        My father, an EOD technician in the South Pacific, taught EOD at Dalhart, Texas just after WWII. His barracks was heated by a pot-belly stove. He knew that TNT would melt, then burn with a bright blue flame, but the other instructors didn’t, so they dove out the windows when he tossed a half-brick on top of the cherry-red stove.

    2. David says:

      I’m sure you know this, but burning C4 is far more sensitive to detonation. Apparently, just hitting it can make it go bang. Remember that before trying to stamp out the flames.

  47. Jonathan says:

    I can’t help but note the recurrence of stories involving picric acid. My uncle once related a tale of a dilapidated lab was being examined by an investor for possible refurbishing or reuse as something else and in one lonely closet they found a 55 gallon drum suspiciously poorly labeled except for “ACID”. Knowing nothing about chemistry except “acid bad!” calls were made, old documents dug up…then one old chum remembered that was the master supply of picric acid for the whole building was kept, back in the ‘cowboy days’ of chemistry as one may have guessed.

    More calls were made, the bomb squad duly showed up, and then it was noticed that the doorway and the immediate hallway were too narrow to remove the drum as the interior had been renovated. Even trying to move the damn thing would involve carving out walls, removing plumbing fixtures, hacking out part of at least one support pillar just for starters. Estimated costs easily exceeded what the old building was worth entirely and it badly needed rewiring to boot. The building sat condemned while lawyers, the insurance company, the EPA and various government officials got in on the fracas while frantically trying to keep it all out of the media. It was a white elephant with a suicide vest.

    In the end the problem was solved somewhat an explosion in the dead of night that blew out a fair part of the building, caused the collapse of a fair part more shortly thereafter, and necessitated the demolition of what was left. There was speculation that someone had deliberately set the drum off to cut the knot and get things moving rather than have the land and investment money sit tied up in litigation for God-knows-how-long. But the rubble was cleared and life went on.

  48. David edwards says:

    What follows is best described as “storage sensu lato”, but one whose details will certainly raise eyebrows, and probably cause some readers to go into full-bore prolapse mode.

    Wind the clock back to World War I. The then War Ministry here in the UK, tapped on the shoulders of the captains of the local chemical industry, and offered them wads of money they couldn’t refuse, to make some, shall we say, “interesting” substances to put into shells for the Western Front.

    The “interesting” substances in question, were Mustard Gas and Lewisite.

    Unfortunately for the War Ministry, right after the local captains of the chemical industry had fulfilled their part of the bargain, and made these substances in quantity (in factories right slap bang to residential areas to boot), the Geneva Convention came along in 1917 and declared these substances illegal under international law. Suddenly, there was an embarrassing job lot of lethal chemicals looking for a permanent home.

    The choice for said permanent home, was a hole in the ground, about half an hour’s cycling time from my home. Which is now, in addition, right under a designated flight path for a major regional airport handling aircraft up to Boeing 757 size.

    Recently, work to cap that site and ensure that the requisite ticking bombs were separated from the surrounding urban areas by a large thickness of material, was concluded. But even so, if the contents of that hole ever make it to the surface and start, to use a favourite Derek aphorism, partying hard, there’s enough there to leave nothing alive for about a five mile radius.

    I’ve spent 50 years of my life close enough to this, to discover what the words “sternutatory” and “lung vesicant” mean the hard way, if the s**t hits the fan.

    At some point, I’ll have to cover in more detail the fun that is our local municipal golf course, built on top of a former chemical waste tip. Even Donald Trump wouldn’t want to own this. At least, not once he found out about the polychlorinated biphenyls, heavy metals (including thallium) and radionuclides that were found there about 15 years ago. I gather the site has become something of a test bed for cutting edge soil remediation research.

    1. Derek Lowe says:

      You could also have some rather hardy microorganisms living in there – might be some interesting species enjoying themselves among all the waste materials. . .

      1. HFM says:

        The origin story I heard about Roundup-resistant GMOs…and I’m not certain if this is lab legend or not…but in any case, supposedly Monsanto brought in a bunch of leading protein modelers to rationally design a resistant enzyme, and got absolutely nowhere. Finally, they brought in a grizzled old-school biochemist. Said biochemist sent minions to the sewer adjacent to the facility where Roundup was manufactured, and quickly found what he was after.

        1. Hap says:

          I think, in Biohazard, Ken Alibek notes that the Russian/Soviet weaponized strain of anthrax was developed from a strain found in one of the sewers near the plant. In a similar vein, he also said that their Marburg strain was obtained from one of their lab team who was infected while working with it; after killing him, apparently the viral species obtained from him was much more robust and stable than the original.

          1. Derek Lowe says:

            That book terrifies me.

          2. Hap says:

            You must be easily scared. I don’t understand why someone (lots of someones, in lots of places) developing strategic weapons to end civilization (and lots of lives – most of the human ones, probably) in ways that look like zombie movies with more blood and other bodily fluids would scare you. Especially when at least some of the weapons are unaccounted for, or can’t be accounted for on any scale that would be reassuring. I mean, I loved The Stand!

            Bioweapons make one long for two liters of Tabun to pour into one’s protective suit, I think.

          3. loupgarous says:

            The scary part about Biohazard came in the very first pages, when Alibek wrote about being summoned to the Kremlin during the Gorbachev years, where they discussed biological loads for ICBMs, and he was told to make the necessary arrangements, it was “on”.

            All the while we were being treated to Gorbachev’s “charm offensive” and Reagan was negotiating getting the tactical nukes out of Europe with him, he had something just as good, perhaps better, and was getting ready to use it. Imagine the surprises Putin has for us.

      2. loupgarous says:

        Speaking of wildlife sporting around radionuclides, here’s a glimpse of 2 meter-long Wels catfish in the Chernobyl reactor cooling pond. Scary bit of nonchalance is the small child feeding the radiofish by hand (in what we have to assume is water from the secondary and probably contaminated cooling loop of a Chernobyl reactor).

        1. joe says:

          actualy 2 meters for a wels catfish.. is a punny one. they get about 1 and a half times that big. They get VERY VERY Big and WILL eat humans. Not a chemist but I keep fish and was looking at what i could do with a 50000 gallon pond.

          1. loupgarous says:

            Well, I wrote that after Derek said “You could also have some rather hardy microorganisms living in there – might be some interesting species enjoying themselves among all the waste materials. . . ” and it struck me that (given that Chernobyl hasn’t entirely “cooled down” radioactively yet) even runty normal catfish in that power plant’s cooling pond would be pretty hardy.

    2. Anonymous says:

      Read about the Love Canal “storage facility” (to stay on topic), near Niagara Falls (NY, USA). en.wikipedia.org / wiki / Love_Canal

      1. loupgarous says:

        The same chemical company that brought us Love Canal (Hooker Chemical Company, and that joke never got old on late-night TV) released enough chlorine and other wastes into the air and water around their Taft, Louisiana plant to kill off the world’s oldest and largest oak tree.

        Not so good times.

    3. Molecular architect says:

      During WWI, the US military did much of their chemical weapons research near the present day campus of American University in the District of Columbia. The site is now an upscale neighborhood of very expensive homes. Every once in a while, someone finds a chemical weapon projectile, glass bottles, drums of unknown chemicals, etc. in their backyard. This has resulted in neighborhood evacuations and decontamination exercises at least three times in the decade that I’ve lived in DC.

    4. Nile says:

      Most of the Mustard gas and Lewisite left over from the Great War ended up in a deepwater trench in the Irish sea.

      There are grim tales of the drums and munitions reappearing on the seashore.

      But the darkest tales of all are rumours about Drigg, a seaport on the Cumbrian coast. No-one talks about it, but chemical weapons were manufacured in the Second World War, too, and they mostly went to Drigg.

      Some were deep-sixed in the Irish Sea, or so I hear. Most were stored in drums in vast concrete-lined pits at Drigg.

      The site became the final repository for ‘recalcitrant’ waste – things we couldn’t dispose of in the sixties and seventies, and probably can’t neutralise now.

      If you remember seafarers tales of of cursed ships carrying a cargo of industrial incinerator waste and forbidden to dock in any harbour, in country after country, those cargoes ended up at Drigg.

      The cargoes that weren’t offloaded for an informal fee in a Third-World county, that is.

      Last I heard of Drigg is images from forty years ago, of those vast pits full of drums, upright and mostly freestanding rather than stacked, unlabelled and losing their paint, corroding in the sea air and the rain.

      The site was taken into the perimeter of the Sellafield reprocessing facility, and disappeared into the secrecy accompanying the not-so-civil nuclear industry. I’m guessing that the glassification technologies developed for high-level nuclear waste were applied to the contents of some of those drums.

      It makes thense: every chemist knows that there are worse things than plutonium.

      But I don’t really know what’s happening in Drigg, and absolutely nothing is in the public domain. It wouldn’t surprise me if the ultra-high temperature incinerators developed for Cold-War era nerve gases and transformer coolants are in use there but – again – I simply do not know.

      Some heavy-metal wastes cannot be incinerated; and some incineraion processes, even the most sophisticated, leave an incombustible solid residue which is, itself, a recalcitrant waste that cannot be disposed of safely. Even Drigg would still need Drigg.

      I know nothing: maybe the drums are still in those pits, corroding slowly under a layer of clay and concrete.

      Someone knows.

      And if any of the industrial chemists here have ever wondered what became of a “recalcitrant’ waste product you couldn’t neutralise, oxidise, incinerate or bury, it was either dumped illegally or shipped to Drigg.

  49. Wheels17 says:

    Shortly after I was hired by a large corporation in the 70s, I was walking through an old chemical storage area in a dye lab. I started looking at the bottles, and ran across an unopened liter bottle of lysergic acid, tagged from the 50s. I mentioned it to a bunch of chemists in the group.

    A few weeks later I wandered through again, and there was a circle in the dust where the bottle had disappeared. I always wondered……

    1. Anonymous says:

      A liter bottle?

      Sounds like a lasting supply – of fun, money or jail time.

  50. Scott says:

    The scary one is in a KMart or WalMart when you see pool supplies right next to automotive.

    Pool chlorine shock (potassium hypochlorite?) and motor oil, right next to each other on the shelf, all under some nice fire sprinklers.

    1. David Antonini says:

      …or the matches sitting amongst an aisle of paper products. I always expected some little kid…

  51. Not So Smart says:

    Way back when bench chemists had to dispose of reactive chemicals themselves, I needed to decompose a 1 liter bottle of sulfur trioxide. Started to do so by pouring a small amount into a plastic container filled with ice. After several rounds of this, some liquid SO3 must have pooled up on the bottom of the container and a hot spot developed and started to “melt” the plastic. I quickly lifted up the container and my lab buddy put a new container under it. After ca. 6 hours of this chaos the job was finally complete and the stack of 6 or 7 plastic containers was tossed.

  52. -Coz- says:

    Way back in the late 80s, the Pharmacy School at Ole Miss had a small “incident” in a chemical storage room. Something (they never told us what) stored in a metal canister experienced a “sudden exothermic reaction” and exploded the can. The shrapnel broke the majority of the other storage containers in the room.

    The results were a mess, fractally. The local fire department and the University had a total of two hazmat suits – the nearest accredited reaction people were in Memphis, an hour away. The fire department ventilated the building, creating a wonderfully acrid cloud which drifted over Fraternity Row, as the University Police evacuated people downwind. The guys trained in hazardous materials were taking 10-minute turns in the hazmat suits, since the hall was full of choking smoke and the storage room was apparently well over a hundred degrees, with “stuff crawling around on the floor” as chemicals randomly reacted.

    The experts arrived about an hour and a half later. It was several days before the building was cleared for use again. I wrote about it for the Daily Mississippian – unfortunately, their archives are down as I write this.

  53. bcpmoon says:

    In University we stored chemicals according to a code: Number of carbons-number of hydrogens-number of hetero Atoms-number of different hetero Atoms, e.g. dichloromethane would have the code 1-2-2-1. In this way you could home in quickly. That was before the Internet so CAS# was not so easy to determine and some more exotic, lab-made substances would not have those anyway. Add in german mixed with english names and a sometimes vague awareness of IUPAC nomenclature and that code was really helpful.
    At one time, we cleared out the storage and disposed of everything that was not clearly labelled in the open-air lab on the roof, having a guess-the-color-of-the fume contest up-wind when someone came up with a bottle of 0-0-4-3 and nothing else on the label. I still wonder what that was, at least it was not very reactive.

    1. Tom Womack says:

      The only thing I can think of, after looking up sulfur and boron chemistry, with 0-0-4-3 is silicon nitride, which is really not very reactive at all.

    2. Design Monkey says:

      0-0-4-3

      From common organic lab chemicals – might have been thionyl chloride.

      1. Design Monkey says:

        SOCl 2 – 0 carbons, 0 hydrogens, 4 heteroatams total, of 3 different kinds. Reacts with water vigorously, but not really explosively. Though, not that anyone should try to test that.

      2. Design Monkey says:

        That was, assuming that mysterious stuff was liquid.

        If solid, then perhaps NaNO2.

        1. Dave says:

          I suspected NaNO2 as a possible solid as well. Couldn’t think of anything else that fits the bill.

  54. Dave says:

    Having managed to avoid chem labs for some years now, the best story I have is disposing of some old theatrical flash power. It was in a small plastic tub with a snap fit lid, and I was worried it might have become unstable through age. I carried it out of the building using a litter picker to keep it away from my body. Prised off the lid very carefully (I did feel scared doing this) and poured the powder on the ground in a wide low pile for minimum self-confinement. Tried unsuccessfully to ignite it with a match. Borrowed a cigarette from a colleague who smoked, and poked the pile with the lit end (at arm’s length, looking away). Cue bright flash. The only damage was to my colleague’s fag, which was mostly destroyed in the process, causing him much displeasure.

  55. anonymous says:

    During my PhD in the late 90s we had a VERY frugal lab technician who used to gas up his car with solvent waste. I asked him why he does so because he was also very “green” (in a political sense) and he replied: “no worries, it’s only halogen-free solvents!”
    The other day he made a big fuzz because he discovered that one of the drying ovens contained asbestos. A new, expensive oven was bought because of worker safety reasons and who took home the old one to desiccate his homegrown fruits? YES, it was our environmentalist….

  56. OmegaPaladin says:

    Back in graduate school, I was asked to correct the deficiencies noted in a recent lab safety inspection, which included “incompatible storage”. I found a tray of extremely water-reactive chemicals (neat sodium hydride, calcium hydride, etc) UNDER A SINK. The can of sodium hydride was rusted…

    I moved it to another cabinet quickly.

    1. flamcabfengshui says:

      We’ve always had rather resourceful researchers. One scavenged an old store display refrigerator to house chemicals. Nearing retirement, the researcher was cleaning out chemicals, but there were a few reagents left that nobody wanted. One was a sodium puck in a cracked glass jar from which the mineral oil had leaked over time. At some point after this, the refrigerator had developed a tendency to allow moisture to condense at the top, and to drop slowly into the secondary containment of the cracked glass jar with sodium puck as it day in and day out dealt with opening and closing the door letting in that humid Houston air.

      All of the researcher’s students had learned of it long before and had slowly moved their chemicals out of the display refrigerator, leaving just that container in there for us to pick up. Puck was peachy, was a great opportunity to show a new coworker why I horde mineral oil.

  57. gippgig says:

    Not a lab, but a local hardware store has concentrated sulfuric acid drain opener (including gallon jugs – yikes!) on the shelf next to the lye-based drain openers. (I suggest any readers in California or other earthquake zones check their local stores and if they find the same thing point out the hazard to the manager.)

    1. Dave says:

      The ease at which conc H2SO4 and NaOH are obtainable is quite scary, There’s a little store near me which has the former on a shelf next to washing power and other cleaning products (probably including hypochlorite bleach).

      1. Gordonjcp says:

        The Fire Brigade have prominent safety briefing notes about approaching cars with apparent suicides in them. Full hazardous chemical PPE, big petrol-driven ventilation fans (“aren’t the exhaust fumes a problem?” “not when they’re diluted with that much air”) and a large cordoned-off area.

        One every couple of months, apparently.

  58. Mark Thorson says:

    At a former employer, we hired a top consultant on polymer formulation to help us with that. He was a bit alarmed to discover we had a kilogram jar of dibenzoyl peroxide. He advised us to separate it into 100 g quantities and store them apart from each other, under refrigeration. It’s used as a thermally activated crosslinker in some polymer curing chemistries.

    1. Falanx says:

      It doesn’t need to be thermally activated for things like polyester or acrylic resins. Quite happy to work it’s magic at room temperature.

  59. gippgig says:

    Would di-tert-butyl ether be resistant to peroxide formation (no hydrogens on the carbons next to the ether)? If so would it be practical to use it as a safer alternative to other ethers?

  60. Nekekami says:

    This little tale, courtesy of my GF, regards the somewhat related area of shipping:

    Customs come visiting the lab, bringing a very anonymous package with them, and an x-ray image showing 2 bottles
    Package is brought to hazardous materials lab, where it’s eventually determined that the bottles contain about 150ml’s of TMA.
    Customs decides that police might want to have a little chat with the recipient, who turns out to be a “hobby pyrotechnician” wanting to use it for “experiments”.

  61. Paul Harrison says:

    Well, it is hard to choose from the many horror stories, but I think my favorite for “storage” was the time our safety committee in chemistry was called in by another Department (which shall remain nameless) for advice on how to handle an old bottle.

    We all know that ethers can form peroxides, and that diethyl ether should be tested every 6 months. Di-isopropyl ether forms free radicals more easily, so is tested every 3 months.

    Well, when we arrived in the above-mentioned anonymous lab, in the early 1990’s, there it was…. a 4 litre bottle of di-isopropyl ether. Examination of the label clearly indicated the expiry date: May 1964! Time for the bomb squad! The bottle had been stored on a geological time scale, a term appropriate for the unnamed department in question!

  62. Michael Ahler says:

    Years ago I had the opportunity to visit the chemistry department at a local community college to see the stockroom technician there on another topic I can’t recall now. What I do recall is noticing the fairly decent separation he had for acids, bases, flammables, oxidizers, etc. in his two small rooms (closets, actually, but bermed and secondarily contained). Near these two storage location was a box on the floor containing dozens of small bottles of various chemicals. I asked what these were and he told me that’s where they keep all the chemicals with long names. Whatever works…

  63. Coxie says:

    It isn’t just you chemist who have this problem, we mechanical engineers have people aspiring for the Darwin awards as well. The dyno test cell in undergrad had a blast wall for just such endeavors. It was used once too! Apparently, some testing was being conducted on flex-fuel engine technology. This wonder device was supposed to run on everything from H2 to Diesel without having to do anything more than connect up a different supply of fuel and punch a few keystrokes into the engine controller. Turns out, running H2 gas through pipes designed for liquid fuels isn’t the best idea. The H2 leaks out and accumulates in the rafters. When the concentration reaches high enough around the florescent light fixtures, all of the oxygen and hydrogen in the air gladly become water and the pressure wave from the explosion pushes the blast wall off it’s mount and into the parking lot. That particular study was done.

    1. Barry says:

      all the ballyhoo about the “Hydrogen economy” focuses on the benign product of oxidation (water) and on the energy density but misses the technical problem of a potent greenhouse gas that leaks right through steel cylinders. When you swap the gram-scale in a highly-ventilated lab for the ton-scale out in the working world, it’s not an attractive fuel.

      1. Gordonjcp says:

        Well, you could stick some carbons to it, that’ll stop it getting out of the bottle 🙂

        I wonder how the chemistry of using other alkanes stacks up? I have an old Range Rover that’s been converted to run on LPG. It’s less energy-dense than petrol so you use a little more (MPG goes down) but you get very much cleaner exhaust emissions – no CO or HC (it runs pretty much bob on stoichiometric), no SOx and very little NOx – cleaner without a catalytic converter than it is on petrol with!

        You do get huge clouds of steam out of the back, which I guess is because a greater proportion of propane is hydrogen, than with octane. I’d love it if someone can confirm or utterly shoot down in flames my back-of-an-envelope high-school chemistry there.

        1. loupgarous says:

          The US Naval Research Laboratories have patented a process for extracting carbon dioxide and hydrogen from seawater.

          The article says: “…the E-CEM has successfully demonstrated proof-of-concept for a simultaneous recovery process of carbon dioxide (CO2) and hydrogen (H2) from seawater. The carbon dioxide and hydrogen gas recovered from the seawater as feedstock are catalytically converted to hydrocarbons in a second additional synthetic process step.”

          Which raises the question of whether sequestration of carbon dioxide from the air to combine with hydrogen made by electrolysis or another non-fossil fuel process, so those gases can be combined in the E-CEM’s catalytic stage to make clean, burnable hydrocarbons is worth pursuing.

          I’m agnostic on that question but it strikes me as perhaps the cleanest way to “put some carbons on that hydrogen.”

          The light alkanes are, as you just pointed out, already used to power motor vehicles. They’re also used as industrial feedstock for numerous processes – the heart of petrochemical industry.

          After peak oil and natural gas supplies are exhausted, our world will need a source for those feedstock gases to make the organics on which its economy turns. It would be enlightened self-interest to make alkanes from sequestered carbon dioxide to make the petrochemical industray, if not carbon-neutral, at least less of a contributor to world carbon dioxide levels.

  64. Michael Ahler says:

    Reading has reminded me of many other tales.
    In the 1970’s I was looking for something else to do with all the chemical waste from our laboratory program (medium size, 4-year university – I was one of 3 chemistry lab technicians at that time).
    Up to that time everything went into the trash or down the drain. I decided to ask around, beginning with the several tenured professors here, all of whom graduated from well established, brand-name universities. I asked several of them about what the chemical waste procedure was when they were “in school”. Each of them told stories with remarkable (but predictable) similarities. The process went much like this in every case:

    At the end of the semester/year the “stockroom guy” would gather up all the chemicals that remained for disposal, load them into a wheelbarrow along with a shovel and a couple gallons of acetone and head out the the empty 50 acre field north of the football stadium. After digging a hole in a different location than last time, he would dump all the discarded materials into the hole and pour in the acetone followed by a lit match and run very fast. After the flames died down he would fill the hole back up with the original soil.

    After 3 or 4 stories like this I stopped asking. In hindsight I now realize I should have expected these responses from men who graduated in the 1940’s and 1950’s.

    Eventually I was able to find (he actually found me on a cold call) a licensed hazardous waste contractor that the university ended up doing business with for about 30 years.

    1. Dave says:

      “After digging a hole in a different location than last time, he would dump all the discarded materials into the hole and pour in the acetone followed by a lit match”

      I’m surprised he needed acetone and a match. And the toxic hazards don’t bear thinking about.

      But it sounds very much like a Max Gergel story !!

  65. bcpmoon says:

    One more Story: While on Holiday in italy, I noticed in a Supermarket that they stored “Eau de Javelle” in nice glass bottles next to the Mineral water section. I had a really nice talk with the Manager…

    1. David Edwards says:

      I had to look that one up, not being familiar with some of the old names for some chemicals. When I discovered what “eau de javel” (the original spelling) was, the thought immediately crossed my mind that your Italian supermarket was setting out to poison hipster American tourists en masse.

      I’m also wondering, referring to Nekekami’s comment above, at the mentality that thought it was a good idea to transport bottles of trimethylaluminium via post. Hmm, Chinese Internet supplier? One that might also be foolish enough to respond to an idiot request for a kilo of dioxygen difluoride in the same manner?

      In the meantime, I recently found a paper covering a topic that will have Derek reaching for his running shoes: uranium azide. Someone actually exerted the effort to synthesise this. Then introduced it to B(C6F5)3.

      1. Lybirby says:

        As an amateur, I’ve had a few things arrive via regular post. Concentrated sulfuric acid, dichloromethane, toluene, xylene, tetrahydrofuran, acetone. All in nice plastic or glass bottles. But such is the life of the hobbyist – no serious chemical supplier will ship to a residential address, so we have to venture to the shady ones who have less concern for safety.

        If you’re wondering, all those solvents were candidates I tried in a search for something which could be used to process 3D prints. Dichloromethane turned out to be the best for PLA plastic. The sulfuric was for electroplating some electronics parts.

  66. Scale it up says:

    moved lab during my PhD which came with the inevitable disposal of anything that was cheaper to buy new later than transport. My job (2nd year PhD) was to dispose of the piranha waste that had for some reason had been allowed to build up and was stored in sealed 2.5 L winchesters.. took me very long time to neutralise all 13+ L of it. Such was the scale, by the end it was poured onto KOH on ice in a bucket by our Australian post doc donning little more than a pair of marigold gloves

    1. David Edwards says:

      My initial confusion about “piranha waste” was compounded by by 35+ years as an aquarist. Once I looked this term up, I learned something new. Though I’m tempted to suggest that Derek might add this mixture to his TIWWW list. 🙂

      This is one of the reasons I keep visiting Derek’s blog. People I’ve never encountered, and probably never will in person (Derek included), add to my knowledge and close the gaps. A far better use of internet bandwidth than all those celebrity selfies.

  67. AT says:

    I must say that my most interesting find was one small shop where they did platings for stuff. They used KCN for this thing. What’s the safest place store a large container of KCN? Well, under the manager’s desk of course. Last place you’d look!

  68. Scott says:

    “An interesting bit about torpedo oxidizer tanks during WW2 is that one of the reasons Japan had the best torpedoes (longer range, larger warhead, faster speed, less visible trails) was that everybody else used compressed air. They used pure oxygen.”
    Yes, the Japanese Type 93 and Type 95 “Long Lance” torpedoes had performance that top-line torpedoes *today* barely have. Though today’s torpedoes are guided, so you only need 1 to get a hit on a ship, instead of a spread of 4-6. And detonate under the hull instead of at the side, so you break the back of the ship (and usually break the ship in half, so it sinks in minutes).

    “Speaking of wildlife sporting around radionuclides, here’s a glimpse of 2 meter-long Wels catfish in the Chernobyl reactor cooling pond. Scary bit of nonchalance is the small child feeding the radiofish by hand (in what we have to assume is water from the secondary and probably contaminated cooling loop of a Chernobyl reactor).”
    Cute little catfish. Call me when it clears 4 meters long. IIRC, Jeremy Wade, the host of River Monsters, caught a sub-1m Wels in the Chernobyl cooling channels, lab tests later determined it to be a stunted runt of a fish that should have been more than 2m long under normal conditions.

    And that’s contaminated water, all right. Chernobyl didn’t use the same kind of setup that the US plants (or even Fukushima) use, where you have the primary loop in direct contact with the reactor, then a heat exchanger to the secondary loop to make steam to spin the turbines, and another heat exchanger to the tertiary loop to finally get rid of that heat into the environment. Chernobyl used primary-loop steam to spin the turbines, and the secondary loop went into the environment. Yes, that means that the turbines would be contaminated. The appropriate descriptive adjectives for that particular piece of Russian engineering are not appropriate for this blog, as they exhaust my personal enlisted-Sailor vocabulary with great rapidity. I start to repeat myself after about 30 seconds.

    “This little tale, courtesy of my GF, regards the somewhat related area of shipping:
    Customs come visiting the lab, bringing a very anonymous package with them, and an x-ray image showing 2 bottles
    Package is brought to hazardous materials lab, where it’s eventually determined that the bottles contain about 150ml’s of TMA.
    Customs decides that police might want to have a little chat with the recipient, who turns out to be a “hobby pyrotechnician” wanting to use it for “experiments”.”
    I’ve received some scary stuff in the mail while I was in the Navy. I was a yeoman, which means I got to deal with all the ship’s mail. Including Registered Mail.

    One heavy Registered Mail box that rattled and clunked contained 3x 9mm pistols. No padding, no nothing. Complete with one magazine each, so they were ready to go as soon as you could find ammunition for them. The Torpedoman in charge of the ship’s small arms was quite glad to get them, but I was NOT happy to see them crossing my desk without warning.

    Worse was getting very light boxes of Registered Mail that were full of packing peanuts and a small box labeled “Morphine Sulfate syringes.” That resulted in an urgent call to the ship’s Corpsman (medic), and stashing the boxes in one of the safes we used for highly-classified materials until the ‘doc’ could pick it up.

  69. Ian B says:

    My scariest moment doesn’t involve chemical storage, but still involves quite a bit of bonehead thinking. I work in an HIV-vaccine lab. We use a modified HIV virus (modified so it can’t integrate into the DNA or reproduce). We further alter it to have an envelope capable of infecting different cell types. Our envelope of choice is VSV, a common one that can infect plenty of cells, human, mouse or otherwise . This isn’t really a problem as long as the virus inside the envelope is safe, which our vaccine viruses are (we hope!).

    However, one post-doc in our lab wanted to do some cell culture experiments with wild-type HIV. She was using mouse cells, so obviously the HIV envelope wouldn’t do. So she whipped up a batch of wild-type, integration-competent and replication-capable virus packed into a VSV envelope, which, as I mentioned, can infect… pretty much anything.

    She presented the experiment results at lab meeting the look on our PI’s face was priceless. Scary, but priceless. That batch of virus was promptly incinerated and a memo was circulated reminding people that we’re trying to protect against HIV, not give it super-powers.

    1. MightBeARedneck says:

      I’m the lead chemist for a firm that handles a lot of Household Hazardous Waste. This is where a company contracts to set up in a municipality on a certain date and time and the citizens can get rid of all the nasties in their basement or garage. Normally, it’s a lot of old paint, pesticides, pool chemicals, the odd thermometer or thermostat and lots of batteries.
      Sometimes, things get interesting. I always kind of look forward to having an event in a college town, You can always tell when one of the chemistry profs has passed. the heirs, or whoever bought the house, come bumping up the road in a pickup truck with a bunch of boxes and bags rattling together in the back. Quart mason jar of Mercury, check. 5 kilos of reagent grade dibenzyl peroxide, check. Jar full of beautiful orange crystals and an old masking tape label with trinitrophenol faintly written on it, check. At least then, I can control the packaging.
      The REALLY fun times is when I receive drums from outside contractors. “Yo Ed, this gallon of acetone was under the table and the flam drum is already on the truck, what do I do?”
      “Hell, just toss it in one of those open drums with the 5.1 sticker”
      “What about this leftover propane cylinder?”
      “Toss it in the other one.”

      Fun times indeed

  70. Thor Fury says:

    Kinda late to the party, but I’ve spent my career in the hazardous waste disposal field. Here’s some entries from my Hall of Fame some of you may enjoy:

    If I had a thousand bucks for each time I’ve been subjected to cyanides being shipped in the same container as acids, I’d be able to pay off my car. Once was thanks to a particularly shit-baggy customer who loose-packed cyanide standards in with mineral acid vials in a 5-gallon pail. Another was someone in my own company who felt the best place for a 5 lb glass jar of sodium cyanide was on top of glass acid bottles in a 55-gallon drum. Hell, I’ve seen customers send in cyanide solutions packed with acids in the same container that they’ve called NON-HAZARDOUS.

    Same customer who shipped the CN/acid vials together once shipped an assortment of pyrophoric materials in glass bottles with no packing material…it was about a 9.5 pucker-factor when I moved the bucket and heard all those bottles smacking into one another.

    SAME customer once tried to ship us some biohazardous chemical (which we aren’t legally permitted to accept). We rejected it back to him twice before he had the brilliant idea of just using a sharpie to black out the biohaz symbol, hoping we wouldn’t notice.

    Seen oxidizers shipped with flammables enough times that I don’t bat an eye anymore. We had a customer that was notorious for not giving a rat’s ass ship us a drum of solid chromic acid as non-hazardous. They just covered all the manufacturer’s markings with non-haz waste labels. Gave the lab tech a hell of a scare when she put the GC extraction solvent on it and it just burst into flames.

    Household hazardous waste collections are always fun. Especially when Joe Homeowner takes an empty pool-oxidizer bucket and uses it in his garage to collect used motor oil – or, better yet, gasoline – and then takes it to the collection and conveniently forgets to mention that the bucket is full of organic liquid. The collection employee doesn’t care to check, so they just pack it with the oxidizers…thankfully the couple of gasoline buckets I’ve encountered didn’t break or leak, but I’ve fished pool oxidizer tablets out of a pool of oil more times than I’m comfortable with…

    Not a dangerous mixture, but once went to do a lab cleanout at a customer’s site and one of the researchers said to me “We have some benzoyl peroxide to get rid of too, but we’ve been keeping that in the oven.” He saw the look on my face and realized he mis-spoke and just yelled “FREEZER, FREEZER!”

    Did another cleanout at a small high school where they stored everything on metal shelves. Glass bottle of some oxidizer (I forget which, might have been copper nitrate) had broken and the stuff hydrolyzed to the point where it ate away at the shelf and began depositing its corrosive oxidizing drippings a few inches from the spools of magnesium ribbon on the shelf below. I’m sure that would have been a fun fire.

    Once had an outside truck driver come to pick up a load, he needed a bucket to catch some drippings from a valve on his tank trailer. We were out of empty buckets, so he took it upon himself to open the nearest bucket of waste so he could use it. The contents happened to be a bottle of high-test methyl ethyl ketone peroxide, which he left on the rear bumper of his tank trailer while pumping flammable liquids on a hot, sunny summer day. He couldn’t fathom why I bitched him out and got all pissy with me about it.

    A potential customer sent in a sample of an organic peroxide spill cleanup that they were hoping we would classify as non-haz. Fat chance…so we didn’t get their business. The lab forgot about the sample for a few years until a thorough cleanout. Not only had the stuff crystallized by then, but the SDS also said it didn’t like metal. Good thing the original customer had sent it to us in a mason jar instead of a proper chemical container. That ended up being a $3000 call to a specialized contractor with a blast trailer to come down and remotely open and dissolve it…

    One of my all-time favorites involved a bucket of what was supposed to be road flares, which are supposed to be shipped under water. Open the bucket and start fishing things out of the liquid…bottle of activated carbon…bag of mothballs…no flares yet. Tilt the bucket to start pouring some of the water out and hear something slide on the bottom. Turned out to be a rusty old metal can of Union Carbide’s finest calcium-based namesake…

    Had another particularly bad customer send us a drum that was supposed to be non-haz, but had a shattered plastic container with white residue and the only legible marking was “NA”. To play it safe, I gathered it and all the parts together and took some of the white stuff into the lab to check for water/acid/base reactivity. It didn’t do anything, so I threw it all into my trash container. 15 minutes later I hear a popping sound coming from it – turns out it WAS sodium after all!

    SAME customer sent us a drum of material that they claimed could be mixed together, but their original list included several poison inhalation hazards and water reactives. Customer promised they removed the offending bottles and I don’t find anything while I’m sorting through the drum and test-pouring everything. I got cautious when I found one bottle with no labeling and poured as little as possible into my test bucket, and promptly got a 5-foot fireball that set the arm of my chemical suit on fire. Turns out they “forgot” to remove the bottle of borane-methyl sulfide complex…

    The one time I thought I was really done was when I opened a drum that was supposed to be ammonia solutions and almost got knocked out by whatever vapor cloud was inside. 30% ammonia is bad enough, this was truly horrendous. Apparently the customer “found more stuff” after everything was packed into drums and waiting for pickup, and the only place they could find room for the leaking 5-gallon container of concentrated hydrochloric acid was in with the leaking ammonia.

    When I worked in the lab, another customer sent us “battery debris” – didn’t bother to tell us it was from lithium batteries. That started a cool little purple fire during the testing procedures…

    It’s been an interesting career thus far. Thankfully the only thing from the Things I Won’t Work With series that I’ve come across has been the nickel carbonyl. The first incinerator I attempted to send that to politely refused, calling it “liquid death”. If only my employer had possessed the same attitude…

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