The Scariest Stuff- Pu and Phosgene

Has anyone else noticed how people behave when they describe plutonium?  Invariably, it is described as the most 1) toxic, 2) hazardous, 3) dangerous material on earth. It seems that no matter the context, these adjectives or strings of other adjectives are used in the preamble. (See! I just did it.)  It is though plutonium really is thought of as a manifestation of the dark forces thrusting upward from the underworld. Certainly the name and applications infer some malevolent attributes.

I think this curious attitude to a chemical element exists because most people have no other reference point. In reality, plutonium is a dense radioactive metal, grey in color and sensitive to water and oxygen. It is/was produced by the reduction of the cation with metallic calcium. Like a number of other metals you can’t handle it in the open or without protective garb and inert atmosphere.

I have never heard a credible comparison of it’s chemical vs radiological hazards.  Is it chemically toxic, or does the radiological insult drive the issue.  My guess is that the radioctivity dominates.

Its radioactivity (Pu-239) and chemical reactivity render it useless for much of anything outside of fission-related uses. It’s not even a good paperweight. You wouldn’t want to have a criticality accident on your desk when you spilled coffee on it. Think of the paperwork. Blue flash and heat pulse …

The same curious treatment is afforded phosgene.  Any mention of this substance outside of a chemistry journal invariably recalls the early uses in trench warfare.  The one time I used it as a post-doc, the purchase order for one mole of phosgene in toluene came back to me in the perspiring hand of the Dean of the College. He called me to his office and wanted to know precisely what kind of harm was I inviting to the University. Literally, he wondered what the neighbors would think.

This university was in a wealthy and exclusive neighborhood of a large city in Tejas. What would the neighboring plutocrats think of having research done with a WW-I war gas in their neighborhood? What if *gulp* there was a release?  That’s a fair question.

I was requested and required to write a letter describing the proper emergency response to a spill and what procedures I would put in place to prevent a mishap. This was not a memo of understanding, but rather it was CYA for the Dean in the case of an accident. He could wave the letter around in the inevitable investigation afterwards. He would hand it to my one remaining arm so I could read it publically from my hospital bed for maximum effect.

Oh yes, at near-threshold levels, phosgene has a fragrance very similar to lilac. 

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About gaussling

Gaussling is a senior scientist in the chemical business. He occasionally breaks glassware and has been known to generate new forms of hazmats. Gaussling also digs aerospace, geology, and community theatre. View all posts by gaussling

11 responses to “The Scariest Stuff- Pu and Phosgene

  • Uncle Al

    COCl2 + N2 bubbled into a big pot of Et3N in CH2Cl2 is an especially fine and inexpensive way to dehydrate formamides to isonitriles on 100g scales. COCl2 is kinetically unreactive to water, so scrub contaminated nitrogen effluent through BuNH2 + NaOH pellets. I’d say it smells more like new-mown grass.

    WWII discovered rubber copolymerized with vinyl cyanide made wonderful fuel hoses. Shipping multi-thousand gallon railroad tanker cars of vinyl cyanide was unthinkable! The chemist was sent back into the lab. A week later he reported acrylonitrile worked just as well, and nitrile rubber was born. Compare the structures of vinyl cyanide and acrylonitrile.

    The most awful stuff I’ve encounted is Me3Al. It is not toxic, persistent, or odorous yet there are undeniable real world hazards associated with it.

  • gaussling

    The vinyl cyanide story is a good one. I don’t think I’ve heard that one before.

    I’ve seen the training tapes for TEAL handling. While I’d be ok with it in the lab, I’d be nervous handling cylinders of it. Really, it is not good to be too comfortable with such things. There should always be some pucker factor.

  • around the corner and down the hall

    As a graduate student I had to work with a boatload of Me3Al, using it to generate methylchloroaluminum amide. This was then used to directly convert an ester into the corresponding Weinreb amide. Although I used it as a 2M solution in toluene, I always had the feeling of impending doom. An unfortunate 1st year graduate student was put in charge of fire extinguisher duty, but never had to use it. He thought that all my precautions were a bit overboard, so one day after injecting the material into my reaction, I turned to him and shot the remaining bits of solution into the hood (of course he did not know I was going to do this). When a bright flame erupted out of the end of my needle, his eyes almost popped out of his head and there were likely several swear words uttered. I’m pretty sure he got the idea that pyrophoric chemicals should always be treated with respect. Well, at least I haven’t heard about him starting any fires…

  • John Spevacek

    The juxtaposition of Pu and phosgene in the same article is unusual, as it is my experience that each science is comfotable working with the hazards of their field, but not of another field.

    I worked with some nuclear physicists once who were paranoid of acrylamide. I’ve had countless biologists tell me that toluene stinks to high heaven and is a carcinogen too.

  • gaussling

    My interest is not so much in the details of the hazards, but how people treat the subject of hazardous materials.

    I’ve seen reports where acrylamide has been found in french fries. It is a thermolysis product from the sugars and proteins in the potato.

    People naturally correlate stink with toxicity. I like to point out that aflatoxin or plutonium almost certainly has little or no smell. Contrast this with fish or certain cheeses. Phosgene actually smells pleasant, at least at first. The odor of benzene is not so bad either.

    But the situation is confused with examples of HCl or H2S- their hazard does correlate with the smell. The biggest stinker I have run across is selenophenol- PhSeH. Imagine 6 skunks wrapped in rubber innertubes and the whole thing is set ablaze. That might approach the metaphysical stench of this material.

  • bill

    Hi Gaussling:

    I was asked to do Be chemistry at one point. My lab partners directed me to an isolated lab in the basement that no one else used and suggested I start working there. I, somehow, ordered the stuff, made lots of noises about beginning to work on it and then let the post doc run out without ever actually using it. In the retrospectoscope I suspect it wasn’t as bad as I feared.

    You can buy teal neat or in solution. I’m told plant operators prefer the neat solution because they notice the little flame that forms if it is leaking more easily.

    When I bike it is not the dog barking at me that I am worried about. It is the big silent one that sneaks up on you and then bites that you have to worry about.

    You know – working with big CO tanks (Ethylene/CO copolymers anyone)

    Any others?

  • bill

    What kind of plant operators you ask?

    ZN plant operators in the big state of Tejas down in coastal plane.

  • gaussling

    ZN technology is going strong all around the world. After Kaminsky’s baby was born, people thought ZN would decline. Not true. It is holding on to market share better than anyone thought.

    We used to use TEAL. Nobody speaks longingly about the good old days pumpin’ TEAL. Fancy that.

  • Things I Won’t Work With: Selenophenol | Healthcare

    [...] are eloquent all the same. A few years ago, Gaussling at the Lamentations on Chemistry blog referred to it as “The biggest stinker I have run across. . .Imagine 6 skunks wrapped in rubber innertubes [...]

  • Toxic Carnival: Day One | ScienceGeist

    [...] In The Pipeline Derek is up first with a post on selenophenol. Quoting Th’Gaussling’s description of this molecule: “The biggest stinker I have run across. . .Imagine 6 skunks wrapped in [...]

  • Great Reeks of the Periodic Table « The Science of Heroes

    [...] for extra credit: scary stuff — plutonium and phosgene by the Gaussling on “Lamentations on Chemistry”.) Share [...]

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