12 ms·

Things I Won’t Work With: Dimethylcadmium (2013)

119 points by djoldman 11y ago

bjackman 11y ago
Enjoyable read! My mum is a painter and was recently involved in a campaign against new cadmium regulation in the UK. It's used to produce a red paint that apparently has no substitute. They argued that since it's very expensive, little of it ends up in drains. I'm pleased to say the regulation went through anyway, but with an exception for oil paints.
daturkel 11y ago
These are always a delight to read. Check out the whole series here: http://blogs.sciencemag.org/pipeline/archives/category/things-i-wont-work-with http://blogs.sciencemag.org/pipeline/archives/category/thing...
- Steko 11y ago
  Sand Won't Save You This Time (the prequel to Chlorine Trifluoride: Some Empirical Findings) is also worth the read. Quoting John Drury Clark: It is, of course, extremely toxic, but that’s the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. http://blogs.sciencemag.org/pipeline/archives/2008/02/26/sand_wont_save_you_this_time http://blogs.sciencemag.org/pipeline/archives/2008/02/26/san...
  - jacinda 11y ago
    His follow-up from 2013 includes video of what actually happens when you pour this substance on various types of protective gear. It really drives his point home (and is full of entertaining explosions). http://blogs.sciencemag.org/pipeline/archives/2013/04/05/chlorine_trifluoride_some_empirical_findings http://blogs.sciencemag.org/pipeline/archives/2013/04/05/chl...
  - mjcohen 11y ago
    That's nothing. Resublimated Thiotimoline dissolves before it hits the water. Look here: https://en.wikipedia.org/wiki/Thiotimoline https://en.wikipedia.org/wiki/Thiotimoline
    - therein 11y ago
      How about azidoazide azide or 1-diazidocarbamoyl-5-azidotetrazole (C2N14)? It will "literally explode if you move it, touch it, disperse it in solution, expose it to x-rays, expose it to light, and even if you did absolutely nothing to it." [1] [1] http://pipeline.corante.com/archives/2013/01/09/things_i_wont_work_with_azidoazide_azides_more_or_less.php http://pipeline.corante.com/archives/2013/01/09/things_i_won...
  - cromulent 11y ago
    Worth the read for me. I Googled the ISBN of the quoted book by Clark "Ignition" and found a PDF copy online. http://library.sciencemadness.org/library/books/ignition.pdf http://library.sciencemadness.org/library/books/ignition.pdf
    - jamessb 11y ago
      There was some discussion when that PDF was posted here 3 weeks ago: https://news.ycombinator.com/item?id=10683778 https://news.ycombinator.com/item?id=10683778
danharaj 11y ago
That was an entertaining read. The comments are worth it as brief glimpses into the wild west of consumer chemicals. I'm glad most of the toxic exotic compounds in my life are safely held within a laptop's plastic casing.
Pxtl 11y ago
... I think I'm going to go through my basement and make sure I don't have any old nicad batteries kicking around now.
- dietrichepp 11y ago
  While cadmium is toxic, organometallic compounds are much worse than what you have in your batteries. For example, you can play with mercury. You definitely SHOULD NOT, but it won't kill you. On the other hand, dimethyl mercury WILL kill you.
  - userbinator 11y ago
    When talking about the toxicity of dimethylmercury, it is almost obligatory to mention https://en.wikipedia.org/wiki/Karen_Wetterhahn https://en.wikipedia.org/wiki/Karen_Wetterhahn exposure to only a few drops of the chemical absorbed through the gloves proved to be fatal after less than a year.
    - goldenkey 11y ago
      "Her husband saw tears rolling down her face. I asked if she was in pain. The doctors said it didn't appear that her brain could even register pain."[5]
    - x0x0 11y ago
      wow. Apparently nobody thought to see if it goes through latex gloves, and it apparently does in seconds! Current safety protocol is now "highly resistant, flexible, plastic-laminate gloves [...]. For increased protection, such thin gloves can be worn under long-cuffed, heavy-duty outer gloves made of, for example, neoprene." Or just not using dimethylmercury.
  - sliverstorm 11y ago
    Presumably the body more readily incorporates organometallics than elemental metal
  - kansface 11y ago
x0x0 11y ago
it's not chemistry, but tangentially, I have another amazing read. Liquid N2 is held in a dewar, consisting of an internal and an external tank with vacuum in between. In case of overpressure, there are blowout valves, designed to relieve pressure in a large hole rather than a small one. You'd rather have a large hole because a high pressure tank with a small hole is basically a rocket. Or a grenade. Also, the N2 liquid to gas expansion factor is roughly 1:700. In any case, some special person at Texas A&M noticed a N2 dewar with a presumably damaged overpressure blowout valve and fucking welded a brass plug in place. Eventually, the tank catastrophically failed, most likely due to corrosion of the internal tank, leading to temperature increase and the aforementioned 1:700 volume increase. According to I believe the tank manufacturer, the tank mechanically fails at 1200 psi. When it finally went boom, it shredded the room it was in, put a 24-in hole through a concrete floor, significantly damaged a concrete/steel support beam, and was eventually stopped by a 3-in water main and other stuff in a mechanical room. Miraculously it went at 3-am or so and no-one was present. When people determined what had happened, some unlucky dude who didn't get paid nearly enough got to frantically inspect every tank in the chemistry building to see if the mystery welder had "upgraded" any others. There's a report pdf somewhere on the internet that I can't find at the moment. I may have some details wrong but the boom part is definitely right =P edit: https://web.archive.org/web/20060901094515/http://finance.tamu.edu/ehsd/report_on_chemistry_301A.pdf https://web.archive.org/web/20060901094515/http://finance.ta... it's worth looking at the pictures in the pdf
- HCIdivision17 11y ago
  I think there should be a category of "there I fixed it" just for over zealous welders. I worked with a robot that had an aluminum tool that got mangled every time the robot got in a fight with the lift table. This was a Kuka 450 (as in kg), and it could really stack. A maintenance guy thought it was an enormous chore rebuilding the tool each time, so he bolted (literally) a 3/8 inch steel plate to the thin aluminum a frame. And when that tore welded the whole shebang. Next time the robot snapped its wrist, since the tool could no longer buckle and absorb the impact, and it rather impressed the service engineer with the... sturdiness of the tool. I wanted to share the story about environmental's efforts to put gas meters on the safety release valves on our large liquid argon dewars, but we thankfully convinced them that accidentally blowing a crater in the plant was a worse OSHA violation than upsetting our local regulators. (An accident in a nearby county with a truck hauling liquid gas dewars resulted in a death by displacing all the air in the intersection with Argon, leading the inert gas to be classified as a dangerous controlled substance that needed to be monitored and metered...)
virlirium 11y ago
I handle vapors of organometallic compounds everyday. dimethyl-X, trimethyl-X, tetramethyl-X and other long name OM compounds that can kill slowly or instantly. Recently theres HF vapors and today its a cyanide compound. I'm lucky to still be alive!
- bmer 11y ago
  1) Why do you have to handle these compounds every day? (if it's for work, what sort of work (oh, and are you well compensated)? if it's for research, research on what? if it's for fun, why?) 2) What sort of personal protective gear do you have to use?
  - virlirium 11y ago
    1) I'm a grad student working on MOCVD and ALD, so no I'm not well compensated :( 2) Not enough. Respirator, coats and gloves.
coldcode 11y ago
In grad school around 1980 I was doing some reaction under a hood using DMSO as the solvent and for some reason it was converted into DMS (DiMethyl Sulfide) and we discovered how bad the vent system was in the building (it was terrible). The building was evacuated and they forced me to go back in to look up how toxic DMS was (stupid grad students are expendable). Thankfully while it is chemical related to Hydrogen Sulfide it was not all that dangerous and in a couple of hours it cleared. However if you ever get to smell it you will run as far as you can and the odor is unstoppable. Forget tear gas, toss some of this into a building and watch everything run out. Cleaning out the hood was a terrible experience.

119 points by djoldman 11y ago

Enjoyable read! My mum is a painter and was recently involved in a campaign against new cadmium regulation in the UK. It's used to produce a red paint that apparently has no substitute. They argued that since it's very expensive, little of it ends up in drains. I'm pleased to say the regulation went through anyway, but with an exception for oil paints.

daturkel 11y ago

These are always a delight to read. Check out the whole series here: http://blogs.sciencemag.org/pipeline/archives/category/things-i-wont-work-with http://blogs.sciencemag.org/pipeline/archives/category/thing...

Steko 11y ago
Sand Won't Save You This Time (the prequel to Chlorine Trifluoride: Some Empirical Findings) is also worth the read. Quoting John Drury Clark: It is, of course, extremely toxic, but that’s the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water-with which it reacts explosively. http://blogs.sciencemag.org/pipeline/archives/2008/02/26/sand_wont_save_you_this_time http://blogs.sciencemag.org/pipeline/archives/2008/02/26/san...
- jacinda 11y ago
  His follow-up from 2013 includes video of what actually happens when you pour this substance on various types of protective gear. It really drives his point home (and is full of entertaining explosions). http://blogs.sciencemag.org/pipeline/archives/2013/04/05/chlorine_trifluoride_some_empirical_findings http://blogs.sciencemag.org/pipeline/archives/2013/04/05/chl...
- mjcohen 11y ago
  That's nothing. Resublimated Thiotimoline dissolves before it hits the water. Look here: https://en.wikipedia.org/wiki/Thiotimoline https://en.wikipedia.org/wiki/Thiotimoline
  - therein 11y ago
    How about azidoazide azide or 1-diazidocarbamoyl-5-azidotetrazole (C2N14)? It will "literally explode if you move it, touch it, disperse it in solution, expose it to x-rays, expose it to light, and even if you did absolutely nothing to it." [1] [1] http://pipeline.corante.com/archives/2013/01/09/things_i_wont_work_with_azidoazide_azides_more_or_less.php http://pipeline.corante.com/archives/2013/01/09/things_i_won...
- cromulent 11y ago
  Worth the read for me. I Googled the ISBN of the quoted book by Clark "Ignition" and found a PDF copy online. http://library.sciencemadness.org/library/books/ignition.pdf http://library.sciencemadness.org/library/books/ignition.pdf
  - jamessb 11y ago
    There was some discussion when that PDF was posted here 3 weeks ago: https://news.ycombinator.com/item?id=10683778 https://news.ycombinator.com/item?id=10683778

danharaj 11y ago

That was an entertaining read. The comments are worth it as brief glimpses into the wild west of consumer chemicals. I'm glad most of the toxic exotic compounds in my life are safely held within a laptop's plastic casing.

Pxtl 11y ago

... I think I'm going to go through my basement and make sure I don't have any old nicad batteries kicking around now.

dietrichepp 11y ago
While cadmium is toxic, organometallic compounds are much worse than what you have in your batteries. For example, you can play with mercury. You definitely SHOULD NOT, but it won't kill you. On the other hand, dimethyl mercury WILL kill you.
- userbinator 11y ago
  When talking about the toxicity of dimethylmercury, it is almost obligatory to mention https://en.wikipedia.org/wiki/Karen_Wetterhahn https://en.wikipedia.org/wiki/Karen_Wetterhahn exposure to only a few drops of the chemical absorbed through the gloves proved to be fatal after less than a year.
  - goldenkey 11y ago
    "Her husband saw tears rolling down her face. I asked if she was in pain. The doctors said it didn't appear that her brain could even register pain."[5]
  - x0x0 11y ago
    wow. Apparently nobody thought to see if it goes through latex gloves, and it apparently does in seconds! Current safety protocol is now "highly resistant, flexible, plastic-laminate gloves [...]. For increased protection, such thin gloves can be worn under long-cuffed, heavy-duty outer gloves made of, for example, neoprene." Or just not using dimethylmercury.
- sliverstorm 11y ago
  Presumably the body more readily incorporates organometallics than elemental metal
- kansface 11y ago

x0x0 11y ago

it's not chemistry, but tangentially, I have another amazing read. Liquid N2 is held in a dewar, consisting of an internal and an external tank with vacuum in between. In case of overpressure, there are blowout valves, designed to relieve pressure in a large hole rather than a small one. You'd rather have a large hole because a high pressure tank with a small hole is basically a rocket. Or a grenade. Also, the N2 liquid to gas expansion factor is roughly 1:700. In any case, some special person at Texas A&M noticed a N2 dewar with a presumably damaged overpressure blowout valve and fucking welded a brass plug in place. Eventually, the tank catastrophically failed, most likely due to corrosion of the internal tank, leading to temperature increase and the aforementioned 1:700 volume increase. According to I believe the tank manufacturer, the tank mechanically fails at 1200 psi. When it finally went boom, it shredded the room it was in, put a 24-in hole through a concrete floor, significantly damaged a concrete/steel support beam, and was eventually stopped by a 3-in water main and other stuff in a mechanical room. Miraculously it went at 3-am or so and no-one was present. When people determined what had happened, some unlucky dude who didn't get paid nearly enough got to frantically inspect every tank in the chemistry building to see if the mystery welder had "upgraded" any others. There's a report pdf somewhere on the internet that I can't find at the moment. I may have some details wrong but the boom part is definitely right =P edit: https://web.archive.org/web/20060901094515/http://finance.tamu.edu/ehsd/report_on_chemistry_301A.pdf https://web.archive.org/web/20060901094515/http://finance.ta... it's worth looking at the pictures in the pdf

HCIdivision17 11y ago
I think there should be a category of "there I fixed it" just for over zealous welders. I worked with a robot that had an aluminum tool that got mangled every time the robot got in a fight with the lift table. This was a Kuka 450 (as in kg), and it could really stack. A maintenance guy thought it was an enormous chore rebuilding the tool each time, so he bolted (literally) a 3/8 inch steel plate to the thin aluminum a frame. And when that tore welded the whole shebang. Next time the robot snapped its wrist, since the tool could no longer buckle and absorb the impact, and it rather impressed the service engineer with the... sturdiness of the tool. I wanted to share the story about environmental's efforts to put gas meters on the safety release valves on our large liquid argon dewars, but we thankfully convinced them that accidentally blowing a crater in the plant was a worse OSHA violation than upsetting our local regulators. (An accident in a nearby county with a truck hauling liquid gas dewars resulted in a death by displacing all the air in the intersection with Argon, leading the inert gas to be classified as a dangerous controlled substance that needed to be monitored and metered...)

virlirium 11y ago

I handle vapors of organometallic compounds everyday. dimethyl-X, trimethyl-X, tetramethyl-X and other long name OM compounds that can kill slowly or instantly. Recently theres HF vapors and today its a cyanide compound. I'm lucky to still be alive!

bmer 11y ago
1) Why do you have to handle these compounds every day? (if it's for work, what sort of work (oh, and are you well compensated)? if it's for research, research on what? if it's for fun, why?) 2) What sort of personal protective gear do you have to use?
- virlirium 11y ago
  1) I'm a grad student working on MOCVD and ALD, so no I'm not well compensated :( 2) Not enough. Respirator, coats and gloves.

coldcode 11y ago

In grad school around 1980 I was doing some reaction under a hood using DMSO as the solvent and for some reason it was converted into DMS (DiMethyl Sulfide) and we discovered how bad the vent system was in the building (it was terrible). The building was evacuated and they forced me to go back in to look up how toxic DMS was (stupid grad students are expendable). Thankfully while it is chemical related to Hydrogen Sulfide it was not all that dangerous and in a couple of hours it cleared. However if you ever get to smell it you will run as far as you can and the odor is unstoppable. Forget tear gas, toss some of this into a building and watch everything run out. Cleaning out the hood was a terrible experience.