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Thanks, But No Thanks

From the “Discretion is the Better Part of Valor” files, here’s Dietmar Seyferth looking back on his chemistry career:

For my research advisor I chose Professor Rochow in inorganic chemistry. . .Rochow had joined Harvard some years earlier after a distinguished research career in organosilicon chemistry at the General Electric Co. Research Laboratory in Schenectady, NY. He had ongoing research projects in a number of fields (organic and inorganic silicon chemistry, organotin chemistry, broad-line NMR spectroscopy), but what intrigued me was his proposal to do research in fluorine chemistry. I had become interested in organofluorine chemistry at UB, where I had done a literature project on that subject. Rochow was pleased to hear of my interest and said, “Well, if you want to do something in fluorine chemistry, first we’ll have to build an electrolytic fluorine cell.” After a session in the library reading about the construction and operation of fluorine cells, I returned to his office and asked, “What else have you got?”

A wise move. This goes in the same collection as Matt Meselson’s story about how his own advisor, Linus Pauling, wanted to put him on a tellurium project. Given a choice between making my own fluorine and trying to crystallize tellurium compounds, I think I’d choose. . .well, hold on a minute. . .truck driving school? Cleaning out grease traps? As a character in the old Pogo strip put it once, “No! I can always rob graves!”. If there were truly no other choice, I suppose I’d take my chances with the tellurium, which might well poison me a bit or make me a social pariah, but would not be actively coming to kill me every second I was in the lab (like the fluorine would be).

Fortunately, I’ve never been faced with an offer to take on a project like either of these. Anyone who has, though, please feel free to share your own experience in the comments. And be sure to tell us whether you took the horrible thing on, or decided that something else suddenly looked a lot more interesting. . .

19 comments on “Thanks, But No Thanks”

  1. Dave says:

    Well, I elected to study electronics. After all, those electrons can only kill you quickly, right?

    Then, again, Hydrogen Fluoride/Hydrofluoric Acid is somewhat common in the field of electronics, in everything from semiconductor processing to etching Quartz crystals to frequency (e.g., Bliley’s famous X-Lap process:

    http://www.bliley.net/XTAL/Story.html#Chapter%208

    ). Oh, well, let me go do something safe like making some printed circuit boards. I have this wonderful recipe for doing electroless Tin plating, based on Stannous Chloride, Sodium Hydroxide, and Sodium Cyanide. Err, watch that bottle of acid…

    Dave

  2. Tim McDaniel says:

    I think this post deserves “Things I Won’t Work With”.

  3. anon electrochemist says:

    I took a synthetic job trying to make large quantities of methylaluminoxane. This basically involves the addition of water to neat trimethylaluminum. For those who haven’t had the pleasure, neat trimethylaluminum is so pyrophoric you can test your glovebox atmosphere with it. If upon wrenching open the double valved metal canister, the bottle merely smokes menacingly, you can be sure you have sub-ppm levels of O2 and moisture. It’s so hellish Sigma Aldrich has stopped selling it (although the less feisty 2M dilution in toluene is still available). Patents describe the understated neccessity of a “controlled addition” of water to the viscous organometallic liquid. The enthalpy for this reaction is an eye-watering 300kJ/mol, about 10% of TNT detonation. Plumes of methane gas violently erupt with each drop of water. The worst part was the stirring: too slow and your solution quickly reaches boiling, too fast and you’ll form an alumina gel in solution which ruins the product and risks catastrophic jamming of the stirring apparatus.

    All of this because management wanted to save a few bucks buying the stuff. The chemists eventually convinced management that having the building consumed in an inferno would offset profit margins.

  4. DrSnowboard says:

    When interviewing for PhD positions, my chat with a big cheese prof in the UK seemed to be going well until he outlined the project – reactivity differences of ammonia adsorbed on charcoal. Clearly my facial expression registered the ‘what else have you got’ feeling as I never got an offer. However, I understand the person who got that project swopped out onto one of his relay syntheses after a year as the subject matter proved underwhelming….

  5. Nekekami says:

    @Dave

    How far have the attempts to reduce the use of ClF3 in the semiconductor industry come? I was told a few years ago that it was going slowly, because the alternatives require you to use larger quantities, and need to be run at higher temperatures to achieve the same effect.

    1. Dave says:

      I’ve only been peripherally involved in the semiconductor industry, but my understanding is that they’re VERY reluctant to change a basic process, especially when it can affect millions of chips being produced. Plus, contamination of the Silicon is a big issue; even a tiny table salt crystal can slowly ruin a whole batch of chips (The Sodium slowly diffuses through the passivation layer, and into the Silicon, where it acts as a dopant, and changes the device’s parameters.).

      I have a bit more association with using HF Acid to etch Quartz, having personally done that. That’s a pretty scary process, since the lethal doze of HF Acid is about a .75 inch diameter splash on your body (It grabs the Ca ions, which upsets the Ca/Na/K balance, which stops the heart.). Thus, one has to keep a decent supply of Calcium Gluconate on hand, and be prepared to use it in the event of an accident. And, even then, it’s still a gamble (although inter-venous Calcium Chloride is supposed to help), and, even if you survive, there is the prospect of very painful, long healing wounds.

      https://en.wikipedia.org/wiki/Hydrofluoric_acid#Health_and_safety

      Yeah, the stuff scares me.

      There has been some work with using the safer Ammonium Bifluoride as an etchant for Quartz, although I’m told that a lot of the industrial Quartz crystal producers still use the HF Acid. Then, again, most of those processes are automated, and they usually have the medical staff on hand to handle accidents.

      Dave

      1. misterjeff says:

        Brrrrrrr! That wikipedia link referenced a Honeywell treatment manual for HF acid injuries. I lost it at debridement, and again at the drilling in the nails.

        http://web.archive.org/web/20090325112238/http://www51.honeywell.com/sm/hfacid/common/documents/HF_medical_book.pdf

  6. sepisp says:

    I know you’re looking for juicy chemical hazard stories, but I can only offer something more abstract: a topic that seems to be pure hype but which is actually going nowhere. I mean, all published attempts to work with it in the literature are essentially failures, and despite all the hype, there’s an ominous silence (failures are usually not published). Fine, difficult topics are common in science, but I think the project was planned so that good, marketable results would be obtained quickly. There was no use trying to do basic science. This required plenty of it, and usually with extensive method development due to its novelty. After banging my head on it for two years to get one half-assed paper published, I noped out and asked my professor for another topic. As of today, the paper is still well entrenched in the “nobody cares” territory.

  7. Johnny-John says:

    Watching Br2 co-reflux with CCl4 over a HgO slurry on 1-L scale was certainly one of the most hypnotically frightening things of my entire career:

    10.1021/jo01333a029

    1. Yazeran says:

      Johnny-John, that is one nasty brew!

      What was it used for? (I’m no chemist, so if it is a common catalyst or so I wouldn’t know…)

      Yazeran.

      Plan: To go to Mars one day with a hammer.

  8. A Nonny Mouse says:

    As for the tellurium:

    A Barton post-doc in our (ancient) lab was trying to make tellurones, but they were very light sensitive. As a consequence, he started working nights with red lights and actually succeeded (his wife was also a post-doc and lovingly brought him his evening meal before we were all kicked out).

  9. A Nonny Mouse says:

    Meant the tellurium equivalent of a ketone (Te instead of O) which is probably something different.

  10. Cymantrene says:

    Well, for tellurium componds as pharmaceuticals, check for Biomas.

  11. Johnny-John says:

    Well, for tellurium componds as pharmaceuticals, check for Biomas. Bioa$$ ?

  12. Khem says:

    There’s a famous old Winstein paper where he reports on the discontinuation of a project because of unusual deaths:

    “Despite the intrinsic interest of these unusual compounds, this laboratory has provisionally discontinued all experimental work requiring the preparation or use of the dibromides or their hydrolysis products. There is no a priori reason to believe that these particular compounds are more dangerous to man than several related substances widely used as industrial chemicals; however, of the three laboratory workers who have used the dibromides and bromohydrin VII, two later developed similar pulmonary disorders which contributed to their subsequent deaths. The third has exhibited minor skin sensitivity reactions.

    Although we are aware of no prior toxicological history of these compounds, one cannot ignore the possibility of an insidious long-term effect unknown to medicine. Until further information is obtained from toxicological testing, we recommend that the compounds be handled only with extreme caution, and that all persons concerned with their use be informed of their possible dangerous propensities.”

    http://pubs.acs.org/doi/abs/10.1021/ja01467a058

  13. Hap says:

    I lost the reference, but I think that a group in Turkey reperformed the work (good news: they knew what happened, but bad news: they knew what happened, and still did it). From Google, JOC in 1996 (pp. 8297-8300?) might be the paper.

  14. See Arr Oh says:

    My advisor once placed two projects in front of me:

    1. Build tiny fragment (C13-C20) of much larger molecule. Invent novel early-metal methodology to do so. Next-to-no literature precedent on similar chemistry. Hope to get funding agencies interested later on.

    2. Assemble small tricyclic alkaloid with fairly-straightforward retrosynthesis, which, if made, had a slew of interesting implications in biological pathways and medicine.

    Guess which one I chose?

  15. tangent says:

    That bicycloheptadiene dibromide story is creepy. Yuck.

    For context, are those not going to be some alkylating mofos? Or is that assumed but these workers handle that kind of thing all the time?

  16. Autolykos says:

    In semiconductor physics, people tend to have a good supply of hydrofluoric acid, phosphine and arsine on hand (just to name a few), sometimes in labs with, er, less-than-optimal safety procedures (they’re doing physics, not chemistry, so what could possibly go wrong?).

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